CN109926023A - Ozone cooperates with ultraviolet light irradiation and improves charcoal oxygen-containing group technique - Google Patents
Ozone cooperates with ultraviolet light irradiation and improves charcoal oxygen-containing group technique Download PDFInfo
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- CN109926023A CN109926023A CN201910282044.0A CN201910282044A CN109926023A CN 109926023 A CN109926023 A CN 109926023A CN 201910282044 A CN201910282044 A CN 201910282044A CN 109926023 A CN109926023 A CN 109926023A
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- ozone
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003610 charcoal Substances 0.000 title claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001301 oxygen Substances 0.000 title claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 11
- 230000002285 radioactive effect Effects 0.000 claims abstract description 8
- 238000005485 electric heating Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 7
- 230000003595 spectral effect Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000686 lactone group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
Abstract
The present invention relates to the techniques that a kind of ozone and ultraviolet irradiation collaboration improve biological carbon materials oxygen-containing group, are characterized mainly in that: will mix after the biological carbon materials prepared sieving, clean drying with ozone, be heated up to 100-500 DEG C.Then biological carbon materials are divided on temperature controlled electric heating plate, ultraviolet radioactive light irradiation in 10-380 nm wave-length coverage keeps in irradiation process charcoal temperature at 200 DEG C, and irradiation time is 24 h, and every 12 h is put into ozone contact stud 1 time, and is passed through ozone again.After ultraviolet irradiation, drying.The technique can significantly improve the oxygen-containing group quantity of biological carbon materials.
Description
Technical field
The invention belongs to biological carbon materials technical field of modification, it is related to a kind of ozone and ultraviolet irradiation collaboration improves charcoal
The technique of oxygen-containing group.
Background technique
In recent years, charcoal is as a kind of New Types of Environmental Materials, prepares from a wealth of sources, low production cost, right because having
The strong feature of contaminant removal capacity, becomes the powerful mean in the prevention and cure of pollution of soil, water body and non-air ambient medium.As
A kind of and completely different material of active carbon, active carbon relies primarily on huge specific surface area and generates physical absorption to pollutant, raw
Object charcoal relies primarily on the chemical functional group for being distributed its surface and pollutant forms new chemical bond, to generate pollutant removal effect
Fruit, and the chemical bond formed between this chemical functional group and pollutant is sufficiently stable, and therefore, charcoal is to pollutant
Removal effect it is more stable.A large amount of research confirms, to the chemical function of the height and biological carbon materials of contaminant removal capacity
Group, especially oxygen-containing group (carboxyl, lactone group, phenolic hydroxyl group) quantity are related.However, non-modified biological carbon materials table
Face oxygen-containing group negligible amounts, this becomes the restriction factor for restricting charcoal in pollutant prevention and control application and therefore improves biology
Charcoal oxygen-containing group quantity becomes technical problem urgently to be resolved.
Forefathers attempt to be modified processing to Carbon Materials with wet chemical, to increase the organo-functional group number of material surface
Amount.Chinese application number 201110409394.2 discloses a kind of diazo reagent processing active carbon, thus in activated carbon surface
Fixed nitrogen-containing functional group.This method introduces outer source ion, and high production cost in generating process.Chinese application number
201380042335.3 disclose a kind of method for increasing surface alkalinty functional group to improve active carbon hydrophily, but this method
Process is tedious, more using chemical reagent, is easy to produce secondary pollution problem.Obviously, in order to obtain more oxygen-containing groups, it is necessary to seek
Look for other technological break-throughs.Non-patent literature 1 and 2([1] Ding Wenchuan, Quan Guoqing, Zeng Xiaolan, Luo Wanshen, Li Xiaoyu, Li Qiao, harmony
Firm ultraviolet irradiation is introduced into oxygen-containing functional group to influence [J] ACTA Scientiae Circumstantiae of benzene in charcoal adsorbed gas and water,
2017, (02): the ultraviolet radiation modified charcoal of 657-663. [2] Li Qiao, Yong Yi, Ding Wenchuan, Hou Jiang, Gao Yutao, Zeng Xiaolan
To Dynamic Adsorption [J] environmental science of VOCs, 2016, (06): 2065-2072.) report that biological carbon materials are ultraviolet in 365 nm
After light irradiation, oxygen-containing group quantity can be significantly improved.Meanwhile also there are some researches prove, the charcoal through ozone oxidation, Ke Yi
Surface forms carboxyl, keeps its surface more hydrophilic, so that pHPZC be made to substantially reduce, is conducive to the removal of polar substances.Cause
This, can use ozone and ultraviolet irradiation collaboration processing charcoal, increase biological carbon materials oxygen-containing group quantity.
We have invented the aftertreatment technology that a kind of pair of biological carbon materials carry out ozone and ultraviolet irradiation collaboration processing, the works
The biological carbon materials oxygen-containing group quantity that skill obtains is significantly higher than independent ozone treatment or the processing of independent ultraviolet irradiation and does not change
Property processing.Present invention process process is simple, and treatment process is polluted without chemical reagent, and low in cost, effect is obvious, and technique is easy to advise
Modelling is promoted.
Summary of the invention
The purpose of the present invention is provide a kind of raising biological carbon materials surface by ozone and the combined modified effect of ultraviolet light
The technique of oxygen-containing group content.
Ozone of the invention is cooperateed with ultraviolet light improves charcoal oxygen-containing group technique, includes the following steps:
(1) biological carbon materials prepared are crossed into 60 meshes, is placed in improved ozone contact tank after cleaning, the wherein throwing of ozone
Entering amount is 2-8mg/L, and the concentration of charcoal is 1%-20%(w/v).
(2) action time of charcoal and ozone is 5-10min, and the mixture of charcoal and ozone is heated to 10-40
DEG C, the magnetic agitation 3-36h under 200rpm revolving speed, filtering.
(3) biological carbon materials are divided on temperature controlled electric heating plate, thickness control is heated up to 100-500 within 3 mm
℃
Range.
(4) it at 50 cm of biological carbon materials vertical direction, places, ultraviolet radioactive main spectral line wave-length coverage is
10-380 nm, radiant power 4-150 w, irradiation time are 12-48 h.In irradiation process, every 12 h stirs charcoal
1 time, and be placed again into ozone contact stud and act on 5-10min.
(5) after ultraviolet irradiation, biological carbon materials are collected into kraft paper bag, are dried to constant weight for 60 DEG C in baking oven
Afterwards,
Obtain high oxygen-containing group charcoal.
Signified biological carbon materials of the invention are with mineral (coal, graphite), plant residue (trunk, branches and leaves, fruit, straw
Stalk) and debirs (sludge, plastics, discarded paper) be raw material, the stabilization armaticity prepared by low temperature pyrolysis technology is solid
Body.
The use ratio of charcoal and ozone is 1%-20%(w/v in the present invention), it is preferably in a proportion of 5%-20%(w/v), most
It is preferably in a proportion of 10%.
The input amount of ozone is 2-8mg/L, preferably 3-5mg/L, most preferably 3mg/L in the present invention.
In charcoal of the present invention with the action time of ozone be 5-10min, preferably 5-8mg/L, most preferably 8mg/L.
In charcoal of the present invention with 10-40 DEG C of ozone blend temperature range, preferably 10-30 DEG C, most preferably 30 DEG C.
The time range of magnetic agitation is 3-36 h, preferably 12-36 h, most preferably 24 h in the present invention.
The temperature range of temperature controlled electric heating plate is controlled at 100-500 DEG C in the present invention, and preferably 100-300 DEG C, most preferably
200℃。
In the present invention ultraviolet radioactive main spectral line wave-length coverage be 10-380 nm, preferably 150--380 nm, most preferably
254 nm。
Ultraviolet radiation lamp power bracket is 4-150 w, preferably 50-150 w, most preferably 100 w in the present invention.
Time of ultraviolet irradiation range is 12-48 h, preferably 12-24 h, most preferably 24 h in the present invention.
Technical principle of the invention is the grafting effect of ozonidation and ultraviolet light.Firstly, ozone can aoxidize life
Surface group in object carbon surface and internal voids increases the number of carboxyl acidic-group in biological carbon materials surface and internal voids
Amount.Secondly, the cardinal principle of ultraviolet radiation graft method is free radical polymerization mechanism, mainly using ultraviolet light-initiated monomer in biology
Carbon surface is graft-polymerized, and increases so as to cause carboxyl, hydroxyl, these polarity oxygen-containing group quantity of lactone group.In addition, ozone
Under ultraviolet light, hydroxyl radical free radical can also be formed, the oxidability of hydroxyl radical free radical is extremely strong, can increase charcoal table
Face oxidation, forms more oxygen-containing groups.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention use only use ozone, not use other chemical reagent, will not to biological carbon materials introduce external source from
Son pollution.
(2) processing cost of the present invention is cheap, easy to operate, assists without large scale equipment, securely and reliably, proper scaleization behaviour
Make.
(3) a large amount of oxygen contained in oxygen and ozone mixed gas can be generated after ozone oxidation and residual ozone can be fast
Speed is converted into oxygen, does not generate secondary pollution, and can increase oxygen in water, and biological activated carbon filter is made to have sufficient dissolved oxygen
(DO), therefore aerobic microbiological is promoted to breed on the activated carbon.
(4) compared with ozone is used alone or ultraviolet irradiation is used alone, the present invention is assisted using hydrogen peroxide and ultraviolet irradiation
Biological carbon materials oxygen-containing group with processing preparation significantly improves.
(5) the modified graft polymerization chain formed of uv photo initiated grafting and biological carbon materials surface chemistry are keyed, and can be stablized and be continued
The oxygen-containing group for keeping surface graft modification to obtain.
(6) ozone has extremely strong oxidability, and oxidation-reduction potential in water is only second to fluorine and second.It utilizes
Ozonidation, preliminary oxidation decompose the simple organic matter of a part and its reducing substances in water, be allowed to become CO2 and
H2O, to reduce the organic loading of biological activated carbon filter.
Detailed description of the invention
Fig. 1 is oxygen-containing group quantity in embodiment 1, embodiment 2, reference examples 1, reference examples 2 and untreated biological carbon materials
In comparison.
Specific embodiment
Face combines specific embodiment, and the invention will be further described.
Embodiment 1
The biological carbon materials prepared to be crossed into 60 meshes, are contacted after cleaning drying with ozone, the use concentration of ozone is 3mg/L,
The concentration of charcoal is 10%(w/v).The mixture of charcoal and ozone is heated up to 30 DEG C, magnetic force stirs under 200 rpm revolving speeds
Mix 24 h.Biological carbon materials are divided on temperature controlled electric heating plate, thickness control is heated up to 200 DEG C within 3 mm.In biology
At 50 cm of Carbon Materials vertical direction, ultraviolet radiation lamp is placed, ultraviolet radioactive main spectral line wave-length coverage is 254 nm, radiant power
100w, irradiation time are 24 h.In irradiation process, every 12 h stirs charcoal 1 time, and is placed again into ozone contact stud and makees
Use 5-10min.After ultraviolet irradiation, biological carbon materials are collected into kraft paper bag, in baking oven 60 DEG C dry to constant weight after,
Obtain high oxygen-containing group charcoal.
Embodiment 2
The biological carbon materials prepared to be crossed into 60 meshes, are contacted after cleaning drying with ozone, the use concentration of ozone is 3mg/L,
The concentration of charcoal is 20%(w/v).The mixture of charcoal and ozone is heated up to 30 DEG C, magnetic force stirs under 200 rpm revolving speeds
Mix 24 h.Biological carbon materials are divided on temperature controlled electric heating plate, thickness control is heated up to 200 DEG C within 3 mm.In biology
At 50 cm of Carbon Materials vertical direction, ultraviolet radiation lamp is placed, ultraviolet radioactive main spectral line wave-length coverage is 254 nm, radiant power
100w, irradiation time are 24 h.In irradiation process, every 12 h stirs charcoal 1 time, and is placed again into ozone contact stud and makees
Use 5-10min.After ultraviolet irradiation, biological carbon materials are collected into kraft paper bag, in baking oven 60 DEG C dry to constant weight after,
Obtain high oxygen-containing group charcoal.
Comparative example 1
The biological carbon materials prepared to be crossed into 60 meshes, are contacted after cleaning drying with ozone, the use concentration of ozone is 3mg/L,
The concentration of charcoal is 20%(w/v).The mixture of charcoal and ozone is heated up to 30 DEG C, magnetic force stirs under 200 rpm revolving speeds
Mix 24 h.After, biological carbon materials are collected into kraft paper bag, are dried for standby.
Comparative example 2
At 50 cm of biological carbon materials vertical direction, ultraviolet radiation lamp is placed, ultraviolet radioactive main spectral line wave-length coverage is 254 nm,
Radiant power 100w, irradiation time are 24 h.In irradiation process, every 12 h stirs charcoal 1 time.After ultraviolet irradiation,
Biological carbon materials are collected into kraft paper bag, are dried for standby.
Analyze the independent ozone treatment of comparative example 1(), the independent ultraviolet irradiation of comparative example 2(), untreated and embodiment 1 and real
The oxygen-containing group result (Fig. 1) of biological carbon materials in example 2 is applied, it is observed that cooperateing with raising to give birth to ultraviolet irradiation using ozone
After object charcoal oxygen-containing group technique, carboxyl, lactone group, phenolic hydroxyl group and total oxygen-containing group quantity are all obviously increased, and are above comparative example 1
(independent ozone treatment), the independent ultraviolet irradiation of comparative example 2(), untreated and embodiment 1 and embodiment 2.This shows the present invention
Biological carbon materials oxygen-containing group quantity can be effectively improved.
Although example of the invention is described in detail, for practical operation personnel, it is possible to understand that do not departing from
A variety of variations, modification can be carried out to example under the principle and spirit of the invention.
Claims (6)
1. ozone is cooperateed with ultraviolet irradiation improves biological carbon materials oxygen-containing group technique, it is characterized mainly in that: the life that will be prepared
The sieving of object Carbon Materials is placed in ozone contact tank after cleaning drying, adds the mixture of charcoal and ozone after acting on 5-10min
Then heat is divided biological carbon materials on temperature controlled electric heating plate to 10-40 DEG C, be heated up to 100-500 DEG C, in 10-380 nm
Ultraviolet radioactive light irradiation in wave-length coverage keeps in irradiation process charcoal temperature at 200 DEG C, and irradiation time is 24 h, phase
Between, every 12 h stirs charcoal 1 time, and is placed again into ozone contact stud and acts on 5-10min, after ultraviolet irradiation, dries
It is dry.
2. according to claim 1, the use ratio of charcoal and ozone is 1%-20%(w/v), it is preferably in a proportion of 5%-20%
(w/v), most preferred ratio 10%, the input amount of ozone are 2-8mg/L, preferably 3-5mg/L, most preferably 3mg/L, in charcoal
Be 5-10min, preferably 5-8mg/L, most preferably 8mg/L with action time of ozone, in charcoal with ozone blend temperature range
10-40 DEG C, preferably 10-30 DEG C, most preferably 30 DEG C, the time range of magnetic agitation are 3-36 h, preferably 12-36 h, most
Preferably 24 h.
3. according to claim 1, the temperature range of temperature controlled electric heating plate is controlled at 100-500 DEG C, and preferably 100-300 DEG C,
Most preferably 200 DEG C.
4. according to claim 1, ultraviolet radioactive main spectral line wave-length coverage be 10-380 nm, preferably 150--380 nm,
Most preferably 254 nm.
5. according to claim 1, ultraviolet radiation lamp power bracket be 4-150 w, preferably 50-150 w, most preferably
100 w。
6. according to claim 1, time of ultraviolet irradiation range is 12-48 h, preferably 12-24 h, most preferably 24 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910282044.0A CN109926023A (en) | 2019-04-09 | 2019-04-09 | Ozone cooperates with ultraviolet light irradiation and improves charcoal oxygen-containing group technique |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910282044.0A CN109926023A (en) | 2019-04-09 | 2019-04-09 | Ozone cooperates with ultraviolet light irradiation and improves charcoal oxygen-containing group technique |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112875679A (en) * | 2021-01-29 | 2021-06-01 | 电子科技大学 | Method for modifying carbon fluoride by ultraviolet radiation and application of carbon fluoride in lithium primary battery |
| CN112892480A (en) * | 2021-01-20 | 2021-06-04 | 宜春惠众生物能源有限公司 | Porous biochar and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170036983A1 (en) * | 2015-08-06 | 2017-02-09 | James Weifu Lee | Ozonized biochar compositions and methods of making and using the same |
| CN106925222A (en) * | 2017-04-28 | 2017-07-07 | 安徽科技学院 | Hydrogen peroxide cooperates with raising charcoal oxy radical technique with ultraviolet irradiation |
| CN108913145A (en) * | 2018-07-03 | 2018-11-30 | 国家林业局竹子研究开发中心 | A kind of preparation method of modification biological charcoal |
-
2019
- 2019-04-09 CN CN201910282044.0A patent/CN109926023A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170036983A1 (en) * | 2015-08-06 | 2017-02-09 | James Weifu Lee | Ozonized biochar compositions and methods of making and using the same |
| CN106925222A (en) * | 2017-04-28 | 2017-07-07 | 安徽科技学院 | Hydrogen peroxide cooperates with raising charcoal oxy radical technique with ultraviolet irradiation |
| CN108913145A (en) * | 2018-07-03 | 2018-11-30 | 国家林业局竹子研究开发中心 | A kind of preparation method of modification biological charcoal |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892480A (en) * | 2021-01-20 | 2021-06-04 | 宜春惠众生物能源有限公司 | Porous biochar and preparation method thereof |
| CN112875679A (en) * | 2021-01-29 | 2021-06-01 | 电子科技大学 | Method for modifying carbon fluoride by ultraviolet radiation and application of carbon fluoride in lithium primary battery |
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