CN106495132A - The method that lignin prepares Graphene - Google Patents
The method that lignin prepares Graphene Download PDFInfo
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- CN106495132A CN106495132A CN201610852057.3A CN201610852057A CN106495132A CN 106495132 A CN106495132 A CN 106495132A CN 201610852057 A CN201610852057 A CN 201610852057A CN 106495132 A CN106495132 A CN 106495132A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention discloses a kind of method that lignin prepares Graphene, belongs to technological field of biochemistry.Purification of the present invention first from lignin raw material is started with, and has obtained highly purified lignin；On this basis, by techniques such as oxidation, carbonization, graphitizations, high-quality Graphene is obtained.Process is simple, easy to spread.Lignin purge process, using special ferment treatment, soft under normal temperature condition removes isolating protein and starch；Digest under room temperature, while it also avoid the side reaction of lignin active group, increased the integrity of lignin macromole.The present invention through special steam explosion processing procedure, using low temperature, environment under high pressure；Condition of high voltage ensure that ethanol to the effective infiltration between raw material cell wall, effectively to go the removal of impurity, low temperature and inert environments greatly to reduce the side reactions such as the oxidation of lignin active group, decomposition, dehydration, esterification；Obvious to the integrity and product quality effect that guarantee lignin macromole, it is to prepare high-quality Graphene to lay a good foundation.
Description
Technical field
The present invention relates to technological field of biochemistry, the method that more particularly to a kind of lignin prepares Graphene.
Background technology
Graphene（Graphene）It is the only one layer of atomic thickness for being stripped out from graphite material, being made up of carbon atom
Two dimensional crystal.As the thickness that has now been found that is most thin, the most strong a kind of novel nano material of maximum intensity, electrical and thermal conductivity performance
Material, Graphene are referred to as " king of new material ".Preferably graphene-structured is plane hexagonal lattice, can be regarded as one layer of quilt
The graphitic molecules of stripping, each carbon atom are sp2 hydridization, and contribute the big π keys that electronically form on a remaining p track, π electricity
Son can be moved freely, and give Graphene good electric conductivity.Two-dimensional graphene structure can be regarded as forming all sp2 hydridization
The basic component units of carbonaceous material.
The synthetic method of Graphene mainly has two kinds at present：Mechanical means and chemical method.Mechanical means include micromechanics
The method of partition method, epitaxy method and heating SiC；Chemical method is chemical reduction method and chemical dissociation method.Main raw material(s)
For non-renewable graphite ore.
Lignin is the aromatic compound containing benzene ring structure being widely present in nature, is that content is only second to fiber
Element and occupy organic carbon resource of deputy natural reproducible, be one of main composition of plant cell wall.According to surveying and determination, wooden
In element, the mass fraction of carbon atom is 60% or so.And the basic structural unit of Graphene is exactly most stable of in organic material
Benzene hexatomic ring.In the high similarity of chemical constitution, high carbon element content, nature, reserves are huge and there is the spies such as recyclability
Point, determines that lignin will likely become and prepares one of of paramount importance raw material of Graphene.
105439135 A of Chinese patent CN disclose a kind of method that utilization lignin prepares Graphene；Chinese patent
105217607 A of CN disclose a kind of graphene preparation method based on lignin.Not to using in above-mentioned binomial invention
Lignin raw material carry out purification process, thus the quality of graphene for finally preparing is not high, have impact on economic worth and makes
With value.
Content of the invention
In order to make up the deficiencies in the prior art, the invention provides a kind of process is simple, easy to spread, economic worth are high
The method that lignin prepares Graphene.
The technical scheme is that：
A kind of method that lignin prepares Graphene, including step：
1）The lignin crude product obtained by straw, forest or its side-product is placed in digester, adds 1-20 times of lignin crude product
Water, be passed through noble gases into digester, after lignin crude product is stirred evenly, add compound protease, interval 1-3 minute, lead to
Enter noble gases, digest 10-80 minutes；Normal temperature type α-amylase is subsequently added, 10-80 minutes are digested；Then pass to steam liter
Temperature is incubated 2-20 minutes, the activity of inactivator to 60-70 DEG C；The compound protease is by the alkaline egg for possessing endopeptidase activity
White enzyme and the E.C. 3.4.21.64 for possessing peptide ending enzyme activity are constituted；The normal temperature type α-amylase is by microwave induced gained variation lichens bud
Spore bacillus secretes gained α-amylase, and the preference temperature of the normal temperature type α-amylase is 22-35 DEG C；
2）The mass fraction for adding ethanol to ethanol after enzyme denaturing is 30-80%, is then intermittently passed through water vapour into digester
And noble gases, to maintain temperature 80-130 DEG C, pressure as 0.5-2MPa；Heat-insulation pressure keeping was spurted after 60-200 minutes；
3）Step 2）Gained spurts slurry solid-liquid separation, obtains filtering residue and filtrate；
4）Filtrate removes particulate matter, then evaporation and concentration through further clarification filtration, after gained solids washed with water drying
Obtain pure lignin；
5）Pure lignin is placed in oxidizing reactor, it is 1-20% to mass fraction to add oxidant, in temperature 30-200
DEG C, be stirred continuously under pressure 0.2-5 MPa, heat-insulation pressure keeping 20-180 minutes；
6）Centrifugation, solid are oxidative lignin, wash the oxidative lignin with water；
7）Oxidative lignin's drying, crushing, obtain oxidative lignin's finished product；
8）Step 7）Gained oxidative lignin finished product carbonization 1-5 minutes in 200-600 DEG C of low-temperature carbonization furnace, then in 1000-
2000 DEG C of high temperature carbonization furnace carbonization 0.2-5 minutes, then the graphitization processing 3-30 second in 2200-3800 DEG C of graphitizing furnace, obtain
Graphite oxide；
9）By step 8）Gained graphite oxide and water are according to 1：The mass ratio mixing of 1-9, is placed in microwave generator, arranges microwave
Power 400-2000W, frequency 500-3000MHz, strong stirring to solution are clarified；
10）To in clear liquor, the mass concentration of hydrazine to hydrazine is added to reach 50-800ppm, back flow reaction 10-50 at 50-150 DEG C
Hour, obtain black particle shape precipitation；Through filtering, drying, Graphene finished product is obtained.
Preferably, step 1）In, the obtaining step of the microwave induced gained variation Bacillus licheniformis is concrete
For：The culture fluid of Bacillus licheniformis is placed in microwave generator, setting microwave power is 850-950W, pulse frequency is
2300MHz, microwave treatment 20s cool down 20s, reciprocal 25-35 time according to this；Culture fluid after by microwave treatment is coated on solid training
On foster base, cultivate 1-2 days under the conditions of 30 DEG C, by the high ground of alpha-amylase activity under four plants of room temperature of screening in the bacterium colony for surviving
The dissociant of clothing bacillus cereuss.
Further, the dissociant amplification culture of alpha-amylase activity highest Bacillus licheniformis under room temperature is selected,
So as to obtain the normal temperature type α-amylase.The normal temperature type α-amylase obtained using the method, at normal temperatures can efficient enzyme
Solution starch, had both reduced energy consumption, turn avoid the generation of side reaction.
Preferably, possess the alkaline protease of endopeptidase activity in the compound protease and possess peptide ending enzyme work
Property E.C. 3.4.21.64 ratio be 1:1-3.
Preferably, the addition of the compound protease meets every kilogram of butt lignin crude product 400-800U,
The addition of the normal temperature type α-amylase meets every kilogram of butt lignin crude product 300-700U.
Preferably, step 3）In, the solid-liquid separation is filter pressing separation, shove separation or centrifugation.
Preferably, step 5）In, the oxidant is hydrogen peroxide, oxygen, the one kind or several in chlorine dioxide
Kind.
Preferably, step 7）In, the drying is that spray drying, hot air drying, fluid bed drying or freezing are dry
Dry.
Beneficial effects of the present invention are：
Purification of the present invention first from lignin raw material is started with, and has obtained highly purified lignin；On this basis, by oxygen
The techniques such as change, carbonization, graphitization, have obtained the Graphene of high-quality.Process is simple, easy to spread and implement.
The purge process of lignin, using special ferment treatment, mildly removes in lignin crude product under normal temperature condition
Protein and starch；Digest under room temperature, while it also avoid the side reaction of lignin active group, increased lignin macromole
Integrity.
In addition, the present invention is through special steam explosion processing procedure, using low temperature, high pressure（Noble gases are provided）Environment；High
Press strip part ensure that ethanol to the effective infiltration between raw material cell wall, effectively to remove the removal of impurity, low temperature and inert environments greatly
The side reactions such as the oxidation of lignin active group, decomposition, dehydration, esterification are reduced, to guaranteeing the integrity of lignin macromole
And product quality effect is substantially.
The present invention has successfully obtained high-purity lignin using measures such as organic solvent, biological enzymolysis, is to prepare high-quality stone
Black alkene is laid a good foundation.
Specific embodiment
Lignin crude product is prepared by steam explosion technology by straw, forest or its side-product and belongs to prior art, the present invention is not
Ao Shu again.
Embodiment 1
A kind of method that lignin prepares Graphene, including step：
1）The lignin crude product obtained by steam explosion isolation technics by wheat stalk is placed in digester, adds lignin crude product 10
Water again, is passed through nitrogen into digester, after lignin crude product is stirred evenly, adds compound protease（500U/Kg butt lignins
Crude product）, intermittently 1 minute, nitrogen is passed through, is digested 40 minutes；It is subsequently added normal temperature type α-amylase（400U/Kg butt lignins
Crude product）, digest 30 minutes；Then pass to steam and be warming up to 65 DEG C, be incubated 10 minutes, the activity of inactivator.
Wherein, compound protease by the alkaline protease for possessing endopeptidase activity and possesses the active E.C. 3.4.21.64 of peptide ending enzyme
Composition, the alkaline protease for possessing endopeptidase activity in compound protease and the ratio for possessing the active E.C. 3.4.21.64 of peptide ending enzyme are
1: 1；The compound protease can effectively hydrolyzing protein at normal temperatures.
Normal temperature type α-amylase is by microwave induced gained variation Bacillus licheniformis secretion gained α-amylase；Microwave induced
The obtaining step of gained variation Bacillus licheniformis is specially：The culture fluid of Bacillus licheniformis is placed in microwave generator, if
Microwave power is put for 900W, pulse frequency is 2300MHz, microwave treatment 20s, cool down 20s, reciprocal 30 times according to this；At microwave
Culture fluid after reason is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, screens four plants by the bacterium colony for surviving
The dissociant of the high Bacillus licheniformis of alpha-amylase activity under room temperature.Select alpha-amylase activity highest lichens under room temperature
The dissociant amplification culture of bacillus cereuss, so that obtain normal temperature type α-amylase；Normal temperature type α-amylase is in 22-35 DEG C of temperature
Under expeditiously hydrolysis starch, it is not necessary to the thermal-stable α-amylase as adopting mostly at present needs high temperature（80-90℃）Condition, because
And reduce energy consumption and also reduce the requirement to equipment, while greatly reduce the generation of side reaction.
Herein can be mildly by protein, Starch Hydrolysis into the peptides of small molecule, aminoacid, maltose, Portugal with enzyme process
Grape sugar etc., so as to successful deproteination matter and starch.
2）The mass fraction for adding 95% ethanol to ethanol after enzyme denaturing is 55%, is then intermittently passed through into digester
Water vapour and nitrogen, to maintain 120 DEG C of temperature, pressure as 0.8MPa；Heat-insulation pressure keeping was spurted after 80 minutes.Vapourss containing ethanol
Ethanol recovery system is entered by cover mouth all.
3）Step 2）Gained spurts slurry by filter pressing solid-liquid separation, obtains filtering residue and filtrate.
4）Filtrate removes particulate matter, then evaporation and concentration through further clarification filtration, gained solids washed with water 2 times,
Pure lignin is obtained after drying.
For guaranteeing high-quality Graphene, raw material wood element must be highly purified, step 1）-4）It is straw steam explosion institute
The purge process of lignin crude product is obtained, through the present invention after purification, the high purity 99.6% of lignin is prepared by following steps
High-quality Graphene is laid a good foundation.
5）Pure lignin is placed in oxidizing reactor, it is 7% to mass fraction to add hydrogen peroxide, in temperature 90
DEG C, be stirred continuously under 1.5 MPa of pressure, heat-insulation pressure keeping 80 minutes.
6）Centrifugation, solid are oxidative lignin, wash oxidative lignin with water.
7）Oxidative lignin is spray-dried（Temperature is less than 120 DEG C）, crush, obtain oxidative lignin's finished product.
8）Step 7）Gained oxidative lignin finished product carbonization 3 minutes in 300 DEG C of low-temperature carbonization furnaces, then high at 1500 DEG C
Warm retort carbonization 1 minute, then graphitization processing 10 seconds in 3000 DEG C of graphitizing furnaces, obtain graphite oxide.
Certainly oxidative lignin's carbonization and graphitizing process are carried out in inert gas environment, charging aperture and discharging opening
Sealed with nitrogen.
9）By step 8）Gained graphite oxide and water are according to 2：3 mass ratio mixing, is placed in microwave generator, arranges micro-
Wave power 1200W, frequency 1500MHz, strong stirring to solution are clarified.
10）To in clear liquor, the mass concentration of hydrazine to hydrazine is added to reach 100ppm, back flow reaction 15 hours, obtain at 90 DEG C
Black particle shape is precipitated；Through filtering, drying, Graphene finished product is obtained.After measured, the graphene film thickness that the present embodiment is prepared
Spend for 0.53nm.
Embodiment 2
A kind of method that lignin prepares Graphene, including step：
1）By poplar（Poplar wood）The lignin crude product obtained by steam explosion isolation technics is placed in digester, adds lignin
The water that 12 times of crude product, is passed through nitrogen into digester, after lignin crude product is stirred evenly, adds compound protease（550U/Kg butts
Lignin crude product）, intermittently 2 minutes, nitrogen is passed through, is digested 35 minutes；It is subsequently added normal temperature type α-amylase（450U/Kg butts
Lignin crude product）, digest 25 minutes；Then pass to steam and be warming up to 62 DEG C, be incubated 15 minutes, the activity of inactivator.
Wherein, compound protease by the alkaline protease for possessing endopeptidase activity and possesses the active E.C. 3.4.21.64 of peptide ending enzyme
Composition, the alkaline protease for possessing endopeptidase activity in compound protease and the ratio for possessing the active E.C. 3.4.21.64 of peptide ending enzyme are
1: 2；The compound protease can effectively hydrolyzing protein at normal temperatures.
Normal temperature type α-amylase is by microwave induced gained variation Bacillus licheniformis secretion gained α-amylase；Microwave induced
The obtaining step of gained variation Bacillus licheniformis is specially：The culture fluid of Bacillus licheniformis is placed in microwave generator, if
Microwave power is put for 900W, pulse frequency is 2300MHz, microwave treatment 20s, cool down 20s, reciprocal 30 times according to this；At microwave
Culture fluid after reason is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, screens four plants by the bacterium colony for surviving
The dissociant of the high Bacillus licheniformis of alpha-amylase activity under room temperature.Select alpha-amylase activity highest lichens under room temperature
The dissociant amplification culture of bacillus cereuss, so that obtain normal temperature type α-amylase；Normal temperature type α-amylase is in 22-35 DEG C of temperature
Under expeditiously hydrolysis starch, it is not necessary to the thermal-stable α-amylase as adopting mostly at present needs high temperature（80-90℃）Condition, because
And reduce energy consumption and also reduce the requirement to equipment, while greatly reduce the generation of side reaction.
Herein can be mildly by protein, Starch Hydrolysis into the peptides of small molecule, aminoacid, maltose, Portugal with enzyme process
Grape sugar etc., so as to successful deproteination matter and starch.
2）The mass fraction for adding 95% ethanol to ethanol after enzyme denaturing is 60%, is then intermittently passed through into digester
Water vapour and nitrogen, to maintain 125 DEG C of temperature, pressure as 1MPa；Heat-insulation pressure keeping was spurted after 70 minutes.
3）Step 2）Gained spurts slurry shove solid-liquid separation, obtains filtering residue and filtrate.
4）Filtrate removes particulate matter, then evaporation and concentration through further clarification filtration, and gained solids washed with water is simultaneously done
Pure lignin is obtained after dry.
For guaranteeing high-quality Graphene, raw material wood element must be highly purified, step 1）-4）It is steam explosion gained wood
The purge process of quality crude product；Through the present invention after purification, the high purity 99.5% of lignin, is that following steps prepare high-quality
Graphene is laid a good foundation.
5）Pure lignin is placed in oxidizing reactor, add oxygen to mass fraction be 5%, 100 DEG C of temperature,
It is stirred continuously under pressure 2MPa, heat-insulation pressure keeping 70 minutes.
6）Centrifugation, solid are oxidative lignin, wash oxidative lignin with water.
7）Oxidative lignin is through hot air drying（Temperature is less than 120 DEG C）, crush, obtain oxidative lignin's finished product.
8）Step 7）Gained oxidative lignin finished product carbonization 4 minutes in 400 DEG C of low-temperature carbonization furnaces, then high at 1800 DEG C
Warm retort carbonization 2 minutes, then graphitization processing 15 seconds in 3100 DEG C of graphitizing furnaces, obtain graphite oxide.
Certainly oxidative lignin's carbonization and graphitizing process are carried out in inert gas environment, charging aperture and discharging opening
Sealed with nitrogen.
9）By step 8）Gained graphite oxide and water are according to 1：1 mass ratio mixing, is placed in microwave generator, arranges micro-
Wave power 1400W, frequency 1800MHz, strong stirring to solution are clarified.
10）To in clear liquor, add the mass concentration of hydrazine to hydrazine to reach 300ppm, back flow reaction 20 hours at 110 DEG C,
Obtain black particle shape precipitation；Through filtering, drying, Graphene finished product is obtained.After measured, the graphene sheet layer that the present embodiment is prepared
Thickness is 0.47nm.
Claims (8)
1. a kind of method that lignin prepares Graphene, it is characterised in that including step：
1）The lignin crude product obtained by straw, forest or its side-product is placed in digester, adds 1-20 times of lignin crude product
Water, be passed through noble gases into digester, after lignin crude product is stirred evenly, add compound protease, interval 1-3 minute, lead to
Enter noble gases, digest 10-80 minutes；Normal temperature type α-amylase is subsequently added, 10-80 minutes are digested；Then pass to steam liter
Temperature is incubated 2-20 minutes, the activity of inactivator to 60-70 DEG C；The compound protease is by the alkaline egg for possessing endopeptidase activity
White enzyme and the E.C. 3.4.21.64 for possessing peptide ending enzyme activity are constituted；The normal temperature type α-amylase is by microwave induced gained variation lichens bud
Spore bacillus secretes gained α-amylase, and the preference temperature of the normal temperature type α-amylase is 22-35 DEG C；
2）The mass fraction for adding ethanol to ethanol after enzyme denaturing is 30-80%, is then intermittently passed through water vapour into digester
And noble gases, to maintain temperature 80-130 DEG C, pressure as 0.5-2MPa；Heat-insulation pressure keeping was spurted after 60-200 minutes；
3）Step 2）Gained spurts slurry solid-liquid separation, obtains filtering residue and filtrate；
4）Filtrate removes particulate matter, then evaporation and concentration through further clarification filtration, after gained solids washed with water drying
Obtain pure lignin；
5）Pure lignin is placed in oxidizing reactor, it is 1-20% to mass fraction to add oxidant, in temperature 30-200
DEG C, be stirred continuously under pressure 0.2-5 MPa, heat-insulation pressure keeping 20-180 minutes；
6）Centrifugation, solid are oxidative lignin, wash the oxidative lignin with water；
7）Oxidative lignin's drying, crushing, obtain oxidative lignin's finished product；
8）Step 7）Gained oxidative lignin finished product carbonization 1-5 minutes in 200-600 DEG C of low-temperature carbonization furnace, then in 1000-
2000 DEG C of high temperature carbonization furnace carbonization 0.2-5 minutes, then the graphitization processing 3-30 second in 2200-3800 DEG C of graphitizing furnace, obtain
Graphite oxide；
9）By step 8）Gained graphite oxide and water are according to 1：The mass ratio mixing of 1-9, is placed in microwave generator, arranges microwave
Power 400-2000W, frequency 500-3000MHz, strong stirring to solution are clarified；
10）To in clear liquor, the mass concentration of hydrazine to hydrazine is added to reach 50-800ppm, back flow reaction 10-50 at 50-150 DEG C
Hour, obtain black particle shape precipitation；Through filtering, drying, Graphene finished product is obtained.
2. the method that lignin as claimed in claim 1 prepares Graphene, it is characterised in that step 1）In, described microwave induced
The obtaining step of gained variation Bacillus licheniformis is specially：The culture fluid of Bacillus licheniformis is placed in microwave generator, if
Microwave power is put for 850-950W, pulse frequency is 2300MHz, and microwave treatment 20s cools down 20s, reciprocal 25-35 time according to this；Will
Culture fluid after microwave treatment is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, is sieved by the bacterium colony for surviving
Select the dissociant of the high Bacillus licheniformis of alpha-amylase activity under four plants of room temperature.
3. the method that lignin as claimed in claim 2 prepares Graphene, it is characterised in that：Select alpha-amylase activity under room temperature
The dissociant amplification culture of highest Bacillus licheniformis, so that obtain the normal temperature type α-amylase.
4. the method that lignin as claimed in claim 1 or 2 prepares Graphene, it is characterised in that：Have in the compound protease
The alkaline protease of standby endopeptidase activity is 1 with the ratio of the E.C. 3.4.21.64 for possessing peptide ending enzyme activity:1-3.
5. the method that lignin as claimed in claim 1 prepares Graphene, it is characterised in that：The addition of the compound protease
Meet every kilogram of butt lignin crude product 400-800U, it is wooden that the addition of the normal temperature type α-amylase meets every kilogram of butt
Plain crude product 300-700U.
6. the method that lignin as claimed in claim 1 prepares Graphene, it is characterised in that：Step 3）In, the solid-liquid separation
Separate or centrifugation for filter pressing separation, shove.
7. the method that lignin as claimed in claim 1 prepares Graphene, it is characterised in that：Step 5）In, the oxidant is
One or more in hydrogen peroxide, oxygen, chlorine dioxide.
8. the method that lignin as claimed in claim 1 prepares Graphene, it is characterised in that：Step 7）In, the drying is spray
Mist drying, hot air drying, fluid bed drying or lyophilization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108298525A (en) * | 2018-03-19 | 2018-07-20 | 广西科学院 | A kind of graphene microcrystal and preparation method thereof |
| CN109205603A (en) * | 2017-06-30 | 2019-01-15 | 中国科学院宁波材料技术与工程研究所 | The dispersing method of graphene |
| CN109292760A (en) * | 2018-11-30 | 2019-02-01 | 长江师范学院 | A method of preparing graphene |
| KR20200020175A (en) * | 2018-08-16 | 2020-02-26 | 울산과학기술원 | A method for producing graphene and hydrogen using biological shells and alcohols |
| CN111675214A (en) * | 2020-06-29 | 2020-09-18 | 中合天成科技发展(北京)有限公司 | Preparation system of palm-based artificial graphite |
| CN111892048A (en) * | 2020-06-29 | 2020-11-06 | 中合天成科技发展(北京)有限公司 | Palm-based artificial graphite and preparation method thereof |
| CN113880078A (en) * | 2021-11-03 | 2022-01-04 | 上海爱普食品工业有限公司 | Preparation method of biomass graphene |
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| CN104292192A (en) * | 2014-08-29 | 2015-01-21 | 济南米铎碳新能源科技有限公司 | Combined production method of high added value product during furfural production |
| CN105439135A (en) * | 2015-12-30 | 2016-03-30 | 成都新柯力化工科技有限公司 | Method for preparing graphene from lignin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292192A (en) * | 2014-08-29 | 2015-01-21 | 济南米铎碳新能源科技有限公司 | Combined production method of high added value product during furfural production |
| CN105439135A (en) * | 2015-12-30 | 2016-03-30 | 成都新柯力化工科技有限公司 | Method for preparing graphene from lignin |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205603A (en) * | 2017-06-30 | 2019-01-15 | 中国科学院宁波材料技术与工程研究所 | The dispersing method of graphene |
| CN108298525A (en) * | 2018-03-19 | 2018-07-20 | 广西科学院 | A kind of graphene microcrystal and preparation method thereof |
| KR20200020175A (en) * | 2018-08-16 | 2020-02-26 | 울산과학기술원 | A method for producing graphene and hydrogen using biological shells and alcohols |
| KR102096865B1 (en) | 2018-08-16 | 2020-04-03 | 울산과학기술원 | A method for producing graphene and hydrogen using biological shells and alcohols |
| CN109292760A (en) * | 2018-11-30 | 2019-02-01 | 长江师范学院 | A method of preparing graphene |
| CN111675214A (en) * | 2020-06-29 | 2020-09-18 | 中合天成科技发展(北京)有限公司 | Preparation system of palm-based artificial graphite |
| CN111892048A (en) * | 2020-06-29 | 2020-11-06 | 中合天成科技发展(北京)有限公司 | Palm-based artificial graphite and preparation method thereof |
| CN113880078A (en) * | 2021-11-03 | 2022-01-04 | 上海爱普食品工业有限公司 | Preparation method of biomass graphene |
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