CN101955181B - Method for preparing active carbon by using carbon byproduct of fast pyrolysis of larchwood - Google Patents

Method for preparing active carbon by using carbon byproduct of fast pyrolysis of larchwood Download PDF

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CN101955181B
CN101955181B CN2010105154120A CN201010515412A CN101955181B CN 101955181 B CN101955181 B CN 101955181B CN 2010105154120 A CN2010105154120 A CN 2010105154120A CN 201010515412 A CN201010515412 A CN 201010515412A CN 101955181 B CN101955181 B CN 101955181B
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pyrolysis oil
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pyrolysis
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CN101955181A (en
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常建民
韩彦雪
张立塔
苟进胜
王鹏起
许守强
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Beijing Forestry University
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Beijing Forestry University
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Abstract

The invention relates to a method for preparing active carbon by using the carbon byproduct of the fast pyrolysis of larchwood, which belongs to the technical field of active carbon preparation. The method comprises the following steps of: fast pyrolyzing the larchwood to obtain pyrolytic carbon and pyrolytic gas; condensing the pyrolytic gas to obtain pyrolytic oil and uncondensable gas, and combusting the uncondensable gas in the air to obtain active gas; and activating the pyrolytic carbon by using the active gas as an activator, and cooling to room temperature to obtain the active carbon, wherein the high-temperature tail gas generated in the activation process is recycled. The method of the invention has the advantages that: an external heat source and the external activator are not used in the activation process; the comprehensive use efficiency of the pyrolytic product is high, and environmental pollution is light; the process for preparing the active carbon is simple, has high energy use efficiency, realizes the recycling of the heat and saves energy sources; and the obtained active carbon has high absorption performance, meets national standards in various indexes and can be widely applied to gas-phase absorption and decolorization of chemical products.

Description

Utilize larchwood fast pyrogenation by product charcoal to prepare process of active carbon
Technical field
The present invention relates to a kind of larchwood fast pyrogenation by product charcoal that utilizes and prepare process of active carbon, belong to the Preparation of Activated Carbon technical field.
Background technology
Gac has flourishing pore texture, huge specific surface area, unique surface functional group, and therefore stronger adsorptive power and good chemicalstability are widely used in industrial every field such as pharmacy, chemical industry, food.The traditional raw material of preparation gac mainly is natural ore deposit plants such as coal, solid wood, but the reserves of coal are limited, and the source of wood material is limited, and it is very necessary therefore selecting a kind of proper raw material, alternative traditional raw material to be used to produce gac.
Biomass energy is a kind of clean reproducible energy, and the biomass fast pyrogenation technology is to be a kind of effective means of biomass energy with Wood Adhesives from Biomass, has become the domestic and international research emphasis.But so far; Applied research about the biomass fast pyrogenation product concentrates on liquid product bio oil optimum preparation condition and application facet mostly; For pyrolysis solid product charcoal, especially the applied research of forest biomass pyrolytic solid product charcoal is fewer.The application mode of pyrolytic carbon mainly contained direct burning, did organic fertilizer or soil sustained release dosage etc. present stage; But directly the incendiary power loss is very big on the one hand; The ash oontent of pyrolytic carbon itself is higher on the other hand; Be unfavorable for directly doing fuel or sustained release dosage, these application modes can not embody the economic worth of pyrolytic carbon.Research shows that the fast pyrogenation charcoal itself has comparatively flourishing pore texture, and specific surface area generally is higher than 250m 2/ g, micropore volume can account for more than 40% of total pore volume, has certain adsorptive power, but can not reach the requirement of commercial gac, therefore needs through further handling to improve its adsorptive power.Improve rapid pyrolysis products utilization ratio and added value, the economic benefit that improves fast pyrolysis technology is the subject matter that the present invention need solve.
It is raw material that the research that at present both at home and abroad prepares gac about pyrolytic carbon concentrates on the waste tyre pyrolytic carbon black mostly; Prepare on the gac through physics or chemical activation method; The forest of employing biomass pyrolytic carbon is seldom arranged, and particularly the biomass fast pyrogenation charcoal prepares the research of gac.
Patent publication No. CN 1491886A; People such as the Zhang Wenhui of Beijing Coal Chemistry Inst., Coal Sciences General Inst. are the charing raw material with coal, timber and shell, adopt the mixed gas of oxidizing gas (water vapour, carbonic acid gas, flue gas and oxygen) and reducing gas (ammonia, hydrogen, methylamine, ethene or acetylene) to prepare gac as acvator.Because mixed gas has changed the character of activated carbon surface; Thereby improved charcoal absorption performance and physicals, its adsorptive power and sweetening power have all improved 10~30%, and product even aperture distribution degree improves; The gas delivery ability strengthens, and product yield has improved 2~15%.Problems such as the process need of this preparation gac is through charing, two steps of activation, and the reducing gas cost in the mixed gas acvator is higher, and soak time is longer, causes the Preparation of Activated Carbon cost high, and energy consumption is high, energy utilization rate is low.
Summary of the invention
The objective of the invention is to propose a kind of larchwood fast pyrogenation by product charcoal that utilizes and prepare process of active carbon; With tamarack fast pyrogenation by product charcoal is raw material; Utilize its high carbon content rate, comparatively flourishing pore texture, bigger advantages such as specific surface area; With the not condensable gases that produces in the fast pyrogenation process directly burning or the high temperature carbon dioxide that obtains with Sweet natural gas mixings afterfire and water vapour as carrying out activation in the acvator feeding activation furnace, with the efficient utilization of realization tamarack rapid pyrolysis products.
The larchwood fast pyrogenation by product charcoal that utilizes that the present invention proposes prepares process of active carbon, may further comprise the steps:
(1) larchwood is carried out fast pyrogenation at 450 ℃~600 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 20 ℃~40 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 750 ℃~1100 ℃; Temperature rise rate is 3 ℃/minute~15 ℃/minute; Soak time is 10 minutes~120 minutes, is cooled to room temperature, obtains gac; Or mix with above-mentioned pyrolytic carbon with above-mentioned heavy pyrolysis oil, the blended mass percent is: the heavy pyrolysis oil: pyrolytic carbon=1: (3~15), and making mixture forming is clavate or sphere; At last the mixture after the moulding is carried out activation; The priming reaction temperature is: 750 ℃~1100 ℃, temperature rise rate is 3 ℃/minute~15 ℃/minute, and soak time is 10 minutes~120 minutes; Be cooled to room temperature, obtain gac;
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
The larchwood fast pyrogenation by product charcoal that utilizes that the present invention proposes prepares process of active carbon; The not condensable gases of utilizing pyrolysis to produce is directly burnt or is acvator with the high hot carbonic acid gas and the water vapour of Sweet natural gas mixing afterfire generation; Need not add external heat source and acvator in the reactivation process; The pyrolysis product comprehensive utilization ratio is high, and environmental pollution is little; The technology of preparation gac is simple, and the charcoal absorption that obtains is functional, and each item index National standard can be widely used in the decolouring of Gas Phase Adsorption and Chemicals; Energy utilization rate is high, has realized the heat recycle, save energy.
Description of drawings
Fig. 1 is a Preparation of Activated Carbon schema of the present invention.
Embodiment
The larchwood fast pyrogenation by product charcoal that utilizes that the present invention proposes prepares process of active carbon, and its flow process is as shown in Figure 1, may further comprise the steps:
(1) larchwood is carried out fast pyrogenation at 450 ℃~600 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 20 ℃~40 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 750 ℃~1100 ℃; Temperature rise rate is 3 ℃/minute~15 ℃/minute; Soak time is 10 minutes~120 minutes, is cooled to room temperature, obtains gac; Or mix with above-mentioned pyrolytic carbon with above-mentioned heavy pyrolysis oil, the blended mass percent is: the heavy pyrolysis oil: pyrolytic carbon=1: (3~15), and making mixture forming is clavate or sphere; At last the mixture after the moulding is carried out activation; The priming reaction temperature is: 750 ℃~1100 ℃, temperature rise rate is 3 ℃/minute~15 ℃/minute, and soak time is 10 minutes~120 minutes; Be cooled to room temperature, obtain gac;
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Below introduce the embodiment of the inventive method:
Embodiment 1:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 35 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 800 ℃, temperature rise rate is 6 ℃/minute, and soak time is 15 minutes, is cooled to room temperature, obtains activated carbon product.Its yield is 42.6%, iodine sorption value 936mg/g, methylene blue adsorption value 173mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 2:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 25 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 850 ℃, temperature rise rate is 10 ℃/minute, and soak time is 30 minutes, is cooled to room temperature, obtains activated carbon product.Its yield is 36.8%, iodine sorption value 987mg/g, methylene blue adsorption value 136mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 3:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 30 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 900 ℃, temperature rise rate is 8 ℃/minute, and soak time is 20 minutes, is cooled to room temperature, obtains activated carbon product.Its yield is 40.2%, iodine sorption value 962mg/g, methylene blue adsorption value 168mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 4:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 30 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 1000 ℃, temperature rise rate is 8 ℃/minute, and soak time is 10 minutes, is cooled to room temperature, obtains activated carbon product.Its yield is 39.8%, iodine sorption value 902mg/g, methylene blue adsorption value 147mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 5:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 30 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 900 ℃, temperature rise rate is 10 ℃/minute, and soak time is 20 minutes, is cooled to room temperature, obtains activated carbon product.In order to increase activated carbon adsorptive capacity, utilize diluted acid that it is carried out cleanup acid treatment, diluted acid can be Hydrogen chloride, rare nitric acid or dilute sulphuric acid, the activated carbon-iodine adsorptive value 1208mg/g that obtains after the cleanup acid treatment, methylene blue adsorption value 237mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 6:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 30 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 900 ℃, temperature rise rate is 8 ℃/minute.Because pyrolysis tail gas is nonflammable, the feeding methane gas is combustion-supporting, treats to stop to feed methane gas after the pyrolysis tail gas trouble-free burning, and activation 20 minutes is cooled to room temperature, obtains activated carbon product.Its yield is 42.6%, iodine sorption value 936mg/g, methylene blue adsorption value 173mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
Embodiment 7:
(1) larchwood is carried out fast pyrogenation at 550 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 30 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) get above-mentioned pyrolytic carbon 100g, with pyrolysis BO uniform mixing, the mixing quality ratio is: the pyrolysis BO: pyrolytic carbon=1: 10; With mixture forming is spherical, utilizes above-mentioned activated gas as acvator, and above-mentioned pyrolytic carbon is carried out activation; The priming reaction temperature is: 1000 ℃, temperature rise rate is 8 ℃/minute, and soak time is 10 minutes; Be cooled to room temperature, obtain the granulated active carbon product.The iodine sorption value 850mg/g of granulated active carbon, methylene blue adsorption value 128mg/g.
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.

Claims (1)

1. one kind is utilized larchwood fast pyrogenation by product charcoal to prepare process of active carbon, it is characterized in that this method may further comprise the steps:
(1) larchwood is carried out fast pyrogenation at 450 ℃~600 ℃, obtain pyrolytic carbon and pyrolysis gas;
(2) above-mentioned pyrolysis gas is carried out condensation at 20 ℃~40 ℃, obtain pyrolysis oil and non-condensable gases, contain heavy pyrolysis oil, middle matter pyrolysis oil and lightweight pyrolysis oil in the pyrolysis oil;
(3) above-mentioned not condensable gases is burnt in air, obtain the activated gas of forming by carbonic acid gas and water vapour;
(4) utilize above-mentioned activated gas as acvator, above-mentioned pyrolytic carbon is carried out activation, the priming reaction temperature is: 750 ℃~1100 ℃; Temperature rise rate is 3 ℃/minute~15 ℃/minute; Soak time is 10 minutes~120 minutes, is cooled to room temperature, obtains gac; Or mix with above-mentioned pyrolytic carbon with above-mentioned heavy pyrolysis oil, the blended mass ratio is: the heavy pyrolysis oil: charcoal=1: (3~15), and making mixture forming is clavate or sphere; At last the mixture after the moulding is carried out activation; The priming reaction temperature is: 750 ℃~1100 ℃, temperature rise rate is 3 ℃/minute~15 ℃/minute, and soak time is 10 minutes~120 minutes; Be cooled to room temperature, obtain gac;
(5) high-temperature tail gas that produces in the reactivation process is back in the activation furnace, recycles.
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CN105236592A (en) * 2015-11-14 2016-01-13 黄海涛 Water purification charcoal material as well as production method and application thereof
CN105692615B (en) * 2016-04-22 2017-11-17 江苏省星霖碳业股份有限公司 The system and method that a kind of gas black prepares activated carbon
CN106276892B (en) * 2016-08-05 2018-01-12 北京林业大学 A kind of method that pressed active carbon is prepared using thermal cracking charcoal as raw material
CN106929051B (en) * 2017-03-23 2023-06-16 华电电力科学研究院有限公司 Method and device for obtaining component single enriched biological oil by using biomass pyrolysis byproducts
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