CN103539115A - 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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- CN103539115A CN103539115A CN201310528465.XA CN201310528465A CN103539115A CN 103539115 A CN103539115 A CN 103539115A CN 201310528465 A CN201310528465 A CN 201310528465A CN 103539115 A CN103539115 A CN 103539115A
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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 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk.
Background technology
China Shi Yige large agricultural country, stalk resource is very abundant, accounts for 30% left and right of whole world stalk total amount.Agricultural Input Factors 55% left/right rotation turns to agricultural crop straw, and the waste of stalk resource, is in fact the waste of arable land, water resources and agriculture input.Stalk is a kind of good bioenergy, wherein contains large nutritive substance, and exploitation have a high potential.At present, in the situation that China's Forest Resources, fossil energy are very nervous, stalk can be used as its effective surrogate.By reasonable approach, utilize stalk, not only can 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 its name suggests, it not only has the intrinsic intrinsic property of carbon material, has again the soft workability of textile fibres concurrently, is fortifying fibre of new generation.Its proportion is less than 1/4 of steel, but intensity is very strong, and its solidity to corrosion is transcendent, is widely used in civilian, military, building, space flight and super sport car field.Carbon fiber can be divided into polyacrylonitrile-radical, asphaltic base, viscose glue base and phenolic aldehyde base etc. by precursor kind, wherein general with polyacrylonitrile carbon fiber and asphalt-based carbon fiber application.
The classical production process of carbon fiber comprises 4 processes such as fiber sprinning, thermostabilization (preoxidation), carbonization, greying, and the chemical transformation of following therebetween comprises, dehydrogenation, cyclisation, preoxidation, oxidation and deoxidation etc.This preparation technology has relatively high expectations to raw material, production cost is high, and there are technology barriers in the production of carbon fibre precursor, reason is that spray silk technique, the polyacrylonitrile polymerization technique of carbon fibre precursor firmly held by Japanese ,Dong Bang Tenax group of Dong Li company and mitsubishi rayon group, has limited its propagation and employment.How a kind of technique with low cost, that technique is simply produced carbon fiber is provided is industry problem demanding prompt solution.
Summary of the invention
It is raw material that castor seeds shell, castor-oil plant stalk are take in the present invention, with calcium chloride, as activator, hydrochloric acid, as additive, has prepared carbon fiber, and concrete technology step is as follows:
(1) dry: castor seeds shell, castor-oil plant stalk water are cleaned, proceed to 40 ℃ of constant temperature dehydration 0.5-1 hour of stoving oven, obtain siccative;
(2) pulverize and soak: siccative being put into pulverizer and be crushed to 60-80 order particle, in material after pulverizing, adding mass concentration is the calcium chloride solution of 30-40%, stirs and soaks 1-3 hour, after immersion finishes, separation soaking liquid and wet stock, obtain particle after wet stock is dried;
(3) charing: the particle of castor seeds shell, castor-oil plant stalk is moved into charring furnace, and 400-600 ℃ of high temperature carbonization, during charing, need constantly stir, obtains work in-process for charing 1-3 hour;
(4) activation: the work in-process that obtain after charing is finished proceed in activation furnace, first, with the steam constant temperature activation 1-2 hour of 70-80 ℃, then under 600-650 ℃ of high temperature, activate 1-2 hour, then activate 1-2 hour at 700 ℃, between pot-life, every upset in 10 minutes once;
(5) clean: after product after to be activated is cooling, washing removes that to be attached to the calcium chloride of carbon fiber surface residual, and scavenging solution is recyclable to be utilized again as soak solution;
(6) metallic element is analysed and is removed: the salt acid elution that is 20-30% by mass concentration by the carbon fiber after cleaning, at the uniform velocity stir lower washing 0.5-1 hour, filtering hydrochloric acid, with tap water, clean 2 ~ 3 times, each cleaning continues 0.5-1 hour, until test water washing lotion pH value is neutrality, then by carbon fiber centrifuge dehydration;
(7) dry: the carbon fiber after centrifuge dehydration is proceeded to freeze-day with constant temperature baking box, first at 70-80 ℃ of freeze-day with constant temperature 0.5-1 hour, then at 140-150 ℃ of freeze-day with constant temperature 1-2 hour, finally at 400-450 ℃ of freeze-day with constant temperature 2-3h, make moisture contained in carbon fiber and hydrochloric acid volatilization clean, obtain carbon fiber finished product.
Preferably, in step (2), the add-on of calcium chloride solution is 10L calcium chloride solution/kg siccative.
Preferably, the carbonization temperature of step (3) is 500 ℃.
Preferably, the activation method of step (4) is first with 80 ℃ of steam constant temperatures activation 1.5 hours, and then 600 ~ 650 ℃ of high-temperature activations are 1 hour, and last 700 ℃ of activation 1 hour, between pot-life, every upset in 10 minutes once.
Preferably, step (4) isolated air in reactivation process carries out, and preferably in nitrogen atmosphere, carries out.
Preferably, in step (6), the mass concentration of hydrochloric acid is 23%, and its consumption is 5L hydrochloric acid/kg carbon fiber.
In the charing stage, prove charing termination to observe the deeply worried blackening of particle, as incomplete in charing, capable of regulating stirring frequency and prolongation carbonization time.The object of the isolated air of activation stage is to avoid air to enter in stove to cause and burn or affect activation effect.By carbon fiber, by the object of salt acid elution, be the metallic impurity that contain in order to remove its surface.
It is raw material that castor seeds shell, castor-oil plant stalk are take in the present invention, with calcium chloride, as activator, hydrochloric acid, as additive, prepares carbon fiber.In traditional fly ash method, produce on the basis of carbon fiber, ratio, soak time, soak time, the activation temperature of ratio, additive and the activator of activator and raw material have been adjusted, castor seeds shell, stalk, the suitable processing condition of carbon fiber have been proposed to prepare, more domestic other carbon fibers of finished product or commercially available carbon fiber are compared, there is superior absorption property.
The present invention processes the castor-oil plant auxiliary products such as castor seeds shell, stalk through physics, chemical process; before processing, raw material is carried out to constant temperature processing; realize the preparation of carbon fiber; in the course of processing; additive recycle; substantially realize zero release, zero and pollute, environment protection and waste agronomic crop occupation of land have been obtained to effective alleviation.Secondly, the additive environmental pollution adopting is little, in whole production process, has reduced the production cost of comparing compared with traditional processing technology.
The present invention has creatively proposed to take the method that castor seeds shell and castor-oil plant stalk are raw material production carbon fiber, and its raw material sources are extensive, and production cost is low, technique is simple, break through external technology barriers, there is promotional value widely, thereby be expected to greatly promote production and the application of carbon fiber.
Embodiment
Embodiment 1
First by castor seeds shell, castor-oil plant stalk hand-sorting, remove the visible foreign material such as earth, with tap water, clean up.Castor seeds shell, the castor-oil plant stalk got after 10kg cleans proceed to 40 ℃ of constant temperature dehydrations of stoving oven 0.5 hour.After first oven dry, siccative is put into pulverizer and be crushed to 60 order particles, in particle after pulverizing, add 100L 40% calcium chloride solution, reaction stirs, this stage need continue approximately 1 hour, after immersion finishes, gets soak-out material and casts aside observation immersion effect, immersion liquid reclaims, and can be used for configuration and again soaks.Then, castor seeds shell, castor-oil plant crushed straw aggregate are moved into charring furnace, 400 ℃ of high temperature carbonizations, during charing, need constantly to stir to prevent that quality product is affected.After 1.5 hours, observe the deeply worried blackening of particle and prove charing termination.After charing finishes, work in-process are proceeded in activation furnace, 80 ℃ of steam constant temperatures activate 1.5 hours, 600 ~ 650 ℃ of high-temperature activations 1 hour, 700 ℃ activate 1 hour, during this period, every upset in 10 minutes once, the high-temperature activation stage, should completely cut off air-activatedly, to avoid air to enter, in stove, cause burning or affect activation effect.Activation finishes, after product is cooling, to weigh, and obtains 3.5kg carbon fiber first product.
Carbon fiber first product, in clean wooden interior washing, is sloughed to be attached to the calcium chloride of carbon fiber surface residual, and scavenging solution is recyclable to be utilized again as soak solution.Then, product is carried out to metallic element and analyse and remove, with the technical hydrochloric acid washing of 17.5L 23%, at the uniform velocity stir, filter place hydrochloric acid after 0.5 hour, cleans 2 ~ 3 times with tap water, and each cleaning continues about approximately 0.5 hour, until test water washing lotion pH value is neutrality.And then by the carbon fiber product centrifuge 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 ℃ of freeze-day with constant temperature 0.5 hour, 150 ℃ of freeze-day with constant temperature 1 hour, 450 ℃ of freeze-day with constant temperature 2h, make moisture contained in high-activity carbon fiber and hydrochloric acid volatilization clean, obtain the finished product 3kg.
After testing, the carbon fiber that utilizes aforesaid method to produce, its tensile strength can be up to 5500MPa, and tensile modulus can reach 500GPa.
Embodiment 2
Castor seeds shell, the castor-oil plant stalk got after 100kg cleans proceed to 40 ℃ of constant temperature dehydrations of stoving oven 0.5 hour.After first oven dry, siccative is put into pulverizer and be crushed to 60 order particles, in particle after pulverizing, add 1000L 40% calcium chloride solution, reaction stirs, this stage need continue approximately 1 hour, after immersion finishes, gets soak-out material and casts aside observation immersion effect, immersion liquid reclaims, and can be used for configuration and again soaks.Then, castor seeds shell, crushed straw aggregate are moved into charring furnace, 400 ℃ of high temperature carbonizations, during charing, need constantly to stir to prevent that quality product is affected.After 1.5 hours, observe the deeply worried blackening of particle and prove charing termination, as incomplete in charing, capable of regulating stirring frequency and prolongation carbonization time.After charing finishes, work in-process are proceeded in activation furnace, 80 ℃ of steam constant temperatures activation 1.5 hours, 600 ~ 650 ℃ of high-temperature activations 1 hour in nitrogen atmosphere then, 700 ℃ of activation 1 hour, during this period, every upset in 10 minutes once.Activation finishes, after product is cooling, to weigh, and obtains 40kg carbon fiber first product.
Carbon fiber first product, in clean wooden interior washing, is sloughed to be attached to the calcium chloride of carbon fiber surface residual, and scavenging solution is recyclable to be utilized again as soak solution.Then, product is carried out to metallic element and analyse and remove, with the technical hydrochloric acid washing of 170L 23%, at the uniform velocity stir, filter place hydrochloric acid after 0.5 hour, cleans 2 ~ 3 times with tap water, and each cleaning continues about approximately 0.5 hour, until test water washing lotion pH value is neutrality.And then by the carbon fiber product centrifuge 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 ℃ of freeze-day with constant temperature 0.5 hour, 150 ℃ of freeze-day with constant temperature 1 hour, 450 ℃ of freeze-day with constant temperature 2h, make moisture contained in high-activity carbon fiber and hydrochloric acid volatilization clean, obtain the finished product 35kg.
After testing, the carbon fiber that utilizes aforesaid method to produce, its tensile strength can be up to 5200MPa, and tensile modulus can reach 510GPa.
The present invention has creatively proposed to take the method that castor seeds shell and castor-oil plant stalk are raw material production carbon fiber, and 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 (7)
1. with castor seeds shell, castor-oil plant stalk, be a method for raw material production carbon fiber, it is characterized in that comprising the following steps:
(1) dry: castor seeds shell, castor-oil plant stalk water are cleaned, proceed to 40 ℃ of constant temperature dehydration 0.5-1 hour of stoving oven, obtain siccative;
(2) pulverize and soak: siccative being put into pulverizer and be crushed to 60-80 order particle, in material after pulverizing, adding mass concentration is the calcium chloride solution of 30-40%, stirs and soaks 1-3 hour, after immersion finishes, separation soaking liquid and wet stock, obtain particle after wet stock is dried;
(3) charing: the particle of castor seeds shell, castor-oil plant stalk is moved into charring furnace, and 400-600 ℃ of high temperature carbonization, during charing, need constantly stir, obtains work in-process for charing 1-3 hour;
(4) activation: the work in-process that obtain after charing is finished proceed in activation furnace, first, with the steam constant temperature activation 1-2 hour of 70-80 ℃, then under 600-650 ℃ of high temperature, activate 1-2 hour, then activate 1-2 hour at 700 ℃, between pot-life, every upset in 10 minutes once;
(5) clean: after product after to be activated is cooling, washing removes that to be attached to the calcium chloride of carbon fiber surface residual, and scavenging solution is recyclable to be utilized again as soak solution;
(6) metallic element is analysed and is removed: the salt acid elution that is 20-30% by mass concentration by the carbon fiber after cleaning, at the uniform velocity stir lower washing 0.5-1 hour, filtering hydrochloric acid, with tap water, clean 2 ~ 3 times, each cleaning continues 0.5-1 hour, until test water washing lotion pH value is neutrality, then by carbon fiber centrifuge dehydration;
(7) dry: the carbon fiber after centrifuge dehydration is proceeded to freeze-day with constant temperature baking box, first at 70-80 ℃ of freeze-day with constant temperature 0.5-1 hour, then at 140-150 ℃ of freeze-day with constant temperature 1-2 hour, finally at 400-450 ℃ of freeze-day with constant temperature 2-3h, make moisture contained in carbon fiber and hydrochloric acid volatilization clean, obtain carbon fiber finished product.
2. as claimed in claim 1 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, it is characterized in that: in step (2), the add-on of calcium chloride solution is 10L calcium chloride solution/kg siccative.
3. as claimed in claim 1 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, it is characterized in that: the carbonization temperature of step (3) is 500 ℃.
4. as claimed in claim 1 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, it is characterized in that: the activation method of step (4) is first with 80 ℃ of steam constant temperature activation 1.5 hours, then 600 ~ 650 ℃ of high-temperature activations are 1 hour, last 700 ℃ of activation 1 hour, between pot-life, every upset in 10 minutes once.
5. as claimed in claim 1 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, it is characterized in that: step (4) isolated air in reactivation process carries out.
6. as claimed in claim 5 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, it is characterized in that: the reactivation process of step (4) is carried out in nitrogen atmosphere.
7. as claimed in claim 1 is the method for raw material production carbon fiber with castor seeds shell, castor-oil plant stalk, 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104131364A (en) * | 2014-07-15 | 2014-11-05 | 李文军 | Crop straw active 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 |
| CN108033447A (en) * | 2017-12-07 | 2018-05-15 | 吉林大学 | Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon |
| 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 |
| CN114775109A (en) * | 2022-04-24 | 2022-07-22 | 承德石油高等专科学校 | Activated carbon fiber and method for preparing activated carbon fiber by adopting 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104131364A (en) * | 2014-07-15 | 2014-11-05 | 李文军 | Crop straw active 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 |
| CN108033447A (en) * | 2017-12-07 | 2018-05-15 | 吉林大学 | Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon |
| 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 |
| CN114775109A (en) * | 2022-04-24 | 2022-07-22 | 承德石油高等专科学校 | Activated carbon fiber and method for preparing activated carbon fiber by adopting humic acid or humate |
| 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 |
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