CN104495838A - Method for preparing activated carbon - Google Patents
Method for preparing activated carbon Download PDFInfo
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- CN104495838A CN104495838A CN201410763157.XA CN201410763157A CN104495838A CN 104495838 A CN104495838 A CN 104495838A CN 201410763157 A CN201410763157 A CN 201410763157A CN 104495838 A CN104495838 A CN 104495838A
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- reaction
- polyamines
- reagent
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- polyacrylonitrile fibre
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Abstract
The invention discloses a preparation method of activated carbon, belonging to the technical field of activated carbon preparation. The method comprises the following steps: by using polyacrylonitrile fiber as a carbon source, adding a polyamine reagent, and heating to perform crosslinking reaction; after reacting for some time, introducing CO2, heating, carbonizing, physically activating, cooling, washing with water, and heating until the water is completely evaporated, thereby obtaining the activated carbon. The obtained material has abundant surface amido functional groups and excellent adsorbability, and can be applied to the fields of toxic gas adsorption, sewage purification, drinking water adsorption and the like. The method has the advantages of simple preparation technique, high efficiency and low cost, and is easy to operate and very beneficial to industrial production.
Description
Technical field
The invention belongs to the preparing technical field of gac, be specifically related to a kind of method preparing gac.
Background technology
Gac, as the multi-functional sorbent material of one, has good absorption property, and multiple natural materials and petrochemical material can be utilized to obtain.Polyacrylonitrile is the good base material of one of preparation activated carbon fiber, may be used for preparing gac.Active charcoal preparing process generally comprises physically activated and chemical activation two kinds of techniques.Chemical activation mainly uses various chemical activating agent, such as, and ZnCl
2, H
2sO
4, H
3pO
4, HCl, KOH.Physical activation method is by first for raw material carbonization, more at high temperature utilizes oxidizing gas, makes the carbon atom partial oxidation in graphite microcrystal form flourishing pore texture, increases internal surface area.
The structure of polyacrylonitrile active carbon fiber is amorphous graphite carbon, containing hexagonal carbon-coating, has the gap of various size in carbon-coating, and is arranged in order to large gap from small gap.The technical process being prepared activated carbon fiber by polyacrylonitrile fibril is as follows: carbonization below P A N precursor ~ preoxidation ~ 700 DEG C ~ simultaneously carry out surface treatment higher than 700 DEG C of carbonizations, activation, curlingly obtains polyacrylonitrile fibre.Easily produce the HCN of severe toxicity in polyacrylonitrile radical active carbon fiber production process, and oxidising process is wayward, is difficult to produce the large product of specific surface area.
Patent CN200810151333.9 discloses a kind of activated carbon fiber and preparation method thereof, the method with functional added ingredientss such as fibre-forming polymer and silver, copper, zinc for raw material, and then obtain activated carbon fiber through preoxidation, carbonization, water vapour nitrogen activation, or obtain activated carbon fiber through sodium-hydroxide treatment, carbonization, steam activation.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 tubular fibre for raw material, dipping pretreatment in phosphorous compound solution, then forms through preoxidation, 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 to be activated through high temperature cabonization by the mixture of polyacrylonitrile, phenolic aldehyde or polyvinyl alcohol and zinc chloride or phosphoric acid and forms.Aforesaid method complicated process of preparation, there is drawback in large-scale promotion application.
Summary of the invention
The object of this invention is to provide a kind of method preparing gac of applicable industrial applications, make the gac prepared have abundant surface functional group and larger specific surface area.
For achieving the above object, the present invention uses chemical exothermal method to carry out fibers carbonization, utilizes chemical reaction to carry out pore-creating, in earlier stage reaction needed thermal source, and later stage carbonization process is without the need to continuing heating.Concrete technical scheme is as follows:
(1) take polyacrylonitrile fibre and be placed in insulation reaction container, add polyamines reaction reagent, polyacrylonitrile fibre is immersed in reaction reagent completely, be warming up to 110 ~ 165 DEG C under nitrogen protection and carry out reaction 0.5 ~ 6h, obtain the polyacrylonitrile fibre be cross-linked;
(2) release part polyamines reaction reagent, stop logical N
2, change and pass into CO
2, insulation continues reaction, crosslinked polypropylene nitrile fiber, polyamines reagent, CO
2react, system temperature is increased to 600-900 DEG C naturally simultaneously, and crosslinked polypropylene nitrile fiber carries out carbonization at such a temperature;
(3) carbonization after completing rear stopping pass into CO
2, pass into air and carry out naturally cooling, system is down to room temperature, with the water purification excessive unreacted polyamines solution of washing and byproduct of reaction, makes washing soln be neutral, heats up and moisture is evaporated completely, obtain gac.
Described polyacrylonitrile fibre is polyacrylonitrile mass percentage fibrous material more than 85%, can be arbitrary form.
Described polyamines reagent is one or more combinations in triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, trolamine; The preferred 130-150 DEG C of step (1) temperature of reaction.
In step (2), crosslinked polyacrylonitrile fibre with polyamines reagent quality than=0.2 ~ 2:1; The amount of the carbonic acid gas passed into: 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 adopt BK122F type specific surface area and pore size distribution tester (the precise and tiny Gao Bo science and technology company limited in Beijing produces) to carry out isothermal adsorption test under 77K.Sample preparation and test condition: after 150 DEG C of heating remove surface adsorption thing in 2 hours, make adsorption medium with high pure nitrogen, be that cold-trap measures with liquid nitrogen.Utilize BET Equation for Calculating specific surface area.
Transamination volumetric determination is with reference to the measuring method of epoxy hardener amine value.
The present invention take polyacrylonitrile fibre as starting material, by techniques such as amination, carbonization, activation, prepares absorbent charcoal material.Its beneficial effect is: polyacrylonitrile fibre is first carried out crosslinking reaction, R-CN+NH
2-R-NH
2→ RCNH-NH-R-NH-CNH-R; In subsequent reactions (step 2), CO
2react with amine, RNH
2+ CO
2→ RNH
2 +cOO
-; Whole process is thermopositive reaction, utilizes reaction heat naturally to rise to high temperature, carries out carbonization to polyacrylonitrile, is conducive to thermal source saving and recycling, and preparation technology is simple, efficiency is high, cost is low, easy to operate, be very beneficial for suitability for industrialized production.The activated carbon product of gained, has compared with large specific surface area and abundant surface amine groups functional group, can meet the application demand of specified conditions.Especially being adsorbed with poisonous gas, purify waste water, the field such as tap water absorption, have good effect.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Take polyacrylonitrile fibre 20.0g, triethylene tetramine 250ml, join in 500ml volumetric flask, pass into N
2carry out under protection being heated to 135 DEG C, react after 3.0 hours, shift out triethylene tetramine reaction reagent 200ml; CO is passed into 10ml/min speed
2, continue reaction 3.5h, temperature is warming up to 730 DEG C naturally, stops logical CO
2, pass into air and cool, until reaction system is down to room temperature, rinse with the gradation of 400ml pure water, dissolve unreacted polyamines solution and byproduct of reaction, until PH test paper test washing water are in neutral; Then reaction product put in air dry oven, 200 DEG C of dry 0.5h, obtain gac.Prepared Properties of Activated Carbon index is: specific surface area 680.32 m
2/ g; Apparent transamination content is 3.5mmol/g.
Embodiment 2
Take polyacrylonitrile fibre 50.0g, triethylene tetramine and trolamine (volume ratio 1:1) 500ml, join in 1000ml volumetric flask, pass into N
2carry out under protection being heated to 150 DEG C, react after 4.0 hours, shift out triethylene tetramine and trolamine reaction reagent 400ml; CO is passed into 12ml/min speed
2, continue reaction 4.0h, temperature is warming up to 760 DEG C naturally, stops logical CO
2, pass into air and cool, until reaction system is down to room temperature, rinse with the gradation of 1000ml pure water, dissolve unreacted polyamines solution and byproduct of reaction, until PH test paper test washing water are in neutral; Then reaction product put in air dry oven, 200 DEG C of dry 1h, obtain gac.Prepared Properties of Activated Carbon index is: specific surface area 820.50 m
2/ g; Apparent transamination content is 3.0mmol/g.
Embodiment 3
Take polyacrylonitrile fibre 5.0g, tetraethylene pentamine 150ml, join in 250ml volumetric flask, pass into N
2carry out under protection being heated to 125 DEG C, react after 6.0 hours, shift out tetraethylene pentamine reaction reagent 140ml; CO is passed into 15ml/min speed
2, continue reaction 6.0h, temperature is warming up to 730 DEG C naturally, stops logical CO
2, pass into air and cool, until reaction system is down to room temperature, rinse with the gradation of 100ml pure water, dissolve unreacted polyamines solution and byproduct of reaction, until PH test paper test washing water are in neutral; Then reaction product put in air dry oven, 200 DEG C of dry 0.5h, obtain gac.Prepared Properties of Activated Carbon index is: specific surface area 625.30m
2/ g; Apparent transamination content is 5.6mmol/g.
Embodiment 4
Take polyacrylonitrile looped fabric 15.3kg, triethylene tetramine: tetraethylene pentamine (volume ratio 1:1) 700L, joins in 1000L reactor, pass into N
2carry out under protection being heated to 140 DEG C, react after 4.0 hours, shift out part triethylene tetramine and tetraethylene pentamine reaction reagent, containing reaction reagent 20.0L in crosslinked polypropylene nitrile looped fabric; CO is passed into 3 L/min speed
2, continue reaction 5.0h, temperature is warming up to 850 DEG C naturally, stops logical CO
2, pass into air and cool, until reaction system is down to room temperature, rinse with the gradation of 200L pure water, dissolve unreacted polyamines solution and byproduct of reaction, until PH test paper test washing water are in neutral; Then reaction product put in air dry oven, 200 DEG C of dry 2.5h, obtain gac.Prepared Properties of Activated Carbon index is: specific surface area 835.50m
2/ g; Apparent transamination content is 3.40mmol/g.
Embodiment 5
Take polyacrylonitrile looped fabric 10.5kg, polyethylene polyamine: trolamine (volume ratio 1:1) 400L, joins in 500L reactor, pass into N
2carry out under protection being heated to 145 DEG C, react after 3.0 hours, shift out part polyethylene polyamine and trolamine reaction reagent, containing reaction reagent 15.0L in crosslinked polypropylene nitrile looped fabric; CO is passed into 2.2 L/min speed
2, continue reaction 6.0h, temperature is warming up to 780 DEG C naturally, stops logical CO
2, pass into air and cool, until reaction system is down to room temperature, rinse with the gradation of 200L pure water, dissolve unreacted polyamines solution and byproduct of reaction, until the test of PH test paper, washing water are in neutral; Then reaction product put in air dry oven, 200 DEG C of forced air drying 3.0h, obtain gac.Prepared Properties of Activated Carbon index is: specific surface area 765.32m
2/ g; Apparent transamination content is 4.60mmol/g.
Claims (3)
1. a preparation method for gac, is characterized in that, is realized by following steps:
(1) take polyacrylonitrile fibre and be placed in insulation reaction container, add polyamines reaction reagent, polyacrylonitrile fibre is immersed in reaction reagent completely, be warming up to 110 ~ 165 DEG C under nitrogen protection and carry out reaction 0.5 ~ 6h, obtain the polyacrylonitrile fibre be cross-linked;
(2), release part polyamines reaction reagent, stop logical N
2, pass into CO
2, insulation continues reaction, crosslinked polypropylene nitrile fiber, polyamines reagent, CO
2react, 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 passing into CO
2, pass into air and carry out naturally cooling, system is down to room temperature, with the water purification excessive unreacted polyamines solution of washing and byproduct of reaction, makes washing soln be neutral, heats up and moisture is evaporated completely, obtain gac;
Polyamines reagent used is one or more combinations in triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, trolamine.
2. the preparation method of gac according to claim 1, it is characterized in that: in step (1), temperature of reaction is 130-150 DEG C.
3. the preparation method of gac according to claim 1, is characterized in that: in step (2), crosslinked polyacrylonitrile fibre: polyamines reagent quality ratio=0.2-2:1.
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| CN104495838B CN104495838B (en) | 2016-08-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200324A (en) * | 2017-06-27 | 2017-09-26 | 东莞理工学院 | A kind of activated carbon, its preparation method and application |
| CN113929249A (en) * | 2020-06-29 | 2022-01-14 | 宝山钢铁股份有限公司 | Cold rolling nanofiltration concentrated water zero-discharge process and process system |
| CN114381829A (en) * | 2022-01-13 | 2022-04-22 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060073338A1 (en) * | 2004-10-01 | 2006-04-06 | Simpson Allen H | Formulation for the manufacture of carbon-carbon composite materials |
| 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 |
-
2014
- 2014-12-12 CN CN201410763157.XA patent/CN104495838B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060073338A1 (en) * | 2004-10-01 | 2006-04-06 | Simpson Allen H | Formulation for the manufacture of carbon-carbon composite materials |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200324A (en) * | 2017-06-27 | 2017-09-26 | 东莞理工学院 | A kind of activated carbon, its preparation method and application |
| CN113929249A (en) * | 2020-06-29 | 2022-01-14 | 宝山钢铁股份有限公司 | Cold rolling nanofiltration concentrated water zero-discharge process and process system |
| CN113929249B (en) * | 2020-06-29 | 2024-01-09 | 宝山钢铁股份有限公司 | Cold rolling nanofiltration concentrated water zero discharge process and system |
| CN114381829A (en) * | 2022-01-13 | 2022-04-22 | 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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| CN104495838B (en) | 2016-08-17 |
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