CN1223515C - Method for preparing active carbon from caudex of sisal - Google Patents
Method for preparing active carbon from caudex of sisal Download PDFInfo
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- CN1223515C CN1223515C CNB031397719A CN03139771A CN1223515C CN 1223515 C CN1223515 C CN 1223515C CN B031397719 A CNB031397719 A CN B031397719A CN 03139771 A CN03139771 A CN 03139771A CN 1223515 C CN1223515 C CN 1223515C
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- sisal
- stems
- activated carbon
- stalk
- activation
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- 244000198134 Agave sisalana Species 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title description 3
- 239000002994 raw material Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 244000060011 Cocos nucifera Species 0.000 description 11
- 235000013162 Cocos nucifera Nutrition 0.000 description 11
- 239000003610 charcoal Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 235000011624 Agave sisalana Nutrition 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000746976 Agavaceae Species 0.000 description 1
- 101100322085 Arabidopsis thaliana CAC3 gene Proteins 0.000 description 1
- 101100514477 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MSI1 gene Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- -1 transportation Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a method for preparing activated carbon from sisal stems as raw materials, which belongs to the technical field of activated carbon preparation. The method comprises the steps as follows: sisal stems are adopted as raw materials and treated with the procedures, such as soak as pretreatment, carbonization, activation, water wash, drying, etc. to prepare block sisal stem base activated carbon. The processes of carbonization and activation are carried out under nitrogen protection, and water vapor is adopted as an activating agent. The prepared product has the advantages of low ash content, large specific surface area, rich mesoporous content of 40 to 70%, definite intensity, good adsorbability and redox function. At present, a few sisal stems are developed and utilized, and many sisal stems are used as fuel or waste. The sisal stems as raw materials have rich source and low price. The method of the present invention can change waste to benefit and provide a new approach for the comprehensive utilization of sisal by-products.
Description
Technical field
The invention belongs to the manufacturing technology field of gac, be meant that specifically a kind of is the feedstock production process of active carbon with the sisal stalk.
Background technology
Gac is a kind of porousness sorbent material, is widely used in fields such as oil, chemical industry, food, medicine, light industry, environmental protection, national defence.The raw material of making gac is varied, and commonly used comprising is wooden, ature of coal, fruit stone, shell, polymer and industrial waste etc.China is vast in territory, ABUNDANT NATUREAL RESOURSES, and also respectively there are characteristics in different areas, and the plant base raw material that can be used for Activated Carbon Production is various in style, wherein has much to have realized suitability for industrialized production, also has some to be in experimental stage.
But along with the enhancing of whole society's Environmental awareness, people more and more are concerned about the importance that protects forest resources.For solving the day by day poor problem of wood activated charcoal raw material, to strengthen regeneration research on the one hand to agricultural and forestry production waste material and industrial production residuum etc., want the new alternative materials of active development on the other hand,
The gac made from fruit stone and shell; because of the physical strength height; granularity is more even; surface property is better; and can repeatedly regenerate and use repeatedly, at gas, liquid absorption, decolorizing and refining; has important purposes as the support of the catalyst and the aspect that extracts gold from, so the research and development of this respect are very active.
In the middle of numerous fruit stone shell gacs, the first-elected gac made from Exocarpium cocois (Cocos nucifera L) that the most ripe and performance is best.Because coconut husk is a kind of harder shell, the gac intensity height of producing, impure few, have extraordinary gas phase and liquid phase adsorption ability.At present, there are Japan and Philippines in the major country of production of cocoanut active charcoal, and throughput is all more than ten thousand tons.Throughput comprises China, the U.S., France and Britain etc. in thousands of tonnes country, also has Thailand's equal yield line below kiloton.But the same with other fruit stone shell gacs, the production of cocoanut active charcoal need be experienced the operation such as fragmentation of charing → fragmentation → activation → again, and technology is complicated, and relevant device is more, and the coconut husk raw material is more expensive, and the activated carbon product price is higher.Because the coconut husk shortage of resources of China is in the state that supply falls short of demand for a long time always, every year all must be from external a large amount of imports.
Sisal hemp (formal name used at school: Agave Sisalana Perrine, English name: Sisal), claim again " sisal hemp ", the Agavaceae per nnial herb, stem is sturdy and shorten, and stem can reach more than 5 meters when blooming.Leaf on the stem of cripetura the generation rosette-stape, shape such as sword, thus the name.Originate in Mexico, property happiness temperature, drought-enduring is adapted at the torrid zone, the cultivation of subtropics wide geographic area, mainly is grown in areas such as Hainan, Guangdong, Guangxi and Fujian in China.It is pure white, strong but pliable in texture that its leaf fibres has a color and luster, high resilience, and pulling force is strong, wear-resisting wiping, water-fast soaking, corrosion-resistant, the characteristics that are difficult for skidding are widely used on the causes such as fishery, navigation, industrial and mineral, transportation, oil field, and are used for weaving daily necessitiess such as sisal hemp carpet, artwork.
The main purpose of cultivation sisal hemp is in order to obtain the hard fiber in its blade, when sisal hemp after the growth several years, stops to break up blade and when taking out axle and blooming, no longer includes results in the production, must eliminate renewal to plant.Prescind the sisal stalk that stays behind the blade (being commonly called as the fiber crops head) the major part use that goes out of use or act as a fuel at present during renewal.
Summary of the invention
The purpose of this invention is to provide a kind of new plant base raw material, be that raw material prepares process of active carbon promptly, thereby accomplish changing waste into valuable, economize on resources, for new way is opened up in the comprehensive utilization of sisal hemp byproduct with inexpensive abundant sisal stalk.
In order to achieve the above object, the present invention is raw material with the sisal stalk, and the concrete operations step of its preparation method is as follows:
Sisal stalk washed be sawn into fritter after drying; be about 10~20cm; wide about 5cm, high about 3cm is after pre-treatment; speed with 5~10 ℃/min under nitrogen protection is warming up to 700~900 ℃ of charings; carbonization time 10~30 minutes feeds the steam activation 10~100 minutes that flow is 1~5mL/min in stationary temperature, makes it cool to room temperature then under nitrogen protection; and in stove, take out product washing (using pickling in case of necessity) to remove ash content and impurity wherein, oven dry.
The pre-treatment of sisal stalk: working concentration is the ammonium dibasic phosphate solution of 3~10wt%, dries raw material soaking standby after 16~24 hours naturally.
It is the gac of feedstock production that the inventive method adopts sisal stalk, and it is big to have general wood activated charcoal specific surface area and a pore volume, reactive behavior height, advantage such as impurity is few.Sisal stalk behind the carbonization-activation still can keep block-shape morphology, can loosely not hold, and ash content is low and certain intensity arranged.Along with the rising of carbonization-activation temperature and the prolongation of soak time, intensity descends to some extent, but still can satisfy the needs of use basically.According to the characteristics of sisal stalk, carbonization-activation can carry out in same equipment continuously, directly enters activation stage after the charing voluntarily, and technology is simple, less energy consumption.Raw material soaks pre-treatment with ammonium dibasic phosphate solution before charing, phosphide and cellulosic molecule form chemical bond and inner complex, forms crosslinkedly at intermolecular and intramolecularly, has prevented the loss of molecular fragment when thermal treatment, so yield is higher, reaches 15~30wt%.The specific surface area of product is 650~900m
2/ g, total pore volume is 0.4~0.6cm
3/ g.Owing to contain more xylogen in the sisal stalk, the gac that makes has flourishing mesopore and macropore, and mesopore volume accounts for 40~70% of total pore volume.The sisal stalk matrix activated carbon of the present invention's preparation has good absorption property, the trichloromethane adsorption rate is 50~65%, the benzene adsorption rate is 30~45%, methylene blue adsorption value 100~250mg/g, iodine sorption value 600~1100mg/g, in addition the toxicant phenol in the aqueous solution is also had and remove ability preferably, adsorptive capacity is greater than 100mg/g; And product also has the redox function, to Au
3+The reduction adsorptive capacity can 45~65% Au wherein be arranged up to 1000mg/g
3+Be reduced to Au simple substance and be adsorbed on activated carbon surface, therefore be expected in gas, liquid absorption, the smelting of gold and recovery wait some purposes top to replace cocoanut active charcoal.
Embodiment
Below be the specific embodiment of the invention:
Embodiment 1~3: dry after sisal stalk is washed, size according to carbonization-activation stove sample cell is sawn into fritter with it, is about 10~20cm, wide about 5cm, high about 3cm is that the ammonium dibasic phosphate solution of 5wt% at room temperature soaks and carried out the stabilization pre-treatment in 24 hours with concentration then; After drying raw material put into the carbonization-activation stove; temperature rise rate with 5 ℃/min under nitrogen protection is heated to 850 ℃ of charings 15 minutes; and remain under this steady temperature, feed the water vapor that flow is about 2mL/min, make raw material activation 30,60 and 90 minutes respectively.Stop heating after reaction finishes and make it to naturally cool to room temperature.In stove, take out reactant, promptly get sisal stalk matrix activated carbon product through washing, oven dry.
Table 1 is the structure and the performance comparison material of sisal stalk matrix activated carbon (SSAC) and commercially available cocoanut active charcoal (CAC).
Table 1, sisal stalk matrix activated carbon (SSAC) and commercially available cocoanut active charcoal
*(CAC) structure and performance comparison
Project | Numbering | |||||
Embodiment 1 | Embodiment 2 | Embodiment 3 | CAC3 | CAC5 | ||
Preparation condition | The carbonization-activation temperature (℃) | 850 | 850 | 850 | - | - |
Soak time (min) | 30 | 60 | 90 | - | - | |
Steam rates (mL/min) | 2 | 2 | 2 | - | - | |
Yield (%) | 18.8 | 18.3 | 16.5 | - | - | |
Pore structure | Specific surface area (m 2/g) | 770 | 767 | 794 | 894 | 724 |
Total pore volume (cm 3/g) | 0.43 | 0.44 | 0.49 | 0.44 | 0.36 | |
Micro pore volume (cm 3/g) | 0.21 | 0.23 | 0.13 | 0.36 | 0.30 | |
Mesopore volume (cm 3/g) | 0.18 | 0.21 | 0.34 | 0.06 | 0.04 | |
Absorption property | Methylene blue adsorption value (mg/g) | 143 | 151 | 232 | 213 | 118 |
Phenol adsorptive value (mg/g) | 151 | 154 | 160 | 219 | 151 | |
Iodine sorption value (mg/g) | 840 | 781 | 1060 | 1169 | 1035 | |
Trichloromethane adsorption rate (%) | 62.5 | 55.9 | 56.3 | 63.1 | 42.8 | |
Benzene adsorption rate (%) | 34.9 | 34.1 | 42.3 | 37.3 | 25.7 | |
Au 3+Reduction adsorptive capacity (mg/g) (reduction percentage %) | 950(53) | 1037(57) | 1002(62) | 984(44) | 571(36) |
(
*CAC3---be used for the cocoanut active charcoal of gas phase treatment; CAC5---be used for the cocoanut active charcoal that liquid phase is handled)
Claims (2)
1. the preparation method of a sisal stalk matrix activated carbon, the concrete steps that it is characterized in that this preparation method are as follows: sisal stalk is washed be sawn into fritter after drying, after pre-treatment, speed with 5~10 ℃/min under nitrogen protection is warming up to 700~900 ℃ of charings, carbonization time 10~30 minutes, feed the steam activation 10~100 minutes that flow is 1~5mL/min in stationary temperature, under nitrogen protection, make it cool to room temperature then, and in stove, take out product washing, oven dry; The pre-treatment working concentration is the ammonium dibasic phosphate solution of 3~10wt%, dries raw material soaking standby after 16~24 hours naturally.
2. method according to claim 1 is characterized in that sisal stalk is sawn into long 10~20cm, wide 5cm, the bulk of high 3cm.
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CNB031397719A CN1223515C (en) | 2003-07-10 | 2003-07-10 | Method for preparing active carbon from caudex of sisal |
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CNB031397719A CN1223515C (en) | 2003-07-10 | 2003-07-10 | Method for preparing active carbon from caudex of sisal |
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CN1223515C true CN1223515C (en) | 2005-10-19 |
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Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2451509B (en) * | 2007-08-02 | 2012-03-14 | Forestry Commission | Charcoals |
CN101181993B (en) * | 2007-12-13 | 2010-10-06 | 中国人民解放军总后勤部军需装备研究所 | Kenaf stalk activated charcoal and preparation method thereof |
KR101400249B1 (en) | 2012-02-10 | 2014-05-28 | 한국에너지기술연구원 | Method for preparing carbon dioxide absorbent based on natural biomass and carbon dioxide absorbent based on natural biomass prepared by the same |
CN105776672B (en) * | 2016-05-12 | 2019-03-29 | 秦皇岛佰工钢铁有限公司 | A kind of energy-efficient waste water treatment process |
CN105964308A (en) * | 2016-05-27 | 2016-09-28 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of carrier material for catalyst for sewage treatment |
CN106365163B (en) * | 2016-08-23 | 2018-10-09 | 中南大学 | A kind of preparation method of sisal fiber activated carbon and the application of the sisal fiber activated carbon in lithium-ion capacitor |
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