CN104826581B - A kind of ammonia processing porous carbon materials and its formaldehyde absorbing application - Google Patents
A kind of ammonia processing porous carbon materials and its formaldehyde absorbing application Download PDFInfo
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- CN104826581B CN104826581B CN201510116852.1A CN201510116852A CN104826581B CN 104826581 B CN104826581 B CN 104826581B CN 201510116852 A CN201510116852 A CN 201510116852A CN 104826581 B CN104826581 B CN 104826581B
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- porous carbon
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Abstract
The present invention relates to a kind of ammonia processing porous carbon materials and its formaldehyde absorbing application.The ammonia processing method of the porous carbon materials includes：1) porous carbon materials are put into heating furnace；2) ammonia is passed through in heating furnace as protective atmosphere, the flow of ammonia is 50 1000mL/min；3) 600 900 DEG C are warming up under 1 20 DEG C/min heating rate；4) constant temperature keeps 0.5 10h；5) it is cooled to room temperature under protection of ammonia；6) porous carbon materials are taken out from heating furnace, vacuum outgas is carried out to it.After the processing of above-mentioned ammonia, porous carbon materials can be filled in the framework of honeycomb fashion filter screen or be adhered on filter screen fiber, for realizing the removing function of formaldehyde in air.The present invention makes porous carbon materials be strengthened for the purification rate of formaldehyde and total adsorption capacity, reduces formaldehyde desorption probability, effectively reduces secondary pollution.
Description
Technical field
The invention belongs to purification of air, formaldehyde absorbing technical field, and in particular to a kind of ammonia processing porous carbon materials and
Its formaldehyde absorbing application.
Background technology
The formaldehyde gas that Long Term Contact exceedes safe concentration limitation is very harmful to health, and this may cause eyes
With the burning sensation of throat, expiratory dyspnea even can cause fatal disease, such as rhinocarcinoma, myelomatosis etc..At present in
State's formaldehyde pollution is still very serious, and nearly 70% newly-decorated house is all perplexed by formaldehyde pollution, therefore is most made in China
The indoor polluted gas that people worries is exactly formaldehyde.
Screen material of the activated carbon as the most frequently used purifying formaldehyde, have larger adsorption capacity and it is cheap into
This.But activated carbon is primarily present two problems when purifying air.First, activated carbon is slower for the rate of adsorption of formaldehyde,
This make it that the purification efficiency of single filtration is unsatisfactory.Second, when activated carbon raises close to adsorption saturation or environment temperature,
Adsorbed formaldehyde easily discharges again, causes secondary pollution.Therefore, it is necessary to by suitable chemical modification to activated carbon
Performance further improved.
Normally, solution methods are used for the chemical modification of activated carbon, such as disclosed in the A of CN 103769053
Method.But solution methods generally require complex multistep reaction.In addition, the chemical substance added in solution can
It can be filled into the pore structure of activated carbon, cause the reduction of specific surface area.Finally, these pass through the introduced official of solution modification
It can roll into a ball and be also possible to come off and cause secondary pollution.
Patent CN201210381226.1 provides a kind of modified active Carbon Materials and preparation method thereof, and the program is with activity
Charcoal is put into tube furnace as raw material, is warming up to 600-900 DEG C under nitrogen protection, is then introduced ammonia thereto.Activity
Charcoal forms modified activated carbon with ammonia reaction 10-120min.The modified active Carbon Materials have in water to perchlorate
Stronger adsorption capacity, modified active Carbon Materials are compared with activated carbon nearly 9 times are improved to the adsorbance of perchlorate.The material
Expect high mechanical strength, have extended cycle life, production cost is low, and preparation method is simple, and can regenerate recycling.It is but this
Modified active Carbon Materials prepared by method are mainly used in the processing of perchlorate contaminated thing in aqueous phase, and dirty for formaldehyde in air
The adsorption rate for contaminating thing is relatively low, it is impossible to meets the practical application request of formaldehyde absorbing.
The content of the invention
The present invention is in view of the above-mentioned problems, provide a kind of porous carbon materials of enhancing, and the application of its formaldehyde adsorption property,
The program uses the porous carbon materials of Ammonia gas disposal as formaldehyde absorbent.
The porous carbon materials provided by the invention handled using ammonia, its ammonia processing method is as shown in figure 1, including as follows
Step：
1) porous carbon materials are put into heating furnace；
2) ammonia is passed through in heating furnace as protective atmosphere (flow of ammonia is 50-1000mL/min)；
3) it is warming up to certain temperature (600-900 DEG C) under certain heating rate (1-20 DEG C/min)；
4) constant temperature certain time (0.5-10h)；
5) it is cooled to room temperature under protection of ammonia；
6) porous carbon materials are taken out from heating furnace, vacuum outgas is carried out to it.
Preferably, the porous carbon materials include activated carbon, carbon black etc..
Preferably, the porous carbon materials are activated carbon, and step 3) is warming up to 700 DEG C.
Preferably, the porous carbon materials are carbon black, and step 3) is warming up to 900 DEG C.
After above-mentioned ammonia processing method, porous carbon materials may be used as formaldehyde absorbent, for example can be filled
In the framework of honeycomb fashion filter screen or it is adhered on filter screen fiber, for realizing the removing function of formaldehyde in air.
Compared with prior art, beneficial effects of the present invention are as follows：
1. porous carbon materials are strengthened for the purification rate of formaldehyde and total adsorption capacity；
2. compared with conventional solution method, processing method of the invention is simpler, and cost is lower；
3. the binding ability of porous carbon materials and formaldehyde is strengthened, reduce formaldehyde desorption probability, effectively reduce
Secondary pollution.After by Ammonia gas disposal, amino and other nitrogen-containing functional groups are produced on the surface of porous carbon materials,
These functional groups add adsorption site, can strengthen the absorption property for formaldehyde.
Brief description of the drawings
Fig. 1 is the overview flow chart of the inventive method.
Fig. 2 is activated carbon and 700 DEG C of ammonia processing activated carbon formaldehyde Static Adsorption curve comparison figures in embodiment 1.
Fig. 3 is that activated carbon different temperatures ammonia handles formaldehyde Static Adsorption rate comparison diagram in embodiment 1.
Fig. 4 is carbon black and 900 DEG C of ammonia treated carbon black formaldehyde Static Adsorption curve comparison figures in embodiment 2.
Fig. 5 is that carbon black different temperatures ammonia handles formaldehyde Static Adsorption rate comparison diagram in embodiment 2.
Fig. 6 is the schematic diagram that the activated carbon granule after being handled in embodiment 3 is filled in the screen frame of honeycomb.
Fig. 7 is that protection of ammonia and nitrogen protect the activated carbon of processing for formaldehyde Static Adsorption rate comparison diagram.
Fig. 8 is the activated carbon of different heating rates processing for formaldehyde Static Adsorption rate comparison diagram.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below by specific embodiment and
Accompanying drawing, the present invention will be further described.
Embodiment 1：
100g commercialization activated carbons are placed in tube furnace.Ammonia is passed through as protective atmosphere using the flow of 500 ml/mins.
700 DEG C are warming up to 10 DEG C/minute of heating rate, and constant temperature 3 hours.Room temperature is naturally cooled to afterwards.Taken out from tube furnace
Sample, which is placed in vacuum chamber, carries out vacuum outgas.Fig. 2 is activated carbon and 700 DEG C of ammonia processing activated carbon formaldehyde Static Adsorption curves
Comparison diagram.From figure 2 it can be seen that after the processing procedure, activated carbon has non-for the Static Adsorption ability of formaldehyde
It is often obvious to improve.The concentration of residual formaldehyde declines clearly particularly in the test starting stage, container.This explanation is modified
Activated carbon afterwards is greatly improved for the rate of adsorption of formaldehyde.
Fig. 3 is activated carbon different temperatures ammonia processing formaldehyde Static Adsorption rate comparison diagram.From figure 3, it can be seen that in difference
At a temperature of the formaldehyde Static Adsorption rate of activated carbon sample that handles it is otherwise varied.Wherein, 700 DEG C are optimal treatment temperatures.First
Aldehyde Static Adsorption rate increases to 78% from the 52% of before processing.In addition, after 700 DEG C of ammonia processing, formaldehyde desorption temperature is from
98 DEG C before reason are improved to 108 DEG C, are significantly reduced desorption probability, are reduced the possibility of secondary pollution.
Embodiment 2：
100g Ketjen blacks (English name KETJINBLACK, a kind of electrode with carbon black materials) are placed in tube furnace.With 500
The flow of ml/min is passed through ammonia as protective atmosphere.900 DEG C are warming up to 10 DEG C/minute of heating rate, and constant temperature 3 hours.
Room temperature is naturally cooled to afterwards.Taking-up sample, which is placed in vacuum chamber, from tube furnace carries out vacuum outgas.Fig. 4 is in the present embodiment
Carbon black and 900 DEG C of ammonia treated carbon black formaldehyde Static Adsorption curve comparison figures.Figure 4, it is seen that by the processing procedure
Afterwards, Ketjen black has for the Static Adsorption ability of formaldehyde and obviously improved.
Fig. 5 is carbon black different temperatures ammonia processing formaldehyde Static Adsorption rate comparison diagram.From fig. 5, it can be seen that in not equality of temperature
The formaldehyde Static Adsorption rate of the Ketjen black sample of the lower processing of degree is otherwise varied.Wherein, 900 DEG C are optimal treatment temperatures.Formaldehyde
Static Adsorption rate increases to 72% from the 21% of before processing.
Embodiment 3：
100g commercialization activated carbons are placed in tube furnace.Ammonia is passed through as protective atmosphere using the flow of 1000 ml/mins.
700 DEG C are warming up to 1 DEG C/minute of heating rate, and constant temperature 0.5 hour.Room temperature is naturally cooled to afterwards.Taken out from tube furnace
Sample, which is placed in vacuum chamber, carries out vacuum outgas.
Embodiment 4：
100g commercialization activated carbons are placed in tube furnace.Ammonia is passed through as protective atmosphere using the flow of 50 ml/mins.With
20 DEG C/minute of heating rate is warming up to 700 DEG C, and constant temperature 10 hours.Room temperature is naturally cooled to afterwards.Sample is taken out from tube furnace
Product, which are placed in vacuum chamber, carries out vacuum outgas.
Embodiment 5：
Using the granular active carbon of commercialization as raw material.After the processing method in by such as embodiment 1, activated carbon
Grain shape can be maintained.So, the activated carbon after handling can be filled into the frame structure of air filter screen.It is right
In the air filter screen of honeycomb, the activated carbon after processing can be filled into honeycomb ducts, in filtration, purification air
Formaldehyde, as shown in Figure 6.
Embodiment 6：
Using the powdered active carbon of commercialization as raw material.After the processing method in by such as embodiment 1, activated carbon
Still maintain powder shape.When filter screen makes, first to being sprayed made of the materials such as non-woven fabrics, papery or glass fibre on filter screen
Adhesive, then the powdered active carbon after processing is combined by modes such as sprinklings with adhesive.To be bonded dose of solvent volatilization
Or after solidification, the Powdered Activated Carbon after processing is adhered on filter screen fiber, for purifying the formaldehyde in air.”
It can be seen from above example, the present invention in heating and cooling processing procedure all use protection of ammonia, heating with
Nitrogen-containing functional group can be generated in temperature-fall period, helps to increase the content of nitrogen-containing functional group, so as to improve for formaldehyde
Adsorption effect.And protected in the patent CN201210381226.1 that background technology is mentioned using nitrogen so that heating and drop
There is no nitrogen-containing functional group generation during temperature；And in cooling, the nitrogen-containing functional group that has generated of part, which can decompose, to be sloughed, and is reduced
For the adsorption effect of formaldehyde.Fig. 7 is under identical conditions, and the activated carbon of protection of ammonia and nitrogen protection processing is quiet for formaldehyde
State adsorption rate comparison diagram, it can be seen that the adsorption rate of the activated carbon PARA FORMALDEHYDE PRILLS(91,95) of protection of ammonia processing is obviously improved.
The heating rate that the present invention uses is theoretical and optimum experimental result, also obvious not with above-mentioned existing patented technology
Together.In the present invention, heating rate is 1-20 DEG C/min, is 50 DEG C/min in above-mentioned patent.The heating rate of the present invention is significantly low
In above-mentioned patented technology.Heating rate is slower, is on the one hand advantageous to the holding of porous carbon pore passage structure, maintains larger ratio surface
Product；On the other hand, it helps in temperature-rise period, more nitrogen-containing functional groups are generated under protection of ammonia.Fig. 8 is same
Under part, the activated carbon of different heating rate processing is for formaldehyde Static Adsorption rate comparison diagram, it can be seen that uses low heating rate
The activated carbon of processing is obviously improved for formaldehyde absorbing rate.
In addition, compared with above-mentioned patented technology, porous carbon materials prepared by the present invention application environment, target contaminant,
It is also different in terms of the mechanism of action.Above-mentioned patent is mainly used in the processing of perchlorate contaminated thing in aqueous phase, removes perchlorate
Mechanism is that nitrogen-containing functional group adds alkalescence of the activated carbon in water, makes the increase of its electropositive, so as to strengthen for perchlorate
Deng the absorption of anion.The present invention can effectively handle the formaldehyde pollutants in air, absorption of the nitrogen-containing functional group for formaldehyde
Mechanism has very big difference.Nitrogen-containing functional group has following nucleophilic addition organic chemistry anti-with aldehyde compound in the present invention
Answer mode：
Above-mentioned reaction equation explanation, nitrogen-containing functional group in porous carbon materials prepared by the present invention can effective formaldehyde adsorption,
So that porous carbon materials are strengthened for the purification rate of formaldehyde and total adsorption capacity.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the ordinary skill of this area
Technical scheme can be modified by personnel or equivalent substitution, without departing from the spirit and scope of the present invention, this
The protection domain of invention should be to be defined described in claims.
Claims (8)
1. a kind of method that porous carbon materials are handled using ammonia, it is heating up and can generate nitrogenous function in temperature-fall period
Group, include to improve the adsorption effect for formaldehyde, the step of this method：
1) porous carbon materials are put into heating furnace；
2) ammonia is passed through in heating furnace as protective atmosphere；
3) it is warming up to 600-900 DEG C under 1-20 DEG C/min heating rate；
4) constant temperature keeps 0.5-10h；
5) it is cooled to room temperature under protection of ammonia；
6) porous carbon materials are taken out from heating furnace, vacuum outgas is carried out to it.
2. the method as described in claim 1, it is characterised in that：Step 1) the porous carbon materials are activated carbon or carbon black.
3. the method as described in claim 1, it is characterised in that：The flow of ammonia is 50-1000mL/min in step 2).
4. the method as described in claim 1, it is characterised in that：The porous carbon materials are activated carbon, and step 3) is warming up to 700
℃。
5. the method as described in claim 1, it is characterised in that：The porous carbon materials are carbon black, and step 3) is warming up to 900
℃。
6. the porous carbon materials using Ammonia gas disposal prepared by method any one of Claims 1 to 5.
7. purposes of the porous carbon materials described in claim 6 as formaldehyde absorbent.
8. purposes as claimed in claim 7, it is characterised in that：The porous carbon materials are filled in the framework of honeycomb fashion filter screen
In or be adhered on filter screen fiber, to adsorb the formaldehyde pollutants in air.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510116852.1A CN104826581B (en) | 2015-03-17 | 2015-03-17 | A kind of ammonia processing porous carbon materials and its formaldehyde absorbing application |
| JP2016050281A JP6224147B2 (en) | 2015-03-17 | 2016-03-14 | Ammonia treatment method for porous carbon material, method for producing porous carbon material, and method for producing formaldehyde absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510116852.1A CN104826581B (en) | 2015-03-17 | 2015-03-17 | A kind of ammonia processing porous carbon materials and its formaldehyde absorbing application |
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| CN104826581A CN104826581A (en) | 2015-08-12 |
| CN104826581B true CN104826581B (en) | 2017-12-19 |
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| CN201510116852.1A Expired - Fee Related CN104826581B (en) | 2015-03-17 | 2015-03-17 | A kind of ammonia processing porous carbon materials and its formaldehyde absorbing application |
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| CN (1) | CN104826581B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106853365B (en) * | 2015-12-08 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of porous carbon materials SO2Electrochemical oxidation catalyst and its preparation method and application |
| CN106587054B (en) * | 2016-11-29 | 2021-04-06 | 徐州国锐环保科技有限公司 | Preparation process of special activated carbon for formaldehyde absorption |
| CN106914217A (en) * | 2017-03-10 | 2017-07-04 | 中国科学院合肥物质科学研究院 | A kind of porous carbon materials formaldehyde adsorbent and preparation method thereof |
| CN108126727A (en) * | 2017-12-19 | 2018-06-08 | 广东省石油与精细化工研究院 | A kind of room temperature degradation of formaldehyde catalyst and its preparation method and application |
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| JPH0252043A (en) * | 1988-03-31 | 1990-02-21 | Matsushita Electric Ind Co Ltd | Air purifying agent |
| CN101642698A (en) * | 2009-08-25 | 2010-02-10 | 北京航空航天大学 | Adsorbent used for separating formaldehyde from air and preparation method thereof |
| CN102872802A (en) * | 2012-10-10 | 2013-01-16 | 上海理工大学 | Modified activated carbon material and preparing method thereof |
| CN104190251A (en) * | 2014-09-09 | 2014-12-10 | 清华大学 | Air purification material and preparation method and application thereof |
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| JP3250773B2 (en) * | 1993-12-22 | 2002-01-28 | クラレケミカル株式会社 | Aliphatic aldehyde adsorbent |
| KR100777951B1 (en) * | 2001-08-23 | 2007-11-28 | 더 프록터 앤드 갬블 캄파니 | Water filter materials, corresponding water filters and processes for using the same |
| CN100354210C (en) * | 2003-02-21 | 2007-12-12 | 宝洁公司 | Processes for manufacturing water filter materials and water filters |
| JP2005263531A (en) * | 2004-03-17 | 2005-09-29 | Dainatsukusu:Kk | Hydrophobizing heat treatment method for carbon |
| JP2010193718A (en) * | 2007-06-15 | 2010-09-09 | Japan Tobacco Inc | Activated carbon for cigarette filter and cigarette with filter |
| WO2012088697A1 (en) * | 2010-12-30 | 2012-07-05 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN102730680B (en) * | 2012-07-23 | 2014-12-03 | 清华大学深圳研究生院 | High-density high-rigidity graphene porous carbon material as well as preparation method and applications thereof |
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2015
- 2015-03-17 CN CN201510116852.1A patent/CN104826581B/en not_active Expired - Fee Related
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- 2016-03-14 JP JP2016050281A patent/JP6224147B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0252043A (en) * | 1988-03-31 | 1990-02-21 | Matsushita Electric Ind Co Ltd | Air purifying agent |
| CN101642698A (en) * | 2009-08-25 | 2010-02-10 | 北京航空航天大学 | Adsorbent used for separating formaldehyde from air and preparation method thereof |
| CN102872802A (en) * | 2012-10-10 | 2013-01-16 | 上海理工大学 | Modified activated carbon material and preparing method thereof |
| CN104190251A (en) * | 2014-09-09 | 2014-12-10 | 清华大学 | Air purification material and preparation method and application thereof |
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| JP6224147B2 (en) | 2017-11-01 |
| JP2016172685A (en) | 2016-09-29 |
| CN104826581A (en) | 2015-08-12 |
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