CN103848435A - Method for preparing hexagonal phase MCM-41 mesoporous molecular sieve from rice hull as silicon source - Google Patents
Method for preparing hexagonal phase MCM-41 mesoporous molecular sieve from rice hull as silicon source Download PDFInfo
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- CN103848435A CN103848435A CN201410099122.0A CN201410099122A CN103848435A CN 103848435 A CN103848435 A CN 103848435A CN 201410099122 A CN201410099122 A CN 201410099122A CN 103848435 A CN103848435 A CN 103848435A
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Abstract
The invention provides a method for preparing a hexagonal phase MCM-41 mesoporous molecular sieve from rice hull as a silicon source. The method is characterized by comprising the following steps: (1) preparing a rice hull ash by adopting a self-propagating method, controlling the combustion temperature at 500-600 DEG C and the heat preservation time at 4-6 hours, grinding to obtain a nano rice hull ash of which the average grain diameter is 40-100nm and the specific surface area is 180-200m<2>/g; (2) purifying the rice hull ash by adopting an alkaline-acid reaction method, so as to prepare silicon dioxide of which the purity is 99%; (3) by taking the prepared silicon dioxide as a silicon source, taking bromohexadecyl pyridine and CPBr as template agents, taking 1M NaOH solution as a pH modifier, and taking deionized water as a solvent, preparing the hexagonal phase MCM-41 mesoporous molecular sieve by adopting a hydrothermal method. The specific surface area of the MCM-41 mesoporous molecular sieve prepared by the method can be up to 1120m<2>/g, and the MCM-41 mesoporous molecular sieve can be applied to the fields such as catalysis, petrochemical engineering and the like.
Description
Technical field
The invention provides a kind of method of preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source, belong to technical field of inorganic nonmetallic materials.
Background technology
Molecular sieve has good catalytic performance, absorption property and ion exchangeable, is widely used in fields such as washing composition, petrochemical industry, medicine and environmental protection.MCM-41 mesopore molecular sieve is a kind of mesoporous nano material, there is good ion-exchange, catalysis and absorption property, in fine chemical industry petrochemical industry, in many fields such as medical and health and environment protection, tool has been widely used and huge application potential. and MCM-41 mesopore molecular sieve purity prepared by traditional low-temperature hydrothermal synthesis technique is high, performance is good and stable, but its raw materials is tetraethoxy, the industrial chemicals such as water glass, price is higher and originate limited, cause preparation cost high, the extensive use of MCM-41 mesopore molecular sieve and further widening of Application Areas are seriously restricted.Therefore, the natural silicate raw mineral materials of cheap and wide material sources is devoted to find in countries in the world, as the alternative industrial chemicals such as kaolin, perlite, foam, potassium felspar sand and natural parastilbite are prepared MCM-41 mesopore molecular sieve.
China is Rice Cropping big country, produces paddy per year more than 200,000,000 t, can obtain rice husk more than 4,000 ten thousand t after processing, and rice husk is difficult for water suction, and being directly applied to field, to make fertilizer not perishable again.Present stage as primary fuel burning, makes a low multiple use mostly.In rice husk, main component is hydrocarbon polymer, contains in addition 15～18% amorphous hydrated silica, contains more than 90% Volcanic-type high reactivity silicon-dioxide in the rice hull ash after burning.Therefore the comprehensive utilization of rice husk is significant, and this can not only solve the pollution problem of a large amount of agricultural by-products, and can also make full use of resource.The exploitation of rice husk silicon to extract SiO from rice husk at present
2be main, have been reported and synthesize A type and P type molecular sieve taking rice husk silicon as raw material, the present invention utilizes the preparation of rice husk silicon to have high-specific surface area six side's phase MCM-41 mesopore molecular sieves.
Summary of the invention
The object of the invention is to propose a kind of preparation method of agricultural wastes rice husk for raw material, the six side's phase MCM-41 mesopore molecular sieves that easy and simple to handle, cost is low, product performance are good that utilize.Its technology contents is:
A kind of method of preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source, it is characterized in that adopting following steps: (1) adopts from spreading method combusting rice hull and makes rice hull ash, temperature of combustion is controlled at 500 ~ 600 DEG C, soaking time is 4 ~ 6 h, and the levigate median size that obtains is that 40 ~ 100nm, specific surface area are 180 ~ 200m
2the nanometer rice hull ash of/g; (2) adopt alkali-acid-respons method to purify to rice hull ash, make purity and be 99% silicon-dioxide; (3) taking prepared silicon-dioxide as silicon source, with bromohexadecane yl pyridines, CPBr is template, taking 1M NaOH solution as pH adjusting agent, taking deionized water as solvent, adopts hydrothermal method to prepare six side's phase MCM-41 mesopore molecular sieves.
A kind of described method of preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source, be characterised in that: in step (2), adopt alkali-acid-respons method to purify to rice hull ash, concrete steps are to be in 1M NaOH solution by 100g rice hull ash/L NaOH Solution Dispersion to concentration by rice hull ash, moltenly after being heated to 90 DEG C obtain silicon sodium solution after boiling 2 h, regulate the pH value 3 ~ 4 of this solution with sulfuric acid, reaction times leaves standstill cooling and aging 4 h by precipitation system after 2 ~ 3 h, centrifugation and washing repeatedly three times, make purity after dry and be 99% SiO 2 powder.
A kind of described method of preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source, is characterised in that: the concrete steps that adopt hydrothermal method to prepare six side's phase MCM-41 mesopore molecular sieves in step (3) are by SiO
2, CPBr, NaOH and H
2o is with mass ratio SiO
2: CPBr:NaOH:H
2the ratio of O=1:0.2:0.2:70 is mixed into gel, and pH is controlled at 11.0 left and right, is placed in reactor crystallization 12 ~ 24h at the temperature of 110 ~ 120 DEG C, after washing and suction filtration, is dried 10h, roasting 5 ~ 6 h and get final product at 500 ~ 550 DEG C at 80 DEG C.
Compared with prior art, its advantage is in the present invention:
1, utilize rice husk for silicon source, environmental protection, turns waste into wealth.
2, purify after rice hull ash in dioxide-containing silica up to more than 99% nanometer grade silica;
3, the specific surface area of six prepared side's phase MCM-41 mesopore molecular sieves is up to 1120m
2more than/g.
brief description of the drawings:
Fig. 1 is the XRD figure of six side's phase MCM-41 mesopore molecular sieves;
Fig. 2 is the SEM figure of six side's phase MCM-41 mesopore molecular sieves.
Embodiment
Embodiment mono-:
1, the preparation of rice hull ash: adopt self-combustion process combusting rice hull, temperature of combustion is controlled at 500 DEG C, and soaking time is 6 h, levigate, crosses 200 mesh sieves, and obtaining median size is that 60 nm, specific surface area are 180 m
2the nanometer rice hull ash of/g left and right;
2, the purification of rice hull ash: be in 1M NaOH solution by 100 g rice hull ash/LNaOH Solution Dispersions to concentration by rice hull ash, moltenly after being heated to 90 DEG C obtain silicon sodium solution after boiling 2 h, regulate the pH value 3 of this solution with sulfuric acid, reaction times leaves standstill cooling and aging 4 h by precipitation system after 2 h, then centrifugation, with distilled water wash, centrifugal three times repeatedly, after being dried, making purity is the silicon-dioxide of 99 % left and right.
3, the preparation of MCM-41 mesopore molecular sieve: taking the silicon-dioxide after purifying as silicon source, with bromohexadecane yl pyridines, CPBr is template, taking 1M NaOH solution as pH adjusting agent, taking deionized water as solvent, with mass ratio SiO
2: CPBr:NaOH:H
2the ratio of O=1:0.2:0.2:70 is prepared mixed gel, at this moment pH is controlled at 11.0 left and right, be placed in reactor crystallization 24 h at the temperature of 110 DEG C, through washing and suction filtration after, at 80 DEG C be dried 10 h be placed on retort furnace at 500 DEG C roasting 6 h obtain six side's phase MCM-41 mesopore molecular sieves.
Embodiment bis-
1, the preparation of rice hull ash: adopt self-combustion process combusting rice hull, temperature of combustion is controlled at 600 DEG C, and soaking time is 4 h, levigate, crosses 200 mesh sieves, and obtaining median size is that 40nm, specific surface area are 200 m
2the nanometer rice hull ash of/g left and right;
2, the purification of rice hull ash: be in 1M NaOH solution by 100 g rice hull ash/LNaOH Solution Dispersions to concentration by rice hull ash, moltenly after being heated to 90 DEG C obtain silicon sodium solution after boiling 2 h, regulate the pH value 4 of this solution with sulfuric acid, reaction times leaves standstill cooling and aging 4 h by precipitation system after 3 h, then centrifugation, with distilled water wash, after centrifugal drying, make the silicon-dioxide that purity is 99% left and right.
3, the preparation of MCM-41 mesopore molecular sieve: taking the silicon-dioxide after purifying as silicon source, with bromohexadecane yl pyridines, CPBr is template, taking 1M NaOH solution as pH adjusting agent, taking deionized water as solvent, with mass ratio SiO
2: CPBr:NaOH:H
2the ratio of O=1:0.2:0.2:70 is prepared mixed gel, at this moment pH is controlled at 11.0 left and right, be placed in reactor crystallization 12 h at the temperature of 120 DEG C, through washing and suction filtration after, at 80 DEG C be dried 10 h be placed on retort furnace at 550 DEG C roasting 5 h obtain six side's phase MCM-41 mesopore molecular sieves.
Claims (3)
1. prepare the method for six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source, it is characterized in that adopting following steps: (1) adopts from spreading method combusting rice hull and makes rice hull ash, temperature of combustion is controlled at 500 ~ 600 DEG C, soaking time is 4 ~ 6 h, and the levigate median size that obtains is that 40 ~ 100nm, specific surface area are 180 ~ 200m
2the nanometer rice hull ash of/g; (2) adopt alkali-acid-respons method to purify to rice hull ash, make purity and be 99% silicon-dioxide; (3) taking prepared silicon-dioxide as silicon source, with bromohexadecane yl pyridines, CPBr is template, taking 1M NaOH solution as pH adjusting agent, taking deionized water as solvent, adopts hydrothermal method to prepare six side's phase MCM-41 mesopore molecular sieves.
2. a kind of method of preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source as described in claim 1, be characterised in that: in step (2), adopt alkali-acid-respons method to purify to rice hull ash, concrete steps are to be in 1M NaOH solution by 100g rice hull ash/L NaOH Solution Dispersion to concentration by rice hull ash, moltenly after being heated to 90 DEG C obtain silicon sodium solution after boiling 2 h, regulate the pH value 3 ~ 4 of this solution with sulfuric acid, reaction times leaves standstill cooling and aging 4 h by precipitation system after 2 ~ 3 h, centrifugation and washing three times repeatedly, after dry, make purity and be 99% SiO 2 powder.
3. the method for preparing six side's phase MCM-41 mesopore molecular sieves taking rice husk as silicon source as described in claim 1, is characterised in that: the concrete steps that adopt hydrothermal method to prepare six side's phase MCM-41 mesopore molecular sieves in step (3) are by SiO
2, CPBr, NaOH and H
2o is with mass ratio SiO
2: CPBr:NaOH:H
2the ratio of O=1:0.2:0.2:70 is mixed into gel, and pH is controlled at 11.0 left and right, is placed in reactor crystallization 12 ~ 24 h at the temperature of 110 ~ 120 DEG C, after washing and suction filtration, is dried 10 h, roasting 5 ~ 6 h and get final product at 500 ~ 550 DEG C at 80 DEG C.
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| US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
| CN1370739A (en) * | 2001-12-04 | 2002-09-25 | 中国科学院兰州化学物理研究所 | Micro emulsion water-in-oil process of synthesizing nano silicon-base mesopore moleecular sieve |
| CN1660697A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | Method for synthesizing molecular sieve in media pores |
| CN102530981A (en) * | 2012-02-20 | 2012-07-04 | 华东师范大学 | Method for synthesizing mobil composition of matters-41(MCM-41) mesoporous molecular sieve |
| CN103420394A (en) * | 2013-09-01 | 2013-12-04 | 山东理工大学 | Method for preparing X-type molecular sieve with rice husks serving as silicon source |
-
2014
- 2014-03-18 CN CN201410099122.0A patent/CN103848435A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
| CN1370739A (en) * | 2001-12-04 | 2002-09-25 | 中国科学院兰州化学物理研究所 | Micro emulsion water-in-oil process of synthesizing nano silicon-base mesopore moleecular sieve |
| CN1660697A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | Method for synthesizing molecular sieve in media pores |
| CN102530981A (en) * | 2012-02-20 | 2012-07-04 | 华东师范大学 | Method for synthesizing mobil composition of matters-41(MCM-41) mesoporous molecular sieve |
| CN103420394A (en) * | 2013-09-01 | 2013-12-04 | 山东理工大学 | Method for preparing X-type molecular sieve with rice husks serving as silicon source |
Non-Patent Citations (2)
| Title |
|---|
| 徐如人 等: "《分子筛与多孔材料化学》", 31 March 2004, 科学出版社 * |
| 王福安 等: "《绿色过程工程引论》", 31 October 2002, 化学工业出版社 * |
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