CN104495838B - A kind of method preparing activated carbon - Google Patents
A kind of method preparing activated carbon Download PDFInfo
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- CN104495838B CN104495838B CN201410763157.XA CN201410763157A CN104495838B CN 104495838 B CN104495838 B CN 104495838B CN 201410763157 A CN201410763157 A CN 201410763157A CN 104495838 B CN104495838 B CN 104495838B
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Abstract
The invention discloses the preparation method of a kind of activated carbon, belong to activated carbon preparing technical field.The method, with polyacrylonitrile fibre as carbon source, adds polyamines reagent intensification cross-linking reaction；Reaction to certain time is passed through CO2Intensification, carbonization, physically activated, cool down, wash, heat up and make moisture evaporate completely, obtain activated carbon.Resulting materials has abundant surface amine groups functional group and excellent absorption property, it is possible to applies and is being adsorbed with poisonous gas, is purifying the field such as sewage, drinking water absorption.Preparation technology is simple, efficiency is high, low cost, easily operate, and is very beneficial for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of activated carbon, be specifically related to a kind of method preparing activated carbon.
Background technology
Activated carbon, as a kind of multi-functional adsorbent, has good absorption property, it is possible to use multiple natural material and petrochemical material prepare.Polyacrylonitrile is a kind of good base material preparing NACF, may be used for preparing activated carbon.Active charcoal preparing process generally comprises physically activated and two kinds of techniques of chemical activation.Chemical activation mainly uses various chemical activating agent, such as, ZnCl2, H2SO4,
H3PO4, HCl, KOH.Physical activation method is by the carbonization of raw material elder generation, more at high temperature utilizes oxidizing gas, makes the carbon atom partial oxidation in graphite microcrystal form the pore structure of prosperity, increases internal surface area.
The structure of polyacrylonitrile active carbon fiber is amorphous graphite carbon, containing hexagonal carbon-coating, has the gap of various sizes, and be arranged in order to big gap from small gap in carbon-coating.The technological process being prepared NACF by polyacrylonitrile fibril is as follows: carbonization below P A N precursor ~ pre-oxidation ~ 700 DEG C ~ simultaneously carry out surface process higher than 700 DEG C of carbonizations, activation, curling obtains polyacrylonitrile fibre.Polyacrylonitrile radical active carbon fiber production process is easily generated the HCN of severe toxicity, and oxidizing process is wayward, it is difficult to produce the product that specific surface area is big.
Patent CN200810151333.9 discloses a kind of NACF and preparation method thereof, the method is with functional adding ingredients such as fibre-forming polymer and silver, copper, zinc as raw material, prepare NACF through pre-oxidation, carbonization, steam nitrogen activation, or prepare NACF through naoh treatment, carbonization, steam activation the most again.Patent CN200510030545.8 discloses a kind of active carbon fibre peacekeeping preparation method with hollow morphology structure, the method with polypropylene for medical article nitrile doughnut as raw material, dipping pretreatment in phosphorous compound solution, then form through pre-oxidation, carbonization, activation.Patent CN200510101946.8 discloses a kind of composite active carbon fibre and preparation method thereof, and this composite active carbon fibre is made up of glass fibre and the porous layer of charcoal being coated on fibreglass outer layers, has abundant micropore and part mesopore in porous carbon layer；Porous layer of charcoal is formed through high temperature cabonization activation by the mixture of polyacrylonitrile, phenolic aldehyde or polyvinyl alcohol with zinc chloride or phosphoric acid., on large-scale promotion application, there is drawback in said method complicated process of preparation.
Summary of the invention
It is an object of the invention to provide a kind of method preparing activated carbon of applicable industrial applications, make the activated carbon prepared have abundant surface functional group and bigger specific surface area.
For achieving the above object, the present invention uses chemical exothermal method to carry out fibers carbonization, utilize chemical reaction to carry out pore-creating, and early stage reaction needs thermal source, and later stage carbonisation is without continuing heating.Concrete technical scheme is as follows:
(1) weigh polyacrylonitrile fibre to be placed in insulation reaction container, add polyamines reaction reagent, make polyacrylonitrile fibre be totally submerged in reaction reagent, be warming up to 110 ~ 165 DEG C under nitrogen protection and carry out reacting 0.5 ~ 6h, obtain the polyacrylonitrile fibre of crosslinking；
(2) release part polyamines reaction reagent, stop logical N2, change and be passed through CO2, insulation continues reaction, crosslinked polypropylene nitrile fiber, polyamines reagent, CO2Reacting, system temperature is increased to 600-900 DEG C naturally simultaneously, and crosslinked polypropylene nitrile fiber carries out carbonization at such a temperature；
(3) stop after after carbonization completes being passed through CO2, it being passed through air and carry out nature cooling, system is down to room temperature, and with the water purification washing unreacted many amine aqueous solutions of excess and byproduct of reaction, making wash solution is neutrality, heats up and makes moisture evaporate completely, obtains activated carbon.
Described polyacrylonitrile fibre is polyacrylonitrile weight/mass percentage composition fibrous material more than 85%, can be arbitrary form.
Described polyamines reagent is one or more combinations in triethylene tetramine, TEPA, polyethylene polyamine, triethanolamine；Preferred 130-150 DEG C of step (1) reaction temperature.
In step (2), the polyacrylonitrile fibre of crosslinking and polyamines reagent quality are than=0.2 ~ 2:1；The amount of the carbon dioxide being passed through: every 100g polyacrylonitrile fibre is 10-30mL/min, and the time is 2-6h.
The specific surface area of activated carbon sample and pore-size distribution use BK122F type specific surface area and pore-size distribution tester (production of precise and tiny Gao Bo, Beijing science and technology Co., Ltd) to carry out isothermal adsorption test under 77K.Sample treatment and test condition: after 150 DEG C of heating remove adsorption thing in 2 hours, make adsorbing medium with high pure nitrogen, be measured for cold-trap with liquid nitrogen.BET equation is utilized to calculate specific surface area.
Amino exchange capacity measures the assay method with reference to epoxy hardener amine value.
The present invention, with polyacrylonitrile fibre as raw material, by techniques such as amination, carbonization, activation, prepares absorbent charcoal material.It provides the benefit that: polyacrylonitrile fibre first carries out cross-linking reaction, R-CN+NH2-R-NH2→RCNH-NH-R-NH-CNH-R；In subsequent reactions (step 2), CO2React with amine, RNH2+CO2→RNH2 +COO-;Whole process is exothermic reaction, utilizes reaction heat naturally to rise to high temperature, and polyacrylonitrile carries out carbonization, beneficially thermal source saving and recycling, and preparation technology is simple, efficiency is high, low cost, easily operate, and is very beneficial for industrialized production.The activated carbon product of gained, has relatively Large ratio surface area and abundant surface amine groups functional group, can meet the application demand of specified conditions.Especially it is being adsorbed with poisonous gas, purifying the field such as sewage, drinking water absorption, having and preferably apply effect.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Weigh polyacrylonitrile fibre 20.0g, triethylene tetramine 250ml, join in 500ml volumetric flask, be passed through N2Carry out being heated to 135 DEG C under protection, after reacting 3.0 hours, remove triethylene tetramine reaction reagent 200ml；It is passed through CO with 10ml/min speed2, continuing reaction 3.5h, temperature warms naturally to 730 DEG C, stops logical CO2, it is passed through air and cools down, until reaction system is down to room temperature, is rinsed by several times with 400ml pure water, dissolves unreacted many amine aqueous solutions and byproduct of reaction, until PH test paper test washings are neutrality；Then product is put to air dry oven, 200 DEG C of dry 0.5h, obtain activated carbon.Prepared Properties of Activated Carbon index is: specific surface area 680.32 m2/g;Apparent amino exchange content is 3.5mmol/g.
Embodiment 2
Weigh polyacrylonitrile fibre 50.0g, triethylene tetramine and triethanolamine (volume ratio 1:1) 500ml, join in 1000ml volumetric flask, be passed through N2Carry out being heated to 150 DEG C under protection, after reacting 4.0 hours, removal triethylene tetramine and triethanolamine reaction reagent 400ml；It is passed through CO with 12ml/min speed2, continuing reaction 4.0h, temperature warms naturally to 760 DEG C, stops logical CO2, it is passed through air and cools down, until reaction system is down to room temperature, is rinsed by several times with 1000ml pure water, dissolves unreacted many amine aqueous solutions and byproduct of reaction, until PH test paper test washings are neutrality；Then product is put to air dry oven, 200 DEG C of dry 1h, obtain activated carbon.Prepared Properties of Activated Carbon index is: specific surface area 820.50 m2/g;Apparent amino exchange content is 3.0mmol/g.
Embodiment 3
Weigh polyacrylonitrile fibre 5.0g, TEPA 150ml, join in 250ml volumetric flask, be passed through N2Carry out being heated to 125 DEG C under protection, after reacting 6.0 hours, remove TEPA reaction reagent 140ml；It is passed through CO with 15ml/min speed2, continuing reaction 6.0h, temperature warms naturally to 730 DEG C, stops logical CO2, it is passed through air and cools down, until reaction system is down to room temperature, is rinsed by several times with 100ml pure water, dissolves unreacted many amine aqueous solutions and byproduct of reaction, until PH test paper test washings are neutrality；Then product is put to air dry oven, 200 DEG C of dry 0.5h, obtain activated carbon.Prepared Properties of Activated Carbon index is: specific surface area 625.30m2/g;Apparent amino exchange content is 5.6mmol/g.
Embodiment 4
Weigh polyacrylonitrile looped fabric 15.3kg, triethylene tetramine: TEPA (volume ratio 1:1) 700L, join in 1000L reactor, be passed through N2Carry out being heated to 140 DEG C under protection, after reacting 4.0 hours, removal part triethylene tetramine and TEPA reaction reagent, the 20.0L Han reaction reagent in crosslinked polypropylene nitrile looped fabric；It is passed through CO with 3 L/min speed2, continuing reaction 5.0h, temperature warms naturally to 850 DEG C, stops logical CO2, it is passed through air and cools down, until reaction system is down to room temperature, is rinsed by several times with 200L pure water, dissolves unreacted many amine aqueous solutions and byproduct of reaction, until PH test paper test washings are neutrality；Then product is put to air dry oven, 200 DEG C of dry 2.5h, obtain activated carbon.Prepared Properties of Activated Carbon index is: specific surface area 835.50m2/g;Apparent amino exchange content is 3.40mmol/g.
Embodiment 5
Weigh polyacrylonitrile looped fabric 10.5kg, polyethylene polyamine: triethanolamine (volume ratio 1:1) 400L, join in 500L reactor, be passed through N2Carry out being heated to 145 DEG C under protection, after reacting 3.0 hours, removal part polyethylene polyamine and triethanolamine reaction reagent, the 15.0L Han reaction reagent in crosslinked polypropylene nitrile looped fabric；It is passed through CO with 2.2 L/min speed2, continuing reaction 6.0h, temperature warms naturally to 780 DEG C, stops logical CO2, it is passed through air and cools down, until reaction system is down to room temperature, is rinsed by several times with 200L pure water, dissolves unreacted many amine aqueous solutions and byproduct of reaction, until the test of PH test paper, washings are neutrality；Then product is put to air dry oven, 200 DEG C of forced air drying 3.0h, obtain activated carbon.Prepared Properties of Activated Carbon index is: specific surface area 765.32m2/g;Apparent amino exchange content is 4.60mmol/g.
Claims (2)
1. the preparation method of an activated carbon, it is characterised in that realized by following steps:
(1) weigh polyacrylonitrile fibre to be placed in insulation reaction container, add polyamines reaction reagent, make polyacrylonitrile fibre be totally submerged in reaction reagent, be warming up to 110 ~ 165 DEG C under nitrogen protection and carry out reacting 0.5 ~ 6h, obtain the polyacrylonitrile fibre of crosslinking；
(2) release part polyamines reaction reagent, stop logical N2, it is passed through CO2, insulation continues reaction, crosslinked polypropylene nitrile fiber, polyamines reagent, CO2Reacting, system temperature is increased to 600-900 DEG C naturally simultaneously, and polyacrylonitrile fibre carries out carbonization at such a temperature；
(3) stop after carbonization being passed through CO2, it being passed through air and carry out nature cooling, system is down to room temperature, and with the water purification washing unreacted many amine aqueous solutions of excess and byproduct of reaction, making wash solution is neutrality, heats up and makes moisture evaporate completely, obtains activated carbon；
Polyamines reagent used is one or more combinations in triethylene tetramine, TEPA, polyethylene polyamine, triethanolamine；
In step (2), the polyacrylonitrile fibre of crosslinking and polyamines reagent quality are than=0.2 ~ 2:1；The amount of the carbon dioxide being passed through: every 100g polyacrylonitrile fibre is 10-30mL/min, and the time is 2-6h.
The most according to claim 1, the preparation method of activated carbon, is characterized in that: in step (1), reaction temperature is 130-150 DEG C.
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| CN114381829B (en) * | 2022-01-13 | 2023-03-21 | 华南理工大学 | Microporous carbon fiber material prepared from polyacrylonitrile and used for separating multiple micromolecular gases in high selectivity manner, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1150607A (en) * | 1995-11-21 | 1997-05-28 | 中国科学院山西煤炭化学研究所 | Method for preparing mesopore active carbon fibre |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
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| US7438839B2 (en) * | 2004-10-01 | 2008-10-21 | Honeywell International Inc. | Formulation for the manufacture of carbon-carbon composite materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1150607A (en) * | 1995-11-21 | 1997-05-28 | 中国科学院山西煤炭化学研究所 | Method for preparing mesopore active carbon fibre |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
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