CN102442665B - Thermally treated active carbon and preparation method thereof - Google Patents
Thermally treated active carbon and preparation method thereof Download PDFInfo
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- CN102442665B CN102442665B CN2011102933743A CN201110293374A CN102442665B CN 102442665 B CN102442665 B CN 102442665B CN 2011102933743 A CN2011102933743 A CN 2011102933743A CN 201110293374 A CN201110293374 A CN 201110293374A CN 102442665 B CN102442665 B CN 102442665B
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Abstract
The invention discloses a thermally treated active carbon and a preparation method thereof. The preparation method comprises the steps of: uniformly mixing active carbon which is subjected to a high temperature treatment with a pore-enlarging agent; and performing a pore-enlarging treatment at 300-1000 DEG C for 0.1-48 hours to obtain thermally treated active carbon with high mesopore and macropore rates. The active carbon obtained by the preparation method disclosed by the invention has the advantages of low carbon loss rate on ignition in the treatment process, low ratio of pore volume of micropores to total pore volume as well as high mesopore and macropore rates, and can be used as a carrier of catalysts.
Description
Technical field
The present invention relates to high heat treatment active carbon of a kind of mesopore and big porosity and preparation method thereof, belong to material science.
Background technology
Active carbon is applied to the carrier of catalyst widely, common activated carbon capillary prosperity, specific area height, but the few shortcoming of hole number in existing.Simultaneously the too high or micropore quantity of charcoal carrier specific area can cause the active metal particles of institute's load too little too much, will be unfavorable for the carrying out of some catalytic reactions, has reduced the utilization rate of reactive metal.As many bibliographical informations in ammonia synthesis reaction, increase the middle porosity of absorbent charcoal carrier and the ammonia synthesis activity that big porosity will help to improve ruthenium catalyst.In addition, in some reaction systems, the stability of common active carbon is not enough, and this greatly influences life of catalyst.Be that ruthenium is the optimal carrier of ammonia synthesis catalyst such as active carbon, but active carbon also can be by ruthenium catalysis generation methanation reaction in the hydrogeneous atmosphere of high temperature.For stability and the methanation resisting ability that improves catalyst, need in inert atmosphere, make it to produce carbonization structure by the high-temperature heat treatment absorbent charcoal carrier usually.But high-temperature heat treatment can greatly reduce the pore size distribution of the specific area of active carbon and pore volume, destruction carrier, thereby is unfavorable for the dispersion of reactive metal and auxiliary agent.Chinese patent CN1382527 introduces the expanding method of absorbent charcoal carrier in a kind of load ruthenium catalyst, be with the active carbon after the heat treatment in gaseous mixture atmosphere (oxygen and nitrogen mixture or nitrogen and steam gaseous mixture) carry out reaming and handle.Chinese patent CN1544146 has described the heat treated expanding method in the gaseous mixture that contains steam and oxygen-containing gas of the active carbon after the heat treatment.The essence of these two kinds of methods all is to utilize the oxygen-containing gas carbon atom gasification that the part of charcoal carrier surface is active to remove to obtain new hole.In order to enlarge the aperture of absorbent charcoal carrier, need when handling, reaming increase the burning mistake rate (percentage that charcoal carrier quality reduces in the processing procedure) of charcoal, only could the generating portion mesopore when higher mistake charcoal amount and the hole of macropore (term " micropore " refer to the maximum 2nm(in aperture comprise 2nm) in the context of the present invention; Term " mesopore " refers to pore diameter range and comprises 50nm greater than 2nm to 50nm() the hole, term " macropore " refers to the aperture greater than the hole of 50nm), also can cause the mechanical strength variation of active carbon this moment.People such as Zhu are at Influence of oxidation on heat-treated activated carbon support properties and metallic dispersion of Ru/C catalyst (Catalysis Letters, 2007,115,13-18.) in reported the different disposal time in the different atmosphere reaming handle mistake charcoal rate and surperficial texture parameter to the absorbent charcoal carrier after the heat treatment, discovery is handled 2 hour through 1900 ℃ with commercial active carbon in argon gas after, be oxidant again with the carbon dioxide, handling 3 hours resultant charcoal carrier burning mistake rates at 850 ℃ is 23.4%, and the micropore pore volume is minimum with total pore volume ratio to be 0.46.Increasing the processing time changes treatment temperature and changes employed oxygen-containing gas kind the burning mistake rate of sample is further increased, and the micropore pore volume increases with total pore volume ratio, and middle porosity and big porosity reduce.
Summary of the invention
The object of the present invention is to provide high heat treatment active carbon of a kind of mesopore and big porosity and preparation method thereof, it is low that this active carbon has processing procedure charcoal burning mistake rate, the micropore pore volume is low with the ratio of total pore volume, and middle porosity and high these advantages of big porosity can be as the carriers of catalyst.
For achieving the above object, the present invention adopts following technical scheme:
A kind of heat treatment active carbon has high mesopore and big porosity, and the total pore volume of this active carbon at least 72% is to be formed by the hole (being mesopore and macropore) of aperture greater than 2nm.Its preparation method: will mix through method and the expanding agent of the active carbon after the high-temperature process by dipping or mechanical mixture, 110-130 ℃ dry 4-6 hour, handled 0.1-48 hour in 300-1000 ℃ of reaming, namely get described high mesopore and the heat treatment active carbon of big porosity after the washing and drying.
Described high-temperature process is carried out in inert gas, and treatment temperature is 1600-2500 ℃, and the time is 0.5-6 hour.
Described expanding agent is the mixture of one or more arbitrary proportions in NaOH, sodium carbonate, potassium hydroxide, potash, aluminium chloride, magnesium chloride, zinc chloride, the phosphoric acid.The mass ratio of expanding agent and active carbon is 0.1-10:1.
Described reaming processing is to carry out under the mist of one or more arbitrary proportions of nitrogen, oxygen, air, steam, carbon dioxide, 0 family's inert gas, and the flow velocity of gas is 5-1000mL/min.
Described washing is to wash with watery hydrochloric acid, rare nitric acid or dilute sulfuric acid earlier, is washed with distilled water to cleaning solution then and is neutral and does not contain acid ion.
The temperature 80-150 of described oven dry ℃, time 2-30 hour.
Remarkable advantage of the present invention is: it is low that active carbon of the present invention has processing procedure charcoal burning mistake rate, the ratio low (its value is not more than 0.28) of micropore pore volume and total pore volume, middle porosity and big porosity height advantages such as (total pore volume in the active carbon more than 72% are to be formed by the hole of aperture greater than 2nm) can be as the carriers of catalyst.
The specific embodiment
Below with specific embodiment technical scheme of the present invention is described, but the scope that comprises of the present invention is not limited thereto:
Embodiment 1:
Get 4g commerce active carbon and place argon gas to handle after 1 hour down for 1850 ℃, be crushed to the 12-16 order, dipping KOH solution is 0.5:1 to the mass ratio of KOH:C, and drying is 4 hours under 120 ℃.Sample is placed in the tube furnace, in the nitrogen of 200 mL/min, handled 2 hours in 700 ℃ of reamings, in above-mentioned atmosphere, be cooled to room temperature, watery hydrochloric acid (0.01 moL/L) with 20mL washs 5 times earlier, be washed with distilled water to cleaning solution then and be neutral and do not contain acid ion, in baking oven, placed 120 dryings 12 hours.
Embodiment 2:
Repeat embodiment 1, just the time that reaming is handled extended to 20 hours from 2 hours.
Embodiment 3:
Repeat embodiment 1, just change KOH into KOH and K
2CO
3Mixture (KOH and K
2CO
3Mass ratio be 1:1).
Embodiment 4:
Repeat embodiment 1, change nitrogen into air, 2 hours processing times changed 0.5 hour into.
Embodiment 5:
Repeat embodiment 1, change nitrogen into nitrogen (70%) and CO
2(30%) gaseous mixture, 2 hours processing times changed 1 hour into.
Comparative Examples 1:
Get the commercial active carbon of 4g and place argon gas to handle after 1 hour down for 1850 ℃, be crushed to the 12-16 order, in the oxygen of 200mL/min, in 700 ℃ of processing 0.5 hour, be cooled to the activated carbon sample after room temperature namely obtains handling.
Comparative Examples 2:
Repeat Comparative Examples 1, change oxygen into steam, temperature changes 500 ℃ into for 700 ℃, and 0.5 hour processing time changed 2 hours into.
For the ease of contrast, also one be listed in table 1 without the commercial activated carbon property of Overheating Treatment.The activated carbon capillary pore volume that uses processing method provided by the invention to obtain as can be seen by table 1 is big with total little, middle porosity of pore volume ratio and big porosity, and the activated carbon sample micropore pore volume that all embodiment obtain all is no more than 0.28 with total pore volume ratio.In addition, the contrast by embodiment and Comparative Examples as can be seen, expanding method provided by the invention has active carbon and burns the low advantage of mistake rate.
The character of the active carbon that table 1 different disposal method obtains
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. heat treatment preparation method of active carbon is characterized in that: described heat treatment active carbon has high mesopore and big porosity;
The preparation method comprises and will mix through active carbon and expanding agent after the high-temperature process, handled 0.1-48 hour in 300-1000 ℃ of reaming;
Described expanding agent is the mixture of one or more arbitrary proportions in NaOH, sodium carbonate, potassium hydroxide, potash, aluminium chloride, magnesium chloride, the zinc chloride;
The mass ratio of expanding agent and active carbon is 0.1-10:1;
Described reaming processing is to carry out under the mist of one or more arbitrary proportions of nitrogen, oxygen, air, steam, carbon dioxide, 0 family's inert gas, and the flow velocity of gas is 5-1000mL/min.
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| CN2011102933743A CN102442665B (en) | 2011-09-28 | 2011-09-28 | Thermally treated active carbon and preparation method thereof |
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| CN102442665B true CN102442665B (en) | 2013-07-03 |
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| CN106689981A (en) * | 2016-12-07 | 2017-05-24 | 曾郴林 | Carbonization material for cooking as well as preparation process and application method thereof |
| CN107973296A (en) * | 2017-11-28 | 2018-05-01 | 福建省鑫森炭业股份有限公司 | A kind of large aperture activated carbon and preparation method thereof |
| CN108993386A (en) * | 2018-07-31 | 2018-12-14 | 郑州工程技术学院 | A kind of cleanser and preparation method thereof for disposing polluted water in oil |
| CN109081344A (en) * | 2018-09-20 | 2018-12-25 | 南通滨海活性炭有限公司 | A kind of macropore active charcoal preparing process |
| CN109607533B (en) * | 2019-01-28 | 2019-12-24 | 贵州梅岭电源有限公司 | Preparation method of stalactite-like macroporous activated carbon |
| CN110255558A (en) * | 2019-05-27 | 2019-09-20 | 榆林学院 | A method of active carbon is prepared using physical chemistry activation method |
| CN110983495B (en) * | 2019-12-17 | 2022-04-29 | 南通大学 | Active carbon fiber hole expanding method |
| CN111689495A (en) * | 2020-05-15 | 2020-09-22 | 内蒙古浦瑞芬环保科技有限公司 | Preparation method of tar-free activated carbon |
| CN113735302A (en) * | 2020-05-28 | 2021-12-03 | 宝山钢铁股份有限公司 | Method and device for removing SCOD (selective catalytic reduction) and total nitrogen in cold-rolling biochemical effluent |
| CN111977653B (en) * | 2020-08-24 | 2023-06-02 | 中国林业科学研究院林产化学工业研究所 | Modified activated carbon for super capacitor and preparation method thereof |
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| CN101905154A (en) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst |
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| CN101905154A (en) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst |
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