CN105417518B - Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material - Google Patents
Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material Download PDFInfo
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- CN105417518B CN105417518B CN201410453563.6A CN201410453563A CN105417518B CN 105417518 B CN105417518 B CN 105417518B CN 201410453563 A CN201410453563 A CN 201410453563A CN 105417518 B CN105417518 B CN 105417518B
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Abstract
A kind of gas phase the invention discloses solid carbonaceous material post-processes reforming apparatus and method, belongs to inorganic chemical synthesis technical field.The method be by solid carbonaceous material at a certain temperature, by closing heating air-born substances, produce the gas phase of certain pressure carries out post-modification treatment to carbon material, carbon material is not directly contacted with air-born substances, modified solid carbonaceous material can be directly used for catalytic reaction as catalyst, recycling, can also be dried to obtain by after washing.Through the solid carbonaceous material of oxidation processes of the present invention, content of surface oxygen significantly rises, and the epoxide selectivities that catalytic oxidation is obtained rise.
Description
Technical field
The present invention relates to inorganic chemical synthesis technical field, and in particular to a kind of post processing reforming apparatus of solid carbonaceous material
And method.
Background technology
CNT (Carbon Nanotubes are referred to as CNTs below) has unique mechanics, electricity, Yi Jihua
Performance is learned, thus is received significant attention, demand and yield increase sharply.The CNTs of non-modified treatment is hydrophobic and chemical lazy
Property, this is unfavorable for its dispersion in polar solvent and further functionalization or prepares composite.Use wet method
Learn the methods such as oxidation, photooxidation, oxygen plasma, gas phase treatment to aoxidize CNTs, can effectively draw on CNTs surfaces
Enter oxygen-containing functional group.These functional groups can not only change the property of CNTs itself, be conducive to it to disperse, can also be directly as
The activated centre of catalytic reaction, while also can be used as the anchored site of further functionalization.In document it has been reported that oxidation change
Property the usual severe reaction conditions of method, the structure of CNTs can be damaged, device it is complex and there may be pollution environment
Waste liquid or tail gas.In above-mentioned method of modifying, gaseous oxidation treatment can avoid separating CNTs from liquid phase, suppress CNTs's
Reunite, be conducive to industrial mass production.
Xia Wei etc. (Carbon 2009, (47), 919-922) is reported and is used nitric acid vapor at 125-250 DEG C to CNTs
Carry out the modified method of atmospheric pressure oxidation.The method breaches the temperature limiting of nitric acid liquid phase oxidation, and (boiling point is under concentrated nitric acid normal pressure
122 DEG C), pattern and the decentralization destruction to CNTs are small.Compare traditional nitric acid liquid phase oxidation to be modified, CNTs changes by the method
Property after, the oxygen-containing functional group quantity on surface is obviously improved, and C=O groups ratio increase.The shortcoming of the method is the use of
Big excessive concentrated nitric acid produces the nitrogen oxides tail gas and acid waste liquid of a large amount of pollution environment, while equipment as steam source
It is complex and easily corroded by acid vapors.
Chen Chunlin etc. (Materials Research Bulletin 2013, (48), 3218-3222) is reported and used
NO2The modified method of atmospheric pressure oxidation is carried out to CNTs as oxidant.Author is had found with the rising for the treatment of temperature, sample oxidation
Modified weight loss increases, and surface oxygen functional group content rises.Meanwhile, modified sample specific surface area has and necessarily carries
Rise, it may be possible to due to NO2Oxidation opens the port of CNTs.The shortcoming of the method be the modified oxygen-containing functional group amount for introducing compared with
It is low, and non-selectivity, while having certain destruction to the structure of CNTs；NO is configured in addition2Gas is cumbersome, the NO tail gas of generation
It is likely to result in pollution.
In sum, oxygen-containing function simply, efficiently, controllably on the surface of CNTs can be introduced there presently does not exist a kind of
The method of modifying of group.
The content of the invention
It is an object of the invention to the weak point for overcoming prior art to exist, there is provided a kind of post processing of solid carbonaceous material
Reforming apparatus and method, post-process by solid carbonaceous material, change its surface functional group composition and content, so as to change
Its process based prediction model.
To achieve the above object, technical solution of the present invention is as follows：
A kind of post processing reforming apparatus of solid carbonaceous material, the device includes the crystallizing kettle with liner, is put in crystallizing kettle
The container of upper opening is put, side wall and the bottom of the container open up some through holes, and container is by support and substrate in crystallizing kettle
Portion mutually separates；The liner is polytetrafluoroethyllining lining.
In the container that the solid carbonaceous material is placed in crystallizing kettle, and the bottom separation for passing through core and container；On container
The size of institute's opened hole should ensure that solid carbonaceous material is not dropped to outside container.
The post processing for carrying out solid carbonaceous material using said apparatus is modified, and method of modifying comprises the following steps：
(1) filling of solid carbonaceous material：
Solid carbonaceous material is fitted into the container in crystallizing kettle liner, liner bottom contain air-born substances, air-born substances with
Solid carbonaceous material is not directly contacted with, and air-born substances is (10~1000) with the weight ratio of solid carbonaceous material: 1；According to the big of container
Small, solid carbonaceous material loads 0.1 gram to 1000 grams；
(2) gas-phase modification treatment：
The liner that will be equipped with solid carbonaceous material and air-born substances loads crystallizing kettle and closes, quiet under the conditions of 80~200 DEG C
Set to 0 .5~100h；
(3) reclaim and separate：
Solid carbonaceous material after being processed through step (2) gas-phase modification, catalytic reaction is used for directly as catalyst；Or warp
Cross and wash, reclaim and be dried to obtain modified solid carbonaceous material.
The solid carbonaceous material is with sp2Or sp3The carbon material of the carbon-carbon bond connection of hydridization, its fusing point is more than 200 DEG C；Institute
It is solid-state or liquid that air-born substances is stated in normal temperature, can be produced by modes such as evaporation, volatilization, decomposition at 80~200 DEG C
Gas.The air-born substances is preferably the salpeter solution of 1~40wt.%.
Compared with prior art, the present invention has following remarkable advantage：
1st, to carry out post processing to solid carbonaceous material using specific device modified for the present invention, solid carbonaceous material and air-born substances without
Directly contact, 0.5~100h is stood in the closed crystallizing kettle under the conditions of 80~200 DEG C；During being somebody's turn to do, the air-born substances exists
80~200 DEG C of generation gases, produced gas produces certain pressure in the crystallizing kettle of closing, and rush is passed the gas through on container
Through hole and core are modified post processing to carbon material.
2nd, operation is simple for the present invention, and process is easily controlled and repeats.
3rd, exhaust emissions amount is low, and air-born substances can be reused.
4th, equipment is simple, and space availability ratio is high, and closed-loop operation, corrosivity is small.
5th, carbon material does not mix with liquid phase, and separation costs are low, reduces and reunites.
6th, the carbon material obtained after oxidation modification of the present invention treatment, compares the carbon materials that liquid phase oxidation under the same terms is obtained
Material, surface oxygen content is significantly improved (10%-20%), and the epoxide selectivities that catalytic oxidation is obtained rise (10%-
20%).
Brief description of the drawings
Fig. 1 is the post processing reforming apparatus structural representation of solid carbonaceous material of the present invention.
Wherein：1- liners；2- containers；3- cores；4- supports；5- solid carbonaceous materials；6- through holes；7- air-born substanceses.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention will be further described.
As shown in figure 1, the post processing reforming apparatus of solid carbonaceous material of the present invention include the crystallizing kettle with liner 1, crystallization
The interior container 2 for placing upper opening of kettle, side wall and the bottom of the container 2 open up some through holes 6, and container 2 is by support 4 and crystalline substance
Change the bottom of kettle liner 1 mutually to separate；The liner 1 is polytetrafluoroethyllining lining.
In the container 2 that the solid carbonaceous material 5 is placed in crystallizing kettle, and the bottom separation for passing through core 3 and container 2；Hold
The size of institute's opened hole 6 should ensure that solid carbonaceous material 5 is not dropped to outside container 2 on device 2.
As seen from Figure 1, solid carbonaceous material 5 is placed in container 3, is not directly contacted with air-born substances 7.Device integrally closed
In corrosion resistant polytetrafluoroethyllining lining, the gas produced by air-born substances 7 produces pressure.If dry carbon is distributed with container
The Minute pores that material cannot pass through, are conducive to mass transferring in gas phase.
The post processing for carrying out solid carbonaceous material using said apparatus is modified, and method of modifying comprises the following steps：
(1) filling of solid carbonaceous material：
Solid carbonaceous material is fitted into the container in crystallizing kettle liner, liner bottom contain air-born substances, air-born substances with
The weight ratio of solid carbonaceous material is (10~1000): 1；
(2) gas-phase modification treatment：
The liner that will be equipped with solid carbonaceous material and air-born substances loads crystallizing kettle and closes, quiet under the conditions of 80~200 DEG C
Set to 0 .5~100h；
(3) reclaim and separate：
Solid carbonaceous material after being processed through step (2) gas-phase modification, catalytic reaction is used for directly as catalyst；Or warp
Cross and wash, reclaim and be dried to obtain modified solid carbonaceous material.
Comparative example 1
Oxidation modification is carried out to CNT in the liquid phase.
(1) CNT is added to mass fraction in 20% diluted nitric acid aqueous solution, the matter of dust technology and CNT
Amount is than being 100: 1.After this mixed liquor is stirred 6 hours at 100 DEG C, filtering, washing obtains liquid phase oxidation modified after drying
CNT CNT-L-1.
Comparative example 2
Oxidation modification is carried out to CNT in the liquid phase.
(1) CNT is added in the concentrated nitric acid aqueous solution that mass fraction is 65%.Concentrated nitric acid and CNT
Mass ratio is 100: 1.After this mixed liquor is stirred 2 hours at 120 DEG C, filtering, washing obtains liquid phase oxidation and is modified after drying
CNT CNT-L-2 afterwards.
Embodiment 1
Oxidation modification is carried out to CNT in the gas phase.
(1) CNT is loaded in the container of apparatus of the present invention, then container is transferred in crystallizing kettle liner, interior substrate
There is the diluted nitric acid aqueous solution that mass fraction is 20% in portion, and carbon material is not directly contacted with liquid, the matter of dust technology and CNT
Amount is than being 500: 1；
(2) liner is loaded into crystallizing kettle, is closed, 6 hours are stood at 100 DEG C, sample is scrubbed, gas phase is obtained after drying
CNT CNT-G-1 after oxidation modification.
Embodiment 2
Oxidation modification is carried out to CNT in the gas phase.
(1) CNT is loaded in the container of apparatus of the present invention, then container is transferred in crystallizing kettle liner, interior substrate
There is the concentrated nitric acid aqueous solution that mass fraction is 65% in portion, and carbon material is not directly contacted with liquid, the matter of concentrated nitric acid and CNT
Amount is than being 500: 1；
(2) liner is loaded into crystallizing kettle, is closed, 2 hours are stood at 120 DEG C, sample is scrubbed, gas phase is obtained after drying
CNT CNT-G-2 after oxidation modification.
Embodiment 3
Oxidation modification is carried out to CNT in the gas phase.
(1) CNT is loaded in the container of apparatus of the present invention, then container is transferred in crystallizing kettle liner, interior substrate
There is the concentrated nitric acid aqueous solution that mass fraction is 65% in portion, and carbon material is not directly contacted with liquid, the matter of concentrated nitric acid and CNT
Amount is than being 500: 1；
(2) liner is loaded into crystallizing kettle, is closed, 10 hours are stood at 120 DEG C, sample is scrubbed, gas is obtained after drying
The modified CNT CNT-G-3 of phase oxidation.
Embodiment 4
Ammonia treatment is carried out to CNT in the gas phase.
(1) CNT is loaded in the container of apparatus of the present invention, then container is transferred in crystallizing kettle liner, interior substrate
There is the concentrated ammonia solution that mass fraction is 26% in portion, and carbon material is not directly contacted with liquid, the quality of concentrated ammonia liquor and CNT
Than being 500: 1；
(2) liner is loaded into crystallizing kettle, is closed, 6h is stood at 100 DEG C, sample is scrubbed, gas phase oxygen is obtained after drying
Change modified CNT CNT-G-4.
Using the epoxidation reaction of styrene as probe reaction, various embodiments above and the modified carbon nanometer of comparative example are assessed
The catalysis activity of pipe.Course of reaction includes：With acetonitrile as solvent, with the TBHP (TBHP) that mass fraction is 65%
The aqueous solution is oxidant, successively by catalyst carbon nanotube, solvent (acetonitrile), reactant (styrene), oxidant (mass fraction
The TBHP aqueous solution for 65%) it is added in reactor, reacted 5 hours in 90 DEG C.Wherein reactant (benzene hexene):Catalyst carbon is received
Mitron:The mass ratio of solvent (acetonitrile) is 1:0.01:70.5, reactant (styrene):The mol ratio of oxidant (TBHP) is 1:
1。
Result is as shown in following table 1-4：
Catalysis activity contrast after 100 DEG C of 1 dust technology liquid/gas phase of table is modified 6 hours
Catalysis activity contrast after 120 DEG C of 2 concentrated nitric acid liquid/gas phase of table is modified 2 hours
Catalysis activity contrast after 120 DEG C of 3 concentrated nitric acid gas phase of table is modified 2,10 hours
Catalysis activity contrast after 4 concentrated nitric acids of table/100 DEG C of concentrated ammonia liquor gas phase is modified 6 hours
As can be seen from the above experimental data, the carbon material for being obtained after oxidation modification treatment of the present invention, compares the same terms
The carbon material that lower liquid phase oxidation is obtained, surface oxygen content is significantly improved, on the epoxide selectivities that catalytic oxidation is obtained
Rise.
It is above preferred embodiments of the present invention, but protection content of the invention is not limited to above-described embodiment, is not carrying on the back
Under the spirit and scope of inventive concept, those skilled in the art it is conceivable that change and advantage be all included in the present invention
In.
Claims (6)
1. a kind of after-treatment modification method of solid carbonaceous material, it is characterised in that：The method is entered using post-processing reforming apparatus
OK, the post processing reforming apparatus include being placed in the crystallizing kettle with liner, crystallizing kettle the container of upper opening, the container
Side wall and bottom open up some through holes, container is mutually separated by support with crystallizing kettle liner bottom；The method includes following step
Suddenly：
(1) filling of solid carbonaceous material：
Solid carbonaceous material is fitted into the container in crystallizing kettle liner, liner bottom contains air-born substances, air-born substances and solid
Carbon material is not directly contacted with, and air-born substances is (10~1000) with the weight ratio of solid carbonaceous material: 1；The solid carbonaceous material is
With sp2Or sp3The carbon material of the carbon-carbon bond connection of hydridization, its fusing point is more than 200 DEG C；The air-born substances is solid-state in normal temperature
Or liquid, can produce gas at 80~200 DEG C；
(2) gas-phase modification treatment：
The liner that will be equipped with solid carbonaceous material and air-born substances loads crystallizing kettle and closes, and 0.5 is stood under the conditions of 80~200 DEG C
~100h；
(3) reclaim and separate：
Solid carbonaceous material after being processed through step (2) gas-phase modification, catalytic reaction is used for directly as catalyst；Or by washing
Wash, reclaim and be dried to obtain modified solid carbonaceous material.
2. the after-treatment modification method of solid carbonaceous material according to claim 1, it is characterised in that：The liner is poly- four
PVF liner.
3. the after-treatment modification method of solid carbonaceous material according to claim 1, it is characterised in that：The solid carbonaceous material
In the container being placed in crystallizing kettle, and the bottom separation for passing through core and container.
4. the after-treatment modification method of solid carbonaceous material according to claim 1, it is characterised in that：Institute's opened hole on container
Size should ensure that solid carbonaceous material is not dropped to outside container.
5. the after-treatment modification method of solid carbonaceous material according to claim 1, it is characterised in that：The air-born substances is
The salpeter solution of 1~40wt.%.
6. the after-treatment modification method of solid carbonaceous material according to claim 1, it is characterised in that：In step (1), according to
The size of container, solid carbonaceous material loads 0.1 gram to 1000 grams.
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| CN201410453563.6A CN105417518B (en) | 2014-09-05 | 2014-09-05 | Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material |
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| CN201410453563.6A CN105417518B (en) | 2014-09-05 | 2014-09-05 | Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material |
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| Publication Number | Publication Date |
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| CN105417518A CN105417518A (en) | 2016-03-23 |
| CN105417518B true CN105417518B (en) | 2017-07-07 |
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| CN113013405A (en) * | 2019-12-21 | 2021-06-22 | 天津大学 | Boron-sulfur co-doped carbon nanotube and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN103212433A (en) * | 2013-04-17 | 2013-07-24 | 太原理工大学 | Composite molecular sieve with core/shell structure and preparation method thereof |
| CN103646868A (en) * | 2013-11-06 | 2014-03-19 | 南阳理工学院 | Method for preparing porous silicon by adopting hydrothermal-vapor etching |
-
2014
- 2014-09-05 CN CN201410453563.6A patent/CN105417518B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN103212433A (en) * | 2013-04-17 | 2013-07-24 | 太原理工大学 | Composite molecular sieve with core/shell structure and preparation method thereof |
| CN103646868A (en) * | 2013-11-06 | 2014-03-19 | 南阳理工学院 | Method for preparing porous silicon by adopting hydrothermal-vapor etching |
Non-Patent Citations (2)
| Title |
|---|
| A highly efficient gas-phase route for the oxygen functionalization of carbon nanotubes based on nitric acid vapor;Wei Xia et al.;《Carbon》;20081224;第47卷;第919-922页 * |
| 蒸汽相中含硼多孔玻璃自转变合成沸石;董维阳等;《化学学报》;20031231;第61卷(第2期);第252页左栏第2段 * |
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