CN107720744A - A kind of method that graphene oxide is prepared using petroleum coke - Google Patents
A kind of method that graphene oxide is prepared using petroleum coke Download PDFInfo
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- CN107720744A CN107720744A CN201711145671.7A CN201711145671A CN107720744A CN 107720744 A CN107720744 A CN 107720744A CN 201711145671 A CN201711145671 A CN 201711145671A CN 107720744 A CN107720744 A CN 107720744A
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Abstract
The present invention relates to a kind of method that graphene oxide is prepared using petroleum coke as raw material, it is raw material from petroleum coke, from sulfuric acid acidifying potassium permanganate as oxidant, through pre- intercalation, intercalation oxidation, peel off three processes, low cost, high yield, multi-functional petroleum coke base graphene oxide are prepared by chemical oxidization method, and by regulating and controlling the composition of cooxidant, controllably synthesis is with different surfaces chemical property, the graphene oxide of structure.
Description
Technical field
The invention belongs to carbon nanomaterial field, and in particular to one kind prepares oxygen using petroleum coke as raw material by chemical oxidation
The method of graphite alkene.
Background technology
Graphene is the novel nano carbon material formed with π-pi-conjugated carbon-coating of individual layer or few layer, with the two of uniqueness
Tieing up structure and physico-chemical property turns into a nova in nanosecond science and technology field, has in multiple fields such as the energy, environment, material, medical science
Have wide practical use.Graphene oxide is one of derivative of graphene, is made on a large scale by chemistry redox method
The important presoma of standby graphene.Compared with graphene, graphene oxide contains substantial amounts of oxygen-containing functional group, has excellent change
Activity is learned, application aspect has more advantages in the field such as composite, energy storage, catalysis, environmental project.Chemical oxidization method is system
Standby the most frequently used method of graphene oxide, the characteristic such as there is low cost, high yield, be easy to modify, can be mass, being most work
One of preparation method of industry prospect.Chemical oxidization method almost all is raw material from natural flake graphite powder at present, certain
The application and development of graphene oxide are limited in degree.
Petroleum coke is the waste material of a large amount of by-products in refinery production, with PETROLEUM PROCESSING amount be continuously increased and petroleum heavy
The continuous lifting of change degree, the yield of petroleum coke are also being continuously increased.Petroleum coke is mainly used in fuel and metallurgical electrode material at present
Material, but the problems such as the impurity such as sulphur in petroleum coke, nitrogen can bring environmental pollution, electrode corrosion, seriously limiting actual production should
With.Increasingly strict with environmental monitoring index, petroleum coke is gradually forbidden as the purposes of fuel, and price becomes in overall downslide
Gesture, the high value added utilization of petroleum coke turn into a great problem of oil refining industry.
The petroleum coke of high-temperature process has the lamellar structure similar with natural flake graphite, is prepared by chemical oxidization method
The potential raw material of petroleum coke base graphene oxide.At the same time, petroleum coke lamella tool irregularities and rich defective, make petroleum coke
Base graphene oxide has more application advantages in fields such as catalysis, energy storage.However, compared to natural flake graphite, oil
Burnt lamellar structure is irregular, and Van der Waals force is not only existed between lamella, is also adhered in the presence of part, and the intermolecular forces of lamella are bigger,
It is more difficult to be oxidized and peel off as graphene oxide.Therefore, by the improve and perfect to chemical oxidization method stripping conditions, improve
The effect and efficiency that chemical oxidation is peeled off, are developed the method that graphene oxide is prepared using petroleum coke as raw material, can both promote oxidation
The preparation and application of graphene, new direction can be provided for the high value added utilization of petroleum coke again, there is important research to anticipate
Justice and practical value.
The content of the invention
For problems of the prior art, oxygen is prepared by raw material of petroleum coke it is an object of the invention to provide one kind
The method of graphite alkene.
In order to achieve the above object, technical scheme is as follows：
The method that graphene oxide is prepared using petroleum coke as raw material, it is raw material from petroleum coke, from the height of sulfuric acid acidifying
Potassium manganate through pre- intercalation, intercalation oxidation, peels off three processes, petroleum coke base oxygen is prepared by chemical oxidization method as oxidant
Graphite alkene.
The preferred needle coke of species of petroleum coke, and primary election can be carried out to petroleum coke by filtering screening, control graphite oxide
The lamella size of alkene product.During petroleum coke is oxidized, mainly play oxidation is potassium permanganate, and sulfuric acid mainly rises
Strengthen the effect of oxidisability, and oxidation effectiveness increases with the increase of potassium permanganate dosage.When petroleum coke and potassium permanganate
Mass ratio is more than 1:When 6, the increase of oxidation effectiveness is no longer obvious.
Pre- intercalation process is carried out at -10~15 DEG C, and petroleum coke, the concentrated sulfuric acid, potassium permanganate and pro-oxidant are uniformly mixed
Close, continuously stir.Generation manganese heptoxide and heat is released due to being reacted when potassium permanganate is mixed into sulfuric acid, is acidified permanganic acid
Potassium petroleum oxidate Jiao can also release heat, and temperature increase can further promote oxidation reaction, just occur when temperature is more than 45 DEG C
Inabundant intercalation is peeling, influences the quality of graphene oxide product, thus controls the temperature of pre- intercalation process particularly heavy
Will.
Intercalation oxidizing process is carried out at 35~45 DEG C, for enhancing oxidation and peeling effect, it is necessary to which the sufficient time is carried out
Intercalation, making sulfuric acid and potassium permanganate, intercalation temperature is advisable with 35~45 DEG C well between petroleum coke lamella, and the intercalation time is
10~24h.
Stripping process is carried out at 90~100 DEG C or 45~60 DEG C, to reduce potassium permanganate or acid solution to petroleum coke lamella
Corrosion, generally require plus temperature brought up to 90~100 DEG C by deionized water, it is unsuitable long to peel off the duration, with 15~
45min is advisable；When adding phosphoric acid, polyphosphoric acids, metaphosphoric acid etc. as pro-oxidant, there is protective effect to petroleum coke, temperature
Degree is maintained at 45~60 DEG C, and splitting time can extend to 1~2h.
30% hydrogen peroxide solution is added untill no bubble produces, is washed with deionized, until supernatant liquor is in weak
It is acid or neutral (pH6~7), obtain graphene oxide solution；The sample washed is subjected to ultrasound, freeze-drying, obtains oxygen
Graphite alkene product.
Beneficial effects of the present invention
Using petroleum coke as raw material, the potassium permanganate from sulfuric acid acidifying is oxidant, by chemical oxidation of gold by oil
Jiao's oxidation intercalation is peeled off, and prepares low cost, high yield, multi-functional petroleum coke base graphene oxide, and by regulating and controlling to aid in oxygen
The composition of agent, controllably synthesis is with different surfaces chemical property, the graphene oxide of structure.The present invention is using petroleum coke as original
Material has synthesized graphene oxide composite material, and the graphite platelet structure of petroleum coke has obtained complete oxidation and fully peeled off, have with it is general
The similar microstructure of logical graphene oxide, it is a kind of multifunctional C nano material of great potential.
Brief description of the drawings
Fig. 1 is that ESEM (SEM) figure of graphene oxide (is followed successively by embodiment 1, embodiment 2, embodiment from left to right
3rd, the graphene oxide prepared by reference examples 1)；
Fig. 2 is that transmission electron microscope (TEM) figure of graphene oxide (is followed successively by embodiment 1, embodiment 2, embodiment from left to right
3rd, the graphene oxide prepared by reference examples 1)；
Fig. 3 is petroleum coke and embodiment 1, embodiment 2, embodiment 3, the X ray of graphene oxide prepared by reference examples 1
Diffraction (XRD) collection of illustrative plates.
Embodiment
Used term in the present invention, unless otherwise specified, typically have those of ordinary skill in the art usual
The implication of understanding.
With reference to specific embodiment, and with reference to the data further detailed description present invention.Following examples simply be
Illustrate the present invention, rather than the scope that limit the invention in any way.
Embodiment 1
5g petroleum cokes, 25g potassium permanganate and 2.5g sodium nitrate are weighed, measures the 200mL concentrated sulfuric acids (concentration 98%).By oil
The mixing of burnt and sodium nitrate, adds the concentrated sulfuric acid, is slowly homogeneously added into potassium permanganate, and lasting stirring makes it well mixed, control temperature
Spend for 10 DEG C.Mixture is moved into water-bath after 2h and ultrasonic wave added intercalation aoxidizes, control temperature continues 10h at 35 DEG C.Slowly
100mL deionized waters are added, moves into afterwards in 98 DEG C of high temperature bath, into the stage, continues to stir after reaching design temperature
30min, now liquid is in khaki.After stopping stirring, 500mL deionized waters are added, add 30% hydrogen peroxide solution to not having
Untill bubble produces.Product is washed with deionized, until supernatant liquor is in faintly acid or neutrality, it is molten to obtain graphene oxide
Liquid.The sample washed is subjected to ultrasound, freeze-drying, obtains graphene oxide.
To graphene oxide progress SEM, TEM, XRD test analysis, SEM, TEM result in Fig. 1, Fig. 2 show product tool
There is the lamellar structure of conventional oxidation graphene.XRD results show petroleum coke as traditional crystalline graphite powder in Fig. 3, in graze
The θ of angle 2 has very strong diffraction maximum when being 26 °, is the diffraction maximum of graphite (002) crystal face.Graphite of the graphene oxide at 26 °
(002) diffraction maximum of crystal face is almost wholly absent, and the substitute is the diffraction maximum of graphite oxide (002) crystal face at 10 °, according to
Bragg equation calculates and learns that its interlamellar spacing is 0.84nm, shows that carbonization structure is completely destroyed, prepared petroleum coke base
Graphene oxide quality is good.
Embodiment 2
5g acicular petroleum cokes and 30g potassium permanganate are weighed, takes the 270mL concentrated sulfuric acids and 30mL concentrated phosphoric acids.By the concentrated sulfuric acid and dense
Phosphoric acid mixes, and adds petroleum coke, is slowly homogeneously added into potassium permanganate, and lasting stirring makes it well mixed, and it is -5 to control temperature
℃.Mixture is moved into water-bath after 1.5h and ultrasonic wave added intercalation aoxidizes, control temperature continues 12h at 45 DEG C.By temperature after
Of continuing rising to 60 DEG C, continue 2h.Remaining operation and condition are same as Example 1.
Obtained graphene oxide is subjected to SEM, TEM, XRD analysis.There is tradition by can see product in Fig. 1, Fig. 2
The lamellar structure of graphene oxide, by Fig. 3 it can be seen that the diffraction maximum of graphite (002) crystal face is almost wholly absent, replace
Be graphite oxide (002) crystal face diffraction maximum, according to Bragg equation calculate learn that its interlamellar spacing is 0.91nm.
Embodiment 3
5g acicular petroleum cokes and 30g potassium permanganate are weighed, takes the 240mL concentrated sulfuric acids and 60mL concentrated nitric acids.By the concentrated sulfuric acid and dense
Nitric acid mixes, and adds petroleum coke.Potassium permanganate slowly is homogeneously added into, lasting stirring makes it well mixed, and it is 0 to control temperature
℃.Mixture is moved into water-bath after 2h and ultrasonic wave added intercalation aoxidizes, control temperature continues 24h at 35 DEG C.Remaining operation and
Condition is same as Example 1.
Obtained graphene oxide is subjected to SEM, TEM, XRD analysis.There is tradition by can see product in Fig. 1, Fig. 2
The lamellar structure of graphene oxide, by Fig. 3 it can be seen that the diffraction maximum of graphite (002) crystal face is almost wholly absent, replace
Be graphite oxide (002) crystal face diffraction maximum, according to Bragg equation calculate learn that its interlamellar spacing is 0.89nm.
Reference examples 1
Potassium permanganate is once added in reaction solution and calls one-step method to prepare the method for graphite oxide；Excessive permanganic acid
The disposable addition of potassium, cause local reaction temperature too high, so that pyrohydrolysis process occurs in advance, one-step oxidation process is controllable
Property is poor.Specific method is：Using 1g acicular petroleum cokes, it is added in the 50mL concentrated sulfuric acids, adds 10g potassium permanganate, low temperature 10
Pre- intercalation 6h at DEG C, intercalation oxidation reaction 8h at 35 DEG C, adds 60mL deionized waters and elevates the temperature to 100 DEG C, peel off afterwards
React 4h.Neutrality is washed to repeatedly.The sample washed is subjected to ultrasound, freeze-drying, obtains graphene oxide.
Obtained graphene oxide is subjected to SEM, TEM, XRD analysis.Reunited sternly by can see product in Fig. 1, Fig. 2
Weight, be not fully exfoliated as lamellar structure, by Fig. 3 it can be seen that, except the diffraction maximum of graphite oxide (002) crystal face, graphite
(002) diffraction maximum of crystal face still has, and is calculated according to Bragg equation and learns that its interlamellar spacing is 0.80nm.As a result illustrate, stone
Oil coke is only partially oxidized, and oxidized partial oxidation degree is also small, causes the spacing between lamella small.Result above shows to pass
System method is not enough to be effectively peeled off petroleum coke.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although with reference to foregoing reality
Example is applied the present invention is described in detail, for the person of ordinary skill of the art, still can be to foregoing implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these are changed or replaced
Change, the essence of appropriate technical solution is departed from the spirit and scope of claimed technical solution of the invention.
Claims (9)
- A kind of 1. method that graphene oxide is prepared using petroleum coke, it is characterised in that：Using petroleum coke as raw material, it is acidified with sulfuric acid Potassium permanganate be that the step chemical oxidation such as oxidant, oxidized, intercalation, stripping prepares petroleum coke base graphite oxide.
- 2. the method for graphene oxide is prepared using petroleum coke according to claim 1, it is characterised in that：Specific steps are such as Under：Petroleum coke, the concentrated sulfuric acid, potassium permanganate and pro-oxidant are slowly uniformly mixed at -10~15 DEG C, carry out pre- intercalation Process；Mixture, which is moved into water-bath, makes temperature rise to 35~45 DEG C, carries out intercalation oxidizing process；Formed according to the difference of pro-oxidant, control temperature is risen to 90~100 DEG C at 45~60 DEG C or by temperature, peeled off Process；30% hydrogen peroxide solution is added untill no bubble produces, is washed with deionized, until supernatant liquor is in faintly acid Or it is neutral, obtain graphene oxide solution；The sample washed is subjected to ultrasound, freeze-drying, obtains graphene oxide product.
- 3. the method for graphene oxide is prepared using petroleum coke according to claim 2, it is characterised in that：The petroleum coke is Acicular petroleum coke or other stratiform petroleum cokes.
- 4. the method for graphene oxide is prepared using petroleum coke according to claim 2, it is characterised in that：The concentrated sulfuric acid is 98% concentrated sulfuric acid or oleum.
- 5. the method for graphene oxide is prepared using petroleum coke according to claim 2, it is characterised in that：The petroleum coke with The mass ratio of potassium permanganate is 1：5~6, dosage >=20mL/g petroleum cokes of the concentrated sulfuric acid.
- 6. the method for graphene oxide is prepared using petroleum coke according to claim 2, it is characterised in that：Pre- intercalation process is held Continuous 1~2h, intercalation oxidizing process continue 10~24h, and stripping process continues 15~45min or 1~2h.
- 7. according to the method that graphene oxide is prepared using petroleum coke of claim 2 or 6, it is characterised in that：The intercalation Oxidizing process uses ultrasound as auxiliary.
- 8. according to the method that graphene oxide is prepared using petroleum coke of claim 2 or 6, it is characterised in that：When addition nitre Acid ion, in stripping process by adding deionized water, makes temperature rise to 90~100 DEG C, stripping process is held as pro-oxidant Continuous 15~45min.
- 9. according to the method that graphene oxide is prepared using petroleum coke of claim 2 or 6, it is characterised in that：It is dense when adding When phosphoric acid, polyphosphoric acids and/or metaphosphoric acid are as pro-oxidant, deionized water is not added with stripping process, temperature control 45~ 60 DEG C, splitting time extends to 1~2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793143A (en) * | 2018-08-15 | 2018-11-13 | 南通百川新材料有限公司 | Industrial production method of graphene |
| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN112811416A (en) * | 2021-01-20 | 2021-05-18 | 陕西榆能集团能源化工研究院有限公司 | Preparation method of single-layer graphene oxide based on semi-coke |
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| CN101830458A (en) * | 2010-05-06 | 2010-09-15 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
| CN104860302A (en) * | 2015-04-28 | 2015-08-26 | 南京信息工程大学 | Preparation method of wide interlayer spacing and easily-striping graphite oxide |
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- 2017-11-17 CN CN201711145671.7A patent/CN107720744A/en active Pending
Patent Citations (2)
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| CN101830458A (en) * | 2010-05-06 | 2010-09-15 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
| CN104860302A (en) * | 2015-04-28 | 2015-08-26 | 南京信息工程大学 | Preparation method of wide interlayer spacing and easily-striping graphite oxide |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793143A (en) * | 2018-08-15 | 2018-11-13 | 南通百川新材料有限公司 | Industrial production method of graphene |
| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN112811416A (en) * | 2021-01-20 | 2021-05-18 | 陕西榆能集团能源化工研究院有限公司 | Preparation method of single-layer graphene oxide based on semi-coke |
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