阅读说明：本技术 一种电解氧化法制备氧化石墨烯的装置及方法 (A kind of electrolytic oxidation prepares the device and method of graphene oxide ) 是由 秦君 李小梅 冯锋 李琳 白云峰 柯佳 卢珍 刘志雄 于 2019-07-31 设计创作，主要内容包括：一种电解氧化法制备氧化石墨烯(GO)的装置及方法,属于氧化石墨烯的规模化生产领域,可解决现有的氧化石墨烯的制备方法中存在的问题。该装置包括GO反应系统、GO快速回收系统、电解液降温与回收系统等核心组成部分。该装置以硫酸作为电解质,以石墨纸作为生产原料。首先,将石墨原料进行电解插层,加大石墨层间距,提高氧化效率。其次,在较高的电压下将插层石墨进行电解氧化,使得石墨烯材料表面连接大量的含氧基团,最终得到GO。生成的GO被快速分离、回收,电解液也同步得到回收和循环再利用。发明的GO生产装置不产生任何重金属离子和其他有害物质排放,并且可根据生产规模进行不同程度的放大设计。(A kind of electrolytic oxidation prepares the device and method of graphene oxide (GO), belongs to the large-scale production field of graphene oxide, can solve the problems, such as the preparation method of existing graphene oxide.The device includes the core components such as GO reaction system, the quick recovery system of GO, electrolyte cooling and recovery system.The device is using sulfuric acid as electrolyte, as a raw material for production with graphite paper.Firstly, graphite raw material is carried out electrolysis intercalation, graphite layers are increased away from raising oxidation efficiency.Secondly, intercalated graphite is carried out electrolytic oxidation at higher voltages, so that grapheme material surface connects a large amount of oxygen-containing group, GO is finally obtained.The GO of generation is separated rapidly after interaction with the target molecules, recycles, and electrolyte, which also synchronizes, to be recycled and cycling and reutilization.The GO process units of invention does not generate any heavy metal ion and other discharge of poisonous waste, and different degrees of Enlargement Design can be carried out according to production scale.)

1. the device that a kind of electrolytic oxidation prepares graphene oxide, it is characterised in that: including console (1), power supply I (2), electricity Source II (3), electrolytic cell I (4), electrolytic cell II (5), elevator, drawing liquid pump (6), cooling tank (7), GO recover (8) and sulfuric acid return Receive slot (9), the output end of console (1) by conducting wire respectively with power supply I (2), power supply II (3), elevator, drawing liquid pump (6) Input terminal connection, elevator are equipped with anode I, and the concentrated sulfuric acid and cathode are equipped in electrolytic cell I (4), is equipped in electrolytic cell II (5) dilute The anode of sulfuric acid and cathode, power supply I (2) is connected by the anode I on conducting wire and elevator, and the cathode of power supply I (2) passes through conducting wire It is connected with the cathode of electrolytic cell I (4), the anode of power supply II (3) is connected by the anode I on conducting wire and elevator, power supply II (3) Cathode connected with the cathode of electrolytic cell II (5) by conducting wire, the both ends of electrolytic cell II (5) are respectively equipped with liquid outlet and feed liquor Mouthful, liquid outlet is connected by acid-proof hose (10) with the entrance of drawing liquid pump (6), and the outlet of drawing liquid pump (6) passes through acid-proof hose (10) it is connected with the entrance of cooling tank (7), the outlet of cooling tank (7) passes through the entrance of acid-proof hose (10) and GO recover (8) Connection, the outlet of GO recover (8) are located within retrieval of sulfuric acid slot (9), and the outlet of retrieval of sulfuric acid slot (9) passes through acid-proof hose (10) it is connected with the inlet of electrolytic cell II (5), the position of retrieval of sulfuric acid slot (9) vertically is higher than electrolytic cell II (5).

2. the device that a kind of electrolytic oxidation according to claim 1 prepares graphene oxide, it is characterised in that: the liter Drop machine includes the orthogonal elevator longitudinal axis (11) and elevator horizontal axis (12), the elevator longitudinal axis (11) and elevator horizontal axis (12) lead screw of elevator (13) or sliding rail are respectively equipped in, elevator horizontal axis (12) passes through pedestal I (14) and the elevator longitudinal axis (11) it connects, elevator horizontal axis (12) is equipped with the pedestal II (15) slided along elevator horizontal axis (12), and anode I passes through bracket (16) it is located on pedestal II (15), electrolytic cell I (4) and electrolytic cell II (5) are located at the bottom at elevator horizontal axis (12) both ends.

3. the device that a kind of electrolytic oxidation according to claim 1 prepares graphene oxide, it is characterised in that: the GO Recover (8) is funneling rapid filter ware, and the quantity of GO recover (8) is more than or equal to 2.

4. the device that a kind of electrolytic oxidation according to claim 1 prepares graphene oxide, it is characterised in that: the sulphur Acid recovery slot (9) bottom is taper, and the outlet of retrieval of sulfuric acid slot (9) is located at bottommost.

5. the device that a kind of electrolytic oxidation according to claim 1 prepares graphene oxide, it is characterised in that: the drop Wen Chi (7) includes sink and acidproof cooler (17), and the sink is round or rectangular or strip, the cooler (17) For interlayer socketed cup type or helix tube type or general spherical shape/snakelike/straight movement type, one end of cooler (17) and going out for drawing liquid pump (6) Mouth connection, the other end are connect with the entrance of GO recover (8).

6. a kind of method that electrolytic oxidation prepares graphene oxide, it is characterised in that: use two one-step electrolysis oxidation technologies, have The electrolytic cell of liquid inlet and outlet, including electrolyte extracts, driving, cooling, quick separating recycles and GO recycling, including walks as follows It is rapid:

The first step carries out electrochemical intercalation by graphite raw material in the electrolytic cell I using the concentrated sulfuric acid as electrolyte at low voltage；

Second step, after the graphite raw material control after intercalation is removed the concentrated sulfuric acid, in the electrolytic cell II using dilute sulfuric acid as electrolyte, in height Electrochemical oxidation is carried out under voltage, obtains graphene oxide layer；

Third step extracts the electrolyte in electrolytic cell II using fluid drive apparatus, by cooling, electrolyte, mistake is recovered by filtration Graphene oxide layer after filter obtains final product graphene oxide through over cleaning.

7. the method that a kind of electrolytic oxidation according to claim 6 prepares graphene oxide, it is characterised in that: including such as Lower step:

Graphite paper is installed on the anode I of horizontal axis (12) of elevator by the first step；

Second step, control elevator are sufficiently soaked in graphite paper insertion electrolytic cell I (4) of anode I in the concentrated sulfuric acid, are arranged Decomposition voltage is constant pressure 1.5V and opens power supply I (2), and the electrolysis intercalation that graphite paper carries out 10-20min in electrolytic cell I (4) is anti- It answers, obtains 5-8 times of volume expansion of sulfuric acid intercalated graphite paper；

Third step controls elevator, and the graphite paper after expansion is increased, and after control removes the concentrated sulfuric acid, is transferred in electrolytic cell II (5), It opens power supply II (3), sets constant voltage+7V, the graphite paper after expansion is immersed into the dilution heat of sulfuric acid in electrolytic cell II (5) In, the graphite paper after expansion is used as lossy anode in dilution heat of sulfuric acid, and the oxygen radical generated with electrolysis water reacts, The cotton-shaped GO for having oxygen-containing group is generated, is fallen off from graphite paper, into dilute sulfuric acid electrolyte；

4th step is opened drawing liquid pump (6), and the GO floccule of generation enters GO recover (8) with dilution heat of sulfuric acid, and GO is returned by GO Device (8) retention is received, dilution heat of sulfuric acid enters retrieval of sulfuric acid slot (9) by GO recover (8)；

5th step, the dilute sulfuric acid in retrieval of sulfuric acid slot (9) are flowed back under the effect of gravity in electrolytic cell II (5), and GO recover (8) is cut After the GO stayed is cleaned 5-7 times with deionized water, GO product is obtained.

Technical field

The invention belongs to the large-scale production technology fields of graphene oxide, and in particular to a kind of electrolytic oxidation prepares oxygen The device and method of graphite alkene (GO).

Background technique

Grapheme material is a kind of new material, and conductive high, chemical stability is good and porous absorption property Outstanding advantages of excellent.Therefore, grapheme material has high application in fields such as new energy, environmental protection, industrial protections Value and potentiality.Graphene oxide GO is the primary raw material (presoma) of synthesizing graphite alkene material, by by GO in certain condition The novel porous adsorbent material such as graphene aerogel can be obtained in lower progress polymerization reaction.Therefore, the synthesis technology and its warp of GO Can Ji property, security relationship to graphene polyporous materials realize large-scale application in various fields.

Existing GO synthesis technology is mainly chemical oxidization method, that is, passes through dense inorganic acid (concentrated sulfuric acid, concentrated phosphoric acid), strong oxygen After agent (potassium permanganate, potassium bichromate etc.) and graphite mixing, progress long-time oxidation reaction, cleaning rear is available repeatedly GO.It is more mature using the GO production technology of chemical oxidization method, but still remain a series of problems: (1) synthetic reaction there are one Fixed risk, the strong oxidizers such as potassium permanganate in concentrated sulfuric acid temperature be higher than 50 DEG C when, the intermediate product of generation easily occurs Explosion；(2) a large amount of Mn are introduced in reaction²⁺、Cr⁶⁺Etc. heavy metal ion, need a large amount of deionized water to be rinsed, simultaneously Also heavy metal ion is caused to be discharged；(3) synthesis reaction period is long, and amplification synthesis device cost is high.

Another emerging GO synthetic method is electrolytic oxidation, this method using graphite material as cell reaction anode, It is in the electrolyte GO by the quick oxidation transformation of graphite.The existing research document report GO composition principle of this method, synthesis GO high oxygen content, good dispersion in water, can be used in synthesizing good grapheme material.Current electrolytic oxidation synthesis GO limitation In laboratory basic research, and there are a series of problems: (1) with the progress of reaction, the GO of generation in general electrolytic pond Electrolyte surface is swum in, the progress of cell reaction is hindered, leads to the quality decline of the GO generated；(2) one-step electrolysis oxidizing process In obtained product, dispersed GO sheet content is higher, it is difficult to carry out quick separating recycling；(3) oxygen content in the GO generated Higher and poorly conductive, generates partial pressure effects in electrolytic cell, leads to the voltage being applied on the expanded graphite paper of anode reduction, Cell reaction speed reduces (4) with the progress of electrolytic oxidation reaction, and electrolyte and electrolytic cell temperature constantly increase, and generates safety Hidden danger；(5) the GO production technology for lacking quick amplification, can not cope with large-scale production demand.

Summary of the invention

The present invention is directed to the problem of preparation method of existing graphene oxide, provides a kind of electrolytic oxidation legal system The device and method of standby graphene oxide, the present apparatus can carry out a certain proportion of amplification, realize the yield of different stage, while really Protect the GO quality with higher of production.

The present invention adopts the following technical scheme:

A kind of electrolytic oxidation prepares the device of graphene oxide, including console, power supply I, power supply II, electrolytic cell I, electrolytic cell II, elevator, drawing liquid pump, cooling tank, GO recover and retrieval of sulfuric acid slot, the output end of console by conducting wire respectively and power supply I, the input terminal connection of power supply II, elevator, drawing liquid pump, elevator are equipped with anode I, are equipped with the concentrated sulfuric acid and yin in electrolytic cell I Pole is equipped with dilute sulfuric acid and cathode in electrolytic cell II, and the anode of power supply I is connected by the anode I on conducting wire and elevator, power supply I Cathode connect with the cathode of electrolytic cell I by conducting wire, the anode of power supply II by the connection of anode I on conducting wire and elevator, The cathode of power supply II is connected by conducting wire with the cathode of electrolytic cell II, and the both ends of electrolytic cell II are respectively equipped with liquid outlet and feed liquor Mouthful, liquid outlet connect with the entrance of drawing liquid pump by acid-proof hose, and the outlet of drawing liquid pump passes through entering for acid-proof hose and cooling tank The outlet of mouth connection, cooling tank is connected by acid-proof hose with the entrance of GO recover, and the outlet of GO recover is returned positioned at sulfuric acid The top of slot is received, the outlet of retrieval of sulfuric acid slot is connected by the inlet of acidproof soft electrolytic cell II, and retrieval of sulfuric acid slot is along vertical The position in direction is higher than electrolytic cell II.

The elevator includes the orthogonal elevator longitudinal axis and elevator horizontal axis, the elevator longitudinal axis and elevator horizontal axis It is inside respectively equipped with lead screw of elevator or sliding rail, elevator horizontal axis is connect with the elevator longitudinal axis by pedestal I, set on elevator horizontal axis There is the pedestal II along the sliding of elevator horizontal axis, anode I is located on pedestal II by bracket, and electrolytic cell I and electrolytic cell II distinguish position In the bottom at elevator horizontal axis both ends.

The GO recover is funneling rapid filter ware, and the quantity of GO recover is more than or equal to 2, it can be ensured that one With other spare continuous production conditions, the funneling optional sand core funnel of rapid filter ware.

The retrieval of sulfuric acid trench bottom is taper, and the outlet of retrieval of sulfuric acid slot is located at bottommost.

The cooling tank includes sink and acidproof cooler, and the sink is round or rectangular or strip, the drop Warm device is interlayer socketed cup type or helix tube type or general spherical shape/snakelike/straight, and one end of cooler and the outlet of drawing liquid pump connect It connects, the other end is connect with the entrance of GO recover.

A kind of method that electrolytic oxidation prepares graphene oxide has liquid inlet and outlet using two one-step electrolysis oxidation technologies Electrolytic cell, including electrolyte extract, driving, cooling, quick separating recycling and GO recycling, include the following steps:

The first step carries out electrochemical intercalation by graphite raw material in the electrolytic cell I using the concentrated sulfuric acid as electrolyte at low voltage；

Second step, after the graphite raw material control after intercalation is removed the concentrated sulfuric acid, in the electrolytic cell II using dilute sulfuric acid as electrolyte, in height Electrochemical oxidation is carried out under voltage, obtains cotton-shaped graphite oxide ene product；

Third step extracts the electrolyte in electrolytic cell II using fluid drive apparatus (drawing liquid pump), by cooling, electricity is recovered by filtration Liquid is solved, filtered graphene oxide floccule obtains final product graphene oxide through over cleaning.

A kind of method that electrolytic oxidation prepares graphene oxide, includes the following steps:

Graphite paper is installed on the anode I of the horizontal axis of elevator by the first step；

Second step, control elevator are sufficiently soaked in the graphite paper insertion electrolytic cell I of anode I in the concentrated sulfuric acid, setting electrolysis Voltage is constant pressure 1.5V and opens power supply I, and graphite paper carries out the electrolysis intercalation of 10-20min in electrolytic cell I, obtains body Product expands 5-8 times of sulfuric acid intercalated graphite paper；

Third step controls elevator, and the graphite paper after expansion is increased, and control is opened except being transferred in electrolytic cell II after the concentrated sulfuric acid Power supply II sets constant voltage+7V, the graphite paper after expansion is immersed in the dilution heat of sulfuric acid in electrolytic cell II, after expansion Graphite paper in dilution heat of sulfuric acid be used as lossy anode, with electrolysis water generate oxygen radical react, generate have contains The GO lamella of oxygen groups, falls off from graphite paper, into dilute sulfuric acid electrolyte；

4th step opens drawing liquid pump, and the GO lamella of generation enters GO recover with dilution heat of sulfuric acid, and GO is cut by GO recover It stays, dilution heat of sulfuric acid enters retrieval of sulfuric acid slot through GO recover；

5th step, the dilute sulfuric acid in retrieval of sulfuric acid slot are flowed back under the effect of gravity in electrolytic cell II, and the GO of GO recover retention is used After deionized water is cleaned 5-7 times, GO product is obtained.

Beneficial effects of the present invention are as follows:

It, can be into as source using the structure of the device 1. the invention devises complete, integrated form graphene oxide process units Row amplification, builds the graphene oxide production line of scale.

It is quickly produced 2. the graphene oxide production line of the invention can carry out graphene oxide, production procedure is shortened to 1 Within hour, time-consuming (is greater than 6 hours) far below conventional oxidation method generated time.

3. the graphene oxide production line of the invention does not introduce manganese (Mn), cadmium (Cd), chromium in graphene oxide production (Cr) etc. heavy metal elements do not contain any metallic element and other impurities in the graphene oxide of production.Belong to environmental-friendly Green syt production line.

4. the production line of the invention uses dense, dilute sulfuric acid as electrolyte, i.e. reusable after simply filtering.

5. the line configuration of the invention has ice (water, oil) bath cooling component, overcome existing for traditional general electrolytic pond The shortcomings that electrolyte heating, product deterioration.

6. the line configuration of the invention has pump group, quickly recycles filter assemblies, vertical fluid driving assembly.It can be fast The graphene oxide produced is removed and is recycled from electrolytic cell II by speed, is overcome graphite oxide in general electrolytic pond and is swum in In electrolyte, the problem of hindering cell reaction or anode conductance rate caused to reduce.

Detailed description of the invention

Fig. 1 is flow chart of the invention；

Fig. 2 is the structural schematic diagram of apparatus of the present invention；

Fig. 3 is the structural schematic diagram of lifting sliding table of the invention；

Wherein: 1- console；2- power supply I；3- power supply II；4- electrolytic cell I；5- electrolytic cell II；6- drawing liquid pump；7- cooling tank；8- GO recover；9- retrieval of sulfuric acid slot；10- acid-proof hose；The 11- elevator longitudinal axis；12- elevator horizontal axis；13- lead screw of elevator； 14- pedestal I；15- pedestal II；16- bracket；17- cooler；

Fig. 4 is the structural schematic diagram of electrolytic cell I of the invention；

Fig. 5 is the structural schematic diagram of electrolytic cell II of the invention；

Fig. 6 is the graphene oxide and graphene hydrogel of preparation of the embodiment of the present invention, wherein A is graphene oxide, and B is oxygen Graphite alkene, C are graphene hydrogel；

Fig. 7 is the scanning electron microscope diagram of the graphene aerogel of preparation of the embodiment of the present invention；

Fig. 8 is quick adsorption figure of the graphene aerogel to n-butanol of preparation of the embodiment of the present invention；

Fig. 9 is the pictorial diagram of cooler of the invention, wherein A is double-jacket cup type, and B is spiral cast, and C is spherical shape/snake Shape/straight；

Figure 10 is the pictorial diagram of GO recover (sand core funnel) of the invention.

Specific embodiment

Elevator is the electric lift controlled by console, is two shaft type screw rods or guide rail structure, the elevator longitudinal axis Height is 40-50cm, and elevator horizontal axis length is 30-40cm, and elevator horizontal axis is mounted on the elevator longitudinal axis by changeover base On, elevator horizontal axis can be gone up and down within the scope of 20-30cm, and electrolytic anode is installed on the sliding on elevator horizontal axis by bracket Pedestal, electrolytic anode can with horizontal transverse movement, by controller realize electrolytic anode move horizontally and elevator horizontal axis Vertically move.

Electrolytic cell I is square groove type, and the concentrated sulfuric acid is added thereto as electrolyte.II both ends of electrolytic cell are respectively equipped with disengaging Mouthful, it is formed into a loop using acid-proof hose connection drawing liquid pump, cooling tank, sand core pond and retrieval of sulfuric acid slot, using 40%(m/m) dilute sulphur Acid is used as electrolyte, is equipped with cooler and ice-water bath (or compressor refrigeration) in cooling tank.