CN104891479B - Plant-based graphene and preparation method thereof - Google Patents
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Abstract
The invention provides plant-based graphene and a preparation method thereof. The preparation method comprises the steps of liquefying and filtering plant raw materials to obtain biological oil; mixing the biological oil with a catalyst to obtain a mixture, placing the mixture into a self-pressurizing reactor, sealing the reactor, catalytically calcining for 1 to 12 hours at the temperature of 500 to 1200 DEG C, cooling, washing by utilizing hydrochloric acid to remove the catalyst, rinsing by utilizing deionized water, and drying to obtain the quasi-graphene. According to the preparation method, the plant raw materials are firstly liquefied into biological oil which mainly includes oligosaccharide and a phenolic substance, then the biological oil is mixed with the catalyst, and under the high temperature and high pressure, the biological oil is converted to quasi-graphene on the surface of the catalyst, so that a novel method for preparing the quasi-graphene material in a mass manner by virtue of cheap plant raw materials is provided.
Description
Technical field
The present invention relates to plant base class grapheme material and preparation method thereof and in particular to plant resourceses through liquefaction, low
Warm catalysis calcination prepares the industrial method of super capacitor active carbon composite.
Background technology
Graphene (graphene) is a kind of two dimension material with carbon element, is single-layer graphene, bilayer graphene and few layer graphene
General designation.Graphene is the thinnest, the hardest nano material in known world, and it also has, and specific surface is big, and conductivity is high, heating power
Learn the feature of function admirable, all can play an important role in life science and energy field.At present, prepare Graphene
Method has graphite oxide reducing process, epitaxial growth method, chemical vapour deposition technique, mechanical stripping method, electrochemical method.Graphite oxide
Reducing process adopts the thinking of reduction after initial oxidation, comprises the concrete steps that and first prepares graphite oxide, then with methods such as ultrasound wave, thermal expansions
Graphene oxide is stripped out as far as possible, finally graphene oxide is changed into by Graphene using suitable reducing agent, such as adopt
Hydrazine hydrate reduces to graphene oxide, and the carbon atom that wherein hybrid form is sp3 is changed into sp2 carbon network lattice composition
Graphene.Carbon is entrained in formation interstitial impurity in rare metal with the method for seeping at high temperature by epitaxial growth method, then with
K cryogenic treatment makes carbon in metal substrate surface indigenous graphite alkene epitaxial.When the first layer graphene is not yet completely covered metal substrate
When, the second layer has begun to grow, because ground floor is entirely different with the chemical key class of the second layer graphene and metal substrate,
Gap between weakness coupling and powerful covalent bond effect makes the second layer graphene be easy to be stripped out.Chemistry
Vapour deposition process, with metal single crystal as substrate, is reached accurately by changing temperature, regulation substrate, exposed amount of control predecessor etc.
Control the purpose of graphene film thickness.Concrete mode is the thick ni film of 300mm to be heated to after 1000 degrees Celsius be exposed to first
In alkane atmosphere, thus forming highly purified graphene film on ni surface.Micromechanics partition method micromechanics partition method is most original
Stripping Graphene method.During concrete operations, make graphite expansion in order to separate frequently with some way, mono-layer graphite can not
Regular occurs in graphite surface, and this method is compared chemical stripping method and is more difficult to control to Graphene form, is unsuitable for high-precision
Degree commercial production.
Yang Rong et al. disclose the conductive carbon material of a species graphene-structured preparation method (application number:
201410134804.0), meerschaum powder, sucrose are mixed homogeneously with deionized water, then ultrasonic disperse, then microwave heating,
Mass fraction be 98.3% concentrated sulphuric acid exsiccator in place 24-144h；In this step, sucrose heated by microwave is converted into
Caramel.Carry out carbonization, caramel carbonization in meerschaum layered framework in protective gas atmosphere.Meerschaum after carbonization is adopted
Alternately it is acidified washing with Fluohydric acid., hydrochloric acid, then using the clean meerschaum of deionized water and fully dry, obtain class graphene-structured
Conductive carbon material.
Burnt odd-prescription (burnt odd-prescription, the preparation of class graphene carbon nanometer fragment and its electrocatalysis characteristic, [academic dissertation], south China
Normal university, 2013) with waste and old lithium ion battery Carbon anode as raw material, through a series of pre-treatment-chemical oxidation-ultrasound wave
Pulverizing-dialysis purification etc. is processed, and obtains oxidation state carbon nanometer fragment, result shows: oxidation state carbon nanometer fragment contour is coarse, thick
Spend for 1.5nm, profile is similar to Graphene, size is from 5nm～2 μm, and contains substantial amounts of oxygen-containing functional group and defect.
Zhu Runliang etc. discloses the preparation method (publication number of the nano-carbon material of a species graphene-structured
cn103058168a).The bentonite having adsorbed dyestuff is dried successively, pulverizes, carbonization, acidifying washing, be dried, obtain class
The nano-carbon material of graphene-structured.This invention, with discarded bentonite as raw material, prepares one kind and has large specific surface area
Novel nano stratiform material with carbon element, simultaneously for solving bentonitic resource after absorbing dye and recycling to provide new way,
Achieve the bentonite resourceization after wastewater treatment to utilize, thus contributing to promoting bentonite in dyestuff/treatment of dyeing wastewater
Application.
Zhou Xufeng discloses a kind of preparation method of Graphene and Graphene patent of invention (publication number cn104477901a).
Metallic catalyst is mixed with water, obtains the aqueous solution of metallic catalyst；Aqueous solution by gel like material and metallic catalyst
Mixing, obtains the hydrogel material being adsorbed with metallic catalyst, described gel like material includes starchy compounds, cellulose family
One or more of compound and synthetic resin；The hydrogel material being adsorbed with metallic catalyst is in protective gas atmosphere or true
Carry out heat treatment under Altitude, obtain Graphene.
Liang Xuelei etc. (Liang Xuelei, Li Wei, guangjun c etc. the impact of the Graphene quality that transfer process grows to cvd
[j]. Science Bulletin, 2014, (33)) Graphene that grown on the metallic substrate using the chemical vapor sedimentation method (cvd).Using drawing
Graceful spectrum and x-ray photoelectron spectroscopy (xps) demonstrate metallic substrates corrosive liquid in transfer process and can introduce in graphenic surface
Pollution, using " rca (radio corporation of america) cleaning (the modified rca of improvement of our development
Clean) " shifting process can remove this pollution effectively, and this has important to the performance of the electronic device improving follow-up preparation
Meaning.
Positive light of Guilin University of Technology Zou etc. [Zou Zhengguang, Yu Huijiang, Long Fei, etc. ultrasonic wave added hummers method prepares go
[j]. Chinese Journal of Inorganic Chemistry, 2011,27 (09): 1753-1757.] low temperature to hummers method (≤10 DEG C), middle temperature respectively
(38 DEG C) and low middle thermophase carry out the ultrasonic wave added of different capacity, explore the impact to hummers method for the ultrasound wave.They send out
Existing go interlamellar spacing is descending to be followed successively by low middle temperature ultrasonic wave added, middle temperature ultrasonic wave added, low temperature ultrasonic auxiliary.Moreover, stone
Black alkene interlamellar spacing becomes positive correlation with ultrasonic power, and spacing is conducive to more greatly monolayer go to peel off it is possible to according to different experiments need
Ask and prepare monolayer go or intercalation go.
Jia Qina etc. [Jia Qina, Zhao Guangchao. the preparation of Graphene solid-phase micro-extraction fibre and the detection to Polychlorinated biphenyls
[j]. analysis test journal, 2013,32 (05): 541-546.] will be molten for the titanium adding Graphene by solid phase micro-extraction technique
Fiber made by glue-gel, makes this fiber have all of advantage of both Graphene and gel, not only possesses quite high specific surface
Long-pending, stronger heat stability and excellent mechanical strength, and have three dimensional structure to provide more adsorption sites.
[critical process of Ren little Meng, Wang Yuansheng, He Te .hummers method synthesizing graphite alkene and the reaction mechanism such as Ren little Meng
[j]. material engineering, 2013 (01): 1-5.] classical hummers method is probed into, during by changing its reaction temperature, temperature control
Between, the amount of reacting substance etc. respectively each group product being detected.Find the optimal temperature in the low-temp reaction stage of hummers method
Degree is that the response time can suitably increase close to 0 DEG C, and the concentrated sulphuric acid in the low-temp reaction stage and potassium permanganate can excessively add,
The addition of sodium nitrate does not interfere with reaction substantially, and the temperature of middle thermophase is adjusted to as 30～45 DEG C, and the response time increases
90min is best, ensures that with this oxidation of graphite is more deep, and lamella peels off more complete.But the most impact yield
Temperature rise period, this seminar finds to be maximum output scope in 90～100 DEG C by temperature control, is gone by repeatedly a small amount of addition
Ionized water, and the response time should be shortened as far as possible, prevent product from reuniting again.
Although above method successfully prepares high-quality Graphene, preparation process is with high costs, pollution is big, is difficult to
Industrialization.Therefore, macroblock quantization production and large scale produce to remain and hinder grapheme material to put into the main of commercialization on a large scale
Bottleneck.At present, there is not yet the preparation method of plant base thunder grapheme material is reported, biomass scale liquefaction technology is ripe,
Therefore, with the low plant base of wide material sources, degree of crystallinity as raw material, class grapheme material is prepared by liquefaction and catalysis calcination, can
Realize extensive industrialization, cost is greatly reduced, and environmental pollution is little, product dispersive property more preferably, is more easy to store.
Content of the invention
Preparation process magnanimity preparation in order to solve prior art presence is difficult, seriously polluted, the problems such as expensive, this
Invention puies forward a kind of plant base liquefied catalytic preparation class grapheme material and its method, can achieve extensive industrialization, preparation process
Cleaning, step is simple, low cost of manufacture, and product dispersive property more preferably, is more easy to store.
The technical scheme is that the preparation method of plant base class Graphene, comprise the steps:
The first step, plant is liquefied: agricultural-forestry biomass raw material and the phenol of drying is liquefied, filters and remove inorganic impurity
After obtain bio oil；
Second step, bio oil is mixed with catalyst: with iron series element nitrate as catalyst, catalyst and bio oil according to
Mass ratio (0.1～1.0) 1.0 is mixed；
3rd step, seals pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is less than anti-
Answer body amass 1/3, carry out airtight pretreatment；
4th step, calcining: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, heat up calcining, treats that calcining terminates
Afterwards, natural cooling, takes out sample, reclaims catalyst through pickling, and deionized water rinses, after being dried, as described plant base class
Graphene sample, electrical conductivity 370s/cm of plant base class Graphene, specific surface area 760m2/ g, thickness 1-3nm.
Plant material described in the first step includes wood flour, bamboo scraps, straw, dries and uses.
Bio oil described in the first step removes solid impurity through filtering off.
In second step, iron series element includes ferrum, nickel, cobalt.
In second step, iron series element nitrate is at the uniform velocity stirred when being mixed with bio oil.
In 4th step, calcining heat is 500～1200 DEG C, calcination time 1-10h.
The Graphene that the preparation method of described plant base class Graphene obtains, electrical conductivity 180～370s/cm, specific surface area
420～760m2/ g, thickness 1-3nm.
The yield of plant base class grapheme material of the present invention, specific surface area, thickness can be by catalyst loadings, activation temperature
Degree, calcining heat and time control.The preparation of plant base class grapheme material: the plant material of drying and phenol are carried out liquid
Change, filter and obtain bio oil after removing inorganic impurity.Bio oil is mixed with catalyst: with iron series element nitrate as catalyst,
Mixed according to mass ratio (0.1～1.0) 1.0 with bio oil.A certain amount of said mixture is placed in spontaneous pressure reactor
Interior, inventory is less than the 1/3 of reactor volume, carries out airtight pretreatment.The spontaneous pressure reactor that will be equipped with material is placed in height
In warm stove, it is warming up to 500-1200 DEG C with certain heating rate, keep 1-10h.After calcining terminates, natural cooling, takes out sample
Product, reclaim catalyst through pickling, and deionized water rinses, after being dried, as described class Graphene sample.Plant base class Graphene
Electrical conductivity 180～370s/cm, specific surface area 420～760m2/ g, thickness 1-3nm.
Beneficial effect:
1. first plant base raw material is liquefied pretreatment.Plant base raw material reduces the crystallization of Plant fiber by liquefaction process
Degree, obtains oligosaccharide and aldehydes matter, reduces graphited activation energy, improves graphitization conversion ratio.And liquefaction technology equipment
Realize industrialization, acquisition can prepare the raw material of Graphene on a large scale.
2. catalyzed graphitization prepares grapheme material.Load Fe-series catalyst, in spontaneous pressure, can obviously reduce graphitization
Temperature, improves Graphene yield.Electrical conductivity 370s/cm of plant base class Graphene, specific surface area 760m2/ g, thickness 1-3nm.
Brief description
Fig. 1 is the embodiment of the present invention 1 plant Graphene electron microscope.
Fig. 2 is the xrd figure of embodiment 1.
Fig. 3 is the atomic force microscopy figure of embodiment 1.
Fig. 4 is the schematic diagram of spontaneous pressure reactor.
1 is resistance furnace, and 2 is thermocouple, and 3 is resistance wire, and 4 is electrically heated rod, and 5 is rustless steel hermetically sealed can, and 6 is blow vent.
Specific embodiment
The present invention is as follows to the method for testing of prepared plant base class grapheme material performance:
(1) specific area measuring: using the mensure to nitrogen adsorption isotherm for the activated carbon under the conditions of liquid nitrogen, public according to bet
Formula calculates specific surface area.
(2) surface topography is using projection Electronic Speculum (tem) and atomic force microscope (afm) test.
(3) conductance measurement: szt-c type four Probe test station measures.
The preparation method of plant base class Graphene, comprises the steps:
The first step, plant is liquefied: the plant material of drying and phenol is liquefied, filters and obtain after removing inorganic impurity
Bio oil.Plant material is converted into by bio oil by liquefaction, composition is mainly oligosaccharide and aldehydes matter.This step can be joined
Kao Wangyuan garden, Ye Lei, Shen Huyan, etc. Caulis Zizaniae caduciflorae abandoned biomass Liquefaction Products in Phenol and its product resin prepare adhesive [j]. and wide
State chemical industry, 2014, (23).；Li Gaiyun, Zhu Xianchao, Zou Xianwu, etc. the quick Liquefaction Products in Phenol of microwave-assisted poplar and Characterization of The Products
[j]. forest-science, 2014, (11) .doi:doi:10.11707/j.1001-7488.20141116.；Sun Fengwen, Li little Ke.
Bamboo wood Liquefaction Products in Phenol and adhesive preparation technology [j]. chemistry of forest product and industry, 2007,27 (6): 65-70.doi:doi:
10.3321/j.issn:0253-2417.2007.06.014.；Take off refined person of outstanding talent, Zhang Qiuhui, Li Jianzhang. Lignum seu Ramulus Cunninghamiae Lanceolatae Liquefaction Products in Phenol thing synthesizes
The research [j] of thermoset phenolic resin. biomass Chemical Engineering, 2007,41 (5): 9-12.doi:doi:10.3969/
j.issn.1673-5854.2007.05.003.；Qin Tefu, Luo Bei, Li Gaiyun. the Liquefaction Products in Phenol of artificial forest wood and resinification
Research. the preparation of liquefied wood base phenolic resin and performance characterization [j]. timber industry, 2006,20 (5): 8-10.doi:doi:
10.3969/j.issn.1001-8654.2006.05.003.；Ma Xiaojun, Zhao Guangjie. it is fine that Wood Liquefaction Products in Phenol product prepares carbon
The Primary Study [j] of dimension. chemistry of forest product and industry, 2007,27 (2): 29-32.doi:doi:10.3321/j.issn:0253-
2417.2007.02.007. the method described in.
Second step, bio oil is mixed with catalyst: with iron series element nitrate as catalyst, with bio oil according to mass ratio
(0.1～1.0) 1.0 is mixed.
3rd step, seals pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is less than anti-
Answer body amass 1/3, carry out airtight pretreatment.
4th step, calcining: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to certain heating rate
500-1200 DEG C, keep 1-10h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, use deionization
Water rinses, after being dried, as described class Graphene sample.Electrical conductivity 370s/cm of plant base class Graphene, specific surface area
760m2/ g, thickness 1-3nm.
Plant material described in the first step includes wood flour, bamboo scraps, the agricultural-forestry biomass raw material such as straw, needs drying and processing.
Bio oil described in the first step need to remove solid impurity through filtering off.
In second step, iron series element includes ferrum, nickel, cobalt.
In second step, iron series element nitrate is at the uniform velocity stirred when being mixed with bio oil.
Described spontaneous pressure reaction unit is outer layer is resistance furnace 1, sets rustless steel hermetically sealed can 5, resistance furnace 1 in resistance furnace 1
Inside it is provided with resistance wire 3, spontaneous pressure reactor is heated by electrically heated rod 4, monitors temperature, resistance furnace 1 by the interior thermocouple 2 setting
It is additionally provided with blow vent 6.
Embodiment 1
(1) plant liquefaction: the bamboo scraps of drying and phenol are liquefied, obtains bio oil through filtering off except inorganic impurity.
(2) bio oil is mixed with catalyst: with nickel nitrate as catalyst, carries out according to mass ratio 0.1 1.0 with bio oil
Mixing.
(3) seal pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is reactor volume
1/3, carry out airtight pretreatment.
(4) calcine: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to 500 with certain heating rate
DEG C, keep 1h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, deionized water rinses, be dried
Afterwards, as described class Graphene sample.Electrical conductivity 180s/cm of plant base class Graphene, specific surface area 420m2/ g, thickness 1-
3nm.
Embodiment 2
(1) plant liquefaction: the bamboo scraps of drying and phenol are liquefied, obtains bio oil through filtering off except inorganic impurity.
(2) bio oil is mixed with catalyst: with nickel nitrate as catalyst, carries out according to mass ratio 1.0 1.0 with bio oil
Mixing.
(3) seal pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is reactor volume
1/3, carry out airtight pretreatment.
(4) calcine: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to 1200 with certain heating rate
DEG C, keep 10h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, deionized water rinses, do
After dry, as described class Graphene sample.Electrical conductivity 327s/cm of plant base class Graphene, specific surface area 590m2/ g, thickness
1-3nm.
Embodiment 3
(1) plant liquefaction: the bamboo scraps of drying and phenol are liquefied, obtains bio oil through filtering off except inorganic impurity.
(2) bio oil is mixed with catalyst: with nickel nitrate as catalyst, carries out according to mass ratio 0.7 1.0 with bio oil
Mixing.
(3) seal pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is reactor volume
1/3, carry out airtight pretreatment.
(4) calcine: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to 1100 with certain heating rate
DEG C, keep 10h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, deionized water rinses, do
After dry, as described class Graphene sample.Electrical conductivity 370s/cm of plant base class Graphene, specific surface area 760m2/ g, thickness
1-3nm.
Embodiment 4
(1) plant liquefaction: the bamboo scraps of drying and phenol are liquefied, obtains bio oil through filtering off except inorganic impurity.
(2) bio oil is mixed with catalyst: with nickel nitrate as catalyst, carries out according to mass ratio 0.7 1.0 with bio oil
Mixing.
(3) seal pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is reactor volume
1/3, carry out airtight pretreatment.
(4) calcine: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to 1200 with certain heating rate
DEG C, keep 10h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, deionized water rinses, do
After dry, as described class Graphene sample.Electrical conductivity 365s/cm of plant base class Graphene, specific surface area 730m2/ g, thickness
1-3nm.
Embodiment 5
(1) plant liquefaction: the bamboo scraps of drying and phenol are liquefied, obtains bio oil through filtering off except inorganic impurity.
(2) bio oil is mixed with catalyst: with iron series element nitrate as catalyst, with bio oil according to mass ratio 1.0
0.7 is mixed.
(3) seal pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is reactor volume
1/3, carry out airtight pretreatment.
(4) calcine: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, is warming up to 1200 with certain heating rate
DEG C, keep 5h.After calcining terminates, natural cooling, takes out sample, reclaims catalyst through pickling, deionized water rinses, be dried
Afterwards, as described class Graphene sample.Electrical conductivity 355s/cm of plant base class Graphene, specific surface area 718m2/ g, thickness 1-
3nm.
Embodiment 6
Bamboo scraps in embodiment 3 are changed to cedar sawdust, remaining, with embodiment 3, obtains the electrical conductivity of plant base class Graphene
369s/cm, specific surface area 751m2/ g, thickness 1-3nm.
Embodiment 7
Bamboo scraps raw material in embodiment 3 is changed to coconut husk, remaining, with embodiment 3, obtains the conductance of plant base class Graphene
Rate 325s/cm, specific surface area 728m2/ g, thickness 1-3nm.
Embodiment 8
Nickel nitrate in embodiment 3 is changed to ferric nitrate, remaining, with embodiment 3, obtains the conductance of plant base class Graphene
Rate 285s/cm, specific surface area 672m2/ g, thickness 1-3nm.
Embodiment 9
Nickel nitrate in embodiment 3 is changed to cobalt nitrate, remaining, with embodiment 3, obtains the conductance of plant base class Graphene
Rate 370s/cm, specific surface area 760m2/ g, thickness 1-3nm.
Claims (6)
1. the preparation method of plant base class Graphene is it is characterised in that comprise the steps:
The first step, plant is liquefied: agricultural-forestry biomass raw material and the phenol of drying is liquefied, filters and obtain after removing inorganic impurity
To bio oil；
Second step, bio oil is mixed with catalyst: with iron series element nitrate as catalyst, catalyst and bio oil are according to quality
Mixed than (0.1～1.0) 1.0；
3rd step, seals pretreatment: a certain amount of said mixture is placed in spontaneous pressure reactor, inventory is less than reactor
The 1/3 of volume, carries out airtight pretreatment；
4th step, calcining: the spontaneous pressure reactor that will be equipped with material is placed in high temperature furnace, heat up calcining, after calcining terminates, from
So cool down, take out sample, reclaim catalyst through pickling, deionized water rinses, after being dried, as described plant base class Graphene
Sample, electrical conductivity 370s/cm of plant base class Graphene, specific surface area 760m2/ g, thickness 1-3nm；Calcining heat be 500～
1200 DEG C, calcination time 1-10h.
2. the preparation method of plant base class Graphene as claimed in claim 1 is it is characterised in that the plant described in the first step is former
Material includes wood flour, bamboo scraps, straw, dries and uses.
3. the preparation method of plant base class Graphene as claimed in claim 1 is it is characterised in that bio oil described in the first step
Remove solid impurity through filtering off.
4. the preparation method of plant base class Graphene as claimed in claim 1 is it is characterised in that iron series element bag in second step
Include ferrum, nickel, cobalt.
5. the preparation method of plant base class Graphene as claimed in claim 1 is it is characterised in that iron series element nitre in second step
At the uniform velocity stirred when hydrochlorate is mixed with bio oil.
6. the preparation method of the arbitrary described plant base class Graphene of claim 1 ~ 5 obtains Graphene is it is characterised in that conductance
Rate 180～370s/cm, specific surface area 420～760m2/ g, thickness 1-3nm.
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