CN103496697A - Method for preparing activated carbon by utilizing rice hull pyrolytic carbon - Google Patents
Method for preparing activated carbon by utilizing rice hull pyrolytic carbon Download PDFInfo
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- CN103496697A CN103496697A CN201310460739.6A CN201310460739A CN103496697A CN 103496697 A CN103496697 A CN 103496697A CN 201310460739 A CN201310460739 A CN 201310460739A CN 103496697 A CN103496697 A CN 103496697A
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- rice hull
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Abstract
The invention relates to a method for preparing activated carbon by utilizing rice hull pyrolytic carbon. The method for preparing the activated carbon by utilizing the rice hull pyrolytic carbon takes residue obtained after rice hull is hydrolyzed for preparing biological oil as a raw material and comprises the steps of removing silicon in the rice hull hydrolytic carbon by adopting 2-6mol/L sodium hydroxide solution and activating 1-2 hours at the temperature of 650-850 DEG C while the rice hull pyrolytic carbon after silicon is removed is under nitrogen protection, thus the activated carbon is obtained. The activation method has the advantages of no pressurization, low equipment requirement, low reaction cost, mild reaction conditions and easy operation, and waste can be changed into available activated carbon with lowest consumption.
Description
Technical field
The present invention relates to a kind of method that is prepared gac by discarded rice husk thermal decomposition charcoal.
Background technology
The method that tradition prepares gac is to using coal and timber as raw material, adopts the KOH activation method, phosphoric acid activation method and ZnCl
2activation method etc.These methods can make the gac that specific surface area is larger, but activator is too strong to the corrodibility of equipment, also needs high-temperature activation, and energy expenditure is too large, and material use efficiency is low.Gac has highly developed pore texture, huge specific surface area, good absorption property, abundant surface functional group and easy reproducibility, thereby is widely used in the various fields such as chemical industry, medical treatment and environmental protection.Along with the development of Green Chemistry, rice husk has been used to catalyse pyrolysis and has prepared bio oil, but a large amount of pyrolysis powdered carbons of this process by-product.The high-valued exploitation of pyrolysis carbon dust are significant.Rice husk thermal decomposition is prepared to remaining residue after bio oil, as the material for preparing gac, not only can solve the pollution problem of residue, but also can improve the comprehensive utilization value of rice husk.
2011, the people such as Li were at Bioresource Technology., had reported in 2011,7002-7003 that take the rice husk thermal decomposition charcoal prepares the silicon-dioxide of high-specific surface area as raw material.Process pyrolytic carbon with sodium hydroxide solution, obtain sodium silicate solution and add again phosphoric acid to adjust pH to 3.2.Add again polyoxyethylene glycol, through calcining, just can obtain the silicon-dioxide of high-specific surface area.
2011, the people such as Liu, at Bioresource Technology., designed a set of spiral heating reactor that can regulate pyrolysis time in 2011,8247-8252.Take rice hull ash as raw material, after 110 ℃ of dryings, put into the spiral heating reactor, under the condition of logical nitrogen, carry out pyrolysis.Regulate pyrolysis time by the spiral heater that can change speed of rotation, pyrolysis temperature is between 400-450 ℃.But the gac specific surface area obtained is very little, at 44.7-139.7m
2between/g.
2012, the people such as Liu, at Cleaner Production., reported in 2012,204-209 with sodium carbonate activation rice hull ash continuous production silicon-dioxide and gac.Rice hull ash is mixed with sodium carbonate, put into the logical nitrogen of silica tube and activate under 850-1000 ℃, the product obtained adds suitable quantity of water to boil, cooling suction filtration, and filtrate is led to carbon dioxide preparation silicon-dioxide, and filter residue is washed to neutral the oven dry.The gac specific surface area obtained can reach 1713m
2/ g, but such reaction method is very large to the corrodibility of conversion unit, and also energy expenditure is very large, and the method cost that this waste huge profit is used is too high.
2012, prince's sincere feeling was reported the simple method of the standby water glass of a kind of rice husk thermal decomposition ash interlock system and gac in CN102515156A.Take rice husk as raw material carries out pyrolysis, obtain the Water Under solution that the pyrolysis ash is heated and pressurizeed with sodium hydroxide solution again, temperature is 150-180 ℃.Can obtain the water glass solution of high-module, the gac that simultaneously also has specific surface area to increase.This method be carried out under alkaline solution is heated pressurized conditions, high to equipment requirements.
Summary of the invention
The purpose of this invention is to provide the low pollution simple to operate of a kind of cost little prepare the method for gac by discarded rice husk thermal decomposition charcoal.
Technical scheme is that to take residue prepared after bio oil by rice husk thermal decomposition be raw material, and screening 40-80 purpose rice husk thermal decomposition charcoal, wash with water, dry under 110 ℃; Process pyrolytic carbon with the 2-6mol/L sodium hydroxide solution, the volume ratio 3:4 of charcoal and sodium hydroxide solution reacts 3-7h under 60-100 ℃; Filter, filter residue washes with water to pH=7-8, dry under 110 ℃; Pyrolytic carbon after processing is contained in silica tube under nitrogen protection, in tube furnace, activated, and activation temperature 650-850 ℃, soak time 1-2h, make gac.
The gac obtained carries out the BET test, and specific surface area is 200-500m
2/ g, mean pore size is at 18-24
carry out the test of Adsorption of Phenol with gac, the Pyrogentisinic Acid has adsorptive capacity preferably again.
The best concentration of sodium hydroxide solution of the present invention is 4-5mol/L, best activation temperature 700-800 ℃.
Compared with the prior art the present invention has following characteristics: residue prepared after bio oil by the rice husk thermal decomposition of 1, take is raw material, with sodium hydroxide solution, removes the silicon in the rice husk thermal decomposition charcoal, and the rice husk thermal decomposition charcoal after silica removal is activated under nitrogen protection.Existing preparation method, adopt the alkali activation, too large to the loss of equipment, and the gac yield obtained is very low, high cost, and react in spiral heater, the gac specific surface area made is less, the purposes of restricted activity charcoal.In patent CN102515156A profit, use a large amount of sodium hydroxide solutions of lower concentration, 150-180 ℃ of reaction in autoclave, obtain sodium silicate solution and the gac of high-module, but still have a large amount of sodium hydroxide in sodium silicate solution, and the conversion unit cost is high.2, activation method does not need pressurization, and low for equipment requirements, reaction cost is low, and the reaction conditions gentleness is simple to operate, can become waste into available gac under minimum consumption.3, the waste material that prepared after bio oil with rice husk thermal decomposition by the present invention prepares gac, and raw material sources are extensive, is the waste material of ton amount rice husk bio oil processed.
Embodiment
Embodiment 1-5: get 10g (150mL) rice husk thermal decomposition charcoal and mix with the 200mL2mol/L sodium hydroxide solution, the three-necked bottle of putting into 500mL is reacted, and reaction is carried out in oil bath pan, 60 ℃-100 ℃ of temperature of reaction, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, under 110 ℃, dries.The charcoal yield is at 44-50%.Product carries out the BET test.Reaction conditions and the results are shown in Table 1.
Table 1
Embodiment 6-10: get 10g (150mL) rice husk thermal decomposition charcoal and mix with the 200mL3mol/L sodium hydroxide solution, the three-necked bottle of putting into 500mL is reacted, and reaction is carried out in oil bath pan, 60 ℃-100 ℃ of temperature of reaction, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, under 110 ℃, dries.The charcoal yield is at 48-52%.Product carries out the BET test.Reaction conditions and the results are shown in Table 2.
Table 2
Embodiment 11-15: get 10g (150mL) rice husk thermal decomposition charcoal and mix with the 200mL4mol/L sodium hydroxide solution, the three-necked bottle of putting into 500mL is reacted, and reaction is carried out in oil bath pan, 60 ℃-100 ℃ of temperature of reaction, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, under 110 ℃, dries.The charcoal yield is at 52-58%.Product carries out the BET test.Reaction conditions and the results are shown in Table 3.
Table 3
Embodiment 16-20: get 10g (150mL) rice husk thermal decomposition charcoal and mix with the 200mL5mol/L sodium hydroxide solution, the three-necked bottle of putting into 500mL is reacted, and reaction is carried out in oil bath pan, 60 ℃-100 ℃ of temperature of reaction, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, under 110 ℃, dries.The charcoal yield is at 55-58%.Product carries out the BET test.Reaction conditions and the results are shown in Table 4.
Table 4
Embodiment 21-25: get 10g (150mL) rice husk thermal decomposition charcoal and mix with the 200mL6mol/L sodium hydroxide solution, the three-necked bottle of putting into 500mL is reacted, and reaction is carried out in oil bath pan, 60 ℃-100 ℃ of temperature of reaction, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, under 110 ℃, dries.The charcoal yield is at 50-54%.Product carries out the BET test.Reaction conditions and the results are shown in table 5.
Table 5
Embodiment 26-30: get the charcoal that the 2g4mol/L sodium hydroxide solution was processed, put into silica tube, heat up at the tube furnace Program; whole process is led to nitrogen protection; activation temperature is respectively 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, activation 1.5h, and temperature drops to room temperature by the time.The gac obtained is labeled as respectively C
4-650, C
4-700, C
4-750, C
4-800, C
4-850.And carry out the BET test.Data are listed in table 6.
Table 6
Embodiment 31-35: get the charcoal that the 2g5mol/L sodium hydroxide solution was processed, put into silica tube, heat up at the tube furnace Program; whole process is led to nitrogen protection; activation temperature is respectively 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, activation 1.5h, and temperature drops to room temperature by the time.The gac obtained is labeled as respectively C
5-650, C
5-700, C
5-750, C
5-800, C
5-850.And carry out the BET test.Data are listed in table 7.
Table 7
Embodiment 36-40: get the charcoal that the 2g6mol/L sodium hydroxide solution was processed, put into silica tube, heat up at the tube furnace Program; whole process is led to nitrogen protection; activation temperature is respectively 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, activation 1.5h, and temperature drops to room temperature by the time.The gac obtained is labeled as respectively C
6-650, C
6-700, C
6-750, C
6-800, C
6-850.And carry out the BET test.Data are listed in table 8.
Table 8
Embodiment 41-43: get the charcoal that the 2g5mol/L sodium hydroxide solution was processed, put into silica tube, heat up at the tube furnace Program, whole process is led to nitrogen protection, 750 ℃ of activation temperatures, and soak time is respectively 1h, 1.5h, 2h; The charcoal obtained is labeled as respectively C
750-1, C
750-1.
5, C
750-2.And carry out the BET test.Data are listed in table 9.
Table 9
Embodiment 44-48: take respectively C
5-650, C
5-700, C
5-750, C
5-800, C
5-850each 0.1g, as in Erlenmeyer flask, gets the phenol solution of 100mL42-43mg/L, puts Erlenmeyer flask into and has filled in bottle stopper, puts into water-bath and keeps 35 ℃.Every 0.25h gets solution in cuvette, carries out the ultraviolet spectrophotometer measurement, measures solution absorbance at wavelength 270nm place.Just reached adsorption equilibrium at the 2h place.The data of adsorptive capacity are listed in table 10.
Table 10
Claims (3)
1. a method that is prepared gac by the rice husk thermal decomposition charcoal, its characteristics are to take that residue prepared after bio oil by rice husk thermal decomposition is raw material, screening 40-80 purpose rice husk thermal decomposition charcoal, wash with water, dry under 110 ℃; Process pyrolytic carbon with the 2-6mol/L sodium hydroxide solution, the volume ratio 3:4 of charcoal and sodium hydroxide solution reacts 3-7h under 60-100 ℃; Filter, filter residue washes with water to pH=7-8, dry under 110 ℃; Pyrolytic carbon after processing is contained in silica tube under nitrogen protection, in tube furnace, activated, and activation temperature 650-850 ℃, soak time 1-2h, make gac.
2. by method claimed in claim 1, it is characterized in that concentration of sodium hydroxide solution 4-5mol/L.
3. by method claimed in claim 1, it is characterized in that activation temperature 700-800 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329892A (en) * | 2015-11-24 | 2016-02-17 | 吉林省凯禹生物质开发利用有限公司 | Method for producing capacitive carbon from rice husks |
| CN105948754A (en) * | 2016-05-03 | 2016-09-21 | 台州东新密封有限公司 | Method for preparing fine-grain silicon carbide ceramic through reaction sintering |
| CN108622897A (en) * | 2018-05-24 | 2018-10-09 | 东北师范大学 | A kind of pine needle active charcoal and its preparation method and application |
| CN108671889A (en) * | 2018-05-24 | 2018-10-19 | 东北师范大学 | A kind of pine needle active charcoal and its preparation method and application |
| CN109179410A (en) * | 2018-09-26 | 2019-01-11 | 南京天博环境检测技术有限公司 | A kind of preparation method of biomass-based active carbon |
| CN110054186A (en) * | 2019-06-06 | 2019-07-26 | 吉林大学 | A method of it producing capacitance carbon desiliconization Sewage treatment and utilizes |
| CN110734062A (en) * | 2018-07-18 | 2020-01-31 | 中国石油天然气股份有限公司 | Preparation method of cassava residue activated carbon |
| CN112246823A (en) * | 2020-09-08 | 2021-01-22 | 新奥生物质能(天津)有限公司 | High ash pyrolytic carbon utilization method and system |
| CN113149000A (en) * | 2021-05-12 | 2021-07-23 | 长春工业大学 | Preparation method of rice husk carbon-based graphitized carbon material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456555A (en) * | 2008-09-04 | 2009-06-17 | 南昌大学 | Method for preparing high mode number waterglass and active carbon by rice hull ash |
| CN101691225A (en) * | 2009-09-29 | 2010-04-07 | 武汉工业学院 | Method for coproducing nano silicon dioxide and active carbon from rice hull ash |
| CN101891189A (en) * | 2010-08-13 | 2010-11-24 | 宁乡县亮之星米业有限公司 | Method for preparing coal gas, top-grade active carbon, water glass and silicate phosphate from rice hulls |
-
2013
- 2013-09-30 CN CN201310460739.6A patent/CN103496697B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456555A (en) * | 2008-09-04 | 2009-06-17 | 南昌大学 | Method for preparing high mode number waterglass and active carbon by rice hull ash |
| CN101691225A (en) * | 2009-09-29 | 2010-04-07 | 武汉工业学院 | Method for coproducing nano silicon dioxide and active carbon from rice hull ash |
| CN101891189A (en) * | 2010-08-13 | 2010-11-24 | 宁乡县亮之星米业有限公司 | Method for preparing coal gas, top-grade active carbon, water glass and silicate phosphate from rice hulls |
Non-Patent Citations (1)
| Title |
|---|
| 马红超 等: "以稻壳为原料制备白炭黑和活性炭", 《大连工业大学学报》, vol. 30, no. 3, 31 May 2011 (2011-05-31) * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329892A (en) * | 2015-11-24 | 2016-02-17 | 吉林省凯禹生物质开发利用有限公司 | Method for producing capacitive carbon from rice husks |
| CN105948754A (en) * | 2016-05-03 | 2016-09-21 | 台州东新密封有限公司 | Method for preparing fine-grain silicon carbide ceramic through reaction sintering |
| CN105948754B (en) * | 2016-05-03 | 2019-02-22 | 浙江东新新材料科技有限公司 | The method that reaction-sintered prepares fine grain silicon carbide ceramics |
| CN108622897A (en) * | 2018-05-24 | 2018-10-09 | 东北师范大学 | A kind of pine needle active charcoal and its preparation method and application |
| CN108671889A (en) * | 2018-05-24 | 2018-10-19 | 东北师范大学 | A kind of pine needle active charcoal and its preparation method and application |
| CN110734062A (en) * | 2018-07-18 | 2020-01-31 | 中国石油天然气股份有限公司 | Preparation method of cassava residue activated carbon |
| CN110734062B (en) * | 2018-07-18 | 2021-09-28 | 中国石油天然气股份有限公司 | Preparation method of cassava residue activated carbon |
| CN109179410A (en) * | 2018-09-26 | 2019-01-11 | 南京天博环境检测技术有限公司 | A kind of preparation method of biomass-based active carbon |
| CN110054186A (en) * | 2019-06-06 | 2019-07-26 | 吉林大学 | A method of it producing capacitance carbon desiliconization Sewage treatment and utilizes |
| CN110054186B (en) * | 2019-06-06 | 2022-07-12 | 吉林大学 | Method for recycling desilication wastewater generated in production of capacitance carbon |
| CN112246823A (en) * | 2020-09-08 | 2021-01-22 | 新奥生物质能(天津)有限公司 | High ash pyrolytic carbon utilization method and system |
| CN113149000A (en) * | 2021-05-12 | 2021-07-23 | 长春工业大学 | Preparation method of rice husk carbon-based graphitized carbon material |
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