CN105289498B - A kind of preparation method of biomass carbon carbon nanomaterial compound - Google Patents
A kind of preparation method of biomass carbon carbon nanomaterial compound Download PDFInfo
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- CN105289498B CN105289498B CN201510834098.5A CN201510834098A CN105289498B CN 105289498 B CN105289498 B CN 105289498B CN 201510834098 A CN201510834098 A CN 201510834098A CN 105289498 B CN105289498 B CN 105289498B
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Abstract
The invention discloses a kind of preparation method of biomass carbon carbon nanomaterial compound, specifically related to using biomass cheap and easy to get as raw material, hybrid transition metal oxide carries out catalyzing and carbonizing, it is catalyst using metal oxide remaining in carbonization process and the metal based biomass charcoal of generation, in its surface vapor deposition growing carbon nanomaterial, biomass carbon carbon nanomaterial compound is prepared.
Description
Technical field
The invention belongs to field of new materials, it is related to a kind of preparation side of metal based biomass charcoal-carbon nanomaterial compound
Method and its application.
Background technology
Biomass resource is widespread in nature and recoverable is played the part of in process of sustainable development because of it
More and more important role.Also the life for being increasingly turned to recycling is utilized from the direct of wasting of resources type to biomass economy
Material conversion process.Wherein, pyrolysis biomass charcoal making directly burns instead of biomass so that artificially discharged every year into air
Carbon reduces 1 12.The biomass carbon rich in carbon prepared by biomass also begin to further investigation.At present
Biomass carbon is widely used in alternative energy source, and soil improvement, adsorbent prepares activated carbon, in terms of sewage disposal, and obtained
Good effect.The utilization of the abandoned biomass such as agriculture and forestry organic waste material, animal excrements, organic food waste, municipal sludge, can both enter
Row changing waste into resources is utilized, and can also improve environment and energy problem.
Carbon nanomaterial includes the isomers of the nano level carbon such as fullerene, CNT, carbon fiber, graphene.Reach a conclusion after weighing a matter
Just the extensive concern of domestic and international researcher has been attract since generation always with unique structure and excellent properties.Carbon nanomaterial because
It has a good mechanical property, heat endurance, special electrical properties, heat conduction, hydrogen storage, absorption and catalytic performance etc. by
The extensive concern of domestic and international researcher.The preparation method of carbon nanomaterial mainly has arc process, laser evaporization method and chemical gas
Phase sedimentation etc..Chemical vapour deposition technique prepares carbon nanomaterial because it is efficient, and yield is big, meets industrial requirement, as master
The preparation technology of stream.During need catalyst carry out catalytic pyrolysis carbon source for growth Carbon Materials.And primarily now use be generally
Metal load type catalyst and Catalyzed by Organometallic Compounds agent, catalytic active component mainly with Fe, Co, Ni, Mg, Al or its
Based on alloy, catalyst carrier SiO2, Al2O3, MgO, La2O3Deng, but the use of these catalyst adds and prepares carbon nanometer
The cost of material, limits the industrialization development of carbon nanomaterial.
The present invention is combined by the way that prepared by biomass catalyzing charing and carbon nanomaterial into two processes, to realize height
Effect, low cost, the preparation flow of charcoal-carbon nanomaterial compound simple to operate.The presence of metal oxide may act as
Biomass carbonated catalyst, while the metal salt of the Metal Substrate charcoal and remnants obtained by charing can be used as carbon nanometer again
The substrate and catalyst of Material growth, not only realize the comprehensive utilization of biomass, and carbon nanomaterial preparation process can be solved again
The high shortcoming of middle catalyst cost, and the biomass carbon-carbon nanomaterial compound prepared needs not move through separation, can be direct
Using the higher catalytic performance of the double properties and metallic of biomass carbon and carbon nanomaterial, in effectively drop low-carbon nano
Material is successfully realized the recycling of discarded object while preparing cost.
The content of the invention
The present invention is intended to provide a kind of preparation method of biomass carbon-carbon nanomaterial compound, gained compound can
Efficiently remove in soil, the heavy metal ion in water, the pernicious gas in absorption air and can utilize biomass carbon simultaneously
Applied with the performance of carbon nanomaterial and metal ion as catalyst carrier or catalyst in methane carbon dioxide reformation
Hydrogen production process, or it is used as the catalyst of water vapour catalytically reforming hydrogen producing.Because of its raw material sources extensively, it is environment-friendly, in catalysis
Agent and absorbent fields have broad application prospects.
The preparation method for the compound that this method is provided comprises the following steps：
（1）Biomass is mixed into different metal oxides solution, uniform stirring stands, dried.Mixture is taken to be placed in CVD
In stove, nitrogen discharge air is passed through, rise temperature is passed through hydrogen and stops 30min-90min, metal oxidation to 400 DEG C -700 DEG C
Thing is hydrogenated.
（2）（1）On the basis of close hydrogen, continuation is passed through nitrogen with former speed, in 600 DEG C of -1000 DEG C of temperature ranges
Interior holding 30min-60min, biomass is in this stage by metallic catalyzing and carbonizing.
（3）Utilize（2）Middle remaining metallic is catalyst with the metal based biomass charcoal generated, is passed through low-carbon gas
Body, in step（2）Within the temperature range of retention time 30min-120min, stop heating, stopping be passed through low-carbon gas, in hydrogen
Under protection, reduction temperature to normal temperature.Now gained compound is biomass carbon-carbon nanomaterial compound in stove.
The purpose of step 1 is that, for mixing biomass and metal salt, reducing metal salt is active metal particles.
It is preferred that, biomass is one kind in agriculture and forestry organic waste material, animal excrements, organic food waste, municipal sludge.
It is preferred that, metal salt is the nitrose material of any of Cu, Fe, Mn, Ni, In or Co metal.
It is preferred that, the flow of protective gas is 50-200ml/min.
It is preferred that, the flow for being passed through hydrogen is 50-200ml/min.
In step 3, low-carbon gas mainly has CH4, CO, C2H4, C2H2, C2H6Deng.
Beneficial effects of the present invention are that required biomass material is all one kind in solid waste, realizes change useless
For precious theory, and wherein chemical vapor deposition processes need not add extra catalyst, but biomass before use
Remaining metallic catalyst in carbonization process, has saved the high shortcoming of catalyst cost, is that industrialized production carbon nano-material is carried
New thinking is supplied.
Sum it up, the present invention has following feature：
1st, it is that there is provided a kind of effective way of biomass trans-utilization for raw material using biomass.
2nd, deposit carbon nanomaterial using the remaining metallic catalyst catalyzed gas of carbonization process, saved catalyst into
This, realizes catalyst circulation, improves catalytic efficiency, saved raw material.
3rd, metallic is still contained in the biomass carbon finally produced-carbon nanomaterial compound, can be same without purifying
The good characteristic and synergy of tri- kinds of compositions of Shi Liyong, preferably play the effect of compound.
4th, this method is simple to operate, is adapted to produce in enormous quantities.
Brief description of the drawings
Fig. 1 is shown makees catalyst in biomass carbon superficial growth carbon nanomaterial preparation biology using residual nitric acid nickel
The flow chart of matter charcoal-carbon nanomaterial compound
Fig. 2 show the electron microscopic picture of the products therefrom of the embodiment of the present invention 1；
Fig. 3 show the N of the products therefrom of the embodiment of the present invention 22Adsorption/desorption curve.
Embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Case study on implementation 1
Using rice husk as biomass material, quantitative rice husk is taken to crush, by biomass：The ratio of metal salt is 10:1 adds nitric acid
Nickel, adds under appropriate amount of deionized water, normal temperature and stirs 3h, dried in 105 DEG C of drying box.The mixture after drying is taken out, is put
In in CVD stoves, be passed through the air in nitrogen, emptying stove by 50ml/min flow, turn on the power, by heating rate be 20 DEG C/
Min raises temperature to 450 DEG C, and nitrogen is closed afterwards, 100ml/min hydrogen is passed through, metal salt is reduced, the recovery time is
2h, closes hydrogen and continues to be passed through nitrogen according to former speed afterwards.
Continue to raise temperature on the basis of said process to 800 DEG C, keep 90min.600 DEG C are cooled to afterwards, then
According to CH4：N2=0.8:1 is passed through mixed gas, and the flow of mixed gas is 180ml/min, and 1 hour is kept under this condition
Afterwards, carbon source is closed, room temperature is cooled under nitrogen protection, now gained biomass carbon-carbon nanomaterial compound, Fig. 2 is institute
Obtain the electron-microscope scanning figure of product.
Case study on implementation 2
Using corncob as biomass material, quantitative corncob is taken to crush, by biomass：The ratio of metal salt is 10:1 adds
Ferric nitrate, adds under appropriate amount of deionized water, normal temperature and stirs 3h, dried in 105 DEG C of drying box.Take out the mixing after drying
Thing, is placed in CVD stoves, is passed through the air in nitrogen, emptying stove by 50ml/min flow, turns on the power, be by heating rate
20 DEG C/min raises temperature to 500 DEG C, and nitrogen is closed afterwards, 100ml/min hydrogen is passed through, metal salt is reduced, and reduces
Time is 2h, and hydrogen is closed afterwards and continues to be passed through nitrogen according to former speed.
Continue 500 DEG C of temperature on the basis of said process, keep 90min.Be warming up to 600 DEG C afterwards, then according to
CH4：H2：N2=1:1:2 are passed through mixed gas, and the flow of mixed gas is 200ml/min, is kept under this condition after 1 hour,
Carbon source is closed, room temperature is cooled under nitrogen protection, now gained biomass carbon-carbon nanomaterial compound, Fig. 3 produces for gained
The N of thing2Adsorption/desorption curve.
Claims (6)
1. the preparation method of a kind of biomass carbon-carbon nanomaterial compound, it is characterised in that realized by following steps：
(1) biomass is well mixed with metal oxide solution, takes mixture to be placed in CVD stoves after drying, be passed through nitrogen row
Go out air, rise temperature is passed through hydrogen and stops 30min-90min, metal oxide is hydrogenated, described to 400 DEG C -700 DEG C
Biomass and the mixed proportion of metal oxide are 5:1~20:Between 1；
(2) hydrogen is closed on the basis of step (1), is passed through nitrogen, 30- is kept in 600 DEG C of -1000 DEG C of temperature ranges
60min, biomass is by metallic catalyzing and carbonizing；
(3) it is catalyst using the metal based biomass charcoal of metallic remaining in step (2) and generation, is passed through low-carbon gas
Body, 600 DEG C of -1000 DEG C of holding 30min-120min, is made biomass carbon-carbon nanomaterial compound.
2. a kind of preparation method of biomass carbon-carbon nanomaterial compound according to claim 1, it is characterised in that institute
Metal in the metal oxide stated is any of Cu, Fe, Mn, Ni, In or Co.
3. a kind of preparation method of biomass carbon-carbon nanomaterial compound according to claim 2, it is characterised in that institute
The metal oxide stated is nitrate.
4. a kind of preparation method of biomass carbon-carbon nanomaterial compound according to claim 1, it is characterised in that institute
The biomass stated is one kind in agriculture and forestry organic waste material, animal excrements, organic food waste or municipal sludge.
5. a kind of preparation method of biomass carbon-carbon nanomaterial compound according to claim 1, it is characterised in that step
Suddenly the heating rate described in (1) is in 10 DEG C/min-25 DEG C/min.
6. a kind of preparation method of biomass carbon-carbon nanomaterial compound according to claim 1, it is characterised in that step
Suddenly in (3), described low-carbon gas is CH4, CO, C2H4, C2H2, C2H6。
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| CN106268739A (en) * | 2016-08-31 | 2017-01-04 | 南昌大学 | A kind of preparation method of C nano material |
| CN108080033A (en) * | 2017-11-28 | 2018-05-29 | 东南大学 | A kind of biological legal manner of efficient degradation industrial wastewater pollution object |
| CN110380032A (en) * | 2019-07-19 | 2019-10-25 | 武汉理工大学 | A kind of preparation method of transition metal oxide/carbon nano-fiber negative electrode material |
| CN110451485B (en) * | 2019-08-30 | 2023-05-12 | 东南大学 | Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof |
| CN110484286B (en) * | 2019-09-02 | 2021-11-23 | 哈尔滨工业大学 | Method for preparing carbon and inhibiting tar through pyrolysis gas deposition in high-volatile coal thermal conversion process |
| CN111389367A (en) * | 2020-04-22 | 2020-07-10 | 徐州工程学院 | Metal sludge-based biochar, preparation method and application in removing nitrogen and phosphorus in water body |
| CN113501647B (en) * | 2021-07-29 | 2022-08-02 | 华中科技大学 | Method for converting water-soluble humic acid by directionally catalyzing sludge pyrolysis oil |
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