CN104098095A - Method for preparing active carbon from phenolic foam wastes - Google Patents
Method for preparing active carbon from phenolic foam wastes Download PDFInfo
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- CN104098095A CN104098095A CN201310126059.0A CN201310126059A CN104098095A CN 104098095 A CN104098095 A CN 104098095A CN 201310126059 A CN201310126059 A CN 201310126059A CN 104098095 A CN104098095 A CN 104098095A
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- gac
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- phenol formaldehyde
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Abstract
The invention provides a method for preparing active carbon from phenolic foam wastes in order to improve the adsorption performance of obtained active carbon. The method comprises the following steps: gasification: carrying out heat treatment on the phenolic foam wastes at 800-1000DEG C under anoxic conditions; activation: activating the phenolic foam wastes by using water vapor at 800-1000DEG C to obtain active carbon; and washing: removing parts of ash in the active carbon by using a washing liquid which preferably uses dilute hydrochloric acid. The method also comprises a forming agent granulation step preferably. The method enables active carbon with high specific surface area to be obtained by effectively using the phenolic foam wastes, and has the advantages of low preparation cost and high yield.
Description
Technical field
The present invention relates to the preparation method of gac, relate in particular to the method that obtains gac from industrial waste.
Background technology
Phenolic foam heat insulation plate is the obturator-type rigid foam being mixed with many kinds of substances such as resol and fire retardant, smoke suppressant, solidifying agent, whipping agent and other auxiliary agents, thermal conductivity is only 0.023W/mk left and right, is the material of a kind of difficult combustion, the low cigarette of preventing fires.Because phenolic foam heat insulation plate is insulation for building, the fire-retardant material of current main flow, its annual production is surprising, produces in process of production a large amount of scrap stock.These scrap stock density are little, quality is light, take large quantity space while banking up; Owing to having added various organic chemical reagents in preparation process, have certain toxicity again, directly discharge pollutes the environment.Therefore, the resource reutilization of phenolic foam heat insulation plate waste material is a very important field.
CN102583372 discloses a kind ofly take phenol formaldehyde foam waste and prepares the method for the ashless gac of high-ratio surface as raw material, its by phenol formaldehyde foam waste under inert gas conditions, airtight charing in charring furnace, at 400-500 ℃ of charing 2-4h, every 20-40min, fully stir material once during this time, before each stirring, need to cool the temperature to below 100 ℃, airtight charing again heats up after stirring fully, until charing completes, cooling discharging; Activation is under 700-900 ℃ of condition, take water vapour as activator carries out in tubular type electrothermal oven, activates 30-60min, can obtain Powdered active carbon with high specific surface area.The method, only by charing and activation, is not effectively removed the ash content in resol, so the space that is also improved of the absorption property of the gac of gained.In addition, the method need to be carried out several times and fully be stirred in carbonization process, and this stirring requires temperature to be reduced to below 100 ℃, this repeatedly lower the temperature, heat up operate in industrial scale production very inconvenient.
Summary of the invention
Invention proposes a kind of new method of being prepared gac by phenol formaldehyde foam waste, further to improve the absorption property of gained gac.
According to the present invention, the method that phenol formaldehyde foam waste is prepared gac comprises: gasification, at the heat-treated phenol formaldehyde foam waste of anoxia condition and 800 ~ 1000 ℃; Activation with phenol formaldehyde foam waste described in steam activation, obtains gac at the temperature of 800 ~ 1000 ℃; Washing, removes part of ash wherein.
In washing step, the gac that can obtain with dilute acid soln washing, is wherein preferably used dilute hydrochloric acid.
Further, after pickling, wash, so that gac is reverted to neutrality.Preferably with hot water, wash.
In another kind of embodiment of the present invention, water washs, and material is applied to microwave simultaneously, can avoid sour use like this, has alleviated the burden of harmless treatment.
In a kind of embodiment of the present invention, also comprise forming step, in forming step, in material, sneak into forming agent, then granulation.Forming agent used is starch suspension, cellulose suspension or carboxymethylcellulose sodium solution, tar, coal tar, polyvinyl alcohol, resol etc. preferably.
The present invention has effectively utilized and has produced a large amount of waste materials that produce in phenolic aldehyde foam thermal insulation material process, and take that it has prepared active carbon with high specific surface area as raw material, and preparation cost is low, yield is high, without deliming process, without the discharge of spent acid salkali waste, effectively solve environmental issue.
Embodiment
Phenolic foam heat insulation plate has added a large amount of organic chemical reagents in the preparation, to its composition analysis: ash content is 10%, fugitive constituent 48.06%, fixed carbon content are 41.73%.The present invention proposes a kind of design, by carbon be wherein converted into can industrial utilization gac.
Of the present invention general aspect, the method for being prepared gac by phenol formaldehyde foam waste comprises three key steps, gasifies, activates and wash.
Gasification is at the temperature of 800 ~ 1000 ℃, waste material to be kept for some time in oxygen deficient atmospheres, make Partial Elements wherein for example hydrogen, oxygen become gaseous volatilization and fall, be improved the carbon content in product.Preferred gasification temperature is 800 ~ 900 ℃.In the present invention, the time of gasification can be controlled at 5 ~ 20 minutes, can select the gasification time according to gasification temperature.In gasification, can in vapourizing furnace, pass into the gases such as argon gas, nitrogen, to maintain anaerobic environment, from the being easy to get property of gas, to consider, nitrogen is preferred.
After having carried out above-mentioned gasification, gained material is activated.In a kind of typical way of the present invention, the temperature with water vapour at 800-1000 ℃ activates.Time can be at 30 ~ 60 minutes.The consumption of water vapour is preferably 0.85-1.5 times of carbonized material weight.
Although do not attempt other activation methods, the present invention does not get rid of other activation methods.Those skilled in the art can be easy to expect using other activation methods such as carbonic acid gas, stack gas, oxygen activation.
After through gasification and activation, phenol formaldehyde foam waste has presented preliminary gac form, can remove the fugitive constituent of 40 left and right wherein, and fixed carbon content is 80% left and right.。Wherein also contain certain ash content being substantially comprised of inorganic salt, these ash content embedding cloth are in gac, and quality accounts for about 30% left and right of gac, significantly reduces absorption property, also can bring secondary pollution to environment for use.Therefore removing these ash contents is favourable to the application of gac.In a kind of exemplary embodiment of the present invention, with dilute acid soln detergent active charcoal, acid can be dissolved rapidly or be consumed inorganic salt wherein, makes its desorption from gac.Operable diluted acid comprises sulfuric acid, phosphoric acid and hydrochloric acid, wherein preferred hydrochloric acid.The concentration of diluted acid can be in the scope of 5-15%.
As another kind of optimal way, can wash by water, in order to improve detersive efficiency, can apply microwave to gac.Under microwave radiation, the inorganic salt in gac also can dissolve in water fast, and this mode can be avoided consumption acids and be conducive to environmental protection.
The in the situation that of above-mentioned use acid elution, for gac of some concrete application (for example, for decontaminating liquid time), can do further washing to it, to remove acid wherein, present neutrality roughly.The temperature that can improve water reaches the object of quick washing, for example, use the hot wash of 40 ℃ or higher temperature.Draw by experiment, with the water washing gac of about 60-70 ℃, water consumption can be reduced to 30% left and right.
Through above-mentioned cleaning, the ash oontent of the gac finally obtaining is reduced to 10% or lower.
Conventionally, phenol formaldehyde foam waste was fractured into less size before gasification, for example, be crushed to the diameter of 1 centimetre or following.In a kind of preferred implementation of the present invention, waste material is crushed to the small-particle of 2-3 millimeter particle diameter, even can be less, this small particle size is more conducive to the gasification of waste material.It is Powdered that waste material after gasification is substantially.In this case, preferably the waste material after gasification is carried out to moulding, this forming step also can carry out after activation step.
Above-mentioned moulding is to point in material to put into forming agent, and then granulation is dry, obtains granulate material.Forming agent is given material initial bonding strength, makes material moulding well when granulation, so that in subsequent process steps, has suitable processing characteristics.Can comprise adhering resin, water-soluble glue, starch, Mierocrystalline cellulose, tar, coal tar, polyvinyl alcohol, resol etc. for forming agent of the present invention.Preferred forming agent is starch suspension, cellulose suspension, Xylo-Mucine etc., and these forming agents are water base, and cohesive force is not too high, can in the course of processing, stir easily material, have again enough initial bonding strengths after granulation.And the effective constituent in forming agent in reactivation process (if activating after forming step) changes into carbon binding agent.
State in the use forming agent and carry out, after moulding, preferably the particle of moulding being cured to processing, here curing is to remove by desiccating method the moisture of being introduced by forming agent in moulding process.This moisture removal is essential, if leave large quantity of moisture, exists, and in reactivation process, heat-up rate is very fast, and the moisture of particle surface also has little time evaporation and will at high temperature react with charcoal, and can become fugitive constituent by too much carbon, reduces the yield of gac.
Embodiment 1:
Phenol formaldehyde foam waste is crushed to fritter when gasification (because fritter can be transformed into pulverous); the tube furnace that is placed in 900 ℃ is incubated 10min under nitrogen protection atmosphere; the CMC solution (Xylo-Mucine) that is 5% with massfraction by the starting material that gasified is by weight for after 1:3 mixes; mediate, moulding, then proceed in baking oven at 120 ℃ and solidify 3 hours.After solidify finishing, proceed in porcelain crucible, put into resistance furnace, temperature rise rate is made as 10 ℃/min and rises to 950 ℃, under water vapour atmosphere, is incubated 40min, water vapour consumption is activated material 0.95 times.The hydrochloric acid soln that activation finishes rear use 1% boil 20min reusable heat tap water by product washing to neutral, vacuum filtration dries to constant weight at 150 ℃, is crushed to certain order number and can obtains finished product gac.
Embodiment 2:
Phenol formaldehyde foam waste is crushed to fritter; the tube furnace that is placed in 850 ℃ is incubated 20min under nitrogen protection atmosphere; the CMC solution that is 5% with massfraction by the starting material that gasified is by weight for after 1:2.8 mixes, and mediates, moulding, then proceeds in baking oven at 120 ℃ curing 3 hours.After solidify finishing, proceed in porcelain crucible, put into resistance furnace, temperature rise rate is made as 10 ℃/min and rises to 900 ℃, under water vapour atmosphere, is incubated 60min, water vapour consumption is activated material 1.25 times.The hydrochloric acid soln that activation finishes rear use 1% boil 20min reusable heat tap water by product washing to neutral, vacuum filtration dries to constant weight at 150 ℃, is crushed to certain order number and can obtains finished product gac.
Comparative example:
The phenol formaldehyde foam waste of the identical bulk of grain is put in charring furnace, passing under the condition of nitrogen, carry out airtight charing operation, at 400 ~ 500 ℃, charing is 3 hours, during charing, every 30 minutes, material is fully stirred once, before each stirring, cool the temperature to 90 ℃, after stirring fully, heat up again and continue charing.Cooling discharging after charing, take water vapour at 700 ℃ and in tubular type electrothermal oven, activates as activator, and soak time 30 minutes, obtains finished product gac.
Table 1 phenolic foam heat insulation plate waste material is prepared the performance of gac
The present invention be take phenol formaldehyde foam waste as raw material, therefrom prepares the Powdered Activated Carbon of excellent performance, and this kind of gac can be for aspects such as liquid phase decolouring, wastewater treatment, gas adsorption.Realizing phenol formaldehyde foam waste turns waste into wealth, and improves its added value.
Claims (8)
1. by phenol formaldehyde foam waste, prepared a method for gac, comprise step below:
Gasification, at the heat-treated phenol formaldehyde foam waste of anoxia condition and 800 ~ 1000 ℃,
Activation with phenol formaldehyde foam waste described in steam activation, obtains gac at the temperature of 800 ~ 1000 ℃,
Washing, removes part of ash wherein.
2. method according to claim 1, wherein, washs the gac obtaining with dilute acid soln.
3. method according to claim 2, wherein, described diluted acid is dilute hydrochloric acid solution.
4. method according to claim 2 wherein, is washed after pickling.
5. method according to claim 4, wherein, washes with hot water.
6. method according to claim 1, wherein, water washs, and material is applied to microwave simultaneously.
7. method according to claim 1, wherein, also comprises forming step, in forming step, sneaks into forming agent, then granulation in material.
8. method according to claim 7, wherein, described forming agent is selected from one or more in starch suspension, cellulose suspension, carboxymethylcellulose sodium solution, tar, coal tar, polyvinyl alcohol and resol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310126059.0A CN104098095A (en) | 2013-04-11 | 2013-04-11 | Method for preparing active carbon from phenolic foam wastes |
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| CN201310126059.0A CN104098095A (en) | 2013-04-11 | 2013-04-11 | Method for preparing active carbon from phenolic foam wastes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629716A (en) * | 2017-01-15 | 2017-05-10 | 河北科技大学 | Device and method for preparing thermosetting-resin-based spherical activated carbon |
| CN107857264A (en) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | Weaken the preparation method of resin base porous carbon material rupture |
| CN110407207A (en) * | 2019-06-03 | 2019-11-05 | 中国石油大学(华东) | A kind of high temperature Co carbonization agent and its application admittedly miscellaneous in plastic refuse carbonization process carburetting |
| CN112573518A (en) * | 2020-12-14 | 2021-03-30 | 江苏宝利金材科技有限公司 | Method for preparing foam activated carbon through phenolic foam heat insulation material |
| WO2024145994A1 (en) * | 2023-01-03 | 2024-07-11 | 广东邦普循环科技有限公司 | Method for preparing hard carbon negative electrode material from waste thermosetting plastic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240220A (en) * | 1998-06-24 | 2000-01-05 | 中国科学院山西煤炭化学研究所 | Process for preparing phenolic resin base globe activated char |
| CN102583372A (en) * | 2012-01-13 | 2012-07-18 | 沈阳化工大学 | Method for preparing ash-free activated carbon with high specific surface area by using phenolic foam waste material as raw material |
-
2013
- 2013-04-11 CN CN201310126059.0A patent/CN104098095A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240220A (en) * | 1998-06-24 | 2000-01-05 | 中国科学院山西煤炭化学研究所 | Process for preparing phenolic resin base globe activated char |
| CN102583372A (en) * | 2012-01-13 | 2012-07-18 | 沈阳化工大学 | Method for preparing ash-free activated carbon with high specific surface area by using phenolic foam waste material as raw material |
Non-Patent Citations (2)
| Title |
|---|
| 纳宏波等: "改性酚醛基活性炭泡沫的制备与表征", 《材料导报：研究篇》 * |
| 陈云嫩: "《废麦糟生物吸附剂 深度净化水体中砷、镉的机理及应用》", 31 May 2011 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629716A (en) * | 2017-01-15 | 2017-05-10 | 河北科技大学 | Device and method for preparing thermosetting-resin-based spherical activated carbon |
| CN107857264A (en) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | Weaken the preparation method of resin base porous carbon material rupture |
| CN110407207A (en) * | 2019-06-03 | 2019-11-05 | 中国石油大学(华东) | A kind of high temperature Co carbonization agent and its application admittedly miscellaneous in plastic refuse carbonization process carburetting |
| CN112573518A (en) * | 2020-12-14 | 2021-03-30 | 江苏宝利金材科技有限公司 | Method for preparing foam activated carbon through phenolic foam heat insulation material |
| WO2024145994A1 (en) * | 2023-01-03 | 2024-07-11 | 广东邦普循环科技有限公司 | Method for preparing hard carbon negative electrode material from waste thermosetting plastic |
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Application publication date: 20141015 |