CN107364942A - It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction - Google Patents
It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction Download PDFInfo
- Publication number
- CN107364942A CN107364942A CN201710734563.7A CN201710734563A CN107364942A CN 107364942 A CN107364942 A CN 107364942A CN 201710734563 A CN201710734563 A CN 201710734563A CN 107364942 A CN107364942 A CN 107364942A
- Authority
- CN
- China
- Prior art keywords
- hydro
- reaction
- carbon composite
- thermal carbon
- thermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000003254 radicals Chemical class 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- 239000003610 charcoal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000007613 environmental effect Effects 0.000 claims abstract description 20
- 230000002688 persistence Effects 0.000 claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 58
- 229940106691 bisphenol a Drugs 0.000 claims description 29
- 239000005416 organic matter Substances 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 21
- -1 monosubstituted hydroxyl Chemical group 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229920005610 lignin Polymers 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- AZHSSKPUVBVXLK-UHFFFAOYSA-N ethane-1,1-diol Chemical compound CC(O)O AZHSSKPUVBVXLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 230000002085 persistent effect Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 claims 1
- 239000003403 water pollutant Substances 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000012620 biological material Substances 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 24
- 239000002351 wastewater Substances 0.000 description 12
- 244000276331 Citrus maxima Species 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000001759 Citrus maxima Nutrition 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a kind of hydro-thermal carbon composite, its preparation method and its application that can be applied to class Fenton's reaction, contain the ortho position centered on carbon on charcoal material surface and connect the free radical of oxygen and the environmental persistence free radical centered on oxygen, this two type frees base being capable of activating hydrogen peroxide progress class Fenton's reaction, i.e. hydro-thermal carbon composite energy and H2O2Form Fenton-like.Hydro-thermal carbon composite surface of the present invention has abundant functional group and unique physicochemical property; wherein biological material is prepared from abandoned biomass hydro-thermal; the recycling of abandoned biomass can either be realized, saves the consumption of the energy, alleviates the energy crisis of getting worse；Hydro-thermal carbon composite and can of the present invention and H2O2Form Fenton-like, can effectively, quickly remove pollutant, reach efficiently remove organic pollutants in water body purpose.The inventive method has the characteristics of easy to operate, contaminant removal efficiency is high, reaction condition is gently easily-controllable.
Description
Technical field
The present invention relates to a kind of Carbon Materials, its preparation method and its application, more particularly to a kind of carbon composite, its system
Preparation Method and its application, a species Fenton's reaction reagent, its preparation method and its application are further related to, applied to containing organic contamination
Waste water treating agent, its preparation method and its organic contamination species Fenton handling process and hydro-thermal Carbon Materials technical field of thing.
Background technology
With urbanization and industrialized development, a large amount of organic wastewaters produce and are discharged into natural water, cause water environment dirty
Contaminate increasingly serious, the pollution of organic matter in water body, have become an environmental problem urgently to be resolved hurrily.
High-level oxidation technology is the focus of current water-treatment technology field research, and Fenton reagent is because of simple to operate, reaction
The advantage such as mild condition and oxidation efficiency height and receive much concern.Feng Yong, Wu Deli, Ma Luming, ferriferous oxide catalysis Fenton-like
React [J] chemical progress, 2013,25 (7):1219-1228 and Zhou Yaliang, Huang Dongyue, the type of Fenton's reaction technology and research
Be in progress [J] Guangdong chemical industry, 2013,40 (1):74 document is recorded, and ferriferous oxide catalysis embryonic stem-like cells can efficiently solve
Catalyst recycles the problems such as difficult Fenton's reaction as a kind of advanced oxidization method for handling organic pollution, but tradition is fragrant
Method of pausing is present:Can not abundant mineralising organic matter；H2O2Utilization rate is not high；The shortcomings of easily being influenceed by pH.Above-mentioned puzzlement tradition
The phenomenon technical problem urgently to be resolved hurrily of Fenton method application.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction are can be applied to, preparing one kind, there is class Fenton to urge
Change the new hydro-thermal Carbon Materials of performance, develop the simple synthesis of carried metal hydro-thermal charcoal and its class to organic pollution
Fenton minimizing technology, using hydrothermal synthesis method, the hydro-thermal charcoal of carried metal is synthesized at a certain temperature, and utilize itself and H2O2Group
The organic pollution in water body is removed into Fenton-like, the degraded removal time to organic pollution is short and has higher effect
Rate.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of hydro-thermal carbon composite that can be applied to class Fenton's reaction, contain on charcoal material surface adjacent centered on carbon
Position connects the free radical of oxygen and the environmental persistence free radical centered on oxygen, wherein the free radical that ortho position connects oxygen centered on carbon is
Monohydroxy organic matter reacts what is formed with metal ion or organic matter, wherein the environmental persistence free radical centered on oxygen is by more
Hydroxyl organic matter and metal cation are acted on and formed, and this two type frees base can activating hydrogen peroxide progress class Fenton it is anti-
Answer, i.e. hydro-thermal carbon composite energy and H2O2Form Fenton-like.
The free radical that the above-mentioned ortho position centered on carbon connects oxygen is preferably that organic matter containing monohydroxy reacts with metal or organic matter
Formed.
The above-mentioned environmental persistence free radical centered on oxygen is preferably by organic matter containing polyhydroxy and molysite cation sites
And formed.
The g values that the above-mentioned ortho position centered on carbon connects the free radical of oxygen are preferably：2.0030<g<2.0040；It is above-mentioned using oxygen as
The g values of the environmental persistence free radical at center are preferably：g>2.0040.
The g values that the above-mentioned ortho position centered on carbon connects the free radical of oxygen are more preferably：2.0032<g<2.0040；With oxygen
Centered on the g values of environmental persistence free radical be more preferably：g>2.0042.
It is a kind of present invention can apply to the preparation method of the hydro-thermal carbon composite of class Fenton's reaction, comprise the following steps：
A. using anaerobic deionized water as solvent, by metal salt and it is dissolved in anaerobic deionized water that metal salt is made is molten
Liquid, the mass ratio according to the metal salt in biomass material and metal salt solution are 20:1 ratio, by biomass material and gold
Category salting liquid is hybridly prepared into the mixed liquor A containing metal cation, and mixed liquor A is imported in high-pressure hydrothermal reaction kettle；It is preferred that
Trivalent iron salt is dissolved in anaerobic deionized water ferric salt solution is made；Biomass material preferably uses waste biomass material
Material, the material of the preparation hydro-thermal charcoal of selection is abandoned biomass, and its cost is relatively low, wide material sources；Biomass material preferably uses
Lignin or pomelo peel；
B. hydrothermal synthesis method is utilized, inert gas N will be passed through in the reactor containing mixed liquor A in step a2Exhaust
After 15min, the reaction temperature in reactor is set not less than 240 DEG C, to carry out hydro-thermal carbonization reaction at least 4h；
C. after hydro-thermal carbonization reaction terminates in the reactor carried out in stepb, reaction product in reactor is poured into burning
Cup, stirring purifying at least 8h, then reaction mixture after purification is washed, wash respectively at least three times using ethanol alcohol respectively, then right
Sediment after washing is filtered, and obtained filter cake dries at least 24h, warp in the vacuum drying chamber not less than 80 DEG C
Cross after drying process and obtain product B, product B be on charcoal material surface containing centered on carbon ortho position connect oxygen free radical and
The hydro-thermal carbon composite of environmental persistence free radical centered on oxygen.
It is a kind of present invention can apply to the application of the hydro-thermal carbon composite of class Fenton's reaction, be catalyzed using with class Fenton
The hydro-thermal carbon composite of characteristic, by hydro-thermal carbon composite and H2O2Fenton-like is formed, to containing organic pollution concentration
Dirty organic pollutants not less than 50mg/L carry out degradation treatment, when carrying out sewage degradation treatment, hydro-thermal charcoal is compound
Material and H2O2It is added in treatment sewage, the uniform stirring under the conditions of lucifuge, controls the anti-of dirty organic pollutants of degrading
Temperature control is answered in the water containing organic pollution not less than 25 DEG C, handled at set time intervals passing through class Fenton
Analysis is sampled, after the pollutants removal rate in water reaches established standardses, treatment reaction terminates.
As preferable technical scheme, using hydro-thermal carbon composite and H2O2When forming Fenton-like, hydro-thermal charcoal is compound
Material and the H that mass percent concentration is 30%2O2The proportioning of solution is preferably 0.25g：1mL.
As preferable technical scheme, present invention is preferably applicable to the organic pollution in the water containing organic pollution to be
Methyl orange, Congo red or bisphenol-A organic matter water treatment process.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. present invention can apply to the surface of the hydro-thermal Carbon Materials of class Fenton's reaction to contain abundant hydroxyl, carboxyl, ester group
Deng oxygen-containing functional group, environmental persistence free radical is formed after loading metal-salt, the present invention in abandoned biomass hydro-thermal by carbonizing
Process introduces metal salt so that the Carbon Materials can form Fenton-like degradable organic pollutant with hydrogen peroxide, and have
Higher removal effect；Hydro-thermal charing, which is carried out, present invention firstly provides abandoned biomass carried metal cation prepares hydro-thermal raw material of wood-charcoal
Material, obtain can be applied to the hydro-thermal Carbon Materials of class Fenton's reaction；
2. hydro-thermal carbon composite of the present invention is synthesized by hydro-thermal method, method is simple, easy to operate, and reaction condition is gentle, and
It is economic and environment-friendly；
3. hydro-thermal carbon composite structure of the present invention is special, with H2O2Formed class Fenton's reaction reach within a short period of time compared with
Good effect, its pollutants removal rate is high, can fully mineralising it is organic, hydro-thermal carbon composite and H2O2Form Fenton-like
H can be improved2O2Utilization rate, pH is overcome to influence the unfavorable factor of water treatment procedure.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention one derives hydro-thermal carbon composite to bisphenol-A solution progress class Fenton using lignin
The design sketch of reaction.
Fig. 2 is that the embodiment of the present invention one derives hydro-thermal carbon composite to bisphenol-A solution progress class Fenton using pomelo peel
The design sketch of reaction.
Embodiment
Such scheme is described further below in conjunction with specific examples of the implementation, the preferred embodiments of the present invention are described in detail such as
Under：
Embodiment one：
In the present embodiment, a kind of hydro-thermal carbon composite that can be applied to class Fenton's reaction, contains on charcoal material surface
There is the ortho position centered on carbon to connect the free radical of oxygen and the environmental persistence free radical centered on oxygen, wherein the ortho position centered on carbon
The free radical for connecing oxygen reacts to be formed for monohydroxy organic matter with metal or organic matter, wherein the environmental persistence centered on oxygen is certainly
Acted on by base and formed by polyhydroxy organic matter and metal cation, and this two type frees base being capable of activating hydrogen peroxide progress class
Fenton's reaction, i.e. hydro-thermal carbon composite energy and H2O2Form Fenton-like.Ortho position connects the free radical of oxygen wherein centered on carbon
React to be formed with metal or organic matter for monohydroxy organic matter.Environmental persistence free radical wherein centered on oxygen is by polyhydroxy
Organic matter is formed with molysite cation sites.
The present embodiment can be applied to the preparation method of the hydro-thermal carbon composite of class Fenton's reaction, comprise the following steps：
A. using anaerobic deionized water as solvent, by trivalent iron salt and it is dissolved in anaerobic deionized water trivalent iron salt is made
Solution, using lignin as biomass material, the mass ratio according to lignin and the trivalent iron salt in ferric salt solution is
20:1 ratio, lignin and ferric salt solution are hybridly prepared into the mixed liquor A containing ferric iron cation, by mixed liquor
A is imported in high-pressure hydrothermal reaction kettle；
B. hydrothermal synthesis method is utilized, inert gas N will be passed through in the reactor containing mixed liquor A in step a2Exhaust
Liner lid is covered after 15min, after ventilation and is put into reactor, reactor is put into baking oven, is set anti-in reactor
It is 240 DEG C to answer temperature, carries out hydro-thermal carbonization reaction 4h；
C. after hydro-thermal carbonization reaction terminates in the reactor carried out in stepb, reaction product in reactor is poured into burning
Cup, stirring purifying 8h, then reaction mixture after purification is washed, wash respectively three times using ethanol alcohol respectively, then to by washing
Sediment afterwards is filtered, and obtained filter cake dries 24h in 80 DEG C of vacuum drying chamber, is produced after drying process
Thing B, product B are containing ortho position connects the free radical of oxygen centered on carbon and the environment centered on oxygen is held on charcoal material surface
The hydro-thermal carbon composite of long free love base.The present embodiment is represented from lignin for biomass, is prepared into lignin and is derived water
Hot charcoal, obtain the hydro-thermal Carbon Materials with class Fenton catalysis characteristics.By the class Fenton's reaction manufactured in the present embodiment of can be applied to
Hydro-thermal carbon composite carries out electron paramagnetic resonance, and the free radical carried out on hydro-thermal Carbon Materials characterizes, and characterization result is the institute of table 1
Show.
In the present embodiment, class Fenton's reaction result of implementation is shown in Fig. 1.Hydro-thermal is derived using lignin manufactured in the present embodiment
The method that carbon composite carries out Fenton processing organic pollutants, with bisphenol-A and fresh anaerobic deionized water compound concentration
For 50mg/L simulative organic wastewater, 250mL waste water is taken in reaction flask.Class Fenton's reaction is can be applied to as the present embodiment
Hydro-thermal carbon composite application, by hydro-thermal carbon composite and H2O2Fenton-like is formed, to dense containing organic pollution
Spend and carry out degradation treatment for 50mg/L dirty organic pollutants, when carrying out sewage degradation treatment, weighing 0.25g will be wooden
The derivative hydro-thermal charcoal of element is added in simulative organic wastewater, while also adds mass percent concentration to the water containing organic pollution
For 30% H2O2Solution 1mL, the uniform stirring under the conditions of lucifuge, the reaction temperature control of the dirty organic pollutants of control degraded
System is sampled to the water containing organic pollution by the processing of class Fenton, centrifuged at 25 DEG C at set time intervals
Separate and analyze the residual concentration of bisphenol-A solution in supernatant, the results showed that, clearance reaches 80% after 2h, sees Fig. 1.Now
After pollutants removal rate in water reaches established standardses, treatment reaction terminates.The effect of the present embodiment processing waste water is by waste water
PH influence very little, H2O2Utilization rate is high, can abundant mineralising organic matter.The present embodiment in abandoned biomass hydro-thermal by carbonizing
Journey introduce metal salt so that the Carbon Materials can with hydrogen peroxide form Fenton-like degradable organic pollutant, and with compared with
High removal effect.Fig. 1 is that the lignin of embodiment one derives class Fenton's reaction design sketch of the hydro-thermal charcoal to bisphenol-A, i.e., individually sharp
The hydro-thermal Carbon Materials prepared with embodiment one directly carry out treatment reaction process and embodiment one by hydro-thermal charcoal to bisphenol-A solution
Composite and H2O2Form the bisphenol-A organic removal rate pair that Fenton-like carries out treatment reaction process to bisphenol-A solution
Than figure, as can be known from Fig. 1, it is anti-that the hydro-thermal Carbon Materials prepared using only embodiment one directly carry out water process to bisphenol-A solution
Answer process bisphenol-A organic removal rate be only capable of reaching 55% level, and embodiment one is by hydro-thermal carbon composite and H2O2Group
The bisphenol-A organic removal rate for carrying out treatment reaction process to bisphenol-A solution into Fenton-like reaches 80%, hence it is evident that is higher than
The bisphenol-A that the hydro-thermal Carbon Materials prepared using only embodiment one directly carry out treatment reaction process to bisphenol-A solution is organic
Thing clearance, while realize again and Fenton-like is made full use of.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of hydro-thermal carbon composite that can be applied to class Fenton's reaction, contains on charcoal material surface
There is the ortho position centered on carbon to connect the free radical of oxygen and the environmental persistence free radical centered on oxygen, wherein the ortho position centered on carbon
The free radical for connecing oxygen reacts to be formed for organic matter containing monohydroxy with metal or organic matter, wherein the environmental persistence centered on oxygen
Free radical is acted on by organic matter containing polyhydroxy and metal cation and formed, and this two type frees base can activating hydrogen peroxide enter
Row class Fenton's reaction, i.e. hydro-thermal carbon composite energy and H2O2Form Fenton-like.Ortho position meets oneself of oxygen wherein centered on carbon
Reacted and formed with metal or organic matter for organic matter containing monohydroxy by base.Environmental persistence free radical wherein centered on oxygen by
Organic matter containing polyhydroxy is formed with molysite cation sites.
The present embodiment can be applied to the preparation method of the hydro-thermal carbon composite of class Fenton's reaction, comprise the following steps：
A. using anaerobic deionized water as solvent, by trivalent iron salt and it is dissolved in anaerobic deionized water trivalent iron salt is made
Solution, using abandoned biomass pomelo peel as biomass material, according to the trivalent iron salt in pomelo peel and ferric salt solution
Mass ratio be 20:1 ratio, pomelo peel and ferric salt solution are hybridly prepared into the mixed liquor containing ferric iron cation
A, mixed liquor A is imported in high-pressure hydrothermal reaction kettle；
B. this step is identical with embodiment one；
C. this step is identical with embodiment one.
The abandoned biomass that the present embodiment is selected is pomelo peel, is prepared into pomelo peel and derives hydro-thermal charcoal, is obtained fragrant with class
The hydro-thermal Carbon Materials of catalysis characteristics.The hydro-thermal carbon composite manufactured in the present embodiment that can be applied to class Fenton's reaction is carried out
Electron paramagnetic resonance, the free radical carried out on hydro-thermal Carbon Materials characterize, and characterization result is shown in table 1.
In the present embodiment, class Fenton's reaction result of implementation is shown in Fig. 2.Hydro-thermal is derived using pomelo peel manufactured in the present embodiment
The method that carbon composite carries out Fenton processing organic pollutants, with bisphenol-A and fresh anaerobic deionized water compound concentration
For 50mg/L simulative organic wastewater, 250mL waste water is taken in reaction flask.Class Fenton's reaction is can be applied to as the present embodiment
Hydro-thermal carbon composite application, by hydro-thermal carbon composite and H2O2Fenton-like is formed, to dense containing organic pollution
Spend and carry out degradation treatment for 50mg/L dirty organic pollutants, when carrying out sewage degradation treatment, weigh 0.25g by shaddock
Skin derives hydro-thermal charcoal and is added in simulative organic wastewater, while also adds mass percent concentration to the water containing organic pollution
For 30% H2O2Solution 1mL, the uniform stirring under the conditions of lucifuge, the reaction temperature control of the dirty organic pollutants of control degraded
System is sampled to the water containing organic pollution by the processing of class Fenton, centrifuged at 25 DEG C at set time intervals
Separate and analyze the residual concentration of bisphenol-A solution in supernatant, the results showed that, clearance reaches 81% after 2h, sees Fig. 2.Fig. 2 is
The residual concentration of bisphenol-A solution in Fenton's reaction supernatant, after now the pollutants removal rate in water reaches established standardses, at water
Reason reaction terminates.The effect of the present embodiment processing waste water is influenceed very little, H by wastewater pH2O2Utilization rate is high, and energy fully mineralising has
Machine thing.The present embodiment in abandoned biomass hydro-thermal carbonization process by introducing metal salt so that the Carbon Materials can be with peroxidating
Hydrogen forms Fenton-like degradable organic pollutant, and has higher removal effect.Fig. 2 is that the pomelo peel of embodiment two derives water
For hot charcoal to the class Fenton's reaction design sketch of bisphenol-A, i.e., the hydro-thermal Carbon Materials prepared using only embodiment two are molten directly to bisphenol-A
Liquid carries out treatment reaction process and embodiment two by hydro-thermal carbon composite and H2O2Fenton-like is formed to bisphenol-A solution
The bisphenol-A organic removal rate comparison diagram for the treatment of reaction process is carried out, as can be known from Fig. 2, is prepared using only embodiment two
Hydro-thermal Carbon Materials directly to bisphenol-A solution carry out treatment reaction process bisphenol-A organic removal rate be only capable of reaching 40%
Level, and embodiment two is by hydro-thermal carbon composite and H2O2Form Fenton-like and treatment reaction is carried out to bisphenol-A solution
The bisphenol-A organic removal rate of process reaches 80%, hence it is evident that direct higher than the hydro-thermal Carbon Materials prepared using only embodiment two
The bisphenol-A organic removal rate for the treatment of reaction process is carried out to bisphenol-A solution, while realizes again and Fenton-like is filled
Divide and utilize.
Experimental test is analyzed：The hydro-thermal carbon composite that can be applied to class Fenton's reaction prepared by above-described embodiment is carried out
Electron paramagnetic resonance, the free radical carried out on hydro-thermal Carbon Materials characterize, and characterization result is shown in table 1.
The electron paramagnetic resonance data drawing list of hydro-thermal Carbon Materials prepared by the embodiment of the present invention one, two of table 1.
As known from Table 1, wherein spin values are free radical quantity, and g values are used for differentiating free radical type, the results showed that above-mentioned reality
Contain free radical in the hydro-thermal carbon composite surface for applying example preparation.
Embodiment one and embodiment two are prepared for the hydro-thermal carbon composite with class Fenton's reaction activity, and its activity produces
Mechanism is the persistent free radicals and H contained using hydro-thermal charcoal material surface2O2Reaction, produce the hydroxyl with strong oxidizing property
Free radical, Organic Pollutants In Water is removed so as to degrade.The advantages of above-described embodiment, is using more simply and easily method
Hydro-thermal Carbon Materials of the synthesis with class Fenton characteristic, the material can be with H2O2Form Fenton-like, the degraded to organic pollution
Remove that the time is short and efficiency high.Above-described embodiment has abundant functional group and unique physics and chemistry special using hydro-thermal charcoal material surface
Property, hydro-thermal Carbon Materials are prepared from abandoned biomass hydro-thermal, can either realize the recycling of abandoned biomass, save the energy
Consumption, alleviate the energy crisis of getting worse；Hydro-thermal Carbon Materials and can and H2O2Fenton-like is formed, can effectively, fast
Ground removes pollutant, reaches the purpose for efficiently removing organic pollutants in water body.This hydro-thermal Carbon Materials can fully degraded it is organic
Thing.Above-described embodiment method has the characteristics of easy to operate, contaminant removal efficiency is high, reaction condition is gently easily-controllable.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with
A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from former present invention can apply to the hydro-thermal carbon composite of class Fenton's reaction, its preparation method and its technology of application
Reason and inventive concept, belong to protection scope of the present invention.
Claims (12)
- A kind of 1. hydro-thermal carbon composite that can be applied to class Fenton's reaction, it is characterised in that：On charcoal material surface contain with Ortho position connects the free radical of oxygen and the environmental persistence free radical centered on oxygen centered on carbon, wherein the ortho position centered on carbon The free radical of oxygen is connect to act on being formed with metal or organic matter containing monosubstituted hydroxyl organic matter, wherein the ring centered on oxygen Border persistent free radicals are formed by being acted on containing polysubstituted hydroxyl organic matter and metal cation, and this two type frees base can Activating hydrogen peroxide carries out class Fenton's reaction, i.e. hydro-thermal carbon composite energy and H2O2Form Fenton-like.
- 2. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 1, it is characterised in that：It is described with carbon Centered on ortho position connect the free radical of oxygen and act on being formed with metal or organic matter for monosubstituted hydroxyl organic matter.
- 3. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 1, it is characterised in that：It is described with oxygen Centered on environmental persistence free radical by being formed containing polysubstituted hydroxyl organic matter with molysite cation sites.
- 4. the hydro-thermal carbon composite of class Fenton's reaction, its feature are can be applied to according to any one in claims 1 to 3 It is：The g values that ortho position connects the free radical of oxygen centered on carbon are：2.0030<g<2.0040；Environmental persistence centered on oxygen The g values of free radical are：g>2.0040.
- 5. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 4, it is characterised in that：Using carbon in The g values that heart ortho position connects the free radical of oxygen are：2.0032<g<2.0040；The g values of environmental persistence free radical centered on oxygen For：g>2.0042.
- 6. can be applied to the preparation method of the hydro-thermal carbon composite of class Fenton's reaction described in a kind of claim 1, its feature exists In comprising the following steps：A. using anaerobic deionized water as solvent, by metal salt and it is dissolved in anaerobic deionized water metal salt solution is made, press Mass ratio according to the metal salt in biomass material and metal salt solution is 20:1 ratio, biomass material and metal salt is molten Liquid is hybridly prepared into the mixed liquor A containing metal cation, and mixed liquor A is imported in high-pressure hydrothermal reaction kettle；B. hydrothermal synthesis method is utilized, inert gas N will be passed through in the reactor containing mixed liquor A in the step a2Exhaust After 15min, the reaction temperature in reactor is set not less than 240 DEG C, to carry out hydro-thermal carbonization reaction at least 4h；C. after hydro-thermal carbonization reaction terminates in the reactor carried out in the step b, reaction product in reactor is poured into burning Cup, stirring purifying at least 8h, then reaction mixture after purification is washed, wash respectively at least three times using ethanol alcohol respectively, then right Sediment after washing is filtered, and obtained filter cake dries at least 24h, warp in the vacuum drying chamber not less than 80 DEG C Cross after drying process and obtain product B, product B be on charcoal material surface containing centered on carbon ortho position connect oxygen free radical and The hydro-thermal carbon composite of environmental persistence free radical centered on oxygen.
- 7. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 6, it is characterised in that：In the step In rapid a, trivalent iron salt is dissolved in anaerobic deionized water ferric salt solution is made.
- 8. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 6, it is characterised in that：In the step In rapid a, the biomass material uses waste biomass material.
- 9. the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 6, it is characterised in that：In the step In rapid a, the biomass material uses lignin or pomelo peel.
- 10. the application of the hydro-thermal carbon composite of class Fenton's reaction is can be applied to described in a kind of claim 1, it is characterised in that： By hydro-thermal carbon composite and H2O2Fenton-like is formed, to containing in sewage of the organic pollution concentration not less than 50mg/L Organic pollution carries out degradation treatment, when carrying out sewage degradation treatment, by hydro-thermal carbon composite and H2O2It is added to pending In sewage, the uniform stirring under the conditions of lucifuge, the reaction temperature of the dirty organic pollutants of control degraded is controlled not less than 25 DEG C, analysis is sampled to the water containing organic pollution by the processing of class Fenton at set time intervals, when in water Pollutants removal rate reach established standardses after, treatment reaction terminates.
- 11. the application of the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 10, it is characterised in that： Using hydro-thermal carbon composite and H2O2When forming Fenton-like, hydro-thermal carbon composite is 30% with mass percent concentration H2O2The proportioning of solution is 0.25g：1mL.
- 12. the application of the hydro-thermal carbon composite of class Fenton's reaction is can be applied to according to claim 10, it is characterised in that： Organic pollution suitable for the water containing organic pollution is methyl orange, Congo red or bisphenol-A organic matter water process work Skill process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710734563.7A CN107364942A (en) | 2017-08-24 | 2017-08-24 | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710734563.7A CN107364942A (en) | 2017-08-24 | 2017-08-24 | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107364942A true CN107364942A (en) | 2017-11-21 |
Family
ID=60310627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710734563.7A Pending CN107364942A (en) | 2017-08-24 | 2017-08-24 | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107364942A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109013693A (en) * | 2018-08-28 | 2018-12-18 | 上海大学 | The green restorative procedure of organic polluted soil |
| CN109046338A (en) * | 2018-08-03 | 2018-12-21 | 华中科技大学 | A kind of palladium catalyst that Carbon Materials are immobilized, its preparation and application |
| CN111392846A (en) * | 2020-03-02 | 2020-07-10 | 上海大学 | Green degradation method for organic pollutants in water |
| CN114939394A (en) * | 2022-03-29 | 2022-08-26 | 南京师范大学 | Preparation method of iron-modified hydrothermal carbon and application of iron-modified hydrothermal carbon in DDT degradation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN103272634A (en) * | 2013-05-28 | 2013-09-04 | 常州大学 | Preparation method of nano metal loaded molecular sieve based catalyst |
| CN105110423A (en) * | 2015-09-08 | 2015-12-02 | 同济大学 | Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof |
| CN105582888A (en) * | 2016-01-21 | 2016-05-18 | 西南科技大学 | Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method |
| CN106065332A (en) * | 2016-06-03 | 2016-11-02 | 浙江科技学院 | A kind of method and the application that utilize pomelo peel hydro-thermal carbonization to prepare charcoal |
| CN106944098A (en) * | 2017-03-27 | 2017-07-14 | 中国科学院福建物质结构研究所 | Carbon material supported copper cobalt dual-metal sulfide composite and its preparation method and application in the treatment of waste water |
-
2017
- 2017-08-24 CN CN201710734563.7A patent/CN107364942A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN103272634A (en) * | 2013-05-28 | 2013-09-04 | 常州大学 | Preparation method of nano metal loaded molecular sieve based catalyst |
| CN105110423A (en) * | 2015-09-08 | 2015-12-02 | 同济大学 | Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof |
| CN105582888A (en) * | 2016-01-21 | 2016-05-18 | 西南科技大学 | Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method |
| CN106065332A (en) * | 2016-06-03 | 2016-11-02 | 浙江科技学院 | A kind of method and the application that utilize pomelo peel hydro-thermal carbonization to prepare charcoal |
| CN106944098A (en) * | 2017-03-27 | 2017-07-14 | 中国科学院福建物质结构研究所 | Carbon material supported copper cobalt dual-metal sulfide composite and its preparation method and application in the treatment of waste water |
Non-Patent Citations (2)
| Title |
|---|
| LOMNICKI S,ET AL: "Copper oxide-based model of persistent free radical formation on combustion-derived particulate matter", 《ENVIRONMENT SCIENCE &TECHNOLOGY》 * |
| 阮秀秀等: "环境持久性自由基的研究进展", 《上海大学学报（自然科学版）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046338A (en) * | 2018-08-03 | 2018-12-21 | 华中科技大学 | A kind of palladium catalyst that Carbon Materials are immobilized, its preparation and application |
| CN109013693A (en) * | 2018-08-28 | 2018-12-18 | 上海大学 | The green restorative procedure of organic polluted soil |
| CN111392846A (en) * | 2020-03-02 | 2020-07-10 | 上海大学 | Green degradation method for organic pollutants in water |
| CN114939394A (en) * | 2022-03-29 | 2022-08-26 | 南京师范大学 | Preparation method of iron-modified hydrothermal carbon and application of iron-modified hydrothermal carbon in DDT degradation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107364942A (en) | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction | |
| Zhuang et al. | Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of heterogeneous catalytic ozonation and biological process | |
| CN106944053A (en) | A kind of sludge carbon base type Fenton catalyst and its preparation method and application | |
| CN104148007B (en) | A kind of preparation method of water treatment multifunctional material and application | |
| CN109675581B (en) | Ferro-manganese bimetal oxide modified biochar photo-Fenton composite material and preparation method thereof | |
| CN107519877A (en) | Catalysis persulfate oxidation goes the method for the catalyst of ammonia nitrogen and catalysis persulfate processing ammonia-nitrogen sewage in water removal | |
| CN108176403B (en) | Co-loaded activated carbon fiber3O4Method for preparing catalytic material | |
| CN109650522B (en) | Method for removing polycyclic aromatic hydrocarbons in water body by using iron-manganese bimetallic oxide modified charcoal photo-Fenton composite material | |
| CN108607507A (en) | A kind of preparation method of the high stability charcoal base cementite of degradation of dye | |
| CN111635025B (en) | Method for treating dye wastewater by using patina/glucose-glucose oxidase catalytic oxidation system | |
| CN105233838B (en) | A kind of O using activated bentonite as carrier3/H2O2Preparation method, catalyst and its application of catalyst | |
| CN107321350A (en) | Sludge base Co/Fe bimetallics are combined type Fenton catalyst and its preparation method and application | |
| CN111547903A (en) | Biochar-based micro-electrolysis filler and application thereof in chemical wastewater treatment | |
| CN109529868A (en) | A kind of ferrimanganic cobalt codope support type fenton catalyst, preparation method and applications | |
| CN106064962B (en) | The method for catalyst particle electrode and application using sludge and coal ash for manufacturing | |
| CN107188293A (en) | Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries | |
| CN113828332A (en) | Cobalt sulfide supported charcoal catalyst and preparation method and application thereof | |
| CN110171863A (en) | The biodegrading process of sulfadimidine in water body | |
| CN110092438B (en) | Method for treating organic wastewater by using electrolytic manganese residues as photocatalyst | |
| CN109364926A (en) | The preparation method of catalyst for desulfurization wastewater class Fenton's reaction removal ammonia nitrogen | |
| CN105921117A (en) | Metal organic framework material and preparing method and application thereof | |
| CN107159175B (en) | It is a kind of using sub- titanium oxide as the catalytic ozonization water treatment method of catalyst | |
| CN107961811A (en) | A kind of loaded catalyst of depth degradation industrial dye waste water and preparation method thereof | |
| CN110115974B (en) | Decolorizing material, preparation method and application thereof, and wastewater decolorizing method | |
| CN106040241A (en) | Method for preparing heterogeneous Fenton catalyst from waste biogas residues and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171121 |
|
| RJ01 | Rejection of invention patent application after publication |