CN112645317A - Preparation method and equipment of graphene oxide or graphite oxide - Google Patents
Preparation method and equipment of graphene oxide or graphite oxide Download PDFInfo
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- CN112645317A CN112645317A CN202011617350.4A CN202011617350A CN112645317A CN 112645317 A CN112645317 A CN 112645317A CN 202011617350 A CN202011617350 A CN 202011617350A CN 112645317 A CN112645317 A CN 112645317A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 114
- 239000010439 graphite Substances 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 165
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000002002 slurry Substances 0.000 claims abstract description 64
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims description 98
- 238000000746 purification Methods 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 52
- 238000011282 treatment Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000005374 membrane filtration Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims 1
- 238000011085 pressure filtration Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005057 refrigeration Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000012806 monitoring device Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000013014 purified material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
Abstract
The invention discloses a preparation method of graphene oxide or graphite oxide, which comprises the following steps: s1, sequentially adding concentrated sulfuric acid, graphite, potassium permanganate and water into a reaction kettle, and under the condition of stirring, obtaining graphene oxide or graphite oxide slurry by controlling reaction temperature and reaction time, wherein salt in the graphene oxide or graphite oxide slurry forms a supersaturated state; s2, purifying the graphene oxide or graphite oxide slurry obtained in the step S1, and separating to remove salt particles; s3: purifying the material obtained in the step S2 to obtain cake material, dry material or slurry material with high solid content; s4: mixing and dispersing the cake material, the dry material or the slurry material obtained in the step S3 with water to form slurry or solution material with low solid content; s5: purifying the slurry or the solution-state material obtained in the step S4 again to obtain cake materials, dry materials or slurry-state materials with higher solid content again; and S6: the steps S4 and S5 may be repeatedly performed several times.
Description
Technical Field
The invention belongs to the field of graphene, and relates to a preparation method and equipment for improving the production efficiency of graphene oxide or graphite oxide.
Background
To date, there are three main methods for preparing graphene oxide: the Brodie method, Staudenmier method and Hummers method. The Hummers method is prominent in the aspects of timeliness, safety and stability of the graphite oxide preparation, and is also an adopted method for preparing the graphite oxide in a large scale in an industrialized mode. The preparation principle of the Hummers method is as follows: intercalation and graphite oxide (powder or micro-tablets) are formed by strong oxide formed by concentrated sulfuric acid and potassium permanganate, the graphite oxide is oxidized and stripped through hydration reaction, and the graphite oxide containing functional groups C, O such as carboxyl, hydroxyl, epoxy, sulfonic group and the like is obtained after multiple times of washing and purification, the graphite oxide can be stripped into graphene oxide through ultrasonic, high-shear intensive stirring, high-pressure stripping and other modes, and stable graphene oxide suspension is formed in water.
Preparation route commonly used in the laboratory by Hummers method (see fig. 1): carrying out oxidation, intercalation and hydration processes of graphite in a beaker or a flask by controlling temperature, time and water addition amount, and washing and purifying the graphite oxide by suction filtration, filter pressing or centrifugation of the materials after the processes are finished;
the preparation route of the Hummers method for industrially producing graphite oxide on a large scale (as shown in figure 2): the oxidation, intercalation and hydration processes of graphite are realized by controlling the temperature, time and water addition amount in a reaction kettle, and the materials after the processes are subjected to suction filtration, filter pressing or centrifugation to wash and purify the graphite oxide;
as can be seen from the comparison of the two methods, the process for preparing graphite oxide in large scale in industrialization is basically the same as the process for preparing graphite oxide in a laboratory, but the production amount is different due to 1; 2. the industrial production has higher efficiency; 3. the cost is the core competitiveness of industrial preparation; therefore, the industrial large-scale production of the graphite oxide/graphene has stronger requirements on higher efficiency and more convenience.
The existing graphene oxide preparation technology focuses on how to optimize the oxidation process, for example, in a graphene oxide preparation method, ferric trichloride and dry ice are introduced on the basis of a Hummers method to improve the oxidation intercalation efficiency, reduce the heat dissipation in the reaction process and improve the oxidation yield, so that graphite oxide (CN111847439A) with higher oxidation degree, smaller particle size and lower cost is prepared; for example, a graphene oxide dispersion liquid, a preparation method and an application thereof are mainly introduced, and the graphene oxide dispersion liquid, the preparation method thereof and the application of the graphene oxide dispersion liquid in the preparation of modified cement mortar are not yet available (CN 111392721A); for example, in a preparation method of graphene oxide dispersion, ultrasound is mainly introduced into a graphite and sulfuric acid mixing section to increase the intercalation effect of sulfuric acid on graphite, and then a Hummers method is continuously adopted to prepare graphite oxide (CN 103787317B); for example, in "method and apparatus for preparing graphene oxide", a premixer, a microchannel reactor, a collection tank, and a cross-flow filtration device are mainly connected in sequence, and the heat problem of graphite oxide in the preparation process is improved by optimizing the heat transfer in the graphite oxide/graphene reaction process (CN 107879337A);
the existing patents aim at proposing the feasibility of preparation, but do not research the preparation efficiency, and do not propose the solution of the problems of long preparation time, low purification efficiency and high content of metal elements in the product in the actual production process. In the conventional preparation, after the reaction, the oxidized graphene containing metal impurities or the oxidized graphite directly enters a washing purification section, a large amount of washing liquid and a long purification time are needed to remove the metal impurities in the product, a large amount of washing liquid needs to be treated, and the treatment of wastewater and waste liquid needs high cost and a long purification time.
Disclosure of Invention
The invention aims to overcome one or more problems in the prior art and provides a preparation method of graphene oxide or graphite oxide, which can effectively improve the production efficiency;
another object of the present invention is to provide an apparatus for producing graphene oxide or graphite oxide, which can effectively perform the above method.
In order to achieve the purpose, the scheme of the invention is as follows:
a method for preparing graphene oxide or graphite oxide, comprising:
s1, sequentially adding concentrated sulfuric acid, graphite, potassium permanganate and water into a reaction kettle, and under the condition of stirring, obtaining graphene oxide or graphite oxide slurry by controlling reaction temperature and reaction time, wherein salt in the graphene oxide or graphite oxide slurry forms a supersaturated state;
s2, purifying the graphene oxide or graphite oxide slurry obtained in the step S1, and separating to remove heavier salt particles;
s3: purifying the material obtained in the step S2 to obtain cake material, dry material or slurry material with high solid content;
s4: mixing and dispersing the cake material, the dry material or the slurry material obtained in the step S3 with water to form slurry or solution material with low solid content;
s5: purifying the slurry or the solution-state material obtained in the step S4 again to obtain cake materials, dry materials or slurry-state materials with higher solid content again; and
s6: the steps S4 and S5 may be repeatedly performed several times.
The invention generally controls the solid content of the material after the first purification treatment to be more than 20 percent, the solid content after the second purification treatment to be more than 25 percent, and the solid content after each purification treatment is maintained to be more than 30 percent.
According to an aspect of the present invention, in S1, the method for controlling temperature uses a method of alternating cooling and heating. Preferably, the cold-heat exchange mode is direct cold/heat exchange, indirect cold/heat exchange or gas heating.
According to an aspect of the invention, in the S1, the temperature is controlled at 30-90 ℃; the time is controlled to be 9-15 h. Preferably, the reaction temperature is raised to 40 plus or minus 2 ℃, the reaction is continued for 5 plus or minus 0.5h while maintaining the temperature, and then the reaction temperature is raised to 85 plus or minus 2 ℃, and the reaction is continued for 5 plus or minus 0.5h while maintaining the temperature.
According to an aspect of the present invention, in the S1, the stirring is performed by magnetic stirring or mechanical stirring.
The method can realize that the salt in the obtained reaction product (the solution containing the graphene oxide or the graphite oxide) is in a supersaturated state by controlling the temperature in a cold-hot alternating mode and adopting a staged reaction. In actual production, crystalline particles of the salt are visible to the naked eye in the reactants, but relatively few particles. The cold and hot alternation efficiency determines the difficulty degree of control of the reaction, and cold/hot exchange is quick correspondingly to extreme and quick cold and hot change, cold/hot exchange is slow, and extreme and quick cold and hot change is slow correspondingly.
According to an aspect of the present invention, in S1, the reaction kettle is a reaction kettle with a cold and hot control device, preferably a jacketed reaction kettle or a coil reaction kettle.
According to an aspect of the present invention, in S2, the purification process crystallizes the salt in the graphene oxide or graphite oxide slurry obtained in step S1.
Preferably, the particle size of the crystalline salt particles is D50 ═ 26 to 28 μm.
Preferably, the purification treatment is to perform centrifugation on the graphene oxide or graphite oxide slurry obtained in step S1 and then perform standing treatment to obtain a deposited crystalline salt.
Preferably, the purification treatment is completed by combining a transfer device and a purifier, and the centrifugal action is realized by combining the feeding pressure when the graphene oxide or graphite oxide slurry enters the purifier with the space arrangement of the purifier.
Preferably, the refiner is configured to have an upper material processing chamber and a lower salt collection chamber, wherein the upper material processing chamber is configured as a chamber in which an upper cylinder and a lower cone communicate, and the oxidized graphene or oxidized graphite slurry enters the refiner from and tangentially to the lower cone of the refiner.
Further preferably, the upper material handling chamber may hold 4-5 tons of the oxidized graphene or oxidized graphite slurry.
Further preferably, the pressure at which the graphene oxide or graphite oxide slurry is fed is controlled to be 0.2 MPa.
Further preferably, the standing treatment time is 1-2h, preferably 1.5 h.
The method realizes the centrifugation of the material by the feeding mode of the purifier, and further stands the material in the purifier, so that the method can realize the accurate control of most of the reaction product (the solution containing graphene oxide or graphite oxide) in the material to be crystallized, and can stably realize the particle diameter of the crystallized salt D50-26-28 mu m. (see detection report of FIG. 7).
According to an aspect of the present invention, in each of the S3 and S5, the purification treatment is performed by a filter press, a suction filtration or a membrane filtration.
According to an aspect of the present invention, in the S4, the weight ratio of the cake, the dry material or the material in the slurry state obtained in the step S3 to the water is 1: (20-30). The excessive water addition amount brings great burden to the next purification, and the generated waste acid has large amount, thereby bringing pressure to the waste acid treatment at the rear end; the water addition amount is too small, and the next purification effect is not good. The research shows that the weight ratio of the materials to the water is 1: (20-30), the whole process is smooth, the effect is high, and the waste acid discharge capacity pressure is not large.
According to one aspect of the invention, the mixing dispersion employs high speed stirring and/or high speed shearing emulsification and/or ultrasonic dispersion.
The invention also provides equipment for producing the graphene oxide or the graphite oxide, which comprises a reaction kettle, a first transfer device, a purifier, a second transfer device, a first purifier, a third transfer device and a first collector,
the first transfer device is arranged between the reaction kettle and the purifier, is connected with the reaction kettle and the purifier, and is used for conveying all products discharged by the reaction kettle into the purifier; the second transfer device is arranged between the purifier and the first purifier, is connected with the purifier and the first purifier, and is used for conveying the graphene oxide or the graphite oxide slurry separated from the purifier into the first purifier; the third transfer device is arranged between the first purifier and the first collector and is used for conveying the graphene oxide or the graphite oxide treated by the first purifier into the first collector.
According to one aspect of the invention, the purifier is provided with an upper material processing chamber and a lower salt collecting chamber, the upper material processing chamber and the lower salt collecting chamber are connected by a first flange, an outlet of the first relay is connected with an inlet of the upper material processing chamber, and an outlet of the upper material processing chamber is connected with a second relay.
According to one aspect of the invention, the lower end of the lower collection chamber is provided with a second flange for connection with an external waste liquid collection device.
According to one aspect of the invention, the upper collecting chamber is set to be a structure that an upper cylinder body is communicated with a lower cone body, and comprises a shell, a plurality of exhaust valves are arranged at the top of the shell, an inlet is arranged on the side wall of the shell, which is positioned on the lower cone body, and is tangent to the arc surface of the lower cone body, a discharge outlet is arranged on the shell, which is positioned on the lower cone body, and is connected with the second transfer device.
According to one aspect of the invention, the first purifier is a filter press, suction filtration or membrane filtration device, preferably an acid resistant filter press device.
According to one aspect of the invention, the first purifier comprises a first inlet, a first outlet and a second outlet, the outlet of the second relay is connected with the inlet of the purifier, the first outlet is connected with the third relay, the third relay sends the cake, dry material or slurry material filtered by the purifier to the first collector, and the second outlet is used for discharging the purified filtrate.
According to an aspect of the present invention, the apparatus for producing graphene oxide or graphite oxide further comprises: and the fourth transfer device is arranged between the collector and the first purifier and is used for sending the material discharged by the collector into the first purifier for purification treatment again. Further, the first purifier 11, the third relay 30, the first collector 12 and the fourth relay 40 may realize the circulation unit 5. The circulation unit 5 can realize circulation purification treatment until the material reaches the purification requirement, and the material is sent into the product collection device from the first purifier 11.
Preferably, the purifier further comprises a second inlet connected to the fourth intermediate transfer vessel.
According to an aspect of the present invention, the apparatus for producing graphene oxide or graphite oxide further comprises: a fourth converter and a second purifier; the fourth transfer device is arranged between the collector and the second purifier and is used for conveying the material discharged by the collector into the second purifier for purification treatment.
According to an aspect of the present invention, the apparatus for producing graphene oxide or graphite oxide further comprises: a fifth transfer device, a second collector, a sixth transfer device and a third purifier; the fifth transfer device is arranged between the second purifier and the second collector and is used for sending the cake materials, the dry materials or the materials in a slurry state filtered by the second purifier into the second collector for mechanical dispersion; and the sixth transfer device is arranged between the second collector and the third purifier and is used for sending the dispersion liquid in the second collector into the third purifier for purification treatment.
According to an aspect of the present invention, the apparatus for producing graphene oxide or graphite oxide further comprises: the seventh transfer device is arranged between the third purifier and the third collector and is used for sending the cake materials, the dry materials or the materials in a slurry state filtered by the third purifier into the third collector for mechanical dispersion; the eighth transfer device is arranged between the third collector and the fourth purifier and is used for sending the dispersion liquid in the third collector into the fourth purifier for purification treatment.
According to one aspect of the invention, the collector is a device with mechanical dispersive mixing functions, such as a storage tank with a stirrer, a storage tank with a shearing device, etc.
According to one aspect of the present invention, the transfer device is a centrifugal pump, an air pump, a mechanical pump, an acid-proof pump, a diaphragm pump, a slurry pump, or the like, which can transfer materials, and preferably, the acid-proof pump is used.
According to one aspect of the invention, the reaction kettle adopts a jacketed reaction kettle and a coil type reaction kettle. Other reactors with thermal and cold controls known to those skilled in the art may be used. The refrigeration equipment is not limited to refrigerators, ice makers and freezers, and other equipment capable of playing a refrigeration role can be used; the heating device is not limited to a water heater and electric heating, and other devices capable of heating can be used. The reaction kettle is provided with the temperature monitoring device for monitoring the temperature of reactants, such as a thermometer, a thermocouple or other equipment capable of monitoring the temperature is arranged on the reaction kettle. The application is as follows. The reaction kettle is provided with a time monitoring device, for example, a clock and a timer are arranged on the reaction kettle, and other devices capable of playing a timing role can be used.
According to the invention, the reaction in the reaction kettle is controlled to enable the salt in the reaction product to form a supersaturated state, and then the purification process is further completed through the configuration of the purifier, so that the particle size of the crystallized salt in the reaction product is accurately and stably controlled, on one hand, most or all of the salt can be effectively crystallized, on the other hand, the control of the particle size is successfully completed for further discharging the crystallized salt, and the blockage of equipment is avoided. Meanwhile, the invention provides a novel preparation method and novel preparation equipment based on research and research on preparation including purification processes. In the preparation method, the purifier is included, and the graphene oxide or the graphite oxide product can be separated from the metal salt impurities in the graphene oxide or the graphite oxide product before the purification section, namely purification is carried out, so that the impurity salt is reduced to enter the subsequent purification section, the purification time is greatly reduced, the preparation efficiency is improved, and the content of the metal impurities in the product is reduced. Compared with the conventional process flow for producing graphene oxide or graphite oxide on a large scale, the method has the following beneficial effects:
1. the novel preparation method and equipment for producing the graphene oxide or the graphite oxide are provided, the equipment is formed by combining a plurality of functional equipment, the preparation period is short, and the content of metal element impurities in a product is low;
2. the preparation method and the equipment for producing the graphene oxide or the graphite oxide comprise a purifier, and the graphene oxide or the graphite oxide can be separated from impurities in the graphene oxide or the graphite oxide, so that a large amount of waste salt is removed in a purification section, and only a small amount of waste salt flows to the purification section, thereby shortening the purification time and reducing the metal element impurities in a finished product;
3. the salt separated in the purifier can be used for preparing additional products such as magnesium sulfate, calcium sulfate and the like after being processed, or can be used as a solid material for disposal after being dried.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the background art;
FIG. 2 is a flow chart of the background art;
FIG. 3 is a schematic view of a production apparatus of example 1 of the present invention;
FIG. 4 is a schematic view of a production apparatus in example 2 of the present invention;
FIG. 5 is a schematic diagram of the purifier of the apparatus of the present invention;
FIG. 6 is a schematic sectional view taken along the line A-A in FIG. 5;
FIG. 7 is a schematic illustration of the inlet and outlet of a purifier in the apparatus of the present invention;
FIG. 8 shows the results of measuring the contents of Mn and K obtained in example 1;
FIG. 9 is a report of the detection of crystallized salt particles after purification treatment in the method of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
referring to fig. 3, this example shows a preferred embodiment of the apparatus for producing graphene oxide or graphite oxide according to the present invention. The equipment comprises a reaction kettle 1, a first transfer device 10, a purifier 2, a second transfer device 20, a first purifier 11, a third transfer device 30, a first collector 12 and a fourth transfer device 40,
the first transfer device 10 is arranged between the reaction kettle 1 and the purifier 2, is connected with the reaction kettle and the purifier, and is used for conveying all products discharged from the reaction kettle into the purifier; the second transfer device 20 is arranged between the purifier 2 and the first purifier 11, is connected with the purifier 2 and the first purifier 11, and is used for conveying the graphene oxide or graphite oxide slurry separated from the purifier 2 into the first purifier 11; the third transfer device 30 is disposed between the first purifier 11 and the first collector 12, and is configured to send the graphene oxide or graphite oxide processed by the first purifier 11 into the first collector 12; the fourth transfer device 40 is disposed between the first collector 12 and the first purifier 11, and is configured to send the material discharged from the first collector 12 to the first purifier 11 for purification again. The first purifier 11, the third transfer device 30, the first collector 12 and the fourth transfer device 40 can realize the circulation unit 5, and can realize circulation purification treatment until the material reaches the purification requirement, and the final product is transferred from the first purifier 11 to the finished product packaging place through the transfer device 100.
The structure of each device in the apparatus shown in this embodiment will be described in further detail below.
Referring to fig. 5 and 6, the purifier 2 is provided with an upper material processing chamber 21 and a lower salt collecting chamber 22, the upper material processing chamber 21 and the lower salt collecting chamber 22 are connected by a first flange 23, an outlet of the first relay 10 is connected to an inlet 26 of the upper material processing chamber 21, and an outlet 27 of the upper material processing chamber 21 is connected to the second relay 20. The upper collection chamber 21 includes a housing 20, which encloses a space including an upper cylinder 211 and a lower cone 212, the upper cylinder 211 and the lower cone 212 are communicated, and the upper cylinder 211 and the lower cone 212 may be integrally formed. The top of the housing 21 is provided with a number of exhaust valves 25, which exhaust valves 25 keep the pressure in the upper material treatment chamber 21 in equilibrium. Referring to fig. 6, the sidewall of the housing 20 located on the lower cone 212 is provided with an inlet 26, the inlet 26 is tangent to the arc surface of the lower cone 212, the housing 20 located on the lower cone 212 is provided with a discharge outlet 27, and the discharge outlet 27 is connected with the second transfer device 20. As a non-optimal way, the discharge opening 27 may be connected to the transfer device 20 at any position of the upper material processing chamber, and not connected to the lower salt collecting chamber. As shown in fig. 5, the lower end of the lower collection chamber 22 is provided with a second flange 24 for connection with an external waste liquid collection device. The purifier 2 is used in the purification treatment process of step S2 of the present invention, that is, the graphene oxide or graphite oxide slurry obtained in step S1 is subjected to centrifugation and then to standing treatment to obtain precipitated crystalline salt. The centrifugation is achieved by the feeding direction, feeding pressure and purifier space settings when the graphene oxide or graphite oxide slurry enters the purifier. The graphene oxide or graphite oxide slurry enters the purifier from the lower cone of the purifier in a tangential direction with the lower cone, the material can form self-centrifugation when entering the purifier under the action of feeding pressure and feeding direction, and saturated salt in the material is further crystallized under the action of the centrifugation. The salt is then further crystallized by further standing and deposited into the salt collection chamber 22. To achieve a better centrifuge effect, the upper process chamber 21 of the purifier has a volume to accommodate 4-5 tons of the product of step S1. During production, the pressure of the oxidized graphene or oxidized graphite slurry during feeding is controlled to be 0.2 MPa. The standing time is 1-2h, preferably 1.5 h. The method realizes the centrifugation of the material by the feeding mode of the purifier, and further stands the material in the purifier, so that the method can realize the accurate control of most of the reaction product (the solution containing graphene oxide or graphite oxide) in the material to be crystallized, and can stably realize the particle diameter of the crystallized salt D50-26-28 mu m. (see detection report of FIG. 9). Purifier 2 is fixed by bracket 28; the number of the brackets 28 is several; specifically 2-4. The structure of the bracket 28 is at least one of triangular, rectangular, square and circular.
Referring to fig. 7, the first purifier 11 is a filter press, suction filtration or membrane filtration device, preferably an acid resistant filter press device. The first purifier 11 comprises a first inlet 111, a first outlet 112, a second inlet 113 and a second outlet 114, the outlet of the second transfer device 20 is connected with the first inlet 111 of the first purifier, the first outlet 112 of the first purifier is connected with the third transfer device 30, the third transfer device 30 sends the filtered cake, dry material or slurry material of the first purifier into the first collector 12, the second inlet 113 of the first purifier is connected with the fourth transfer device 40, and the fourth transfer device 40 sends the material in the first collector into the first purifier for purification again. The second outlet 114 of the first purifier is used to discharge the purified filtrate or final product. Before the purification is finished, the second outlet 114 is used for discharging the filtrate, and after the purification meets the requirement, the final product is discharged from the second outlet 114 and is sent to the finished product packaging place through the transfer 100. In particular, a three-way valve and corresponding valve may be connected to the second outlet to effect switching between discharge of filtrate and discharge of final product.
In this embodiment, the collector is a device with a mechanical dispersing and blending function, such as a storage tank with a stirrer, a storage tank with a shearing device, and the like. The rotating device adopts equipment which can transfer materials, such as a centrifugal pump, an air pump, a mechanical pump, an acid-proof pump, a diaphragm pump, a slurry pump and the like, and preferably selects the acid-proof pump. The reaction kettle adopts a jacketed reaction kettle and a coil type reaction kettle. Other reactors with thermal and cold controls known to those skilled in the art may be used. The refrigeration equipment is not limited to refrigerators, ice makers and freezers, and other equipment capable of playing a refrigeration role can be used; the heating device is not limited to a water heater and electric heating, and other devices capable of heating can be used. The reaction kettle is provided with the temperature monitoring device for monitoring the temperature of reactants, such as a thermometer, a thermocouple or other equipment capable of monitoring the temperature is arranged on the reaction kettle. The application is as follows. The reaction kettle is provided with a time monitoring device, for example, a clock and a timer are arranged on the reaction kettle, and other devices capable of playing a timing role can be used.
Example 2:
referring to fig. 4, this example shows a preferred embodiment of the apparatus for producing graphene oxide or graphite oxide according to the present invention. The structures of the devices are the same, and the difference is the combination mode of the devices in the equipment. As shown in fig. 4, the present embodiment shows an apparatus including: the reactor comprises a reaction kettle 1, a first transfer device 10, a purifier 2, a second transfer device 20, a first purifier 11, a third transfer device 30, a first collector 12, a fourth transfer device 40, a second purifier 13, a fifth transfer device 50, a second collector 14, a sixth transfer device 60, a third purifier 15, a seventh transfer device 70, a third collector 16, an eighth transfer device 80 and a fourth purifier 17.
The first transfer device 10 is arranged between the reaction kettle 1 and the purifier 2, is connected with the reaction kettle and the purifier, and is used for conveying all products discharged from the reaction kettle into the purifier; the second transfer device 20 is arranged between the purifier 2 and the first purifier 11, is connected with the purifier 2 and the first purifier 11, and is used for conveying the graphene oxide or graphite oxide slurry separated from the purifier 2 into the first purifier 11; the third transfer device 30 is disposed between the first purifier 11 and the first collector 12, and is configured to send the graphene oxide or graphite oxide processed by the first purifier 11 into the first collector 12; the fourth transfer device 40 is disposed between the first collector 12 and the second purifier 13, and is configured to send the material discharged from the first collector 12 to the second purifier 13 for purification again. The first purifier 11, the third relay 30, the first collector 12 and the fourth relay 40 are combined into one purification unit 6. By analogy, each purifier, one collector and two repeaters can be combined into one purification unit. As shown in fig. 4, this embodiment also has purification units 7 and 8, and the final reaction product is discharged from the fourth purifier 17 and sent to the final product package through the transfer 100. In practice, the number of purification units can be further increased to achieve a better purification effect, and can also be correspondingly reduced according to actual production requirements.
Example 3:
a preparation method of graphene oxide or graphite oxide adopts the equipment shown in example 1, and specifically comprises the following steps:
adding 98 wt% concentrated sulfuric acid into a reactor, sequentially adding graphite and potassium permanganate into the reactor 1, wherein the weight ratio of graphite to potassium permanganate is as follows: preparing 98 wt% concentrated sulfuric acid according to 1g:4g:30 mL;
after the concentrated sulfuric acid, the graphite and the potassium permanganate are added, raising the temperature of the reactor 1 to 40 ℃, and continuously reacting for 5 hours;
after the reaction time is up, adding water to adjust the reaction temperature to 85 ℃, and continuing to react for 5 hours;
the reaction-completed material was passed through the apparatus of FIG. 3 and washed 5 times in configuration 5.
Specifically, the method for preparing graphene oxide comprises the following steps: the production was carried out using the apparatus described in example 1 according to the following procedure:
1) concentrated sulfuric acid, graphite, potassium permanganate and pure water are sequentially added into a reactor 1, under the condition of keeping mechanical mixing, cold and heat exchange is carried out through refrigeration equipment and heating equipment, and the reaction time of materials is ensured through a timer;
in the step 1), the reactor 1 is a reaction kettle with cold and hot control; in particular to a jacketed reaction kettle or a coil tube type reaction kettle;
the mechanical mixing mode is at least one of high-speed stirring, high-speed shearing emulsification and ultrasonic dispersion;
the refrigeration equipment is a refrigerator, an ice maker or a freezer;
the heating equipment is a water heater or electric heating equipment;
the cold-heat exchange mode is direct cold/heat exchange, indirect cold/heat exchange or gas heating;
the temperature monitoring device is a thermometer or a thermocouple;
the time monitoring device is a clock or a timer.
2) Transferring the product obtained in the step 1) into a purifier 2 through a transfer device 10;
in the step 2) of the said step,
the processing speed of the purifier 2 is controlled by the first transfer device 10;
the first transfer vessel 10 is connected to an inlet 26 of the upper material handling chamber of the purifier 2; the material enters along the tangential direction of a cone of the lower disposal chamber, the material can form self-centrifugation when entering the purifier under the action of the feeding pressure and the feeding direction, and saturated salt in the material is further crystallized under the action of the centrifugation. The salt is then further crystallized by further standing and deposited into the salt collection chamber 22. To achieve a better centrifuge effect, the upper process chamber 21 of the purifier has a volume to accommodate 4-5 tons of the product of step S1. During production, the pressure of the oxidized graphene or oxidized graphite slurry during feeding is controlled to be 0.2 MPa. The standing time is 1-2h, preferably 1.5 h. The method realizes the centrifugation of the material by the feeding mode of the purifier, and further stands the material in the purifier, so that the method can realize the accurate control of most of the reaction product (the solution containing graphene oxide or graphite oxide) in the material to be crystallized, and can stably realize the particle diameter of the crystallized salt D50-26-28 mu m. (see detection report of FIG. 9).
3) Transferring the material treated in the step 2) into a purifier 11 through a transfer device 20, and processing the material into a cake material, a dry material or a slurry material in the purifier 11 after the material transfer is finished;
4) transferring the material purified in the step 3) into a collector 12 through a transfer device 30, and changing the material treated in the step 3 into a slurry or solution state in the collector 12 by a mechanical dispersing and uniformly mixing method after the material transfer is finished;
5) transferring the material treated in the step 4) from the collector 12 to the purifier 11 through the transfer device 40, and treating the material into a cake material, a dry material or a slurry material in the purifier 13 after the material transfer is finished;
6) repeating the step 4) and the step 5) for a plurality of times to obtain a purified material;
in the step 6), the number of times can be 1 time, 2 times, 3 times or 4 times;
7) the purified material of step 6) is transported to a packaging place through a transfer 100.
The conversion rate of the product is 180 percent, and the Mn content in the finished product is 124 ppm.
The production equipment comprises a purifier which can separate the graphene oxide or the graphite oxide from impurities in the graphene oxide or the graphite oxide, so that a large amount of waste salt is removed in a purification section, and only a small amount of waste salt flows to the purification section, thereby shortening the purification time and reducing the metal element impurities in a finished product; as shown in fig. 8, for the material processed by the purification tank, we selected the material in the same washing stage (second washing) and monitored the content of K and Mn ions in the filtrate in one stage, and as can be seen from the parallel data shown in fig. 1, the content of Mn in the filtrate of the material processed by the purification tank is reduced by one time when the material is processed by the same number of post-treatments, and the content of K is basically stabilized at a value.
Example 4:
a preparation method of graphene oxide or graphite oxide adopts the equipment and specific method described in embodiment 1, and only mixing graphite, potassium permanganate: the amount ratio of 98 wt% concentrated sulfuric acid and the temperature of the reactor 1 were replaced as follows:
adding 98 wt% concentrated sulfuric acid into a reactor, sequentially adding graphite and potassium permanganate into the reactor 1, wherein the weight ratio of graphite to potassium permanganate is as follows: preparing 98 wt% concentrated sulfuric acid according to 1g:3g:30 mL;
after the sulfuric acid, the graphite and the potassium permanganate are added, the temperature of the reactor 1 is raised to 40 ℃, and the reaction is continued for 5 hours;
after the reaction time is up, adding water to adjust the reaction temperature to 85 ℃, and continuing to react for 5 hours;
the reacted material was washed 5 times in structure 5 by the scheme of fig. 3;
the conversion rate of the product is 175 percent, and the Mn content in the finished product is 103 ppm.
Example 4:
a preparation method of graphene oxide or graphite oxide adopts the equipment of embodiment 2, and comprises the following steps:
adding 98 wt% concentrated sulfuric acid into a reactor, sequentially adding graphite and potassium permanganate into the reactor 1, wherein the weight ratio of graphite to potassium permanganate is as follows: preparing 98 wt% concentrated sulfuric acid according to 1g:4g:30 mL;
after the sulfuric acid, the graphite and the potassium permanganate are added, the temperature of the reactor 1 is raised to 40 ℃, and the reaction is continued for 5 hours;
after the reaction time is up, adding water to adjust the reaction temperature to 85 ℃, and continuing to react for 5 hours;
the reaction-completed material was completed by the apparatus of FIG. 4.
Specifically, the method for preparing graphene oxide or graphite oxide comprises the following steps: the production was carried out using the apparatus described in example 2 according to the following procedure:
1) concentrated sulfuric acid, graphite, potassium permanganate and pure water are sequentially added into a reactor (1), and under the condition of keeping mechanical mixing, cold and heat exchange is carried out through refrigeration equipment and heating equipment so as to ensure the reaction temperature of the materials, and the reaction time of the materials is ensured through a timer;
2) transferring the product obtained in the step 1) into a purifier (2) through a transfer device (10);
3) transferring the material treated in the step 2) into a purifier (11) through a transfer device (20), and processing the material into a cake material, a dry material or a slurry material in the purifier (11) after the material transfer is finished;
4) transferring the material purified in the step 3) into a collector (12) through a transfer device (30), and changing the material treated in the step 3) into a slurry or solution state in the collector (12) by a mechanical dispersing and uniformly mixing method after the material transfer is finished.
5') transferring the materials treated in the step 4) from the collector (12) to a purifier (13) through a transfer device (40), and treating the materials into materials in a cake, dry materials or slurry state in the purifier (13) after the material transfer is finished;
6 ') transferring the material purified in the step 5') from the purifier (13) to a collector (14) through a transfer device (50), and mechanically dispersing and uniformly mixing the material in the collector (14) to prepare slurry or solution after the material is transferred;
7 ') transferring the materials treated in the step 6') from the collector (14) to a purifier (15) through a transfer device (60), and processing the materials into materials in a cake, dry materials or slurry state in the purifier (15) after the material transfer is finished;
8 ') transferring the material purified in the step 7') from the purifier (15) to a collector (16) through a transfer device (70), and mechanically dispersing and uniformly mixing the material in the collector (16) to prepare slurry or solution after the material transfer is finished;
9 ') transferring the materials treated in the step 8') from the collector (16) to a purifier (17) through a transfer device (80), and processing the materials into cakes, dry materials or slurry materials in the purifier (17) after the transfer is finished;
10 ') the material purified in step 9') is transferred from the purifier (17) to the final package by means of a transfer device (100).
The conversion rate of the product is 178%, and the Mn content in the finished product is 113 ppm.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A method for preparing graphene oxide or graphite oxide, comprising:
s1, sequentially adding concentrated sulfuric acid, graphite, potassium permanganate and water into a reaction kettle, and under the condition of stirring, obtaining graphene oxide or graphite oxide slurry by controlling reaction temperature and reaction time, wherein salt in the graphene oxide or graphite oxide slurry forms a supersaturated state;
s2, purifying the graphene oxide or graphite oxide slurry obtained in the step S1, and separating to remove salt particles;
s3: purifying the material obtained in the step S2 to obtain cake material, dry material or slurry material with high solid content;
s4: mixing and dispersing the cake material, the dry material or the slurry material obtained in the step S3 with water to form slurry or solution material with low solid content;
s5: purifying the slurry or the solution-state material obtained in the step S4 again to obtain cake materials, dry materials or slurry-state materials with higher solid content again; and
s6: the steps S4 and S5 may be repeatedly performed several times.
2. The method for preparing graphene oxide or graphite oxide according to claim 1, wherein in S1, the method for controlling temperature is a method of alternately cooling and heating;
preferably, the cold-heat exchange mode is direct cold/heat exchange, indirect cold/heat exchange or gas heating
Preferably, the temperature is controlled at 30-90 ℃; the time is controlled to be 9-15 h;
further preferably, the reaction temperature is increased to 40 plus or minus 2 ℃, the reaction is kept for 5 plus or minus 0.5h under the temperature, then the reaction temperature is adjusted to 85 plus or minus 2 ℃, and the reaction is kept for 5 plus or minus 0.5h under the temperature;
preferably, the stirring is magnetic stirring or mechanical stirring.
3. The method for preparing graphene oxide or graphite oxide according to claim 1, wherein in the step S1, the reaction kettle is a reaction kettle with a cold and heat control device, preferably a jacketed reaction kettle or a coil reaction kettle.
4. The method according to claim 1, wherein in S2, the purification treatment crystallizes the salt in the graphene oxide or graphite oxide slurry obtained in step S1, and preferably the particle size of the crystallized salt particles is D50-28 μm;
preferably, the purification treatment is to perform a centrifugal action on the graphene oxide or the graphite oxide slurry obtained in the step S1 and then to perform a standing treatment to obtain a deposited crystalline salt;
preferably, the purification treatment is completed by combining a transfer device and a purifier, and the centrifugal action is realized by combining the feeding pressure when the graphene oxide or graphite oxide slurry enters the purifier with the space arrangement of the purifier;
preferably, the purifier is provided in a structure with an upper material processing chamber and a lower salt collecting chamber, wherein the upper material processing chamber is provided as a chamber communicated with the upper cylinder and the lower cone, and the oxidized graphene or oxidized graphite slurry enters the purifier from the lower cone of the purifier and forms a tangential direction with the lower cone;
further preferably, the upper material handling chamber may hold 4-5 tons of the oxidized graphene or oxidized graphite slurry;
further preferably, the pressure at which the oxidized graphene or graphite oxide slurry is fed is controlled to be 0.2 MPa;
preferably, the standing treatment time is 1-2h, preferably 1.5 h.
5. The method according to claim 1, wherein in each of the steps S3 and S5, the purification treatment is performed by pressure filtration, suction filtration or membrane filtration.
6. The method for preparing graphene oxide or graphite oxide according to claim 1, wherein in step S4, the weight ratio of the cake, dry material or slurry material obtained in step S3 to water is 1: (20-30);
preferably, the mixing and dispersing adopt high-speed stirring and/or high-speed shearing emulsification and/or ultrasonic dispersion.
7. An apparatus for producing graphene oxide or graphite oxide, which is characterized by comprising a reaction kettle, a first transfer device, a purifier, a second transfer device, a first purifier, a third transfer device and a first collector,
the first transfer device is arranged between the reaction kettle and the purifier, is connected with the reaction kettle and the purifier, and is used for conveying all products discharged by the reaction kettle into the purifier; the second transfer device is arranged between the purifier and the first purifier, is connected with the purifier and the first purifier, and is used for conveying the graphene oxide or the graphite oxide slurry separated from the purifier into the first purifier; the third transfer device is arranged between the first purifier and the first collector and is used for conveying the graphene oxide or the graphite oxide treated by the first purifier into the first collector.
8. The apparatus of claim 7, wherein the purifier is provided with an upper material processing chamber and a lower salt collecting chamber, the upper material processing chamber and the lower salt collecting chamber are connected by a first flange, an outlet of the first transfer device is connected to an inlet of the upper material processing chamber, and an outlet of the upper material processing chamber is connected to a second transfer device.
9. The apparatus for producing graphene oxide or graphite oxide according to claim 8, wherein the lower end of the lower collection chamber is provided with a second flange for connecting with an external waste liquid collection device.
10. The apparatus according to claim 8, wherein the upper collection chamber is configured to communicate the upper cylinder with the lower cone, and comprises a housing, a plurality of exhaust valves are disposed on a top of the housing, an inlet is disposed on a sidewall of the housing, the sidewall of the housing is located on the lower cone, the inlet is tangent to an arc surface of the lower cone, a discharge outlet is disposed on the lower cone, and the discharge outlet is connected to the second transfer device.
11. The apparatus for producing graphene oxide or graphite oxide according to claim 7, wherein the first purifier is a filter press, suction filtration or membrane filtration apparatus, preferably an acid-resistant filter press apparatus;
preferably, the first purifier comprises a first inlet, a first outlet and a second outlet, the outlet of the second relay is connected with the inlet of the purifier, the first outlet is connected with the third relay, the third relay sends the cake, dry material or slurry material filtered by the purifier into the first collector, and the second outlet is used for discharging the purified filtrate.
12. The apparatus for producing graphene oxide or graphite oxide according to claim 7, further comprising: the fourth transfer device is arranged between the collector and the first purifier and is used for sending the material discharged by the collector into the first purifier for purification again;
preferably, the purifier further comprises a second inlet connected to the fourth intermediate transfer vessel.
13. The apparatus for producing graphene oxide or graphite oxide according to claim 7, further comprising: a fourth converter and a second purifier; the fourth transfer device is arranged between the collector and the second purifier and is used for conveying the material discharged by the collector into the second purifier for purification treatment;
preferably, the first purifier 11, the third relay 30, the first collector 12 and the fourth relay 40 may realize the circulation unit 5.
Preferably, the apparatus for producing graphene oxide or graphite oxide further comprises: a fifth transfer device, a second collector, a sixth transfer device and a third purifier; the fifth transfer device is arranged between the second purifier and the second collector and is used for sending the cake materials, the dry materials or the materials in a slurry state filtered by the second purifier into the second collector for mechanical dispersion; the sixth transfer device is arranged between the second collector and the third purifier and is used for sending the dispersion liquid in the second collector into the third purifier for purification treatment;
preferably, the apparatus for producing graphene oxide or graphite oxide further comprises: the seventh transfer device is arranged between the third purifier and the third collector and is used for sending the cake materials, the dry materials or the materials in a slurry state filtered by the third purifier into the third collector for mechanical dispersion; the eighth transfer device is arranged between the third collector and the fourth purifier and is used for sending the dispersion liquid in the third collector into the fourth purifier for purification treatment.
14. The apparatus for producing graphene oxide or graphite oxide according to any one of claims 7 to 13, wherein the collector is an apparatus having a mechanical dispersion and homogenization function, such as a storage tank with a stirrer, a storage tank with a shearing device, and the like.
15. The apparatus for producing graphene oxide or graphite oxide according to any one of claims 7 to 13, wherein the transfer device is a centrifugal pump, an air pump, a mechanical pump, an acid-proof pump, a diaphragm pump, a slurry pump, or the like, preferably an acid-proof pump, which is capable of transferring materials.
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