CN110272058A - A kind of MCM-41 ordered mesoporous material and preparation method thereof - Google Patents
A kind of MCM-41 ordered mesoporous material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of MCM-41 ordered mesoporous material and preparation method thereof, preparation method includes being leached using iron tailings as raw material with inorganic strong acid solution, is separated by solid-liquid separation, is washed and is dried after heating stirring, obtains sour insoluble slag；The ratio that sour insoluble slag and alkali metal hydroxide are 1:1.4~2.4 in mass ratio is mixed, carries out hydro-thermal reaction after adding deionized water, then be separated by solid-liquid separation to obtain silicon source；Silicon source is mixed with surfactant, deionized water, ethyl alcohol, adjusts the pH value of mixed solution, generation gel reaction, then washed, drying and grinding is stirred at room temperature, obtains presoma；Presoma is calcined into 5~9h at 540~850 DEG C, obtains MCM-41 ordered mesoporous material.The above method is easy to operate, and silicon source recovery rate is high, improves iron tailings comprehensive utilization ratio；Gained mesoporous material cellular structure is regular, pore size is adjustable, specific surface area is high.
Description
Technical field
The present invention relates to technical field of function materials, in particular to a kind of MCM-41 ordered mesoporous material and its preparation side
Method.
Background technique
Ordered mesoporous material is rapidly growing novel nano structure material the 1990s in last century, it is once being born
The great attention of international physics, chemistry and material educational circles is obtained, and is rapidly developed as one of research hotspot interdisciplinary.It is situated between
The synthesis of Porous materials just had begun early in 1971, but until Mobil company report in 1992 synthesizes M41S series
Mesoporous material just attracts much attention.MCM-41 mesoporous material is one kind of M41S series, and duct is in six side's ordered arrangements, big
It is small uniformly, aperture can be continuously adjusted within the scope of 2~10nm, large specific surface area, have excellent ion exchange, catalysis and absorption
Performance has in many fields such as fine chemical industry petro chemical industry, medical and health and environmental protection and has been widely used
With huge application potential.
Currently, the conventional preparation techniques of MCM-41 mesoporous material use low-temperature hydrothermal, prepares raw material and be generally positive silicic acid second
The industrial chemicals such as ester, waterglass, time-consuming, energy consumption that there are preparation processes prepare that cost of material is higher and limited source, while certain
Silicon source toxicity with higher results in the harm to environment, this seriously constrain MCM-41 mesoporous material large-scale use and
Application field is further widened.Therefore, development technology condition is loose, synthesizes efficiently preparation process, while it is low to find price
The two big key points for preparing raw material and being to speed up MCM-41 mesoporous material large-scale application honest and clean, from a wealth of sources and environmentally friendly.
Iron tailings is the waste after the ore dressing of iron ore factory, is the important component of industrial solid castoff.According to endless
Full statistics, the iron tailings total amount nearly 4.5 × 10 that China is now stored up9T accounts for about the 30% of national tailing total amount.The stacking of iron tailings
A large amount of soils are not only occupied, and bring serious pollution and harm to the production of the mankind, life, meanwhile, as mineral products provide
A large amount of developments and utilizations in source, ore resource is increasingly poor, iron tailings as secondary resource recycling by countries in the world
Extensive attention.Iron tailings contains many useful components as a kind of silicates inorganic material, especially contains a large amount of silicon
Element, can silicon source by purification processes as synthesising mesoporous silicon materials.By the end of currently, being original about using iron tailings
Material prepares the paper studies report of MCM-41 ordered mesoporous material using Conventional cryogenic hydrothermal process, such as Northeastern University researcher benefit
The specific surface area of the MCM-41 mesoporous material prepared with iron tailings is about 527m2/g(Honghao Yu,Xiangxin Xue,
Dawei Huang.Synthesis of mesoporous silica materials(MCM-41)from iron ore
tailings.Materials Research Bulletin.44(2009),2112–2115.)；China University of Geosciences researcher
It is prepared for MCM-41 mesoporous material by raw material of iron tailings, its silicon source recovery rate is about 65% in preparation process, the MCM- of preparation
41 specific surface area is only 882m2/g(Guang Yang,Yanxi Deng,Hao Ding,Zhixiang Lin,Yuankai
Shao,Yan Wang.A facile approachtosynthesize MCM-41mesoporous
materialsfromironore tailing:Influence of the synthesis conditions on
thestructural properties.Applied Clay Science.111(2015),61–66.)；It is original with iron tailings
Material obtains silicon source and prepares in the research of mesoporous material, two problems is primarily present, first is that silicon source recovery rate is lower, second is that being mesoporous
Material preparation process is cumbersome, and time-consuming, energy consumption and mesoporous material specific surface area are lower, the serious mesoporous material for restricting iron tailings preparation
Development and application.Therefore, it is necessary to improve silicon source recovery rate in iron tailings, provide that a kind of process conditions are loose, and synthesis is efficiently
Method prepares the MCM-41 ordered mesoporous material of high-specific surface area.
Summary of the invention
The present invention provides a kind of MCM-41 ordered mesoporous materials and preparation method thereof, and its purpose is to be with iron tailings
Raw material, prepares the MCM-41 ordered mesoporous material of high-specific surface area, while improving silicon source recovery rate, and simplifies preparation work
Skill shortens manufacturing cycle.
In order to achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of MCM-41 ordered mesoporous material, includes the following steps:
(1) it using iron tailings as raw material, is leached with inorganic strong acid solution, is separated by solid-liquid separation, is washed and is done after heating stirring
It is dry, obtain sour insoluble slag；
It (2) is in mass ratio that the ratio of 1:1.4~2.4 is mixed by sour insoluble slag and alkali metal hydroxide obtained by step (1)
It closes, carries out hydro-thermal reaction after deionized water is added, then obtain silicon source through being separated by solid-liquid separation；Wherein, silicon source recovery rate is greater than 95%；
It (3) is in molar ratio Si by silicon source obtained by step (2) and surfactant, deionized water, ethyl alcohol: surface-active
Agent: H2O: ratio mixing in ethyl alcohol=1:0.1~0.2:500~600:7~120 adjusts the pH value of mixed solution to 8~12,
It is stirred generation gel reaction, then washed, drying and grinding at room temperature, obtains presoma；
(4) presoma obtained by step (3) is calcined at 540~850 DEG C 5~9h, obtains MCM-41 ordered mesoporous material.
Preferably, the solid-to-liquid ratio of iron tailings and inorganic strong acid solution is 1:1.5~6 (g/mL) in step (1).
Preferably, inorganic strong acid solution concentration described in step (1) is 2~8mol/L.
Preferably, heating stirring described in step (1) is specially at a temperature of magnetic agitation 3~6h at 100~150 DEG C.
Preferably, acid insoluble slag described in step (2) and alkali metal hydroxide are solid matter, the solid matter with
The solid-to-liquid ratio of deionized water is 1:1.5~3 (g/mL).
Preferably, hydrothermal temperature described in step (2) is 160~220 DEG C；Time is 6~12h.
Preferably, surfactant described in step (3) be cetyl trimethylammonium bromide, concentration be 0.0075~
0.015mol/L。
Preferably, it is 25~40 DEG C that temperature is stirred to react described in step (3)；Reaction time is 1~7h.
Preferably, calcination atmosphere is air atmosphere in step (4)；The heating rate of calcination process is 1~3 DEG C/min；It forges
Burning mode is one-step calcination or step calcination.
The present invention also provides the ordered mesoporous materials that a kind of MCM-41 is prepared by above-mentioned any one method, are given an account of
The specific surface area of Porous materials is 969~1677m2/g。
It is prepared in the research of mesoporous material currently, obtaining silicon source as raw material using iron tailings, there are problems that two, first is that silicon source
Recovery rate is lower, second is that mesoporous material preparation process is cumbersome, time-consuming, energy consumption and mesoporous material specific surface area are lower, serious to restrict
The development and application of the mesoporous material of iron tailings preparation.By the present invention in that non-aqueous with the processing of high temperature acid solution, hydro-thermal alkali soluble and room temperature
Thermal process, can silicon source recovery rate significantly, while mesoporous material preparation process condition is loose, and synthesis is quick, MCM-41 obtained
Ordered mesoporous material has more high-specific surface area.
The present invention soaks industry innovatively using iron tailings as raw material, by high temperature acidleach-hydro-thermal alkali, solves to utilize iron tailings
The problem that silicon source recovery rate is low existing for MCM-41 mesoporous material is prepared, more pure silicon sources are obtained, then with cationic surface
Activating agent is template, using the non-aqueous heat gel reaction method preparation cellular structure of room temperature is regular, pore size is adjustable, compares table
The higher MCM-41 ordered mesoporous material of area, simple process are quick.Method proposed by the present invention is the extensive comprehensive of iron tailings
It closes to utilize and provides important thinking.
Above scheme of the invention have it is following the utility model has the advantages that
(1) present invention is using iron tailings as raw material, by high temperature acidleach-hydro-thermal alkali soaking technology, solves to prepare using iron tailings
The low problem of silicon source recovery rate existing for MCM-41 mesoporous material obtains more pure silicon sources, to prepare more mesoporous materials
Material, effectively improves the yield that mesoporous material is prepared using iron tailings.Then using cationic surfactant as template, using room
The non-aqueous heat gel reaction method of temperature obtains that cellular structure is regular, pore size is adjustable, the higher MCM-41 of specific surface area is orderly
Mesoporous material.
(2) silicon source extractive technique chemical agent usage amount of the invention is few, and silicon source recovery rate is high, and it is comprehensive to improve iron tailings
Utilization rate；Preparation process environmental pollution is small, and preparation process is simple, and time-saving energy-saving, raw material is easy to get, low in cost.
(3) duct of the MCM-41 ordered mesoporous material prepared by the present invention is parallel to each other, and cross section is in Hexagonal array, tool
There is regular two-dimentional hexagonal structure, specific surface area is up to 1677m2/ g, pore volume can reach 1.112cm3/ g or more, aperture point
Cloth is concentrated, and pore performance is good.The bigger specific surface area of MCM-41 ordered mesoporous material can effectively improve the applications such as absorption, catalysis
Performance.
Detailed description of the invention
Fig. 1 is iron tailings X-ray diffraction (XRD) figure of the invention；
Fig. 2 is the small angle XRD diagram of the embodiment of the present invention 1MCM-41 mesoporous material；
Fig. 3 is the wide angle XRD diagram of the embodiment of the present invention 1MCM-41 mesoporous material；
Fig. 4 is the nitrogen adsorption desorption curve figure of the embodiment of the present invention 1MCM-41 mesoporous material；Graph of pore diameter distribution；
Fig. 5 is the graph of pore diameter distribution of the embodiment of the present invention 1MCM-41 mesoporous material；
Fig. 6 is scanning electron microscope (SEM) figure of embodiment 1MCM-41 mesoporous material；
Fig. 7 is embodiment 1MCM-41 mesoporous material transmission electron microscope (TEM) figure.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
Embodiment 1
(1) using iron tailings as raw material, iron tailings chemical component composition analysis is as shown in table 1, object phase composition such as 1 institute of attached drawing
Show, the hydrochloric acid solution of 8mol/L is leaching agent, takes iron tailings and aqueous hydrochloric acid solution according to the ratio that solid-to-liquid ratio is 1:1.5 (g/mL)
Mixing, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, filtered after being cooled to room temperature, to filtering institute
Solid matter with deionized water is washed to neutral (identical as deionized water pH), dried at a temperature of 60 DEG C, it is insoluble to obtain acid
Slag, sour insoluble slag chemical component composition analysis are as shown in table 1.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma, the small angle XRD and width angle XRD of presoma at a temperature of 60 DEG C
As shown in Figure 2 and Figure 3.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1419m are obtained2/ g, pore volume are
0.954m3/ g, the small angle XRD and width angle XRD of average pore size 1.96nm, MCM-41 ordered mesoporous material are as shown in Figure 2 and Figure 3,
The nitrogen adsorption desorption curve figure and graph of pore diameter distribution of MCM-41 mesoporous material are as shown in Figure 4, Figure 5, MCM-41 mesoporous material
Scanning electron microscope (SEM) is as shown in fig. 6, MCM-41 mesoporous material transmission electron microscope (TEM) is as shown in Figure 7.
X-ray fluorescence spectrometry (XRF) result of 1 iron tailings of table, sour insoluble slag and alkali insoluble slag
Embodiment 2
(1) using iron tailings as raw material, the sulfuric acid solution of 4mol/L is leaching agent, is the ratio of 1:3 (g/mL) according to solid-to-liquid ratio
Example takes iron tailings and combined, 100 DEG C at a temperature of magnetic agitation 6h after obtain dirty solution, be cooled to room
It is filtered after temperature, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1308m are obtained2/ g, pore volume are
1.013m3/ g, average pore size 2.157nm.
Embodiment 3
(1) using iron tailings as raw material, the hydrochloric acid solution of 2mol/L is leaching agent, is the ratio of 1:6 (g/mL) according to solid-to-liquid ratio
Example takes iron tailings and combined, 120 DEG C at a temperature of magnetic agitation 5h after obtain dirty solution, be cooled to room
It is filtered after temperature, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1328m are obtained2/ g, pore volume are
1.003m3/ g, average pore size 2.127nm.
Embodiment 4
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:1.4 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1256m are obtained2/ g, pore volume are
0.992m3/ g, average pore size 2.178nm.
Embodiment 5
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.4 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1192m are obtained2/ g, pore volume are
0.972m3/ g, average pore size 2.138nm.
Embodiment 6
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2 (g/ according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
G), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:1.5 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1162m are obtained2/ g, pore volume are
0.962m3/ g, average pore size 2.118nm.
Embodiment 7
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:3 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 25 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1152m are obtained2/ g, pore volume are
0.964m3/ g, average pore size 2.121nm.
Embodiment 8
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 160 DEG C at a temperature of hydro-thermal 12h after obtain dirty solution, carried out after being cooled to room temperature
It filters, filtrate is spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 40 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1226m are obtained2/ g, pore volume are
0.989m3/ g, average pore size 2.153nm.
Embodiment 9
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, sublevel section calcining, one section in 250 DEG C of heat preservation 2h, two sections
In 540 DEG C of temperature lower calcination heat preservation 5h (heating rate is 2 DEG C/min), surfactant is removed, MCM-41 is obtained and is orderly situated between
Porous materials, specific surface area 1677m2/ g, pore volume 1.112m3/ g, average pore size 2.74nm.
Embodiment 10
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
3 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1269m are obtained2/ g, pore volume are
0.997m3/ g, average pore size 2.173nm.
Embodiment 11
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 850 DEG C of temperature lower calcination heat preservation 4h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 969m are obtained2/ g, pore volume are
0.897m3/ g, average pore size 1.731nm.
Embodiment 12
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 220 DEG C at a temperature of hydro-thermal 6h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 8 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 9h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1359m are obtained2/ g, pore volume are
1.029m3/ g, average pore size 2.164nm.
Embodiment 13
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 12 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution,
Magnetic agitation 3h at a temperature of 30 DEG C of room temperature, obtains the mixing suspension containing white gels product, by product deionized water
Washing to supernatant is free of CTAB, and drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
1 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1216m are obtained2/ g, pore volume are
0.922m3/ g, average pore size 2.179nm.
Embodiment 14
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.1:525:60], take the cation of 0.37g
Surfactant cetyl trimethylammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until solution
It is transparent, 34mL ethyl alcohol is instilled, the concentration of CTAB is 0.0075mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 3h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1116m are obtained2/ g, pore volume are
0.862m3/ g, average pore size 2.042nm.
Embodiment 15
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.2:525:60], take the cation of 0.75g
Surfactant cetyl trimethylammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until solution
It is transparent, 34mL ethyl alcohol is instilled, the concentration of CTAB is 0.015mol/L at this time, stirs 5min, and alkali soluble obtained in step (2) is added
Filtrate silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room temperature
Magnetic agitation 3h at a temperature of 30 DEG C obtains that product being washed with deionized containing the mixing suspension of white gels product
CTAB is free of to supernatant, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1466m are obtained2/ g, pore volume are
0.992m3/ g, average pore size 2.008nm.
Embodiment 16
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 1h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1324m are obtained2/ g, pore volume are
1.012m3/ g, average pore size 2.185nm.
Embodiment 17
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:525:60], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 96mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 34mL ethyl alcohol, and the concentration of CTAB is 0.01mol/L at this time, stirs 5min, and alkali obtained in step (2) is added
Lixiviation liquid silicon source obtains mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution, in room
Magnetic agitation 7h at a temperature of 30 DEG C of temperature, obtains that product being washed with deionized water containing the mixing suspension of white gels product
It washs to supernatant and is free of CTAB, drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1391m are obtained2/ g, pore volume are
0.902m3/ g, average pore size 1.899nm.
Embodiment 18
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:500:7], take the cation of 0.5g
Surfactant cetyl trimethylammonium bromide (CTAB), is dissolved in the deionized water of 91.5mL, and ultrasonic agitation is until molten
Liquid is transparent, instills 4.15mL ethyl alcohol, and the concentration of CTAB is 0.0143mol/L at this time, stirs 5min, is added in step (2) and obtains
Alkali soluble filtrate silicon source, obtain mixed solution.It is 9 by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution,
In 30 DEG C of room temperature of at a temperature of magnetic agitation 7h, the mixing suspension containing white gels product is obtained, by product deionization
Water washing to supernatant is free of CTAB, and drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1351m are obtained2/ g, pore volume are
0.912m3/ g, average pore size 2.229nm.
Embodiment 19
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:600:7], take the cation of 0.5g
Surfactant cetyl trimethylammonium bromide (CTAB), is dissolved in the deionized water of 109.73mL, ultrasonic agitation until
Solution is transparent, instills 4.15mL ethyl alcohol, and the concentration of CTAB is 0.0125mol/L at this time, stirs 5min, is added in step (2) and obtains
The alkali soluble filtrate silicon source arrived obtains mixed solution.It is by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution
9, in 30 DEG C of room temperature of at a temperature of magnetic agitation 7h, obtain the mixing suspension containing white gels product, by product spend from
Sub- water washing to supernatant is free of CTAB, and drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1311m are obtained2/ g, pore volume are
0.902m3/ g, average pore size 2.219nm.
Embodiment 20
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:600:120], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 109.73mL, and ultrasonic agitation is straight
It is transparent to solution, 71.15mL ethyl alcohol is instilled, the concentration of CTAB is 0.0076mol/L at this time, stirs 5min, is added in step (2)
Obtained alkali soluble filtrate silicon source obtains mixed solution.By regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution
It is 9, in 30 DEG C of room temperature of at a temperature of magnetic agitation 7h, obtains spending product containing the mixing suspension of white gels product
The supreme clear liquid of ion water washing is free of CTAB, and drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1111m are obtained2/ g, pore volume are
0.852m3/ g, average pore size 2.009nm.
Embodiment 21
(1) using iron tailings as raw material, the hydrochloric acid solution of 8mol/L is leaching agent, is 1:1.5 (g/mL) according to solid-to-liquid ratio
Ratio takes iron tailings and combined, 150 DEG C at a temperature of magnetic agitation 3h after obtain dirty solution, be cooled to
It is filtered, is washed with deionized to obtained solid product is filtered to neutral (identical as deionized water pH), 60 DEG C after room temperature
At a temperature of dry, obtain sour insoluble slag.
It (2) is 1:2.2 according to the mass ratio of sour insoluble slag and sodium hydroxide using sour insoluble slag obtained by step (1) as raw material
(g/g), the solid-to-liquid ratio of solid matter (sour insoluble slag and sodium hydroxide) and deionized water is 1:2 (g/mL), takes sour insoluble slag, hydrogen
Sodium oxide molybdena and deionized water mixing, 200 DEG C at a temperature of hydro-thermal 8h after obtain dirty solution, taken out after being cooled to room temperature
Filter, filtrate are spare as silicon source.
(3) according to gel reaction system [Si:CTAB:H2O: ethyl alcohol]=[1:0.135:500:120], take 0.5g sun from
Sublist face lammonium bromide (CTAB), is dissolved in the deionized water of 91.5mL, ultrasonic agitation until
Solution is transparent, instills 71.15mL ethyl alcohol, and the concentration of CTAB is 0.0085mol/L at this time, stirs 5min, is added in step (2) and obtains
The alkali soluble filtrate silicon source arrived obtains mixed solution.It is by regulating and controlling mixed solution pH value using 0.5~6mol/L aqueous hydrochloric acid solution
9, in 30 DEG C of room temperature of at a temperature of magnetic agitation 7h, obtain the mixing suspension containing white gels product, by product spend from
Sub- water washing to supernatant is free of CTAB, and drying, grinding, obtain presoma at a temperature of 60 DEG C.
(4) presoma obtained by step (3) is put into Muffle furnace, (heating rate is by 540 DEG C of temperature lower calcination heat preservation 6h
2 DEG C/min), surfactant is removed, MCM-41 ordered mesoporous material, specific surface area 1009m are obtained2/ g, pore volume are
0.816m3/ g, average pore size 2.012nm.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of MCM-41 ordered mesoporous material, which comprises the steps of:
(1) it using iron tailings as raw material, is leached with inorganic strong acid solution, is separated by solid-liquid separation, is washed and is dried after heating stirring, obtained
To sour insoluble slag；
(2) in mass ratio it is that the ratio of 1:1.4~2.4 mixes by sour insoluble slag and alkali metal hydroxide obtained by step (1), adds
Hydro-thermal reaction is carried out after entering deionized water, then obtains silicon source through being separated by solid-liquid separation；Wherein, silicon source recovery rate is greater than 95%；
It (3) is in molar ratio Si by silicon source obtained by step (2) and surfactant, deionized water, ethyl alcohol: surfactant: H2O:
Ratio mixing in ethyl alcohol=1:0.1~0.2:500~600:7~120 adjusts the pH value of mixed solution to 8~12, at room temperature
It is stirred generation gel reaction, then washed, drying and grinding, obtains presoma；
(4) presoma obtained by step (3) is calcined at 540~850 DEG C 5~9h, obtains MCM-41 ordered mesoporous material.
2. preparation method according to claim 1, which is characterized in that iron tailings and inorganic strong acid solution consolidates in step (1)
Liquor ratio is 1:1.5~6 (g/mL).
3. preparation method according to claim 1, which is characterized in that inorganic strong acid solution concentration described in step (1) be 2~
8mol/L。
4. preparation method according to claim 1, which is characterized in that heating stirring described in step (1) be specially 100~
3~6h of magnetic agitation at a temperature of 150 DEG C.
5. preparation method according to claim 1, which is characterized in that acid insoluble slag described in step (2) and alkali metal hydrogen-oxygen
Compound is solid matter, and the solid-to-liquid ratio of the solid matter and deionized water is 1:1.5~3 (g/mL).
6. preparation method according to claim 1, which is characterized in that hydrothermal temperature described in step (2) be 160~
220℃；Time is 6~12h.
7. preparation method according to claim 1, which is characterized in that surfactant described in step (3) is cetyl
Trimethylammonium bromide, concentration are 0.0075~0.015mol/L.
8. preparation method according to claim 1, which is characterized in that being stirred to react temperature described in step (3) is 25~40
℃；Reaction time is 1~7h.
9. preparation method according to claim 1, which is characterized in that calcination atmosphere is air atmosphere in step (4)；It is calcined
The heating rate of journey is 1~3 DEG C/min；Calcining manners are one-step calcination or step calcination.
10. the ordered mesoporous material that a kind of MCM-41 is prepared by claim 1~8 any one the method, feature
It is, the specific surface area of the mesoporous material is 969~1677m2/g。
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