CN103496697B - A kind of method being prepared gac by rice husk thermal decomposition charcoal - Google Patents
A kind of method being prepared gac by rice husk thermal decomposition charcoal Download PDFInfo
- Publication number
- CN103496697B CN103496697B CN201310460739.6A CN201310460739A CN103496697B CN 103496697 B CN103496697 B CN 103496697B CN 201310460739 A CN201310460739 A CN 201310460739A CN 103496697 B CN103496697 B CN 103496697B
- Authority
- CN
- China
- Prior art keywords
- rice husk
- thermal decomposition
- gac
- charcoal
- husk thermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Silicon Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method being prepared gac by rice husk thermal decomposition charcoal; the present invention prepares the residue after bio oil for raw material with rice husk thermal decomposition; with the silicon in 2-6mol/L sodium hydroxide solution removing rice husk thermal decomposition charcoal; rice husk thermal decomposition charcoal after silica removal under nitrogen protection; 650-850 DEG C is carried out activation 1-2h, obtained gac.Activation method does not need pressurization, and low for equipment requirements, reaction cost is low, and reaction conditions is gentle, simple to operate, can become waste into available gac under minimum consumption.
Description
Technical field
The present invention relates to a kind of method being prepared gac by discarded rice husk thermal decomposition charcoal.
Background technology
The method that tradition prepares gac is using coal and timber as raw material, adopts KOH activation method, phosphoric acid activation method and ZnCl
2activation method etc.These methods can obtain the larger gac of specific surface area, 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, is thus 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 carbon of this process by-product.The high-valued exploitation of pyrolysis carbon dust are significant.Residue remaining after bio oil being prepared by rice husk thermal decomposition, as the material 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, at Bioresource Technology., reported in 2011,7002-7003 with rice husk thermal decomposition charcoal as the silicon-dioxide of high-specific surface area prepared by raw material.With sodium hydroxide solution process pyrolytic carbon, obtain sodium silicate solution and add phosphoric acid tune pH again to 3.2.Add polyoxyethylene glycol again, just can obtain the silicon-dioxide of high-specific surface area through calcining.
2011, the people such as Liu, at Bioresource Technology., devised a set of spiral heating reactor that can regulate pyrolysis time in 2011,8247-8252.Take rice hull ash as raw material, after 110 DEG C of dryings, put into 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 DEG C.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 mixed with sodium carbonate, put into the logical nitrogen of silica tube and activate at 850-1000 DEG C, the product obtained adds suitable quantity of water and boils, cooling suction filtration, and filtrate leads to carbon dioxide preparation silicon-dioxide, and filter residue is washed to neutral 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 of this waste huge profit is too high.
2012, prince's sincere feeling reported the simple method of a kind of rice husk thermal decomposition ash interlock system for water glass and gac in CN102515156A.Be that raw material carries out pyrolysis with rice husk, obtain the Water Under solution that pyrolysis ash uses sodium hydroxide solution temperature-pressure again, temperature is 150-180 DEG C.The water glass solution of high-module can be obtained, also have the gac that specific surface area increases simultaneously.This method, will carry out under alkaline solution temperature-pressure condition, high to equipment requirements.
Summary of the invention
The object of this invention is to provide the method being prepared gac by discarded rice husk thermal decomposition charcoal that the low pollution simple to operate of a kind of cost is little.
Technical scheme prepares the residue after bio oil for raw material with rice husk thermal decomposition, and screening 40-80 object rice husk thermal decomposition charcoal, washes with water, dry at 110 DEG C; With 2-6mol/L sodium hydroxide solution process pyrolytic carbon, the volume ratio 3:4 of charcoal and sodium hydroxide solution, reacts 3-7h at 60-100 DEG C; Filter, filter residue washes with water to pH=7-8, dry at 110 DEG C; Pyrolytic carbon after process to be contained in silica tube under nitrogen protection, activates, activation temperature 650-850 DEG C, soak time 1-2h in tube furnace, obtained gac.
The gac obtained carries out 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 again with gac, Pyrogentisinic Acid has good adsorptive capacity.
The best concentration of sodium hydroxide solution of the present invention is 4-5mol/L, best activation temperature 700-800 DEG C.
Compared with the prior art the present invention has following features: 1, prepare the residue after bio oil for raw material with rice husk thermal decomposition, and with the silicon in sodium hydroxide solution removing rice husk thermal decomposition charcoal, the rice husk thermal decomposition charcoal after silica removal activates under nitrogen protection.Existing preparation method, adopts alkali activation, too large to the loss of equipment, and the gac yield obtained is very low, high cost, and reacts in spiral heater, and obtained gac specific surface area is less, the purposes of restricted activity charcoal.In patent CN102515156A profit, use a large amount of sodium hydroxide solution of lower concentration, in autoclave, 150-180 DEG C of reaction, obtains sodium silicate solution and the gac of high-module, but still there is a large amount of sodium hydroxide in sodium silicate solution, and conversion unit cost is high.2, activation method does not need pressurization, and low for equipment requirements, reaction cost is low, and reaction conditions is gentle, simple to operate, can become waste into available gac under minimum consumption.3, the waste material after the present invention's rice husk thermal decomposition prepares bio oil prepares gac, and raw material sources are extensive, are the waste materials of ton amount rice husk bio oil.
Embodiment
Embodiment 1-5: get 10g (150mL) rice husk thermal decomposition charcoal and mix with 200mL2mol/L sodium hydroxide solution, the three-necked bottle putting into 500mL reacts, and reacts and carries out in oil bath pan, temperature of reaction 60 DEG C-100 DEG C, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, dries at 110 DEG C.Carbon yield is at 44-50%.Product carries out 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 200mL3mol/L sodium hydroxide solution, the three-necked bottle putting into 500mL reacts, and reacts and carries out in oil bath pan, temperature of reaction 60 DEG C-100 DEG C, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, dries at 110 DEG C.Carbon yield is at 48-52%.Product carries out 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 200mL4mol/L sodium hydroxide solution, the three-necked bottle putting into 500mL reacts, and reacts and carries out in oil bath pan, temperature of reaction 60 DEG C-100 DEG C, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, dries at 110 DEG C.Carbon yield is at 52-58%.Product carries out 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 200mL5mol/L sodium hydroxide solution, the three-necked bottle putting into 500mL reacts, and reacts and carries out in oil bath pan, temperature of reaction 60 DEG C-100 DEG C, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, dries at 110 DEG C.Carbon yield is at 55-58%.Product carries out 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 200mL6mol/L sodium hydroxide solution, the three-necked bottle putting into 500mL reacts, and reacts and carries out in oil bath pan, temperature of reaction 60 DEG C-100 DEG C, reaction times 3-7h.Suction filtration after cooling, filter residue washes with water to pH=7-8, dries at 110 DEG C.Carbon yield is at 50-54%.Product carries out BET test.Reaction conditions and the results are shown in table 5.
Table 5
Embodiment 26-30: the charcoal getting the process of 2g4mol/L sodium hydroxide solution, puts into silica tube, heats up at tube furnace Program; whole process leads to nitrogen protection; activation temperature is 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C respectively, and activation 1.5h, temperature drops to room temperature by the time.The gac obtained is labeled as C respectively
4-650, C
4-700, C
4-750, C
4-800, C
4-850.And carry out BET test.Data are listed in table 6.
Table 6
Embodiment 31-35: the charcoal getting the process of 2g5mol/L sodium hydroxide solution, puts into silica tube, heats up at tube furnace Program; whole process leads to nitrogen protection; activation temperature is 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C respectively, and activation 1.5h, temperature drops to room temperature by the time.The gac obtained is labeled as C respectively
5-650, C
5-700, C
5-750, C
5-800, C
5-850.And carry out BET test.Data are listed in table 7.
Table 7
Embodiment 36-40: the charcoal getting the process of 2g6mol/L sodium hydroxide solution, puts into silica tube, heats up at tube furnace Program; whole process leads to nitrogen protection; activation temperature is 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C respectively, and activation 1.5h, temperature drops to room temperature by the time.The gac obtained is labeled as C respectively
6-650, C
6-700, C
6-750, C
6-800, C
6-850.And carry out BET test.Data are listed in table 8.
Table 8
Embodiment 41-43: the charcoal getting the process of 2g5mol/L sodium hydroxide solution, puts into silica tube, and heat up at tube furnace Program, whole process leads to nitrogen protection, activation temperature 750 DEG C, and soak time is respectively 1h, 1.5h, 2h; The charcoal obtained is labeled as C respectively
750-1, C
750-1.
5, C
750-2.And carry out BET test.Data are listed in table 9.
Table 9
Embodiment 44-48: take C respectively
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 is stoppered bottle stopper, puts into water-bath and keeps 35 DEG C.Every 0.25h gets solution in cuvette, carries out ultraviolet spectrophotometer measurement, measures solution absorbance at wavelength 270nm place.Just adsorption equilibrium is reached at 2h place.The data of adsorptive capacity are listed in table 10.
Table 10
Claims (3)
1. prepared a method for gac by rice husk thermal decomposition charcoal, its feature is to prepare the residue after bio oil for raw material with rice husk thermal decomposition, and screening 40-80 object rice husk thermal decomposition charcoal, washes with water, dry at 110 DEG C; With 2-6mol/L sodium hydroxide solution process pyrolytic carbon, the volume ratio 3:4 of charcoal and sodium hydroxide solution, reacts 3-7h at 60-100 DEG C; Filter, filter residue washes with water to pH=7-8, dry at 110 DEG C; Pyrolytic carbon after process to be contained in silica tube under nitrogen protection, activates, activation temperature 650-850 DEG C, soak time 1-2h in tube furnace, obtained gac.
2., by method according to claim 1, it is characterized in that concentration of sodium hydroxide solution 4-5mol/L.
3., by method according to claim 1, it is characterized in that activation temperature 700-800 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310460739.6A CN103496697B (en) | 2013-09-30 | 2013-09-30 | A kind of method being prepared gac by rice husk thermal decomposition charcoal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310460739.6A CN103496697B (en) | 2013-09-30 | 2013-09-30 | A kind of method being prepared gac by rice husk thermal decomposition charcoal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103496697A CN103496697A (en) | 2014-01-08 |
| CN103496697B true CN103496697B (en) | 2015-10-07 |
Family
ID=49861991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310460739.6A Expired - Fee Related CN103496697B (en) | 2013-09-30 | 2013-09-30 | A kind of method being prepared gac by rice husk thermal decomposition charcoal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103496697B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329892B (en) * | 2015-11-24 | 2017-04-12 | 吉林省凯禹生物质开发利用有限公司 | Method for producing capacitive carbon from rice husks |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (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 |
| CN101691225B (en) * | 2009-09-29 | 2012-02-15 | 武汉工业学院 | Method for coproducing nano silicon dioxide and active carbon from rice hull ash |
| CN101891189B (en) * | 2010-08-13 | 2011-11-23 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN103496697A (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103496697B (en) | A kind of method being prepared gac by rice husk thermal decomposition charcoal | |
| CN101244826B (en) | Method for producing silicon dioxide silica aerogel by drying in atmosphere pressure with rice hull as raw material | |
| CN102205962B (en) | Device and method for preparing activated carbon material for electrochemical capacitor | |
| CN103771407B (en) | Take biomass power plant ash as the method that super-activated carbon prepared by raw material | |
| CN106467390B (en) | A kind of graphene boccaro composite material and its manufactured boccaro ware, preparation method | |
| CN104724703A (en) | Method for preparing adsorptive activated carbon from Musaceae plants | |
| CN106345491B (en) | A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification | |
| CN103084187A (en) | Carbon-based solid acid and preparation method thereof | |
| CN102515156B (en) | Simple method for synchronous preparation of water glass and activated carbon with rice husk pyrolyzed ash | |
| CN106824157A (en) | A kind of modified composite titania material and preparation method thereof, application | |
| CN107999110A (en) | A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application | |
| CN107337204A (en) | Biomass pyrolytic, which is combined, prepares magnetic active carbon and the method rich in synthesis gas gas | |
| CN102936512A (en) | Method for preparing liquid fuel oil through catalytic cracking of biological oil by using alkaline MCM-41 | |
| CN102417179B (en) | Preparation method of activated carbon material for electrochemical capacitor | |
| CN104291350A (en) | Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method | |
| CN103920518A (en) | High-visible-light-activity sulfur-modified carbon nitride photocatalyst as well as synthetic method and application of photocatalyst | |
| CN107176613A (en) | A kind of multi-stage porous zeolite crystal embeds the preparation method of Fe nanoparticle catalysts | |
| CN104326471A (en) | Method for preparing active carbon from licorice waste residue | |
| CN110227503A (en) | A kind of method of one step of room temperature preparation halogenation oxygen bismuth nanometer sheet | |
| CN102674346A (en) | Process for preparing high-specific surface area composite pore structure coal-based activated carbon by using low dosage of KOH | |
| CN102218335B (en) | Preparation method of hydrophobic immobilized photocatalyst with solar photocatalysis activity | |
| CN106115699A (en) | Zinc oxide method prepares activated carbon | |
| CN105621435A (en) | Method for treating high-concentration ammonia-nitrogen wastewater with molecular sieve prepared from flyash | |
| CN102424383A (en) | Method for preparing mesoporous carbon material for electrochemical capacitor | |
| CN104445145B (en) | A kind of simple method for preparing with hierarchical pore structure porous charcoal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151007 Termination date: 20200930 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |