CN103539115B - Method for producing carbon fiber with castor seed shells and castor straws as raw materials - Google Patents
Method for producing carbon fiber with castor seed shells and castor straws as raw materials Download PDFInfo
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- CN103539115B CN103539115B CN201310528465.XA CN201310528465A CN103539115B CN 103539115 B CN103539115 B CN 103539115B CN 201310528465 A CN201310528465 A CN 201310528465A CN 103539115 B CN103539115 B CN 103539115B
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Abstract
The invention relates to a method for producing carbon fiber with castor seed shells and castor straws as raw materials. The method comprises the following steps of drying, crushing and soaking, carbonizing, activating, washing, separating-out of metallic elements, drying and the like with calcium chloride as an activating agent and hydrochloric acid as an additive, thus preparing the carbon fiber. The method has the advantages of wide source of raw materials, low production cost, simple process, high product yield and high intensity.
Description
Technical field
The invention belongs to carbon fiber production field, specifically a kind of castor bean shell, castor-oil plant stalk are the method that carbon fiber produced by raw material.
Background technology
China is a large agricultural country, and stalk resource is very abundant, accounts for about 30% of whole world stalk total amount.Countryside tax system key element 55% left/right rotation turns to agricultural crop straw, the waste of stalk resource, be in fact plough, the waste of water resource and countryside tax system product.Stalk is a kind of well bioenergy, and wherein containing large nutriment, developing and utilizingpotentiality is huge.At present, when China's Forest Resources, fossil energy are very nervous, stalk can be used as its effective substitute.Utilize stalk by reasonable approach, can not only alleviate or solve the pollution problem of agricultural wastes, also bring huge economic benefit simultaneously.Therefore, strengthen agricultural crop straw comprehensive utilization, become the focus of countries in the world research.
Carbon fiber (carbon fiber), as the term suggests it not only has the intrinsic intrinsic property of material with carbon element, having again the soft machinability of textile fabric concurrently, is fortifying fibre of new generation.Its proportion is less than 1/4 of steel, but intensity is very strong, and its corrosion resistance is transcendent, is widely used in civilian, military, building, space flight and Super Car field.Carbon fiber can be divided into polyacrylonitrile-radical, asphaltic base, viscose glue base and phenolic aldehyde base etc. by precursor kind, wherein applies the most general with polyacrylonitrile carbon fiber and asphalt-based carbon fiber.
The classical production process of carbon fiber comprises 4 processes such as fibre spinning, thermostabilization (pre-oxidation), carbonization, graphitization, and chemical change adjoint therebetween comprises, dehydrogenation, cyclisation, pre-oxidation, oxidation and deoxidation etc.The requirement of this preparation technology to raw material is higher, production cost is high, and there are technology barriers in the production of carbon fibre precursor, reason is the spinning process of carbon fibre precursor, polyacrylonitrile polymerization technique is firmly held by the Dong Li company of Japan, Dong Bang Tenax group and mitsubishi rayon group, limits its propagation and employment.A kind of technique with low cost, that technique simply produces carbon fiber how is provided to be industry problem demanding prompt solution.
Summary of the invention
The present invention is with castor bean shell, castor-oil plant stalk for raw material, and prepared carbon fiber as activator, hydrochloric acid as additive with calcium chloride, concrete technology step is as follows:
(1) dry: castor bean shell, castor-oil plant stalk water are cleaned, proceed to drying oven 40 DEG C of constant temperature dehydration 0.5-1 hour, obtain siccative;
(2) pulverize and soak: siccative being put into pulverizer and be crushed to 60-80 order particle, add the calcium chloride solution that mass concentration is 30-40% in material after being pulverized, stir and soak 1-3 hour, soak after terminating, separation soaking liquid and wet stock, obtain particle by after wet stock drying;
(3) carbonize: the particle of castor bean shell, castor-oil plant stalk is moved into retort, and 400-600 DEG C of high temperature carbonization, during charing, need constantly stir, carbonize 1-3 hour and obtain semi-finished product;
(4) activate: the semi-finished product obtained after charing being terminated proceed in activation furnace, first with the steam constant temperature activation 1-2 hour of 70-80 DEG C, then under 600-650 DEG C of high temperature, activate 1-2 hour, then activate 1-2 hour at 700 DEG C, between pot-life, every upset in 10 minutes once;
(5) clean: after the product cooling after to be activated, the calcium chloride that washing removing is attached to carbon fiber surface remains, and cleaning fluid is recyclable to be utilized again as soak;
(6) metallic element is analysed and is removed: the salt acid elution by the carbon fiber mass concentration after cleaning being 20-30%, at the uniform velocity stir lower washing 0.5-1 hour, filtering hydrochloric acid, with running water cleaning 2 ~ 3 times, each cleaning continues 0.5-1 hour, till test water washing lotion pH value is neutrality, then by carbon fiber centrifugal dehydration;
(7) dry: the carbon fiber after centrifugal dehydration is proceeded to freeze-day with constant temperature baking box, first at 70-80 DEG C of freeze-day with constant temperature 0.5-1 hour, then at 140-150 DEG C of freeze-day with constant temperature 1-2 hour, last at 400-450 DEG C of freeze-day with constant temperature 2-3h, make moisture contained in carbon fiber and hydrochloric acid volatilization totally, obtain carbon fiber finished product.
Preferably, in step (2), the addition of calcium chloride solution is 10L calcium chloride solution/kg siccative.
Preferably, the carbonization temperature of step (3) is 500 DEG C.
Preferably, the activation method of step (4) first activates 1.5 hours with 80 DEG C of steam constant temperatures, then 600 ~ 650 DEG C of high-temperature activations 1 hour, last 700 DEG C of activation 1 hour, between pot-life, every upset in 10 minutes once.
Preferably, step (4) isolated air in activation process carries out, and preferably carries out in nitrogen atmosphere.
Preferably, in step (6), the mass concentration of hydrochloric acid is 23%, and its consumption is 5L hydrochloric acid/kg carbon fiber.
Carbonization stage, then proves charing termination to observe the deeply worried blackening of particle, as carbonized not exclusively, and adjustable stirring frequency and prolongation carbonization time.The object that activation stage completely cuts off air avoids air to enter in stove cause burning or affect activation effect.The metal impurities contained to remove its surface by the object of carbon fiber salt acid elution.
The present invention for raw material, prepares carbon fiber as activator, hydrochloric acid as additive with calcium chloride with castor bean shell, castor-oil plant stalk.Produce on the basis of carbon fiber in traditional fly ash method, have adjusted the ratio of the ratio of activator and raw material, additive and activator, soak time, soak time, activation temperature, propose and prepare the suitable process conditions of castor bean shell, stalk, carbon fiber, finished product other carbon fibers more domestic or commercially available carbon fiber are compared, there is superior absorption property.
The castor-oil plant auxiliary products such as castor bean shell, stalk are processed through physics, chemical method by the present invention; before processing constant temperature process is carried out to raw material; realize the preparation of carbon fiber; in process; additive recycles; substantially realize zero-emission, no pollution, environmental protection and waste agronomic crop are taken up an area and obtains effective alleviation.Secondly, the additive environmental pollution adopted is little, in whole production process, reduces the production cost compared compared with traditional processing technology.
The method that it is raw material production carbon fiber that the present invention creatively proposes with castor bean shell and castor-oil plant stalk, its raw material sources are extensive, and production cost is low, technique is simple, breach external technology barriers, there is promotional value widely, thus be expected to the production and the application that greatly promote carbon fiber.
Detailed description of the invention
Embodiment 1
First by castor bean shell, castor-oil plant stalk hand-sorting, remove the visible foreign material such as earth, clean up with running water.Get 10kg clean after castor bean shell, castor-oil plant stalk proceed to drying oven 40 DEG C of constant temperature and dewater 0.5 hour.After first oven dry completes, siccative is put into pulverizer and be crushed to 60 order particles, 100L 40% calcium chloride solution is added in particle after being pulverized, reaction stirs, this stage need continue about 1 hour, soaks after terminating, and gets soak-out material and casts aside observation immersion effect, immersion liquid reclaims, and can be used for configuration and again soaks.Then, castor bean shell, castor-oil plant crushed straw aggregate are moved into retort, 400 DEG C of high temperature carbonizations, during charing, need constantly to stir to prevent product quality to be affected.After 1.5 hours, observe the deeply worried blackening of particle and then prove charing termination.After charing terminates, semi-finished product are proceeded in activation furnace, 80 DEG C of steam constant temperatures activate 1.5 hours, 600 ~ 650 DEG C of high-temperature activations 1 hour, 700 DEG C activate 1 hour, during this period, every upset in 10 minutes once, the high-temperature activation stage, should completely cut off air-activated, enter in stove to avoid air and cause burning or affect activation effect.Activation end, after product cooling, is weighed, is obtained 3.5kg carbon fiber first product.
By carbon fiber first product in clean wooden interior washing, slough the calcium chloride being attached to carbon fiber surface and remain, cleaning fluid is recyclable to be utilized again as soak.Then, carry out metallic element to product and analyse and remove, wash, at the uniform velocity stir, filter place hydrochloric acid after 0.5 hour with the technical hydrochloric acid of 17.5L 23%, with running water cleaning 2 ~ 3 times, each cleaning continues about 0.5 hours, till test water washing lotion pH value is neutrality.And then by the carbon fiber product centrifugal dehydration after cleaning, water content in high-activity carbon fiber is reduced.Finally, carbon fiber is proceeded to freeze-day with constant temperature baking box, 80 DEG C of freeze-day with constant temperature 0.5 hour, 150 DEG C of freeze-day with constant temperature 1 hour, 450 DEG C of freeze-day with constant temperature 2h, make moisture contained in high-activity carbon fiber and hydrochloric acid volatilization clean, obtain final products 3kg.
After testing, utilize the carbon fiber that said method is produced, its hot strength can up to 5500MPa, and stretch modulus can reach 500GPa.
Embodiment 2
Get 100kg clean after castor bean shell, castor-oil plant stalk proceed to drying oven 40 DEG C of constant temperature and dewater 0.5 hour.After first oven dry completes, siccative is put into pulverizer and be crushed to 60 order particles, 1000L 40% calcium chloride solution is added in particle after being pulverized, reaction stirs, this stage need continue about 1 hour, soaks after terminating, and gets soak-out material and casts aside observation immersion effect, immersion liquid reclaims, and can be used for configuration and again soaks.Then, castor bean shell, crushed straw aggregate are moved into retort, 400 DEG C of high temperature carbonizations, during charing, need constantly to stir to prevent product quality to be affected.After 1.5 hours, the deeply worried blackening of observation particle then proves charing termination, as carbonized not exclusively, and adjustable stirring frequency and prolongation carbonization time.Proceed in activation furnace by semi-finished product after charing terminates, 80 DEG C of steam constant temperatures activate 1.5 hours, then 600 ~ 650 DEG C of high-temperature activations 1 hour in nitrogen atmosphere, 700 DEG C of activation 1 hour, during this period, every upset in 10 minutes once.Activation end, after product cooling, is weighed, is obtained 40kg carbon fiber first product.
By carbon fiber first product in clean wooden interior washing, slough the calcium chloride being attached to carbon fiber surface and remain, cleaning fluid is recyclable to be utilized again as soak.Then, carry out metallic element to product and analyse and remove, wash, at the uniform velocity stir, filter place hydrochloric acid after 0.5 hour with the technical hydrochloric acid of 170L 23%, with running water cleaning 2 ~ 3 times, each cleaning continues about 0.5 hours, till test water washing lotion pH value is neutrality.And then by the carbon fiber product centrifugal dehydration after cleaning, water content in high-activity carbon fiber is reduced.Finally, carbon fiber is proceeded to freeze-day with constant temperature baking box, 80 DEG C of freeze-day with constant temperature 0.5 hour, 150 DEG C of freeze-day with constant temperature 1 hour, 450 DEG C of freeze-day with constant temperature 2h, make moisture contained in high-activity carbon fiber and hydrochloric acid volatilization clean, obtain final products 35kg.
After testing, utilize the carbon fiber that said method is produced, its hot strength can up to 5200MPa, and stretch modulus can reach 510GPa.
The method that it is raw material production carbon fiber that the present invention creatively proposes with castor bean shell and castor-oil plant stalk, its raw material sources are extensive, and production cost is low, and technique is simple, and product yield is high, and intensity is good, has promotional value widely.
Claims (4)
1. be a method for raw material production carbon fiber with castor bean shell, castor-oil plant stalk, it is characterized in that comprising the following steps:
(1) dry: castor bean shell, castor-oil plant stalk water are cleaned, proceed to drying oven 40 DEG C of constant temperature dehydration 0.5-1 hour, obtain siccative;
(2) pulverize and soak: siccative being put into pulverizer and be crushed to 60-80 order particle, add the calcium chloride solution that mass concentration is 30-40% in material after being pulverized, stir and soak 1-3 hour, soak after terminating, separation soaking liquid and wet stock, obtain particle by after wet stock drying;
(3) carbonize: the particle of castor bean shell, castor-oil plant stalk is moved into retort, and 400-600 DEG C of high temperature carbonization, during charing, need constantly stir, carbonize 1-3 hour and obtain semi-finished product;
(4) activate: the semi-finished product obtained after charing being terminated proceed in activation furnace, first activate 1.5 hours, then in nitrogen atmosphere with 80 DEG C of steam constant temperatures, 600 ~ 650 DEG C of high-temperature activations 1 hour, last 700 DEG C of activation 1 hour, between pot-life, every upset in 10 minutes once;
(5) clean: after the product cooling after to be activated, the calcium chloride that washing removing is attached to carbon fiber surface remains, and cleaning fluid is recyclable to be utilized again as soak;
(6) metallic element is analysed and is removed: the salt acid elution by the carbon fiber mass concentration after cleaning being 20-30%, at the uniform velocity stir lower washing 0.5-1 hour, filtering hydrochloric acid, with running water cleaning 2 ~ 3 times, each cleaning continues 0.5-1 hour, till test water washing lotion pH value is neutrality, then by carbon fiber centrifugal dehydration;
(7) dry: the carbon fiber after centrifugal dehydration is proceeded to freeze-day with constant temperature baking box, first at 70-80 DEG C of freeze-day with constant temperature 0.5-1 hour, then at 140-150 DEG C of freeze-day with constant temperature 1-2 hour, last at 400-450 DEG C of freeze-day with constant temperature 2-3h, make moisture contained in carbon fiber and hydrochloric acid volatilization totally, obtain carbon fiber finished product.
2., as claimed in claim 1 by the method that castor bean shell, castor-oil plant stalk are raw material production carbon fiber, it is characterized in that: in step (2), the addition of calcium chloride solution is 10L calcium chloride solution/kg siccative.
3., as claimed in claim 1 by the method that castor bean shell, castor-oil plant stalk are raw material production carbon fiber, it is characterized in that: the carbonization temperature of step (3) is 500 DEG C.
4., as claimed in claim 1 by the method that castor bean shell, castor-oil plant stalk are raw material production carbon fiber, it is characterized in that: in step (6), the mass concentration of hydrochloric acid is 23%, and its consumption is 5L hydrochloric acid/kg carbon fiber.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104131364B (en) * | 2014-07-15 | 2016-01-20 | 李文军 | Agricultural crop straw carbon fiber production method |
| CN105907406A (en) * | 2016-05-11 | 2016-08-31 | 江苏润通生物科技有限公司 | Method for carbonizing organic solid waste by high-temperature coal gas to realize gas and charcoal co-production |
| CN105907437A (en) * | 2016-05-13 | 2016-08-31 | 云南昌阔农业科技有限公司 | Method for producing charcoal by Ricinus communis L. straws |
| CN108033447B (en) * | 2017-12-07 | 2021-06-15 | 吉林大学 | Preparation method of porous biomass carbon, porous biomass carbon and application |
| CN113479878A (en) * | 2021-08-02 | 2021-10-08 | 玉山县三清活性炭有限公司 | Activated carbon product and phosphoric acid method activated carbon production method and equipment thereof |
| CN114775109B (en) * | 2022-04-24 | 2023-08-25 | 承德石油高等专科学校 | Activated carbon fiber and method for preparing activated carbon fiber by humic acid or humate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102812A (en) * | 1975-10-02 | 1978-07-25 | Laporte Industries, Limited | Production of carbon from coal granules prepared in a fluid energy mill |
| CN1115796A (en) * | 1994-07-28 | 1996-01-31 | 刘智仁 | Prepn of high-adsorption active carbon fibre |
| CN1166541A (en) * | 1997-04-18 | 1997-12-03 | 中山大学 | Preparation method of natural fibre-based active carbon fibre |
| CN1673076A (en) * | 2005-01-27 | 2005-09-28 | 西北农林科技大学 | Active carbon producing process with mixed stalk material |
| CN101121512A (en) * | 2007-04-29 | 2008-02-13 | 武汉理工大学 | Preparation method for plant active carbon fibre column |
| CN101230502A (en) * | 2007-12-13 | 2008-07-30 | 中国人民解放军总后勤部军需装备研究所 | Method for preparing anesthesia activated carbon fiber |
-
2013
- 2013-10-31 CN CN201310528465.XA patent/CN103539115B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102812A (en) * | 1975-10-02 | 1978-07-25 | Laporte Industries, Limited | Production of carbon from coal granules prepared in a fluid energy mill |
| CN1115796A (en) * | 1994-07-28 | 1996-01-31 | 刘智仁 | Prepn of high-adsorption active carbon fibre |
| CN1166541A (en) * | 1997-04-18 | 1997-12-03 | 中山大学 | Preparation method of natural fibre-based active carbon fibre |
| CN1673076A (en) * | 2005-01-27 | 2005-09-28 | 西北农林科技大学 | Active carbon producing process with mixed stalk material |
| CN101121512A (en) * | 2007-04-29 | 2008-02-13 | 武汉理工大学 | Preparation method for plant active carbon fibre column |
| CN101230502A (en) * | 2007-12-13 | 2008-07-30 | 中国人民解放军总后勤部军需装备研究所 | Method for preparing anesthesia activated carbon fiber |
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