CN107879337A - Prepare the method and its equipment of graphene oxide - Google Patents
Prepare the method and its equipment of graphene oxide Download PDFInfo
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- CN107879337A CN107879337A CN201711123560.6A CN201711123560A CN107879337A CN 107879337 A CN107879337 A CN 107879337A CN 201711123560 A CN201711123560 A CN 201711123560A CN 107879337 A CN107879337 A CN 107879337A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- 238000009295 crossflow filtration Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims description 37
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 239000000376 reactant Substances 0.000 abstract description 2
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 239000012263 liquid product Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- -1 Graphite alkene Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Abstract
The present invention provides a kind of method and apparatus for preparing graphene oxide, and the equipment includes premixed device, micro passage reaction, collecting tank and cross-flow filtration device, and the premixed device, micro passage reaction, collecting tank and cross-flow filtration device are sequentially connected.Production equipment provided by the invention, using micro passage reaction as reaction unit, it is designed according to the characteristics of reactant and course of reaction, premixed device, measuring pump, cross-flow reaction unit and collecting tank is organically assembled, improve reaction efficiency and production security.Production equipment provided by the invention is more suitable for mass producing graphene oxide.
Description
Technical field
The present invention relates to a kind of preparation method of graphene oxide and its device, belongs to chemical process safety and equipment design
Field.
Background technology
The preparation method of graphene oxide mainly has three kinds：Brod i e methods, Staudenma ier methods and
Hummers methods.Wherein also compare in the ageing relatively preferable and preparation process of the preparation process of Hummers methods
Safety, it is one kind the most frequently used at present.It uses the potassium permanganate in the concentrated sulfuric acid with after the oxidized reaction of powdered graphite, obtaining
Brown has derivative carboxylic acid group at edge and is mainly the graphite flake of phenolic hydroxyl group and epoxide group in the plane, this graphite flake
It is graphene oxide that layer can be stirred vigorously stripping through ultrasound or high shear, and stable, the individual layer oxygen of light brown is formed in water
Graphite alkene suspension.
Existing graphene oxide technology of preparing all uses traditional tank reactor, referring to shown in accompanying drawing 1, wherein:1-
Transmission device, 2- axle envelopes, 3- enter hole (or charge door), 4- bearings, 5- blow-off pipes, 6- agitating shafts, 7- chucks, 8- kettlies, 9-
Agitator.The heat exchange area of traditional tank reactor will not be linearly increasing with volume increase, therefore with production capacity demand
Increase, reactor volume increase therewith, and heat exchange area increase is limited, and this certainly will cause reaction system heat and mass slower, make
RT of the material in reactor is elongated.Reaction mass is in traditional tank reactor in course of reaction, close to kettle wall
Local temperature is relatively low, and the local temperature further away from kettle wall is higher, whole system non-uniform temperature, the unmanageable standard of reaction temperature
Really.The discharge gate of traditional tank reactor in bottom, reaction mass (especially potassium permanganate) can valve discharge gate with
Assemble in short tube between the discharge port of reactor bottom, and the aggregation of potassium permanganate can make local temperature acute in this reaction system
Strong rise, there is the risk that overtemperature explodes.It can be seen that due to being limited by tank reactor itself, exist reaction system heat and mass compared with
Slowly, reaction temperature control is inaccurate, causes that feed stock conversion is relatively low, the reaction time is long, degree of oxidation is uneven, and has super
The risk of temperature blast.
The technology contents listed in the prior art only represent the technology that inventor is grasped, and are not considered as naturally
It is the novelty and creativeness that prior art and being used for evaluates the present invention.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of system of the high graphene oxide of production efficiency
Preparation Method；
It is a further object of the present invention to provide the equipment for the above method.
The purpose of the present invention implements by the following technical programs：
A kind of method for preparing graphene oxide, including：
Raw graphite, the concentrated sulfuric acid and potassium permanganate are premixed at low temperature；
Reaction；With
Collect, filter and graphene oxide dispersion product is obtained after washing.
Further, in addition to graphene oxide dispersion it is dried, obtains graphene oxide powder product.It is preferred that
Ground, it is described dry using spray drying.
According to an aspect of the present invention, the pre-compounding process control material temperature is at 0-15 DEG C.
According to an aspect of the present invention, the reaction is carried out at 20-65 DEG C, and the reaction time of the reaction is 3-
9h；It is preferred that react 6h at 35-55 DEG C.
According to an aspect of the present invention, the reaction is carried out using in micro passage reaction.
Preferably, the micro passage reaction uses micro- reaction channel of heart-shaped structure.
Preferably, material residence time in micro- reaction channel of each heart-shaped structure is 5-70S, preferably 15-20S.
Preferably, the reaction is completed by three groups of micro passage reactions, and 400- is provided with every group of micro passage reaction
Micro- reaction channel of 600 heart-shaped structures, the temperature of the temperature control reaction mass of the chuck by setting micro passage reaction.
Preferably, micro- reaction channel reaction temperature, three groups of micro passage reactions are controlled by the chuck of micro passage reaction
Jacket temperature be from upstream to downstream and be followed successively by 35 DEG C, 45 DEG C, 65 DEG C.
According to an aspect of the present invention, pre- be mixed in premixed device is carried out, and is obtained after premixed liquid by measuring pump control
Micro- reaction channel into micro passage reaction of flow processed is reacted.
According to an aspect of the present invention, reaction product is collected together by the collection using collecting tank.
According to an aspect of the present invention, the filtering and washing are entered the reaction product of collection using cross-flow filtration device
Row filtering and washing.
Preferably, cross-flow filtration device temperature control is at≤60 DEG C, membrane flux≤500ml/mi n.
According to an aspect of the present invention, graphite, the concentrated sulfuric acid and potassium permanganate are pressed 1 by the premix:2:30 are premixed.
A kind of equipment for preparing graphene oxide, including premixed device, micro passage reaction, collecting tank and cross-flow filtration
Device, mixed device, micro passage reaction, collecting tank and the cross-flow filtration device are sequentially connected.
The premixed device is used for the mixing of graphite, the concentrated sulfuric acid and potassium permanganate；
The micro passage reaction carries out reaction generation graphene oxide for graphite, the concentrated sulfuric acid and potassium permanganate；
The collecting tank, the mixture for collecting reaction product, i.e. graphene oxide and waste acid liquor；
The cross-flow filtration device, for isolating graphene dispersing solution and waste acid liquor, the graphene dispersion isolated
Liquid is washed simultaneously in cross-flow filtration device.
According to an aspect of the present invention, it is provided with measuring pump between the premixed device and micro passage reaction.
According to an aspect of the present invention, the micro passage reaction uses micro- reaction channel of heart-shaped structure.
According to an aspect of the present invention, it is described that three groups of micro passage reactions are provided between premixed device and collecting tank.
Micro- reaction channel of 400-600 heart-shaped structure is provided with every group of micro passage reaction.
According to an aspect of the present invention, drying device is set in the downstream of cross-flow filtration device, the drying device is adopted
Use spray dryer.
The unique heat transfer characteristic of micro passage reaction is strongly exothermic by some, and the reaction that autoclave can not amplify production can obtain
Control, and accomplish scale production.The heat exchange area of micro passage reaction is 1000 times of common tank reactor.By fast
Quick change heat, the focus for reacting production are eliminated, and so as to realize safety in production, effectively improve reaction yield and selectivity.Using
It is typically strong exothermal reaction that oxidizing process, which prepares graphene oxide, can produce the accessory substance permanganic acid with explosive in the reaction
Acid anhydride, 55 DEG C decomposition, 95 DEG C blast, thus be one kind in Chemical Manufacture than relatively hazardous reaction.Using micro passage reaction from
Solve the problems, such as that its pyroreaction is dangerous high in line with the angle of safety.
It is typically strong exothermal reaction to prepare graphene oxide using oxidizing process, can produce the pair with explosive in the reaction
Product permanganic anhydride, 55 DEG C decomposition, 95 DEG C blast, thus be one kind in Chemical Manufacture than relatively hazardous reaction.In oxidizing process
Prepare in graphene oxide field also with tank reactor, this prepares graphene oxide large-scale production to oxidizing process and caused
Limitation.With constantly increasing graphene oxide production capacity demand, inventor to oxidizing process by preparing graphite oxide
Reaction mechanism, reaction heat, reaction mass and the product of alkene and the further investigation of intermediate product situation, it have devised a kind of using micro-
Channel reactor carries out the process and production equipment system of graphene oxide production.Production technology is not only improved, is improved
Production efficiency, is also prevented from technique explosion issues occur.
The reaction case contrast of production technology and conventional oxidation graphene production technology disclosed by the invention：
(1) in still reaction, reaction temperature generally selects 10 DEG C-medium temperature of low temperature, 35 DEG C-high temperature, 65 DEG C of three warm areas and come instead
Should, in still reaction, reaction temperature can only be limited under a relatively low safe temperature (such as less than 30 DEG C) progress, and be difficult to
Temperature control is accurate；And as long as temperature controls a temperature can between 35-55 DEG C in micro passage reaction, in order to realize
More preferable effect, three microchannels can be used.
(2) in still reaction, due to being limited by equipment itself, heat and mass is slower, and reaction temperature control is inaccurate, temperature control
Precision is typically at ± 6 DEG C；And temperature-controlled precision can reach ± 2 DEG C in micro passage reaction.
(3) in still reaction, one batch of production is usually more than 20 hours；It is and continuous 6 small in micro passage reaction
When one batch.
(4) strict temperature control can effectively improve the selectivity and yield of reaction.Product yield is from autoclave
150% bring up in micro passage reaction 180%.The oxygen carbon mol ratio of product also brings up to 0.7 by original 0.5.Receive
Rate=GO weight/graphite weight * 100%, oxygen carbon mol ratio is by elementary analysis and calculates acquisition (O-4*S)/C.
Production equipment provided by the invention, using micro passage reaction as reaction unit, according to reactant and reacted
The characteristics of journey, is designed, and premixed device, measuring pump, cross-flow reaction unit and collecting tank are organically assembled, and is improved anti-
Answer efficiency and production security.Production equipment provided by the invention is more suitable for mass producing graphene oxide.
Brief description of the drawings
Fig. 1 is traditional tank reactor structural representation；
Fig. 2 is the device structure schematic diagram that the present invention prepares graphene oxide；
Fig. 3 is the structural representation of the single pellet reactor in micro passage reaction in equipment disclosed by the invention；
Wherein, 1- transmission devices, 2- axle envelopes, 3- enter hole (or charge door), 4- bearings, 5- blow-off pipes, 6- agitating shafts, 7-
Chuck, 8- kettlies, 9- agitators, 10- premixed devices, 20,30,40- micro passage reactions, 50- collecting tanks, 60- cross-flow filtrations dress
Put, the micro- reaction channels of 70-, 80- measuring pumps, 90- collecting tanks (collection graphene oxide dispersion), 100- collecting tanks (collect oxygen
Graphite alkene powder), 110- spray dryers, 120- waste collection tanks.
Embodiment
Hereinafter, some exemplary embodiments are simply just described.As one skilled in the art will recognize that
Like that, without departing from the spirit or scope of the present invention, can be by increasing, deleting, the various different modes such as changing
The described embodiment of modification.Therefore, description is considered essentially illustrative rather than restrictive.
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1：
(1) equipment for preparing graphene oxide, as shown in Fig. 2 including：Premixed device 10, micro passage reaction 20-40, receive
Collect tank 50 and cross-flow filtration device 60, the premixed device 10, micro passage reaction 20-40, collecting tank 50 and cross-flow filtration dress
Put 60 to be sequentially connected, measuring pump 80 is provided between the premixed device 10 and micro passage reaction 20.The concentrated sulfuric acid, graphite and Gao Meng
Sour potassium carries out low-temperature mixed in premixed device 10, micro passage reaction 20-40 is pumped into through measuring pump 80, in micro passage reaction
20-40 flows into collecting tank 50 after reacting, the product mixtures collected in 50 are carried out cross-flow filtration by cross-flow filtration device 60,
Obtain graphene oxide dispersion and be collected into go out with the product of cross-flow filtration device 60 after the filtering of cross-flow filtration device 60
In the connected collecting tank 90 of mouth, the waste liquid (mainly containing sulfuric acid, potassium sulfate, manganese sulfate and water) for filtering and cementing out is collected into
Filtrate collecting tank 120.Such as crossing needs graphene oxide dispersion product, the equipment of the present embodiment to this.If necessary to
To graphene oxide powder, then spray dryer 110 is set in the downstream of cross-flow reactor 60, the graphite oxide obtained after drying
Alkene powder is collected into collecting tank 100.The micro passage reaction 2-4, is reacted for graphite, the concentrated sulfuric acid and potassium permanganate
Generate graphene oxide.As shown in figure 3, micro- reaction channel 70 in the micro passage reaction is heart-shaped structure.
(2) method for preparing graphene oxide, including：
Premixed at 10 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 match somebody with somebody in premixed device 1
System is completed；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 35 DEG C, single
Heart-shaped micro- reaction channel reaction time is 20s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 165%.The oxygen carbon mol ratio of product is 0.52.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Embodiment 2：
(1) equipment of graphene oxide is prepared with embodiment 1.
(2) method for preparing graphene oxide, including：
Premixed at 0 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 match somebody with somebody in premixed device 1
System；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 45 DEG C, single
Heart-shaped micro- reaction channel reaction time is 20s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 172%.The oxygen carbon mol ratio of product is 0.58.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Embodiment 3：
(1) equipment of graphene oxide is prepared with embodiment 1.
(2) method for preparing graphene oxide, including：
Premixed at 15 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 prepare in premixed device 1；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 55 DEG C, single
Heart-shaped micro- reaction channel reaction time is 20s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 180%.The oxygen carbon mol ratio of product is 0.65.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Embodiment 4：
(1) equipment of graphene oxide is prepared with embodiment 1.
(2) method for preparing graphene oxide, including：
Premixed at 0 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 match somebody with somebody in premixed device 1
System；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 45 DEG C, single
Heart-shaped micro- reaction channel reaction time is 5s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 170%.The oxygen carbon mol ratio of product is 0.58.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Embodiment 5：
(1) equipment of graphene oxide is prepared with embodiment 1.
(2) method for preparing graphene oxide, including：
Premixed at 15 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 prepare in premixed device 1；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 55 DEG C, single
Heart-shaped micro- reaction channel reaction time is 70s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 180%.The oxygen carbon mol ratio of product is 0.68.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Embodiment 6：
(1) equipment of graphene oxide is prepared with embodiment 1.
(2) method for preparing graphene oxide, including：
Premixed at 10 DEG C, premix liquid proportional is according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 match somebody with somebody in premixed device 1
System is completed；
Premixed liquid is fed into micro passage reaction 2-4 by measuring pump 8 to be reacted, reaction temperature is 35 DEG C, single
Heart-shaped micro- reaction channel reaction time is 15s；With
Product enters collecting tank 5 after the completion of reaction, and can obtain graphene oxide after the washing of cross-flow filtration device 6 disperses
Liquid product.
Product yield is 172%.The oxygen carbon mol ratio of product is 0.63.
Graphene oxide dispersion obtains graphene oxide powder product through being further dried.
Comparative example 1：
(1) device：Conventional reactor.As shown in Figure 1.
(2) method for preparing graphene oxide, including：
Liquid proportional is premixed according to graphite：Potassium permanganate：The concentrated sulfuric acid=1:3:30 prepare in premix kettle；
Premixed liquid is transferred into reactor by delivery pump to react, reaction temperature is 10 DEG C-medium temperature of low temperature, 35 DEG C-high temperature 65
DEG C, reaction time is 3 hours；With
Product enters collecting tank after the completion of reaction, and graphene oxide dispersion is can obtain after cross-flow filtration washs.
Product yield is 150%.The oxygen carbon mol ratio of product is 0.7.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (11)
1. a kind of method for preparing graphene oxide, including：
Raw graphite, the concentrated sulfuric acid and potassium permanganate are premixed at low temperature；
Reaction；With
Collect, filter and graphene oxide dispersion product is obtained after washing.
2. preparing the method for graphene oxide according to claim 1, in addition to graphene oxide dispersion is dried,
Obtain graphene oxide powder product；Preferably, it is described dry using spray drying.
3. the method according to claim 1 or 2 for preparing graphene oxide, it is characterised in that the pre-compounding process control
Temperature of charge is at 0-15 DEG C.
4. the method according to claim 1 or 2 for preparing graphene oxide, it is characterised in that the reaction is at 20-65 DEG C
Lower progress, the reaction time of the reaction is 3-9h；It is preferred that react 6h at 35-55 DEG C.
5. the method according to claim 1 or 2 for preparing graphene oxide, it is characterised in that the reaction is using micro-
Channel reactor is carried out；Preferably, the micro passage reaction uses micro- reaction channel of heart-shaped structure；It is further preferred that
Material residence time in micro- reaction channel of each heart-shaped structure is 5-70S, preferably 15-20S；It is it is further preferred that described
Reaction is completed by three groups of micro passage reactions, be provided with every group of micro passage reaction 400-700 heart-shaped structure it is micro- instead
Answer passage；It is further preferred that micro- reaction channel reaction temperature, three groups of microchannel plates are controlled by the chuck of micro passage reaction
Answer the jacket temperature of device to be from upstream to downstream and be followed successively by 35 DEG C, 45 DEG C, 65 DEG C；
It is further preferred that pre- be mixed in premixed device is carried out, obtain controlling after premixed liquid the entrance of flow by measuring pump
Micro- reaction channel of micro passage reaction is reacted.
6. the method according to claim 1 or 2 for preparing graphene oxide, it is characterised in that described to collect using collection
Reaction product is collected together by tank；And/or the filtering and washing are entered the reaction product of collection using cross-flow filtration device
Row filtering is washed simultaneously；Preferably, the cross-flow filtration device temperature control is at≤60 DEG C, membrane flux≤500ml/min.
7. the method according to claim 1 for preparing graphene oxide, it is characterised in that described to premix graphite, dense sulphur
Acid and potassium permanganate press 1:2:30 are premixed.
A kind of 8. equipment for preparing graphene oxide, it is characterised in that including premixed device, micro passage reaction, collecting tank and
Cross-flow filtration device, the premixed device, micro passage reaction, collecting tank and cross-flow filtration device are sequentially connected.
9. the equipment according to claim 8 for preparing graphene oxide, it is characterised in that the premixed device and microchannel plate
Answer and be provided with measuring pump between device.
10. the equipment for preparing graphene oxide according to claim 8 or claim 9, it is characterised in that the micro passage reaction
Using micro- reaction channel of heart-shaped structure；Preferably, it is described be provided between premixed device and collecting tank three groups of microchannel plates should
Device, micro- reaction channel of 400-600 heart-shaped structure is provided with every group of micro passage reaction.
11. according to the equipment for preparing graphene oxide described in claim any one of 8-10, it is characterised in that in cross-flow filtration
The downstream of device sets drying device, and the drying device uses spray dryer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862267A (en) * | 2018-08-08 | 2018-11-23 | 南京工业大学 | A kind of preparation method of high concentration liquid crystalline phase single-layer graphene oxide dispersion liquid |
| CN111377437A (en) * | 2018-12-31 | 2020-07-07 | 浙江工业大学 | Device and method for stripping layered material |
| CN111994903A (en) * | 2020-08-28 | 2020-11-27 | 西安近代化学研究所 | Synthetic method of 3-aminopropyltriethoxysilane modified graphene oxide |
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| CN112811417A (en) * | 2021-02-10 | 2021-05-18 | 中国科学技术大学先进技术研究院 | Method for preparing graphene oxide through microfluidics |
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