CN105502366A - Method for preparing graphene by using biomass as raw materials - Google Patents
Method for preparing graphene by using biomass as raw materials Download PDFInfo
- Publication number
- CN105502366A CN105502366A CN201511010959.4A CN201511010959A CN105502366A CN 105502366 A CN105502366 A CN 105502366A CN 201511010959 A CN201511010959 A CN 201511010959A CN 105502366 A CN105502366 A CN 105502366A
- Authority
- CN
- China
- Prior art keywords
- rotary kiln
- graphene
- dram
- biomass
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing graphene by using biomass as raw materials. The specific preparation method comprises the first step of mixing raw materials; the second step of preparing a graphene precursor by using a drying cylinder; the third step of carbonizing at a high temperature through a gyral kiln; and the fourth step of smashing and stripping by a jet mill. The grahpene prepared by the method disclosed by the invention can be used as an electrode material of supercapacitors and lithium ion batteries, also can be added into resin and rubber to enhance the physical properties of the resin and the rubber. The method for preparing graphene by using biomass as raw materials disclosed by the invention is simple in production process, low in cost, safe and environmentally friendly, capable of being used for continuous industrial production, and wide in market prospect.
Description
Technical field
The invention belongs to field of new, being specifically related to a kind of take biomass as the method that Graphene prepared by raw material.
Background technology
2004, Britain graceful Chester university scientific man reported, separates mono-layer graphite with adhesive tape from graphite---Graphene, and find that this thin, the hardest known nano material has abnormal unique physical properties: transmittance reaches 97.7%; Thermal conductivity up to 5300W/mK, higher than carbon nanotube and diamond; Under normal temperature, its electronic mobility is more than 15000cm2/Vs, higher than CNT (carbon nano-tube) or silicon crystal; And resistivity only about 10-6 Ω cm, than copper or silver lower, be the minimum material of current known resistivity; And the quantum hall effect of Graphene can be observed at normal temperatures.These peculiar physical propertiess allow scientists believe firmly Graphene is revolutionary novel material, become the base mateiral of generation semiconductor information industry by replacing silicon.
China Patent Publication No. is preparation method and the Graphene that CN104386684A discloses a kind of Graphene, comprise the following steps: A) biological material is carried out pre-treatment, obtain pretreated biological material, described biological material comprises one or more in agriculture and forestry organic waste material, tealeaves and seaweed plant; B) by metal catalyst, solvent and described steps A) in the mixing of pretreated biological material, obtain the biological material that load has catalyzer; C) by pore-forming material and described step B) load that obtains has the biological material of catalyzer to mix, and heat 0.5 ~ 10 hour at 700 ~ 1200 DEG C, obtain Graphene.Preparation method's environmentally safe of this invention take biological material as carbon source, and the material cost of carbon source is low and easily obtain, and solves existing carbon source cost high.But the preparation method of this invention is only applicable to laboratory preparation, be difficult to be applied to industry preparation.
China Patent Publication No. is the preparation method that CN104386679A discloses graphene oxide and Graphene, this invention comprises the following steps: the preparation method of graphene oxide: by graphite raw material, solvent and oxygenant mix, be placed in closed reaction vessel, stirring reaction 0.5 ~ 6h at 40 ~ 120 DEG C, decompression, suction filtration, after washing, by overanxious thing vacuum-drying, milled processed, product after drying and grinding is dispersed in deionized water, oxygenant is added under acidic conditions, in 0 ~ 4 DEG C of stirring reaction 1 ~ 4h, be warming up to 20 ~ 40 DEG C of stirring reaction 1 ~ 2h, by reacted suspension liquid separating-purifying, be scattered in spraying dry in deionized water and be graphene oxide.The Graphene purity that this invention obtains is high; But Graphene output prepared by this invention is little, and productive rate is low.
China Patent Publication No. is the ball milling preparation method that CN103466608A discloses a kind of Graphene, the mass volume ratio of hexa-atomic to graphite carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant is that 1:2 ~ 1:15 and deionized water mix and be loaded on ball grinder by this invention, is fixed on ball mill with the rotating speed ball milling 5-30 hour of 200-500rpm; Proceed to again in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, obtained different concns graphene aqueous solution.The graphene dispersion that this invention is produced is in the aqueous solution, and concentration is high, and tensio-active agent easily can be removed with ethanol, environmental protection and be conducive to the widespread use of Graphene; But the preparation method of this invention is not suitable for biological material prepares Graphene.
Along with the fast development of economy and industrial technology, Graphene more and more comes into one's own, and the problem such as existing graphene preparation method exists complicated process of preparation, production security is poor, production cost is high, severe reaction conditions, output and productive rate are low, be difficult to suitability for industrialized production, greatly limit the application and development of grapheme material, therefore, develop a kind of preparation technology simple, production safety environmental protection, production cost is low, and output is high, the graphene preparation method that can be continuously produced, to enriching Graphene preparation technology, promote that the development of Graphene is significant.
Summary of the invention
The object of the invention: in order to enrich the preparation method of Graphene, the invention provides a kind of biomass is the method that grapheme material prepared by raw material, and its preparation technology is simple, production safety environmental protection, production cost is low, and output is high, can be continuously produced, the preparation method for Graphene provides more selection.
The technical solution used in the present invention: existing graphene preparation method exists complex process, production security is poor, production cost is high in order to solve, reaction required equipment complexity, severe reaction conditions, the problem such as yield poorly, providing a kind of biomass is the method that grapheme material prepared by raw material, comprises the following steps:
(1) be 15 DEG C-25 DEG C by lignocellulose and catalyzer in service temperature, be mixed with mixed solution through being uniformly mixed, agitator speed is 150rpm-300rpm, churning time 30min-60min;
(2) mixed solution step (1) obtained filters at service temperature is 15 DEG C-25 DEG C, dry through dram deoxidation after filtration, dram rotating speed is 10rpm-60rpm, and dram gradient is 0.1%-0.5%, in dram, temperature is 110 DEG C-135 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1100 DEG C-1450 DEG C, rotary kiln rotating speed is 10rpm-60rpm, rotary kiln gradient is 0.1%-0.5%, and the mixed gas passing into CO, CO2, N2 does shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 15 DEG C-25 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Further, catalyzer described in described step (1) is mixed by FeCl2 and FeCl3 and forms, and the quality proportioning of FeCl2 and FeCl3 is between 0.5:1 and 1:0.5.
Further, in described step (2), raw material drying time in dram can be controlled by regulating dram rotating speed and dram gradient.
Further; in described step (3); raw material carbonization time in rotary kiln can be controlled by regulating rotary kiln rotating speed and rotary kiln gradient; described rotary kiln is using a kind of fuel in Sweet natural gas, liquefied gas, coal gas, oil fuel as fuel, and the mixed gas of CO, CO2, N2 of generating after fuel combustion passes into rotary kiln and does shielding gas.
Further, micronizer mill circulation pipe air flow crasher in described step (4).
Outstanding feature of the present invention and beneficial effect are:
(1) a kind of method with biomass being Graphene prepared by raw material of the present invention adopts lignocellulose to prepare Graphene for carbon source, reduces production cost;
(2) of the present invention a kind of with biomass be raw material prepare the method for Graphene can consecutive production, the Graphene output of preparation is large, and productive rate is high;
(3) the present invention is a kind of is that raw material prepares the method production technique of Graphene simply with biomass, and with low cost, safety and environmental protection, has higher market application foreground.
Embodiment
Be further described the present invention according to specific embodiment below, the following stated is only the preferred embodiment of the present invention, and under same principle, can make part and improve, these improvement also belong in protection scope of the present invention:
Embodiment 1:
A kind of take biomass as the method that Graphene prepared by raw material:
(1) by lignocellulose, the quality proportioning of FeCl2 and FeCl3 is the catalyzer of 0.5:1 is 15 DEG C in service temperature, and be mixed with mixed solution through being uniformly mixed, agitator speed is 150rpmrpm, churning time 30minmin;
(2) mixed solution step (1) obtained filters at service temperature is 15 DEG C, and dry through dram deoxidation after filtration, dram rotating speed is 10rpmrpm, and dram gradient is 0.5%, and in dram, temperature is 110 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1100 DEG C, and rotary kiln rotating speed is 10rpm, and rotary kiln gradient is 0.5%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 15 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Embodiment 2:
A kind of take biomass as the method that Graphene prepared by raw material:
(1) by lignocellulose, the quality proportioning of FeCl2 and FeCl3 is the catalyzer of 1:0.5 is 25 DEG C in service temperature, and be mixed with mixed solution through being uniformly mixed, agitator speed is 300rpm, churning time 60min;
(2) mixed solution step (1) obtained filters at service temperature is 25 DEG C, and dry through dram deoxidation after filtration, dram rotating speed is 60rpm, and dram gradient is 0.1%, and in dram, temperature is 135 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1450 DEG C, and rotary kiln rotating speed is 60rpm, and rotary kiln gradient is 0.1%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 25 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Embodiment 3:
A kind of take biomass as the method that Graphene prepared by raw material:
(1) by lignocellulose, the quality proportioning of FeCl2 and FeCl3 is the catalyzer of 1:1 is 20 DEG C in service temperature, and be mixed with mixed solution through being uniformly mixed, agitator speed is 200rpm, churning time 40min;
(2) mixed solution step (1) obtained filters at service temperature is 21 DEG C, and dry through dram deoxidation after filtration, dram rotating speed is 20rpm, and dram gradient is 0.2%, and in dram, temperature is 120 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1250 DEG C, and rotary kiln rotating speed is 30rpm, and rotary kiln gradient is 0.3%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 20 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Embodiment 4:
A kind of take biomass as the method that Graphene prepared by raw material:
(1) by lignocellulose, the quality proportioning of FeCl2 and FeCl3 is the catalyzer of 0.8:1 is 25 DEG C in service temperature, and be mixed with mixed solution through being uniformly mixed, agitator speed is 240rpm, churning time 45min;
(2) mixed solution step (1) obtained filters at service temperature is 15 DEG C, and dry through dram deoxidation after filtration, dram rotating speed is 25rpm, and dram gradient is 0.15%, and in dram, temperature is 115 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1300 DEG C, and rotary kiln rotating speed is 45rpm, and rotary kiln gradient is 0.25%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 25 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Embodiment 5:
A kind of take biomass as the method that Graphene prepared by raw material:
(1) by lignocellulose, the quality proportioning of FeCl2 and FeCl3 is the catalyzer of 1:0.6 is 15 DEG C in service temperature, and be mixed with mixed solution through being uniformly mixed, agitator speed is 250rpm, churning time 50min;
(2) mixed solution step (1) obtained filters at service temperature is 20 DEG C, and dry through dram deoxidation after filtration, dram rotating speed is 45rpm, and dram gradient is 0.4%, and in dram, temperature is 135 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1100 DEG C, and rotary kiln rotating speed is 35rpm, and rotary kiln gradient is 0.3%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 20 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
Claims (5)
1. biomass are the method that grapheme material prepared by raw material, it is characterized in that: comprise the following steps:
(1) be 15 DEG C-25 DEG C by lignocellulose and catalyzer in service temperature, be mixed with mixed solution through being uniformly mixed, agitator speed is 150rpm-300rpm, churning time 30min-60min;
(2) mixed solution step (1) obtained filters at service temperature is 15 DEG C-25 DEG C, dry through dram deoxidation after filtration, dram rotating speed is 10rpm-60rpm, and dram gradient is 0.1%-0.5%, in dram, temperature is 110 DEG C-135 DEG C, obtains Graphene presoma;
(3) Graphene presoma step (2) obtained is through rotary kiln carbonizing treatment at temperature is 1100 DEG C-1450 DEG C, and rotary kiln rotating speed is 10rpm-60rpm, and rotary kiln gradient is 0.1%-0.5%, and passes into CO, CO
2, N
2mixed gas do shielding gas, obtain Graphene Primary product;
(4) Graphene Primary product step (3) obtained is pulverized through micronizer mill and is peeled off at temperature is 15 DEG C-25 DEG C, obtains the grapheme material of the number of plies between 10 layers and 200 layers.
2. prepare the method for biomass Graphene according to claim 1 with rotary kiln, it is characterized in that: described in described step (1), catalyzer is by FeCl
2and FeCl
3mixing composition, and FeCl
2and FeCl
3quality proportioning between 0.5:1 and 1:0.5.
3. preparing the method for biomass Graphene according to claim 1 with rotary kiln, it is characterized in that: in described step (2), raw material drying time in dram can be controlled by regulating dram rotating speed and dram gradient.
4. the method for biomass Graphene is prepared according to claim 1 with rotary kiln, it is characterized in that: in described step (3), raw material carbonization time in rotary kiln can be controlled by regulating rotary kiln rotating speed and rotary kiln gradient, described rotary kiln using a kind of fuel in Sweet natural gas, liquefied gas, coal gas, oil fuel as fuel, CO, CO of generating after fuel combustion
2, N
2mixed gas pass into rotary kiln and do shielding gas.
5. prepare the method for biomass Graphene according to claim 1 with rotary kiln, it is characterized in that: micronizer mill circulation pipe air flow crasher in described step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511010959.4A CN105502366A (en) | 2015-12-30 | 2015-12-30 | Method for preparing graphene by using biomass as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511010959.4A CN105502366A (en) | 2015-12-30 | 2015-12-30 | Method for preparing graphene by using biomass as raw materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105502366A true CN105502366A (en) | 2016-04-20 |
Family
ID=55710753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511010959.4A Pending CN105502366A (en) | 2015-12-30 | 2015-12-30 | Method for preparing graphene by using biomass as raw materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105502366A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365153A (en) * | 2016-06-08 | 2017-02-01 | 中国矿业大学 | Simple preparation method of biomass-based three-dimensional multi-element co-doped graphene |
| CN106975448A (en) * | 2017-04-18 | 2017-07-25 | 浙江大学 | A kind of super-high specific area adsorbent material and preparation method thereof |
| CN107177399A (en) * | 2017-06-01 | 2017-09-19 | 吴锋 | A kind of preparation technology of high concentration high stable wear resistence graphene lube oil additive |
| US10494263B2 (en) | 2015-03-04 | 2019-12-03 | Heilongjiang University | Method for preparing biomass graphene by using cellulose as raw material |
| CN111470495A (en) * | 2020-04-24 | 2020-07-31 | 山东龙力生物科技股份有限公司 | Raw material for preparing graphene and method for preparing graphene by using raw material |
| CN113086975A (en) * | 2021-05-06 | 2021-07-09 | 常州富烯科技股份有限公司 | Graphene microsphere and high-thermal-conductivity gasket prepared from same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104724699A (en) * | 2015-03-04 | 2015-06-24 | 黑龙江大学 | Method for preparing biomass graphene employing cellulose as raw material |
-
2015
- 2015-12-30 CN CN201511010959.4A patent/CN105502366A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104724699A (en) * | 2015-03-04 | 2015-06-24 | 黑龙江大学 | Method for preparing biomass graphene employing cellulose as raw material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10494263B2 (en) | 2015-03-04 | 2019-12-03 | Heilongjiang University | Method for preparing biomass graphene by using cellulose as raw material |
| CN106365153A (en) * | 2016-06-08 | 2017-02-01 | 中国矿业大学 | Simple preparation method of biomass-based three-dimensional multi-element co-doped graphene |
| CN106975448A (en) * | 2017-04-18 | 2017-07-25 | 浙江大学 | A kind of super-high specific area adsorbent material and preparation method thereof |
| CN106975448B (en) * | 2017-04-18 | 2019-11-15 | 浙江大学 | A kind of super-high specific area adsorbent material and preparation method thereof |
| CN107177399A (en) * | 2017-06-01 | 2017-09-19 | 吴锋 | A kind of preparation technology of high concentration high stable wear resistence graphene lube oil additive |
| CN111470495A (en) * | 2020-04-24 | 2020-07-31 | 山东龙力生物科技股份有限公司 | Raw material for preparing graphene and method for preparing graphene by using raw material |
| CN113086975A (en) * | 2021-05-06 | 2021-07-09 | 常州富烯科技股份有限公司 | Graphene microsphere and high-thermal-conductivity gasket prepared from same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105502366A (en) | Method for preparing graphene by using biomass as raw materials | |
| CN104724699B (en) | Method for preparing biomass graphene employing cellulose as raw material | |
| CN107827102A (en) | A kind of method for preparing graphene | |
| CN106082202A (en) | A kind of preparation method and application of graphene aerogel | |
| JP6106339B2 (en) | Dispersant, method for producing the same, and dispersion composition of carbon-based material including the same | |
| CN103922330A (en) | Method for preparing graphene powder by using dry process | |
| CN106315540A (en) | Method for preparing graphene quantum dot from asphalt | |
| CN103395769B (en) | A kind of porous carbon preparation method for material based on ion thermal process | |
| CN103359702A (en) | Preparation method of mesophase carbon microspheres with different particle sizes | |
| Yu et al. | Removal of phenols from aqueous solutions by graphene oxide nanosheet suspensions | |
| CN107934934A (en) | A kind of method for efficiently preparing asphalt base mesocarbon microspheres | |
| CN104016408A (en) | Synthetic method of sodium niobate nanowire | |
| CN110117006A (en) | A kind of method that high-efficiency environment friendly prepares grapheme material | |
| CN107352529A (en) | A kind of method for preparing grapheme material using discarded object banana skin for raw material | |
| CN105271191B (en) | A kind of redox graphene and preparation method and application | |
| CN103601180B (en) | A kind of Nano-size Porous Graphite alkene material and preparation method thereof | |
| CN102502610A (en) | Simple method for preparing a large amount of graphene | |
| CN107381559A (en) | Two-dimensional graphene and preparation method thereof | |
| CN105668558B (en) | A kind of method that graphene is prepared with recycling material of waste asphalt | |
| CN103346326A (en) | Preparation method for carbon cathode material of lithium ion battery | |
| CN104449916B (en) | In brown coal, high-concentration coal-water slurry method is prepared in warm upgrading | |
| CN110550623B (en) | Method for preparing high-quality large-size graphene on large scale | |
| CN105060272B (en) | A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT | |
| CN104449917B (en) | High-concentration coal-water slurry method is prepared in the upgrading of brown coal low temperature | |
| CN106744884A (en) | A kind of Graphene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160420 |