CN105439135B - A kind of method that utilization lignin prepares graphene - Google Patents
A kind of method that utilization lignin prepares graphene Download PDFInfo
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- CN105439135B CN105439135B CN201511007072.XA CN201511007072A CN105439135B CN 105439135 B CN105439135 B CN 105439135B CN 201511007072 A CN201511007072 A CN 201511007072A CN 105439135 B CN105439135 B CN 105439135B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of method that utilization lignin prepares graphene, methods described includes：A. it is 1 by lignin and aqueous slkali mixing solid-liquid volume ratio:5 10, heated solution temperature is to 70 100 DEG C, and the isothermal holding time is 13 hours；B. the material after alkali process filtered, wash and obtain solid pretreatment lignin is dried to obtain at 60 80 DEG C；C. catalyst will be added in the pretreatment lignin obtained by b step, is sufficiently mixed using high pressure homogenizer, non-homogeneous lignin is homogenized and is cracked, cracking carbon is homogenized with catalyst in acquisition higher-energy state；D. mixture is put into autoclave, is filled with inert gas, pressure is increased to 20 50MPa with 0.1 1MPa/s speed, 500 DEG C 800 DEG C are heated the mixture to, normal temperature and pressure is down to by processing, graphene is obtained.The present invention decomposes lignin using HTHP, obtains the carbon atom of high-energy, graphene is grown in the presence of catalyst, the above method not only reduces graphene preparation temperature, and preparation process is simple, economic and environment-friendly, is suitable for industrial production.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, more particularly to a kind of graphene preparation method.
Background technology
Grapheme material is successfully prepared within 2004, has triggered the upsurge of new ripple carbon materials research since then.Graphene
The plane carbon nanomaterial being made up of one layer of carbon atom, is to be currently known most thin two-dimensional material, and its thickness is only
0.335nm, it is made up of the lattice of hexagon.Connected between carbon atom in graphene by σ keys, impart graphene extremely excellent
Different mechanical property and structural rigidity.Moreover, in graphene, each carbon atom has the p electronics of a non-bonding, these p
Electronics can be moved freely in crystal, and movement velocity is up to the 1/300 of the light velocity, impart the good electric conductivity of graphene.
In optics aspect, graphene is almost fully transparent, only absorbs 2.3% light.By these peculiar mechanics, optics and electricity
Property is learned, graphene possesses very vast potential for future development.
In order to allow outstanding grapheme material to realize industrialized production and application, must just develop one kind can give birth on a large scale
Production and the number of plies and the controllable preparation method of size.The preparation method of current graphene has mechanical stripping method, epitaxial growth method, oxidation
Reducing process, ultrasonic stripping method, organic synthesis method, solvent-thermal method, chemical vapour deposition technique etc..In these methods, in these sides
In method, mechanical stripping method and epitaxial growth method preparation efficiency are very low, it is difficult to meet large-scale needs.Though chemical vapour deposition technique
The continuous graphene film of large scale can so be obtained, it is adaptable to electronic device or transparent conductive film, can not but meet big rule
The demand of mould production.Oxidation-reduction method prepares the realization with low cost and easy of grapheme material powder, but can produce a large amount of
Waste liquid, severe contamination is caused to environment, the extensive industrialized development of graphene is limited.These methods are all with graphite ore
As former material, this mineral resources are not recyclable regeneratives, are unfavorable for the large-scale production of graphene.
Lignin is a kind of natural reproducible resource, there is many excellent properties, there is high in modern chemical industry
Potential using value.Its yield is huge, but application is extremely low.About 65% carbon from its chemical constituent analysis, lignin,
There is great potential in terms of preparing carbon material.
China Patent Publication No. 103466613A discloses a kind of method that graphene is prepared by raw material of lignin.The party
Method will be equipped with lignin first and the porcelain example boat of catalyst is put into hinge tube furnace, at the uniform velocity be passed through inert protective gas,
Sample is heated to from room temperature by target temperature with constant heating rate in stove simultaneously, and kept under target temperature, sample is treated
When product temperature degree is down to room temperature, sample is taken out, washs, be filtered by vacuum through deionized water, after low temperature drying, producing graphene.This
The preparation technology of invention is easy, and gained quality of graphene is excellent, and yield is considerable.However, this method is sintered using anaerobic, sintering
Temperature reaches 1500 DEG C, high to equipment requirement, and equipment prepares cost and improved, it is impossible to applied to large-scale production.
China Patent Publication No. 103935986A discloses a kind of side that graphene is prepared with biological carbon source material high yield
Method, comprises the following steps：It is added to after biological carbon source material is microwaved in acid solution, then through washing, drying process, obtains pre-
The biological carbon source material of processing；The biological carbon source material of pretreatment is mixed with catalyst, deposited in 600-1600 DEG C, protective gas
In lower calcining 1-12h, described graphene is obtained after cooling.This method significantly reduces production cost, realizes graphene
Large-scale industrial production.However, using some noble metal catalysts have been arrived in this method, not only cost is improved, preparation
Graphene area is small, and it is poor to crystallize, and is unfavorable for the industrialized development of graphene.
In summary, prepared now using lignin in the method for graphene is not had also without a kind of to production equipment
Particular/special requirement, is adapted to large-scale production, the preparation method of low production cost.
The content of the invention
In order to solve the deficiency and defect of the above method, the present invention develops the side that a kind of utilization lignin prepares graphene
Method, lignin is decomposed using HTHP, obtains the carbon atom of high-energy, graphene is grown in the presence of catalyst.This hair
The bright offer above method not only reduces graphene preparation temperature, and preparation process is simple, economic and environment-friendly, is suitable for work
Industry is produced.
The present invention provides a kind of method that utilization lignin prepares graphene, it is characterised in that methods described includes following
Step：
A. it is 1 by lignin and aqueous slkali mixing solid-liquid volume ratio:5-10, heated solution temperature to 70-100 DEG C,
The isothermal holding time is 1-3 hours；
B. the material after alkali process filtered, wash and obtain solid and liquid, solid is done at 60-80 DEG C
It is dry to obtain pre-processing lignin；
C. catalyst will be added in the pretreatment lignin obtained by b step, is sufficiently mixed using high pressure homogenizer, homogeneous
After machine up time pressure reaches that 20-100MPa, material are clashed by high-pressure homogeneous nozzle, collect the homogenizing valve for flowing to slit, make non-
Homogeneous lignin is homogenized and cracked, and cracking carbon is homogenized with catalyst in acquisition higher-energy state；
D. the mixture obtained in step c is put into autoclave, pours inert gas, increased with 0.1-1MPa/s speed
Sample is heated to 500 by mixture by plus-pressure with 30-60 DEG C/min fixation heating rate to 20-50MPa from room temperature
DEG C -800 DEG C, and 30-120min is kept at this temperature, normal temperature and pressure is down to by processing, graphene is obtained.
It is preferred that, the aqueous slkali is the aqueous solution of at least one of sodium hydroxide, potassium hydroxide, ammoniacal liquor.
It is preferred that, the aqueous slkali alkali charge is the 10-30% of the weight of lignin.
It is preferred that, the catalyst is at least one of iron powder, nickel powder, copper powder, nickel nitrate, iron oxide.
It is preferred that, the high pressure homogenizer operating pressure parameter is 80MPa.
It is preferred that, the inert gas is at least one of argon gas, helium, nitrogen.
Said one or multiple technical schemes in the embodiment of the present application, are at least imitated with following one or more technologies
Really：
1st, the present invention decomposes lignin using HTHP, obtains the carbon atom of high-energy, raw in the presence of catalyst
Long graphene.The present invention provides the above method and not only reduces graphene preparation temperature, and preparation process is simple.
2nd, the present invention is using common metal and metal ion compound as catalyst, and safety non-toxic is with low cost.
3rd, the present invention is using lignin as carbon source, and materials are extensive, advantageously reduce production cost, is conducive to raw in industry
Production.
Embodiment
By embodiment, the present invention is described in further detail, but this should not be interpreted as to the model of the present invention
Enclose and be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill knowledge
The various replacements or change made with customary means, should be included in the scope of the present invention.
Embodiment one
The present embodiment comprises the following steps：
1kg lignin is taken to be put into 10kg sodium hydroxide solutions, quality containing sodium hydroxide is in sodium hydroxide solution
0.1kg, heated solution temperature is to 70 DEG C, and the isothermal holding time is 1 hour, after next being handled through sodium hydroxide solution
Material is filtered, washs obtained solid matter dry 20 hours acquisition pretreatment lignin at 60 DEG C.Will pretreatment wood
12g iron powders are added in quality, high pressure homogenizer operating pressure is set to 20MPa, after material is clashed by high-pressure homogeneous nozzle,
Collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is homogenized with catalyst in acquisition
Higher-energy state, fully obtains the lignin and iron mixture of mixing pretreatment, the mixture of acquisition is put into autoclave, filled
Enter nitrogen, pressure is increased to 20MPa with 0.1MPa/s speed, by mixture with 30 DEG C/min fixation heating rate from room
Temperature is heated to 500 DEG C, and keeps 30min at 500 DEG C, and normal temperature and pressure is down to by processing, obtains graphene.After testing, it is real
The average thickness for applying the graphene sheet layer prepared in example one is 0.82 nm, and yield is 3.9%.
Embodiment two
The present embodiment comprises the following steps：
1kg lignin is taken to be put into 10kg sodium hydroxide solutions, quality containing sodium hydroxide is in sodium hydroxide solution
0.1kg, heated solution temperature is to 70 DEG C, and the isothermal holding time is 1 hour, after next being handled through sodium hydroxide solution
Material is filtered, washs obtained solid matter dry 20 hours acquisition pretreatment lignin at 60 DEG C.Will pretreatment wood
100g iron powders are added in quality, high pressure homogenizer operating pressure 20MPa are set to, material is clashed by high-pressure homogeneous nozzle
Afterwards, collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is in catalyst homogenizing and obtain
Higher-energy state is obtained, the lignin and iron mixture of mixing pretreatment is fully obtained, the mixture of acquisition is put into autoclave,
Be filled with nitrogen, pressure increased to 20MPa with 0.1MPa/s speed, by mixture with 30 DEG C/min fixation heating rate from
Room temperature is heated to 500 DEG C, and keeps 30min at 500 DEG C, and normal temperature and pressure is down to by processing, obtains graphene.After testing,
The average thickness of the graphene sheet layer prepared in embodiment two is 0.72 nm, and yield is 4.7%.
Embodiment three
The present embodiment comprises the following steps：
Take 1kg lignin to be put into 10kg potassium hydroxide solutions, be containing potassium hydroxide quality in potassium hydroxide solution
0.1kg, heated solution temperature is to 85 DEG C, and the isothermal holding time is 1 hour, after next being handled through potassium hydroxide solution
Material is filtered, washs obtained solid matter dry 20 hours acquisition pretreatment lignin at 60 DEG C.Will pretreatment wood
100g iron powders are added in quality, high pressure homogenizer operating pressure 40MPa are set to, material is clashed by high-pressure homogeneous nozzle
Afterwards, collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is in catalyst homogenizing and obtain
Higher-energy state is obtained, the lignin and iron mixture of mixing pretreatment is fully obtained, the mixture of acquisition is put into autoclave,
Be filled with nitrogen, pressure increased to 20MPa with 0.1MPa/s speed, by mixture with 30 DEG C/min fixation heating rate from
Room temperature is heated to 500 DEG C, and keeps 30min at 500 DEG C, and normal temperature and pressure is down to by processing, obtains graphene.After testing,
The average thickness of the graphene sheet layer prepared in embodiment three is 0.58 nm, and yield is 6.1%.
Example IV
The present embodiment comprises the following steps：
Take 1kg lignin to be put into 10kg potassium hydroxide solutions, be containing potassium hydroxide quality in potassium hydroxide solution
0.1kg, heated solution temperature is to 85 DEG C, and the isothermal holding time is 3 hours, after next being handled through potassium hydroxide solution
Material is filtered, washs obtained solid matter dry 10 hours acquisition pretreatment lignin at 80 DEG C.Will pretreatment wood
80g nickel powders are added in quality, high pressure homogenizer operating pressure is set to 40MPa, after material is clashed by high-pressure homogeneous nozzle,
Collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is homogenized with catalyst in acquisition
Higher-energy state, fully obtains the lignin and nickel powder mixture of mixing pretreatment, the mixture of acquisition is put into autoclave, filled
Enter nitrogen, pressure is increased to 35MPa with 0.5MPa/s speed, by mixture with 50 DEG C/min fixation heating rate from room
Temperature is heated to 600 DEG C, and keeps 60min at 600 DEG C, and normal temperature and pressure is down to by processing, obtains graphene.After testing, it is real
The average thickness for applying the graphene sheet layer prepared in example four is 0.78 nm, and yield is 5.6%.
Embodiment five
The present embodiment comprises the following steps：
Take 3kg lignin to be put into 10kg potassium hydroxide solutions, be containing potassium hydroxide quality in potassium hydroxide solution
0.25kg, heated solution temperature is to 100 DEG C, and the isothermal holding time is 2 hours, after next being handled through potassium hydroxide solution
Material filtered, wash obtained solid matter at 80 DEG C dry 15 hours obtain pretreatment lignin.Will pretreatment
10g nitric acid nickel by powder is added in lignin, high pressure homogenizer operating pressure 80MPa is set to, material passes through high-pressure homogeneous spray
After mouth head-on collision, collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is homogenized with catalyst
In higher-energy state is obtained, the lignin and nickel nitrate mixture of powders of mixing pretreatment are fully obtained, by the mixing of acquisition
Thing is put into autoclave, is filled with nitrogen, increases pressure to 50MPa with 1MPa/s speed, by mixture consolidating with 60 DEG C/min
Determine heating rate and be heated to 800 DEG C from room temperature, and 120min is kept at 800 DEG C, normal temperature and pressure is down to by processing, obtain
Graphene.After testing, the average thickness of the graphene sheet layer prepared in embodiment five is 0.68 nm, and yield is 6.9%.
Embodiment six
The present embodiment comprises the following steps：
Take 5kg lignin to be put into 10kg potassium hydroxide solutions, be containing potassium hydroxide quality in potassium hydroxide solution
1.3kg, heated solution temperature is to 100 DEG C, and the isothermal holding time is 2 hours, after next being handled through potassium hydroxide solution
Material is filtered, washs obtained solid matter dry 15 hours acquisition pretreatment lignin at 80 DEG C.Will pretreatment wood
50g nickel powders are added in quality, high pressure homogenizer operating pressure is set to 80MPa, after material is clashed by high-pressure homogeneous nozzle,
Collect the homogenizing valve for flowing to slit, non-homogeneous lignin is homogenized and is cracked, cracking carbon is homogenized with catalyst in acquisition
Higher-energy state, fully obtains the lignin and nickel powder mixture of mixing pretreatment, the mixture of acquisition is put into autoclave, filled
Enter nitrogen, pressure is increased to 50MPa with 1MPa/s speed, by mixture with 60 DEG C/min fixation heating rate from room temperature
800 DEG C are heated to, and 120min is kept at 800 DEG C, normal temperature and pressure is down to by processing, graphene is obtained.After testing, it is real
The average thickness for applying the graphene sheet layer prepared in example six is 0.63 nm, and yield is 7.6%.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these changes and modification.
Claims (6)
1. a kind of method that utilization lignin prepares graphene, it is characterised in that pass through high-pressure homogeneous machine nozzle head-on collision cracking wood
Quality prepares graphene, the described method comprises the following steps：
A. it is 1 by lignin and aqueous slkali mixing solid-liquid volume ratio:5-10, heated solution temperature is to 70-100 DEG C, insulation
Processing time is 1-3 hours；
B. the material after alkali process is filtered, washed, the solid of acquisition is dried to obtain pretreatment at 60-80 DEG C
Lignin；
C. catalyst will be added in the pretreatment lignin obtained by b step, is sufficiently mixed using high pressure homogenizer, homogenizer is suitable
When pressure reach 20-100MPa, after material is clashed by high-pressure homogeneous nozzle, collect the homogenizing valve for flowing to slit, make non-homogeneous
Lignin be homogenized and crack, cracking carbon and catalyst is homogenized in obtaining higher-energy state；
D. the mixture obtained in step c is put into autoclave, is filled with inert gas, increased with 0 .1-1MPa/s speed and pressed
Mixture is heated to 500-800 DEG C to 20-50MPa by power with 30-60 DEG C/min fixation heating rate from room temperature, and
30-120min is kept at a temperature of this, normal temperature and pressure is down to by processing, graphene is obtained.
2. the method that a kind of utilization lignin according to claim 1 prepares graphene, it is characterised in that the aqueous slkali
For the aqueous solution of at least one of sodium hydroxide, potassium hydroxide, ammoniacal liquor.
3. the method that a kind of utilization lignin according to claim 1 prepares graphene, it is characterised in that the aqueous slkali
Alkalinity is the 10-30% of lignin quality.
4. the method that a kind of utilization lignin according to claim 1 prepares graphene, it is characterised in that the catalyst
For at least one of iron powder, nickel powder, copper powder, nickel nitrate, iron oxide, the catalyst is 0.01- with lignin quality ratio
0.1：10.
5. the method that a kind of utilization lignin according to claim 1 prepares graphene, it is characterised in that the high pressure is equal
Matter machine operating pressure parameter is 80MPa.
6. the method that a kind of utilization lignin according to claim 1 prepares graphene, it is characterised in that the indifferent gas
Body is at least one of argon gas, helium, nitrogen.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256761B (en) * | 2015-06-16 | 2018-02-16 | 宋玉军 | A kind of method that batch prepares graphene and doped graphene |
| CN106241780B (en) * | 2016-07-19 | 2018-02-27 | 华南理工大学 | A kind of method that graphene is prepared using lignin as raw material |
| CN106495132A (en) * | 2016-09-27 | 2017-03-15 | 济南米铎碳新能源科技有限公司 | The method that lignin prepares Graphene |
| CN106564874B (en) * | 2016-10-18 | 2018-12-21 | 宁波工程学院 | A kind of lignin-base two dimension carbon nanomaterial and its preparation method and application |
| CN106669415B (en) * | 2017-01-20 | 2019-05-14 | 杭州启澄科技有限公司 | A kind of catalysis high-pressure decomposing reactor handling industrial waste gas |
| 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 |
| CN107235484B (en) * | 2017-08-03 | 2019-08-06 | 中南林业科技大学 | A method of graphene is prepared using black liquor rugose wood element |
| CN108751171A (en) * | 2018-06-15 | 2018-11-06 | 广西大学 | A method of preparing graphene film using lignin |
| CN109437168B (en) * | 2019-01-03 | 2021-11-05 | 兖矿集团有限公司 | Graphene hydrogel and preparation method thereof |
| CN111454497B (en) * | 2019-01-22 | 2021-06-01 | 南京工业大学 | Graphene modified lignin enhanced polyolefin wood-plastic composite material and preparation method thereof |
| CN111072014B (en) * | 2019-12-26 | 2021-10-12 | 安徽理工大学 | Preparation method of graphene |
| CN112607731B (en) * | 2020-12-24 | 2021-08-10 | 广东工业大学 | Device and method for preparing graphene powder |
| CN116100646B (en) * | 2023-02-22 | 2024-03-19 | 中南林业科技大学 | Modified wood loaded with imitated blade-shaped graphene layer, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103466613A (en) * | 2013-10-11 | 2013-12-25 | 中南林业科技大学 | Method for preparing graphene from lignin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103466613A (en) * | 2013-10-11 | 2013-12-25 | 中南林业科技大学 | Method for preparing graphene from lignin |
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