CN110894070A

CN110894070A - Device and method for continuously preparing graphite oxide

Info

Publication number: CN110894070A
Application number: CN201911242306.7A
Authority: CN
Inventors: 陈成猛; 孔庆强; 孙国华; 苏方远; 李晓明; 刘卓; 黄显虹; 李树珍; 李正杰; 康文杰
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2019-12-06
Filing date: 2019-12-06
Publication date: 2020-03-20

Abstract

The invention relates to a device and a method for continuously preparing graphite oxide, belonging to the technical field of graphite oxide preparation and comprising the following steps: adding graphite powder, sodium nitrate, sulfuric acid and an oxidant into a low-temperature reactor, fully mixing, and then entering a medium-temperature tubular reactor for oxidation reaction; adding a solvent when the material flows to a solvent tubular mixer, reacting in a high-temperature tubular reactor, and cooling to room temperature in a cooling tubular reactor; adding a reducing agent when the material flows to the reducing agent tubular mixer, and carrying out post-treatment to obtain the graphite oxide. The invention controls the mixing and reaction modes of materials through the pipeline and the pipeline mixer, overcomes the defects that a pure kettle type reactor cannot continuously produce materials and the mixing of the pure pipeline reactor is not uniform, has safe and high-efficiency production process and stable product quality, ensures the mixing uniformity of the materials in the reaction process, ensures the continuity and is beneficial to industrial production.

Description

Device and method for continuously preparing graphite oxide

Technical Field

The invention belongs to the technical field of graphite oxide preparation, and particularly relates to a device and a method for continuously preparing graphite oxide.

Background

Graphene is a novel carbon material with a two-dimensional honeycomb lattice structure composed of a single layer of carbon atoms. Due to the unique structure and excellent performance, the composite material has wide application in the fields of composite materials, energy storage, corrosion prevention, electromagnetic shielding and the like. The redox method is a mainstream method for preparing graphene powder on a large scale at present, and has the advantages of low cost and high stripping degree. The graphite oxide is an important intermediate for preparing graphene by a redox method, and the performance of the graphite oxide directly determines the quality of the prepared graphene material. In addition, the special properties of the polymer also enable the polymer to be widely applied to biomedicine, modified polymer materials and the like.

The first synthesis of graphite oxide dates back to the Brodie method in 1898, after which Staudenmaier and Hummers methods, etc. appeared. In all three oxidation methods, graphite is treated with a strong protonic acid to form a graphite intercalation compound, and then a strong oxidant is added to oxidize the graphite intercalation compound. Wherein the Brodie method adopts fuming HNO₃And KClO₃As oxidizing agent, the Staudemaier process uses concentrated H₂SO₄And fuming HNO₃The mixed acid of (2) is used for treating graphite, and KClO is also adopted₃As an oxidizing agent. Both the Staudenmeier and Brodie processes produce toxic ClO₂Gas, both reactions should be carried out in a fume hood. Hummers' law uses concentrated H₂SO₄、NaNO₃And KMnO₄As an oxidizing agent, the method is superior to other two methodsThe method is safer, the excessive high manganese acid radical ions used in the method can cause pollution, and H is required to be used₂O₂The treatment was carried out and then the separation was carried out thoroughly by washing with water. The preparation process of Hummers method is deeply studied by Friedel and the like, and is divided into three stages of low-temperature, medium-temperature and high-temperature reaction, and graphite and KMnO are pointed out₄Dosage, concentration H₂SO₄The volume, the reaction time at low temperature, the water addition method in the reaction at high temperature are the main factors affecting the structure and performance of the final product, and the reaction starts from the edge of graphite and is oxidized at KMnO₄Driven to form H₂SO₄-a graphite intercalation compound. In the Hummers method, concentrated sulfuric acid and potassium permanganate are mixed to generate high-activity manganese dioxide, and when a traditional kettle-type reactor is adopted, the reaction temperature needs to be strictly controlled, otherwise, safety accidents are easily caused. In addition, the graphite oxide prepared by the kettle type reactor has the defects of uneven material mixing and the like.

CN106882803B discloses a method and an apparatus for preparing graphene oxide, but the method only uses a mixing kettle for mixing graphite, acid and oxidant, and when continuous feeding and discharging, the materials enter the subsequent pipeline reactor without being mixed uniformly, which affects the consistency of the product; after the reaction of the first pipeline reactor is finished, the temperature of the materials is 20-150 ℃, the concentrated acid can be diluted after the solvent is added into the mixer, so that a large amount of dilution heat is generated, and the temperature of the reaction liquid in the mixer is further increased to be far higher than the decomposition temperature (55 ℃) of manganese sesquioxide due to the fact that the mixer is not externally connected with a cooler, so that explosion can be caused. In addition, in the patent, a reducing agent (hydrogen peroxide) and a solvent are added into a mixer at the same time, the hydrogen peroxide is decomposed violently at an excessively high temperature, potassium permanganate and manganese dioxide cannot be reduced into soluble divalent manganese ions, and a large amount of manganese impurities still exist in the obtained graphene oxide after subsequent purification treatment.

Disclosure of Invention

In order to overcome the defects of the technical problems, the invention provides a device and a method for continuously preparing graphite oxide.

The invention is realized by the following technical scheme.

An apparatus for continuously preparing graphite oxide, wherein: the system comprises a low-temperature reactor, a medium-temperature reactor, a solvent mixer, a high-temperature reactor, a cooling reactor, a reducing agent mixer, a buffer tank and an aftertreatment system which are connected in sequence;

the low-temperature reactor is a low-temperature tubular reactor, one end of the low-temperature tubular reactor is provided with a feed inlet, the other end of the low-temperature tubular reactor is provided with a discharge outlet, the first feeder 2 and the second feeder 3 are communicated with the feed inlet of the low-temperature tubular reactor through pipelines, the sulfuric acid storage tank is communicated with the feed inlet of the low-temperature tubular reactor through a pipeline, and a delivery pump 13, an adjusting valve 6 and a flowmeter 10 are sequentially arranged on the pipeline communicated with the feed inlet of the low-temperature tubular reactor along the flow direction of sulfuric acid; the outside of the low-temperature tubular reactor is wrapped by a temperature control jacket 23, and two ends of the temperature control jacket 23 are respectively provided with a low-temperature circulating liquid interface A1 and a low-temperature circulating liquid interface A2;

the upper end of the medium-temperature reactor is provided with a discharge hole, the lower end of the medium-temperature reactor is provided with a feed hole, the discharge hole of the low-temperature tubular reactor is communicated with the feed hole of the medium-temperature reactor through a pipeline, the outside of the medium-temperature reactor is wrapped by a temperature control jacket 24, and the upper part and the lower part of the temperature control jacket 24 are respectively provided with medium-temperature circulating liquid interfaces B1 and B2;

the upper end of the solvent mixer is provided with a discharge hole, the lower end of the solvent mixer is provided with a feed hole, the discharge hole of the medium temperature reactor is communicated with the feed hole of the solvent mixer through a pipeline, the solvent storage tank is communicated with the feed hole of the solvent mixer through a pipeline 30, and a conveying pump 14, an adjusting valve 7 and a flow meter 11 are sequentially arranged on the pipeline 30 along the flowing direction of the solvent; the solvent mixer is externally wrapped with a temperature control jacket 25, and the upper part and the lower part of the temperature control jacket 25 are respectively provided with medium-temperature circulating liquid interfaces B3 and B4;

the upper end of the high-temperature reactor is provided with a discharge hole, the lower end of the high-temperature reactor is provided with a feed hole, the discharge hole of the solvent mixer is communicated with the feed hole of the high-temperature reactor through a pipeline 31, the outside of the high-temperature reactor is wrapped by a temperature control jacket 26, and the upper part and the lower part of the temperature control jacket 26 are respectively provided with high-temperature circulating liquid interfaces C1 and C2;

the upper end of the cooling reactor is provided with a discharge hole, the lower end of the cooling reactor is provided with a feed hole, the discharge hole of the high-temperature reactor is communicated with the feed hole of the cooling reactor through a pipeline 32, the outside of the cooling reactor is wrapped by a temperature control jacket 27, and the upper part and the lower part of the temperature control jacket 27 are respectively provided with medium-temperature circulating liquid interfaces B5 and B6;

the upper end of the reducing agent mixer is provided with a discharge hole, the lower end of the reducing agent mixer is provided with a feed hole, the discharge hole of the cooling reactor is communicated with the feed hole of the reducing agent mixer through a pipeline 33, the reducing agent storage tank is communicated with the feed hole of the reducing agent mixer through a pipeline 34, and a delivery pump 15, an adjusting valve 8 and a flow meter 12 are sequentially arranged on the pipeline 34 along the flow direction of the reducing agent;

the upper end of buffer tank is provided with the feed inlet, and the lower extreme of buffer tank is provided with the discharge gate, and discharge gate department is provided with baiting valve 9, the discharge gate of reductant blender passes through pipeline 35 and the feed inlet intercommunication of buffer tank, and the discharge gate of buffer tank passes through pipeline 36 and aftertreatment system's feed inlet intercommunication.

Further, the low-temperature reactor comprises at least two low-temperature kettle type reactors connected in parallel, and each low-temperature kettle type reactor is alternately communicated with the medium-temperature reactor.

Further, the low-temperature kettle type reactor comprises a first low-temperature kettle type reactor and a second low-temperature kettle type reactor which are connected in parallel, the upper end of the first low-temperature kettle type reactor and the upper end of the second low-temperature kettle type reactor are set as feed inlets, the lower end of the first low-temperature kettle type reactor and the lower end of the second low-temperature kettle type reactor are set as discharge outlets, the discharge outlets are communicated with the conveying pump 38 through a pipeline 28, and

discharge valves

41 and 42 are arranged at the discharge outlets; the

first feeding machines

2A and 2B and the

second feeding machines

3A and 3B are respectively communicated with the feeding holes of the first low-temperature kettle type reactor and the second low-temperature kettle type reactor through pipelines, the sulfuric acid storage tank is respectively communicated with the feeding holes of the first low-temperature kettle type reactor and the second low-temperature kettle type reactor through pipelines, and a conveying pump 13, an adjusting valve 6 and a flowmeter 10 are sequentially arranged on a main pipeline of the sulfuric acid storage tank communicated with the first low-temperature kettle type reactor and the second low-temperature kettle type reactor; the outside of the first low-temperature kettle type reactor and the second low-temperature kettle type reactor is respectively wrapped with

temperature control jackets

23A and 23B, and the upper parts and the lower parts of the

temperature control jackets

23A and 23B are respectively provided with low-temperature circulating liquid interfaces A1, A2, A3 and A4; the delivery pump 38 is communicated with the feed inlet of the medium-temperature reactor through a pipeline, and a flow meter 39 and an adjusting valve 40 are sequentially arranged on the pipeline for communicating the delivery pump 38 with the feed inlet of the medium-temperature reactor.

Further, the medium temperature reactor, the solvent mixer, the high temperature reactor, the cooling reactor and the reducing agent mixer are all tubular reactors.

Further, the

first feeders

2A and 2B are graphite powder and sodium nitrate mixture feeders, and the

second feeders

3A and 3B are potassium permanganate feeders.

Furthermore, low-temperature circulating liquid ports A1, A2, A3 and A4 are communicated with the low-temperature tank through pipelines to form a low-temperature circulating liquid loop, medium-temperature circulating liquid ports B5 and B6 are communicated with the medium-temperature tank through pipelines to form a medium-temperature circulating liquid loop, and high-temperature circulating liquid ports C1 and C2 are communicated with the high-temperature tank through pipelines to form a high-temperature circulating loop.

A method for continuously preparing graphite oxide using an apparatus for continuously preparing graphite oxide, comprising the steps of:

s1, weighing raw materials including graphite powder, sodium nitrate, sulfuric acid and potassium permanganate, wherein the mass ratio of the graphite powder to the sodium nitrate to the sulfuric acid to the potassium permanganate is 1 (0.1-1) to 30-80 (1-5), adding the raw materials into a low-temperature reactor, and mixing at the temperature of-5 ℃ for 1-2 hours to prepare a first mixture;

s2, conveying the first mixture prepared in the step S1 to a medium-temperature reactor, and reacting at the temperature of 30-45 ℃ for 1-5 hours to prepare a second mixture;

s3, conveying the second mixture obtained in the step S2 to a solvent mixer, and diluting the second mixture by using a solvent to obtain a third mixture; the solvent is deionized water, and the mass ratio of the solvent to the graphite powder is 40-100: 1;

s4, conveying the third mixture prepared in the step S3 to a high-temperature reactor, and reacting at the temperature of 90-110 ℃ for 1-5 hours to prepare a fourth mixture;

s5, conveying the fourth mixture prepared in the step S4 to a cooling reactor, and cooling to 30-45 ℃ to prepare a fifth mixture;

s6, conveying the fifth mixture prepared in the step S5 to a reducing agent mixer, and reducing the fifth mixture by using a reducing agent to prepare a sixth mixture;

and S7, carrying out post-treatment on the sixth mixture prepared in the step S6 by a post-treatment system to prepare a graphite oxide solution, and drying the graphite oxide solution to prepare graphite oxide powder.

Further, in the step S2, the flow rate of the first mixture in the medium temperature reactor is 0.7-3.5 m/min.

Further, in the step S6, the reducing agent is hydrogen peroxide, and the mass ratio of the reducing agent to the graphite powder is 1-20: 1.

Further, in the step S7, the post-treatment includes one or a combination of sedimentation, centrifugation and filtration.

Further, in the step S7, the oxygen content of the prepared graphite oxide powder is 25 to 48 wt%.

According to the technical scheme, raw materials of graphite powder, sodium nitrate, sulfuric acid and potassium permanganate are added into a low-temperature reactor to perform low-temperature reaction, then the mixture is conveyed into a medium-temperature reactor to perform medium-temperature reaction, a second mixture of a product obtained through the medium-temperature reaction is conveyed into a solvent mixer to be diluted by a solvent, then the mixture is conveyed into the high-temperature reactor to perform high-temperature reaction, a fourth mixture of a product obtained after the high-temperature reaction is cooled in a cooling reactor, a fifth mixture obtained after the cooling is subjected to reduction reaction in a reducing agent mixer, and then the sixth mixture is subjected to post-treatment such as settling, centrifuging and filtering to obtain a graphite oxide solution. The raw materials are carried out under the coordination of the reaction conditions, the graphite oxide solution with stable product quality can be continuously prepared, the oxygen content of the graphite oxide powder obtained after drying can reach 25-48wt%, the purity is more than or equal to 99.9 wt%, the content of metal impurities is extremely low, and the manganese content is less than or equal to 50 ppm.

Meanwhile, the invention also provides a special device for realizing the preparation method, which comprises a low-temperature reactor, a medium-temperature tubular reactor, a solvent tubular mixer, a high-temperature tubular reactor, a cooling tubular reactor, a reducing agent tubular mixer, a buffer tank and a post-treatment system which are connected in sequence, wherein the low-temperature reactor is a low-temperature tubular reactor and/or a low-temperature kettle type reactor.

If the low-temperature reactors are low-temperature kettle type reactors, the number of the low-temperature kettle type reactors is at least two, the outlet ends of the two low-temperature kettle type reactors are connected with the inlet end of the medium-temperature tubular reactor, and the outlet ends of the two low-temperature kettle type reactors are provided with regulating valves so as to realize the alternate communication of the two low-temperature kettle type reactors and the medium-temperature tubular reactor and further realize the continuous production of the graphite oxide. If the low-temperature reactor is a low-temperature tubular reactor, the low-temperature tubular reactor is directly mixed with the medium-temperature tubular reactor, the raw materials are fully mixed by controlling the reaction of the raw materials in the low-temperature tubular reactor, and then the raw materials are continuously fed into the medium-temperature tubular reactor, so that the continuous production of the graphite oxide is realized.

Furthermore, the low-temperature reactor in the device provided by the invention is provided with a feed inlet, a feeder and a liquid conveyor are arranged at the feed inlet, and the liquid conveyor comprises a liquid storage tank, a conveying pump, a flowmeter and an adjusting valve which are communicated with the low-temperature reactor through a pipeline; wherein, the peripheries of the low-temperature reactor, the medium-temperature tubular reactor, the solvent tubular mixer and the high-temperature tubular reactor are all provided with constant-temperature jackets.

The constant-temperature jackets are arranged on the peripheries of the low-temperature reactor, the medium-temperature tubular reactor, the solvent tubular mixer and the high-temperature tubular reactor, and the temperature of the constant-temperature jackets on the periphery of the low-temperature reactor is kept between-5 ℃ and 5 ℃, so that reaction materials can be fully and uniformly mixed before the medium-temperature reaction starts.

If a low-temperature kettle type reactor is adopted, the feeder is positioned at the upper part of the feed inlet of the low-temperature reaction kettle and is connected with the feed inlet through a pipeline; if a low-temperature tubular mixer is adopted, the guide pipes connected with the low-temperature tubular mixer are respectively provided with a feeding machine; the liquid storage tank is a sulfuric acid storage tank, the input end of the low-temperature kettle type reactor (or the low-temperature tubular mixer) is connected with the sulfuric acid storage tank through a pipeline, and a sulfuric acid delivery pump, a flow meter and an adjusting valve are sequentially arranged on the pipeline connecting the sulfuric acid storage tank and the low-temperature kettle type reactor (or the low-temperature tubular mixer).

Furthermore, the input end of the solvent tube mixer is connected with a solvent storage tank through a pipeline, and a solvent delivery pump, a flow meter and an adjusting valve are sequentially arranged on the pipeline connecting the solvent storage tank and the solvent tube mixer; the input end of the reducing agent tubular mixer is connected with a reducing agent storage tank through a pipeline, and a reducing agent delivery pump, a flowmeter and an adjusting valve are sequentially arranged on the pipeline connecting the reducing agent storage tank and the reducing agent tubular mixer.

In the invention, the output end of the low-temperature kettle type reactor (or the low-temperature tubular mixer) is connected with the input end of the medium-temperature tubular reactor through a connecting pipeline, a delivery pump, a flowmeter and a regulating valve are arranged on the connecting pipeline, the output end of the medium temperature tubular reactor is connected with the input end of the solvent tubular mixer through a connecting pipeline, the output end of the solvent tubular mixer is connected with the input end of the high-temperature tubular reactor through a connecting pipeline, the output end of the high-temperature tubular reactor is connected with the input end of the cooling tubular reactor through a connecting pipeline, the output end of the cooling tubular reactor is connected with the input end of the reducing agent tubular mixer through a connecting pipeline, the output end of the reducing agent tubular mixer is connected with the buffer tank through a connecting pipeline, and the input end of the post-treatment system is connected with a valve at the bottom of the buffer tank through a connecting pipeline.

According to the technical scheme of the invention, the inventor of the invention finds that the method for preparing the graphite oxide is matched with the device, so that the continuous preparation of the high-quality graphite oxide can be further effectively realized. The oxygen content of the graphite oxide powder obtained by drying the graphite oxide solution prepared by the method is 25-48wt%, the purity is more than or equal to 99.9 wt%, the content of metal impurities is extremely low, and the content of manganese is less than or equal to 50 ppm.

The invention has the beneficial effects that: the invention controls the mixing and reaction modes of materials through the pipeline and the pipeline mixer, overcomes the defects that the common kettle type reactor can not continuously produce and the material mixing of a simple pipeline reactor is not uniform, is carried out at the temperature of 30-45 ℃ in the stages of adding water and hydrogen peroxide, prevents the temperature of reaction liquid from being overhigh, ensures the safety and the high efficiency of the production process, has low manganese content of products, ensures the uniformity of material mixing in the reaction process, ensures the continuity and is beneficial to industrial production.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a schematic view of the overall structure of a tubular reactor using a low temperature according to the present invention;

in the figure 1, 1 is a sulfuric acid storage tank, 2 is a graphite powder and sodium nitrate mixture feeder, 3 is a potassium permanganate feeder, 4 is a solvent storage tank, 5 is a reducing agent storage tank, 6-8 is a regulating valve, 9 is a discharge valve, 10-12 are flow meters, 13-15 are delivery pumps, 16 is a low-temperature tubular mixer, 17 is an intermediate-temperature tubular reactor, 18 is a solvent tubular mixer, 19 is a high-temperature tubular reactor, 20 is a cooling tubular reactor, 21 is a reducing agent tubular mixer, 22 is a buffer tank, 23-27 are temperature-control jackets, 28-36 are connecting pipes, 37 is a post-treatment system, A1 and A2 are low-temperature circulating liquid interfaces, B1, B2, B3, B4, B5 and B6 are intermediate-temperature circulating liquid interfaces, and C1 and C2 are high-temperature circulating liquid interfaces.

FIG. 2 is a schematic structural diagram of the present invention in which two low-temperature reaction vessels are alternately used;

in fig. 2, 1 is a sulfuric acid storage tank, 2A and 2B are graphite powder and sodium nitrate mixture feeders, 3A and 3B are potassium permanganate feeders, 4 is a solvent storage tank, 5 is a reducing agent storage tank, 9, 41 and 42 are discharge valves, 6 to 8 and 40 are regulating valves, 10 to 12 and 39 are flow meters, 13 to 15 and 38 are delivery pumps, 16A to 16B are low-temperature reaction kettles, 17 is a medium-temperature tubular reactor, 18 is a solvent tubular mixer, 19 is a high-temperature tubular reactor, 20 is a cooling tubular reactor, 21 is a reducing agent tubular mixer, 22 is a buffer tank, 23A and 23B, 24-27 are temperature control jackets, 28-36 are connecting pipes, 37 is a post-treatment system, A1, A2, A3 and A4 are low-temperature circulating liquid interfaces, B1, B2, B3, B4, B5 and B6 are medium-temperature circulating liquid interfaces, and C1 and C2 are high-temperature circulating liquid interfaces.

Detailed Description

Example 1

A special device for preparing graphite oxide (as shown in figure 1) comprises a low-temperature tubular mixer 16, an intermediate-temperature tubular reactor 17, a solvent tubular mixer 18, a high-temperature tubular reactor 19, a cooling tubular reactor 20, a reducing agent tubular mixer 21, a buffer tank 22 and a post-treatment system 37, wherein the output end of the low-temperature tubular mixer 16 is connected with the input end of the intermediate-temperature tubular reactor 17 through a connecting pipeline 28, the output end of the intermediate-temperature tubular reactor 17 is connected with the input end of the solvent tubular mixer 18 through a connecting pipeline 29, the output end of the solvent tubular mixer 18 is connected with the input end of the high-temperature tubular reactor 19 through a connecting pipeline 31, the output end of the high-temperature tubular reactor 19 is connected with the input end of the cooling tubular reactor 20 through a connecting pipeline 32, the output end of the cooling tubular reactor 20 is connected with the reducing agent tubular mixer 21 through a connecting pipeline 33, the output end of the reducing agent tubular mixer 21 is connected with the input end of the buffer tank 22 through a connecting pipeline 35, and the output end of the buffer tank 22 is connected with an after-treatment system 37.

A constant temperature jacket 23 is arranged outside the low temperature tubular mixer 16, an inlet A1 of the constant temperature jacket 23 is connected with a port a of the low temperature tank, and an outlet A2 is connected with a port b of the low temperature tank; a constant temperature jacket 24 is arranged outside the medium temperature tubular reactor 17, an inlet B1 of the constant temperature jacket 24 is connected with a connector a of the medium temperature tank, and an outlet B2 is connected with a connector B of the medium temperature tank; a constant temperature jacket 25 is arranged outside the solvent tubular mixer 18, an inlet B3 of the constant temperature jacket 25 is connected with a connector a of the medium temperature tank, and an outlet B4 is connected with a connector B of the medium temperature tank; a constant temperature jacket 26 is arranged outside the high temperature tubular reactor 19, an inlet C1 of the constant temperature jacket 26 is connected with a port a of the high temperature tank, and an outlet C2 is connected with a port b of the high temperature tank; the cooling tube reactor 20 is provided with a constant temperature jacket 27 on the outside, the inlet B5 of the constant temperature jacket 27 is connected with the interface a of the medium temperature tank, and the outlet B6 is connected with the interface B of the medium temperature tank.

The input end of the low-temperature tubular mixer 16 is also connected with the feeders 2 and 3 respectively; the input end of the low-temperature tubular mixer 16 is also connected with a sulfuric acid storage tank 1, and a guide pipe connecting the sulfuric acid storage tank 1 and the low-temperature tubular mixer 16 is sequentially provided with a material conveying pump 13, a flowmeter 10 and a regulating valve 6.

The input end of the solvent pipe type mixer 18 is also connected with a solvent storage tank 4, and a guide pipe connecting the solvent storage tank 4 and the solvent pipe type mixer 18 is sequentially provided with a material conveying pump 14, a flow meter 11 and a regulating valve 7.

The input end of the reducing agent tube mixer 21 is also connected with a reducing agent storage tank 5, and a guide pipe connecting the reducing agent storage tank 5 and the reducing agent tube mixer 21 is sequentially provided with a material conveying pump 15, a flow meter 12 and a regulating valve 8.

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 0.7, placing the mixture in a bin of a feeder 2, placing potassium permanganate in the bin of the feeder 3, placing 98% concentrated sulfuric acid in a sulfuric acid storage tank 1, controlling the temperature of a low-temperature tubular mixer 16 to be-1 ℃ by using a constant-temperature jacket 23 and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 to be 38 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 to be 103 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 to be 38 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 to be 38 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, continuously inputting the concentrated sulfuric acid into the low-temperature tubular mixer 16 by a delivery pump 13, adjusting the opening of a valve to make the flow rate be 1.17m/min, starting the feeders 2 and 3, inputting, and adjusting the feeding speed of the feeder to ensure that the mass ratio of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is 1: 0.7: 60: 3, carrying out oxidation intercalation reaction for 3 hours when the material flow passes through the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when a material flow passes through a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the feeding mass ratio of the deionized water to the graphite powder is 75: 1, after being mixed by a solvent tubular mixer 18, the material flows through a high-temperature tubular reactor 19 to carry out high-temperature reaction for 3 hours at 103 ℃, and then flows through a cooling tubular reactor 20 to reduce the temperature to 38 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the feeding mass ratio of the hydrogen peroxide to the graphite powder is 13: 1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, a graphite oxide solution is obtained through sedimentation and centrifugal treatment, and after drying, graphite oxide powder is obtained, and the oxygen content is measured to be 39wt%, the purity is 99.9 wt%, and the manganese content is 21 ppm.

Example 2

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 0.9, placing the mixture in a bin of a feeder 2, placing potassium permanganate in the bin of the feeder 3, placing 98% concentrated sulfuric acid in a sulfuric acid storage tank 1, controlling the temperature of a low-temperature tubular mixer 16 to be-3 ℃ by using a constant-temperature jacket 23 and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 to be 42 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 to be 106 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 to be 42 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 to be 42 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, continuously inputting the concentrated sulfuric acid into the low-temperature tubular mixer 16 by a delivery pump 13, adjusting the opening of a valve to ensure that the flow rate is 0.875m/min, starting the feeders 2 and 3, and adjusting the feeding speed of the feeder to ensure that the mass ratio of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is 1: 0.9: 70: 4, carrying out oxidation intercalation reaction for 4h when the material flow passes through the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when a material flow passes through a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the feeding mass ratio of the deionized water to the graphite powder is 90: 1, after mixing by the solvent tubular mixer 18, the material was passed through the high temperature tubular reactor 19 for high temperature reaction at 106 ℃ for 4h, and then passed through the cooling tubular reactor 20 to reduce the temperature to 42 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the feeding mass ratio of the hydrogen peroxide to the graphite powder is 17: 1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, a graphite oxide solution is obtained through sedimentation and centrifugal treatment, and the graphite oxide powder obtained after drying has oxygen content of 43wt%, purity of 99.9 wt% and manganese content of 18 ppm.

Example 3

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 1, placing the mixture in a bin of a feeder 2, placing potassium permanganate in the bin of the feeder 3, placing 98% concentrated sulfuric acid in a sulfuric acid storage tank 1, controlling the temperature of a low-temperature tubular mixer 16 to be-5 ℃ by using a constant-temperature jacket 23 and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 to be 45 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 to be 110 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 to be 45 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 to be 45 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, continuously inputting the concentrated sulfuric acid into the low-temperature tubular mixer 16 by a delivery pump 13, adjusting the opening degree of a valve to make the flow rate be 0.7m/min, starting the feeders 2 and 3, and adjusting the feeding speed of the feeder to ensure that the mass ratio of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is 1: 1: 80: 5, carrying out oxidation intercalation reaction for 5h when the material flow passes through the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when a material flow passes through a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the feeding mass ratio of the deionized water to the graphite powder is 100:1, after being mixed by a solvent tubular mixer 18, the material flows through a high-temperature tubular reactor 19 to carry out high-temperature reaction for 5 hours at 110 ℃, and then flows through a cooling tubular reactor 20 to reduce the temperature to 45 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the feeding mass ratio of the hydrogen peroxide to the graphite powder is 20:1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, a graphite oxide solution is obtained through sedimentation, centrifugation and filtration, and the graphite oxide powder obtained after drying has an oxygen content of 48wt%, a purity of 99.9 wt% and a manganese content of 10 ppm.

Example 4

A special device for preparing graphite oxide (as shown in figure 2) comprises low-temperature reaction kettles 16A and 16B, an intermediate-temperature tubular reactor 17, a solvent tubular mixer 18, a high-temperature tubular reactor 19, a cooling tubular reactor 20, a reducing agent tubular mixer 21, a buffer tank 22 and a post-treatment system 37, wherein the output ends of the low-temperature reaction kettles 16A and 16B are connected with the input end of the intermediate-temperature tubular reactor 17 through a connecting pipeline 28, a feed delivery pump 38, a flow meter 39 and a regulating valve 40 are arranged on the connecting pipeline 28, the output end of the intermediate-temperature tubular reactor 17 is connected with the input end of the solvent tubular reactor 18 through a connecting pipeline 29, the output end of the solvent tubular mixer 18 is connected with the input end of the high-temperature tubular reactor 19 through a connecting pipeline 31, the output end of the high-temperature tubular reactor 19 is connected with the input end of the cooling tubular reactor 20 through a connecting pipeline 32, the output end of the cooling tube type reactor 20 is connected with the reducing agent tube type mixer 21 through a connecting pipeline 33, the output end of the reducing agent tube type mixer 21 is connected with the input end of the buffer tank 22 through a connecting pipeline 35, and the output end of the buffer tank 22 is connected with an aftertreatment system 37 through a discharge valve 9.

Constant temperature jackets 23A and 23B are respectively arranged outside kettle bodies of the low temperature reaction kettles 16A and 16B, inlets A1 and A3 of the constant temperature jackets 23A and 23B are connected with a connector a of a low temperature tank, and outlets A2 and A4 are connected with a connector B of the low temperature tank; a constant temperature jacket 24 is arranged outside the medium temperature tubular reactor 17, an inlet B1 of the constant temperature jacket 24 is connected with a connector a of the medium temperature tank, and an outlet B2 is connected with a connector B of the medium temperature tank; a constant temperature jacket 25 is arranged outside the solvent tubular mixer 18, an inlet B3 of the constant temperature jacket 25 is connected with a port a of the medium temperature tank, and an outlet B4 is connected with a port B of the medium temperature tank; a constant temperature jacket 26 is arranged outside the high temperature tubular reactor 19, an inlet C1 of the constant temperature jacket 26 is connected with a port a of the high temperature tank, and an outlet C2 is connected with a port b of the high temperature tank; the cooling tube reactor 20 is provided with a constant temperature jacket 27 on the outside, the inlet B5 of the constant temperature jacket 27 is connected with the interface a of the medium temperature tank, and the outlet B6 is connected with the interface B of the medium temperature tank.

The feed inlets of the low-

temperature reaction kettles

16A and 16B are also respectively connected with the

feeders

2A and 2B and the

feeders

3A and 3B; the feed inlets of the low-

temperature reaction kettles

16A and 16B are also connected with a sulfuric acid storage tank 1 through a connecting pipeline, and the pipeline connecting the sulfuric acid storage tank 1 with the low-

temperature reaction kettles

16A and 16B is sequentially provided with a material conveying pump 13, a flow meter 10 and a regulating valve 6.

The input end of the solvent pipe type mixer 18 is also connected with a solvent storage tank 4, and a material conveying pump 14, a flow meter 11 and a regulating valve 7 are sequentially arranged on a pipeline connecting the solvent storage tank 4 and the solvent pipe type mixer 18.

The input end of the reducing agent tube mixer 21 is also connected with a reducing agent storage tank 5, and a material conveying pump 15, a flow meter 12 and a regulating valve 8 are sequentially arranged on a pipeline connecting the reducing agent storage tank 5 and the reducing agent tube mixer 21.

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 0.1, placing the mixture into bins of feeders 2A and 3A, placing potassium permanganate into bins of feeders 2B and 3B, placing 98% concentrated sulfuric acid into a sulfuric acid storage tank 1, controlling the temperatures of low-temperature reaction kettles 16A and 116B at 5 ℃ by using constant-temperature jackets 23A and 23B and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 at 30 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 at 90 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 at 30 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 at 30 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, adding 30kg of concentrated sulfuric acid into the low-temperature reaction kettle 16A by using a delivery pump 13, a flowmeter 10 and a regulating valve 6, starting the feeder 2A, adding 1.1kg of a mixture of, starting the feeder 3A, adding 1kg of potassium permanganate into the low-temperature reaction kettle 16A, stirring for 60min, conveying to the intermediate-temperature tubular reactor 17 through the material conveying pump 38, adjusting the opening of the valve to enable the liquid flow rate to be 3.5m/min, and performing oxidation intercalation reaction on the materials in the intermediate-temperature tubular reactor 17 at the temperature of 30 ℃ for 1 h. After the low-temperature reaction vessel 16A starts to discharge, the low-temperature reaction vessel 16B is charged in a similar manner. After all the materials in the low-temperature reaction kettle 16A enter the medium-temperature tubular reactor 17, closing the discharge valve 41, opening the discharge valve 42, continuously supplying the materials to the medium-temperature tubular reactor 17 through the low-temperature reaction kettle 16B, and continuously repeating the steps to ensure that the materials are always input into the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when the material flows to a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the mass ratio of the deionized water to the graphite powder is 40: 1, after being fully mixed by a solvent tubular mixer 18, the material flows through a high-temperature tubular reactor 19 to carry out high-temperature reaction for 1 hour at 90 ℃, and then flows through a cooling tubular reactor 20 to reduce the temperature to 30 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the mass ratio of the hydrogen peroxide to the graphite powder is 1: 1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, a graphite oxide solution is obtained through sedimentation and filtration treatment, and the graphite oxide powder obtained after drying has 25wt% of oxygen content, 99.9 wt% of purity and 50ppm of manganese content.

Example 5

A special device for preparing graphite oxide (as shown in figure 2) comprises low-temperature reaction kettles 16A and 16B, an intermediate-temperature tubular reactor 17, a solvent tubular mixer 18, a high-temperature tubular reactor 19, a cooling tubular reactor 20, a reducing agent tubular mixer 21, a buffer tank 22 and a post-treatment system 37, wherein the output ends of the low-temperature reaction kettles 16A and 16B are connected with the input end of the intermediate-temperature tubular reactor 17 through a connecting pipeline 28, a feed delivery pump 38, a flow meter 39 and a regulating valve 40 are arranged on the connecting pipeline 28, the output end of the intermediate-temperature tubular reactor 17 is connected with the input end of the solvent tubular mixer 18 through a connecting pipeline 29, the output end of the solvent tubular mixer 18 is connected with the input end of the high-temperature tubular reactor 19 through a connecting pipeline 31, the output end of the high-temperature tubular reactor 2519 is connected with the input end of the cooling tubular reactor 20 through a connecting pipeline 32, the output end of the cooling tube type reactor 20 is connected with the reducing agent tube type mixer 21 through a connecting pipeline 33, the output end of the reducing agent tube type mixer 21 is connected with the input end of the buffer tank 22 through a connecting pipeline 35, and the output end of the buffer tank 22 is connected with an aftertreatment system 37 through a discharge valve 9.

Constant temperature jackets 23A and 23B are respectively arranged outside kettle bodies of the low temperature reaction kettles 16A and 16B, inlets A1 and A3 of the constant temperature jackets 23A and 23B are connected with a connector a of a low temperature tank, and outlets A2 and A4 are connected with a connector B of the low temperature tank; a constant temperature jacket 24 is arranged outside the medium temperature tubular reactor 71, an inlet B1 of the constant temperature jacket 24 is connected with a connector a of the medium temperature tank, and an outlet B2 is connected with a connector B of the medium temperature tank; a constant temperature jacket 25 is arranged outside the solvent tubular mixer 18, an inlet B3 of the constant temperature jacket 25 is connected with a port a of the medium temperature tank, and an outlet B4 is connected with a port B of the medium temperature tank; a constant temperature jacket 26 is arranged outside the high temperature tubular reactor 19, an inlet C1 of the constant temperature jacket 26 is connected with a port a of the high temperature tank, and an outlet C2 is connected with a port b of the high temperature tank; the cooling tube reactor 20 is provided with a constant temperature jacket 27 on the outside, the inlet B5 of the constant temperature jacket 27 is connected with the interface a of the medium temperature tank, and the outlet B6 is connected with the interface B of the medium temperature tank.

The feed inlets of the low-

temperature reaction kettles

16A and 16B are also respectively connected with the

feeders

2A and 2B and the

feeders

3A and 3B; the feed inlets of the low-temperature reaction kettles A16 and 16B are also connected with a sulfuric acid storage tank 1 through a connecting pipeline, and the pipeline connecting the sulfuric acid storage tank 1 with the low-

temperature reaction kettles

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 0.3, placing the mixture into bins of feeders 2A and 3A, placing potassium permanganate into bins of feeders 2B and 3B, placing 98% concentrated sulfuric acid into a sulfuric acid storage tank 1, controlling the temperatures of low-temperature reaction kettles 16A and 16B at 2 ℃ by using constant-temperature jackets 23A and 23B and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 at 33 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 at 95 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 at 33 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 at 33 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, adding 40kg of concentrated sulfuric acid into the low-temperature reaction kettle 16A by using a delivery pump 13, a flowmeter 10 and a regulating valve 6, starting the feeder 2A, adding 1.3kg of a mixture of, and starting the feeder 3A, adding 2kg of potassium permanganate into the low-temperature reaction kettle 16A, stirring for 90min, conveying the mixture into the intermediate-temperature tubular reactor 17 through the material conveying pump 38, adjusting the opening of the valve to enable the liquid flow rate to be 1.75m/min, and performing oxidation intercalation reaction on the material in the intermediate-temperature tubular reactor 17 at the temperature of 33 ℃ for 2 h. After the low-temperature reaction vessel 16A starts to discharge, the low-temperature reaction vessel 16B is charged in a similar manner. After all the materials in the low-temperature reaction kettle 16A enter the medium-temperature tubular reactor 17, closing the discharge valve 41, opening the discharge valve 42, continuously supplying the materials to the medium-temperature tubular reactor 17 through the low-temperature reaction kettle 16B, and continuously repeating the steps to ensure that the materials are always input into the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when the material flows to a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the mass ratio of the deionized water to the graphite powder is 50: 1, after being fully mixed by a solvent tubular mixer 18, the material flows through a high-temperature tubular reactor 19 to carry out high-temperature reaction for 2 hours at 95 ℃, and then flows through a cooling tubular reactor 20 to reduce the temperature to 33 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the mass ratio of the hydrogen peroxide to the graphite powder is 5: 1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, a graphite oxide solution is obtained through sedimentation and centrifugal treatment, and the graphite oxide powder obtained after drying has the oxygen content of 30wt%, the purity of 99.9 wt% and the manganese content of 42 ppm.

Example 6

The feed inlets of the low-

temperature reaction kettles

16A and 16B are also respectively connected with the

feeders

2A and 2B and the

feeders

3A and 3B; the feed inlets of the low-

temperature reaction kettles

When the device is used for preparing graphite oxide, graphite powder and sodium nitrate are mixed according to the proportion of 1: 0.5, placing the mixture into bins of feeders 2A and 3A, placing potassium permanganate into bins of feeders 2B and 3B, placing 98% concentrated sulfuric acid into a sulfuric acid storage tank 1, controlling the temperatures of low-temperature reaction kettles 16A and 16B at 0 ℃ by using constant-temperature jackets 23A and 23B and a low-temperature tank, controlling the temperature of a medium-temperature tubular reactor 17 at 35 ℃ by using a constant-temperature jacket 24 and a medium-temperature tank, controlling the temperature of a high-temperature tubular reactor 19 at 100 ℃ by using a constant-temperature jacket 26 and a high-temperature tank, controlling the temperature of a cooling tubular reactor 20 at 35 ℃ by using a constant-temperature jacket 27 and a medium-temperature tank, controlling the temperature of a solvent tubular mixer 18 at 35 ℃ by using a constant-temperature jacket 25 and a medium-temperature tank, adding 50kg of concentrated sulfuric acid into the low-temperature reaction kettle 16A by using a delivery pump 13, a flowmeter 10 and a regulating valve 6, starting the feeder 2A, adding 1.5kg of a mixture of, starting the feeder 3A, adding 2.5kg of potassium permanganate into the low-temperature reaction kettle 16A, stirring for 120min, conveying to the intermediate-temperature tubular reactor 17 through the conveying pump 38, adjusting the opening of the valve to enable the liquid flow rate to be 1.4m/min, and performing oxidation intercalation reaction on the materials in the intermediate-temperature tubular reactor 17 at the temperature of 35 ℃ for 2.5 h. After the low-temperature reaction vessel 16A starts to discharge, the low-temperature reaction vessel 16B is charged in a similar manner. After all the materials in the low-temperature reaction kettle 16A enter the medium-temperature tubular reactor 17, closing the discharge valve 41, opening the discharge valve 42, continuously supplying the materials to the medium-temperature tubular reactor 17 through the low-temperature reaction kettle 16B, and continuously repeating the steps to ensure that the materials are always input into the medium-temperature tubular reactor 17.

Placing deionized water in a solvent storage tank 4, starting a material conveying pump 14 when the material flows to a solvent tubular mixer 18, and adjusting the opening of a valve to ensure that the mass ratio of the deionized water to the graphite powder is 65: 1, after being fully mixed by a solvent tubular mixer 18, the material flows through a high-temperature tubular reactor 19 to carry out high-temperature reaction for 2.5 hours at 100 ℃, and then flows through a cooling tubular reactor 20 to reduce the temperature to 35 ℃.

Placing 30% hydrogen peroxide in a reducing agent storage tank 5, starting a material conveying pump 15 when a material flow passes through a reducing agent tubular mixer 21, and adjusting the opening of a valve to ensure that the mass ratio of the hydrogen peroxide to the graphite powder is 10: 1, reacting the added hydrogen peroxide with potassium permanganate and manganese dioxide in the material to reduce the potassium permanganate and the manganese dioxide into soluble divalent manganese ions.

Finally, the material flows into a buffer tank 22, and is settled and filtered to obtain a graphite oxide solution, and the graphite oxide solution is dried to obtain graphite oxide powder, wherein the oxygen content of the graphite oxide powder is 35wt%, the purity of the graphite oxide powder is 99.9 wt%, and the manganese content of the graphite oxide powder is 26 ppm.

Comparative example 1

A graphite oxide solution was prepared as in example 4, except that: the number of the low-temperature reaction kettles is 1, and the reaction liquid is conveyed to the medium-temperature reactor through a pump while feeding and mixing.

The graphite oxide powder prepared by the method contains part of unreacted graphite powder, the oxygen content of the graphite oxide powder is 23wt%, the purity is 94.2 wt%, and the manganese content is 1800 ppm.

Comparative example 2

A graphite oxide solution was prepared as in example 4, except that: the temperature of the medium temperature tubular reactor 17 was controlled at 25 ℃. The graphite oxide powder prepared by the method contains part of unreacted graphite powder, the oxygen content of the graphite oxide powder is 20wt%, the purity is 93.5 wt%, and the manganese content is 1600 ppm.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.

Claims

1. An apparatus for continuously preparing graphite oxide, which is characterized in that: comprises a low-temperature reactor, a medium-temperature reactor (17), a solvent mixer (18), a high-temperature reactor (19), a cooling reactor (20), a reducing agent mixer (21), a buffer tank (22) and a post-treatment system (37) which are connected in sequence;

the low-temperature reactor is a low-temperature tubular reactor (16), one end of the low-temperature tubular reactor (16) is provided with a feed inlet, the other end of the low-temperature tubular reactor (16) is provided with a discharge outlet, the first feeder (2) and the second feeder (3) are communicated with the feed inlet of the low-temperature tubular reactor (16) through pipelines, the sulfuric acid storage tank (1) is communicated with the feed inlet of the low-temperature tubular reactor (16) through a pipeline, and a delivery pump (13), an adjusting valve (6) and a flow meter (10) are sequentially arranged on the pipeline communicated with the feed inlet of the low-temperature tubular reactor (16) along the flow direction of sulfuric acid on the pipeline; the outside of the low-temperature tubular reactor (16) is wrapped with a temperature control jacket (23), and two ends of the temperature control jacket (23) are respectively provided with a low-temperature circulating liquid interface (A1, A2);

a discharge hole is formed in the upper end of the medium-temperature reactor (17), a feed hole is formed in the lower end of the medium-temperature reactor (17), the discharge hole of the low-temperature tubular reactor (16) is communicated with the feed hole of the medium-temperature reactor (17) through a pipeline, a temperature control jacket (24) is wrapped outside the medium-temperature reactor (17), and medium-temperature circulating liquid interfaces (B1 and B2) are respectively arranged on the upper portion and the lower portion of the temperature control jacket (24);

a discharge hole is formed in the upper end of the solvent mixer (18), a feed hole is formed in the lower end of the solvent mixer (18), the discharge hole of the medium-temperature reactor (17) is communicated with the feed hole of the solvent mixer (18) through a pipeline (29), the solvent storage tank (4) is communicated with the feed hole of the solvent mixer (18) through a pipeline (30), and a conveying pump (14), an adjusting valve (7) and a flow meter (11) are sequentially arranged on the pipeline (30) along the flowing direction of the solvent; the solvent mixer (18) is externally wrapped with a temperature control jacket (25), and the upper part and the lower part of the temperature control jacket (25) are respectively provided with medium-temperature circulating liquid interfaces (B3 and B4);

a discharge hole is formed in the upper end of the high-temperature reactor (19), a feed hole is formed in the lower end of the high-temperature reactor (19), the discharge hole of the solvent mixer (18) is communicated with the feed hole of the high-temperature reactor (19) through a pipeline (31), a temperature control jacket (26) is wrapped outside the high-temperature reactor (19), and high-temperature circulating liquid interfaces (C1 and C2) are respectively arranged on the upper portion and the lower portion of the temperature control jacket (26);

a discharge hole is formed in the upper end of the cooling reactor (20), a feed hole is formed in the lower end of the cooling reactor (20), the discharge hole of the high-temperature reactor (19) is communicated with the feed hole of the cooling reactor (20) through a pipeline (32), a temperature control jacket (27) is wrapped outside the cooling reactor (20), and medium-temperature circulating liquid interfaces (B5 and B6) are respectively arranged on the upper portion and the lower portion of the temperature control jacket (27);

a discharge hole is formed in the upper end of the reducing agent mixer (21), a feed hole is formed in the lower end of the reducing agent mixer (21), the discharge hole of the cooling reactor (20) is communicated with the feed hole of the reducing agent mixer (21) through a pipeline (33), the reducing agent storage tank (5) is communicated with the feed hole of the reducing agent mixer (21) through a pipeline (34), and a conveying pump (15), an adjusting valve (8) and a flowmeter (12) are sequentially arranged on the pipeline (34) along the flow direction of the reducing agent;

the upper end of buffer tank (22) is provided with the feed inlet, and the lower extreme of buffer tank (22) is provided with the discharge gate, and discharge gate department is provided with baiting valve (9), the discharge gate of reductant blender (21) passes through the feed inlet intercommunication of pipeline (35) and buffer tank (22), and the discharge gate of buffer tank (22) passes through the feed inlet intercommunication of pipeline (36) and aftertreatment system (37).

2. The apparatus for continuously preparing graphite oxide according to claim 1, wherein: the low-temperature reactor comprises at least two low-temperature kettle type reactors connected in parallel, and each low-temperature kettle type reactor is alternately communicated with the medium-temperature reactor (17).

3. The apparatus for continuously preparing graphite oxide according to claim 2, wherein: the low-temperature kettle type reactor comprises a first low-temperature kettle type reactor (16A) and a second low-temperature kettle type reactor (16B) which are connected in parallel, the upper end of the first low-temperature kettle type reactor (16A) and the upper end of the second low-temperature kettle type reactor (16B) are arranged as feed inlets, the lower end of the first low-temperature kettle type reactor (16A) and the lower end of the second low-temperature kettle type reactor (16B) are arranged as discharge outlets, the discharge outlets are communicated with a conveying pump (38) through a pipeline (28), and discharge valves (41 and 42) are arranged at the discharge outlets; the first feeding machines (2A, 2B) and the second feeding machines (3A, 3B) are respectively communicated with the feeding holes of the first low-temperature kettle type reactor (16A) and the second low-temperature kettle type reactor (16B) through pipelines, the sulfuric acid storage tank (1) is respectively communicated with the feeding holes of the first low-temperature kettle type reactor (16A) and the second low-temperature kettle type reactor (16B) through pipelines, and a conveying pump (13), a regulating valve (6) and a flow meter (10) are sequentially arranged on a main pipeline of the sulfuric acid storage tank (1) communicated with the first low-temperature kettle type reactor (16A) and the second low-temperature kettle type reactor (16B); the first low-temperature kettle type reactor (16A) and the second low-temperature kettle type reactor (16B) are respectively wrapped with temperature control jackets (23A, 23B), and the upper part and the lower part of each temperature control jacket (23A, 23B) are respectively provided with a low-temperature circulating liquid interface (A1, A2, A3, A4); the conveying pump (38) is communicated with a feed inlet of the medium-temperature reactor (17) through a pipeline, and a flow meter (39) and an adjusting valve (40) are sequentially arranged on the pipeline through which the conveying pump (38) is communicated with the feed inlet of the medium-temperature reactor (17).

4. The apparatus for continuously preparing graphite oxide according to claim 1, wherein: the medium-temperature reactor (17), the solvent mixer (18), the high-temperature reactor (19), the cooling reactor (20) and the reducing agent mixer (21) are all tubular reactors.

5. The apparatus for continuously preparing graphite oxide according to claim 1, wherein: the first feeders (2A, 2B) are graphite powder and sodium nitrate mixture feeders, and the second feeders (3A, 3B) are potassium permanganate feeders.

6. The apparatus for continuously preparing graphite oxide according to claim 1, wherein: the low-temperature circulating liquid interfaces (A1, A2, A3 and A4) are communicated with the low-temperature tank through pipelines to form a low-temperature circulating liquid loop, the medium-temperature circulating liquid interfaces (B5 and B6) are communicated with the medium-temperature tank through pipelines to form a medium-temperature circulating liquid loop, and the high-temperature circulating liquid interfaces (C1 and C2) are communicated with the high-temperature tank through pipelines to form a high-temperature circulating loop.

7. A method for continuously preparing graphite oxide using the apparatus for continuously preparing graphite oxide according to claim 1, comprising the steps of:

s2, conveying the first mixture prepared in the step S1 to a medium-temperature reactor (17), and reacting at the temperature of 30-45 ℃ for 1-5 hours to prepare a second mixture;

s3, conveying the second mixture prepared in the step S2 to a solvent mixer (18), and diluting the second mixture by using a solvent to prepare a third mixture; the solvent is deionized water, and the mass ratio of the solvent to the graphite powder is 40-100: 1;

s4, conveying the third mixture prepared in the step S3 to a high-temperature reactor (19), and reacting at the temperature of 90-110 ℃ for 1-5 hours to prepare a fourth mixture;

s5, conveying the fourth mixture prepared in the step S4 to a cooling reactor (20), and cooling to 30-45 ℃ to prepare a fifth mixture;

s6, conveying the fifth mixture prepared in the step S5 to a reducing agent mixer (21), and reducing the fifth mixture by using a reducing agent to prepare a sixth mixture;

and S7, carrying out post-treatment on the sixth mixture prepared in the step S6 by a post-treatment system (37) to prepare a graphite oxide solution, and drying the graphite oxide solution to prepare graphite oxide powder.

8. The method for continuously preparing graphite oxide according to claim 7, wherein: in the step S2, the flow rate of the first mixture in the medium temperature reactor is 0.7-3.5 m/min.

9. The method for continuously preparing graphite oxide according to claim 7, wherein: in the step S6, the reducing agent is hydrogen peroxide, and the mass ratio of the reducing agent to the graphite powder is 1-20: 1.

10. The method for continuously preparing graphite oxide according to claim 7, wherein: in step S7, the post-treatment includes one or more of sedimentation, centrifugation, and filtration.

11. The method for continuously preparing graphite oxide according to claim 7, wherein: in the step S7, the oxygen content of the prepared graphite oxide powder is 25 to 48 wt%.