CN108793148A - A kind of continuous production device and method of amination graphene - Google Patents
A kind of continuous production device and method of amination graphene Download PDFInfo
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- CN108793148A CN108793148A CN201811068471.0A CN201811068471A CN108793148A CN 108793148 A CN108793148 A CN 108793148A CN 201811068471 A CN201811068471 A CN 201811068471A CN 108793148 A CN108793148 A CN 108793148A
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Abstract
The invention discloses a kind of continuous production devices and method of amino graphene, belong to the preparing technical field of graphene.The continuous production device includes sequentially connected acid treatment device, oxidation unit, first washing Suction filtration device, second washing Suction filtration device, decentralized processing device, first homogenization processing unit, first micro-reaction device, first pipe reaction device, second pipe reaction device, first filters redisperse device, second micro-reaction device, third pipe reaction device, 4th pipe reaction device, second filters redisperse device, third filters redisperse device, first reaction product storage tank, second homogenization processing unit, third uniforms processing unit and the second reaction product storage tank, static mixer is equipped in material conveying pipe.The piece diameter of modified amido graphite alkene produced by the invention is small, flake diameter distribution is narrow, single layer rate is high, pollution-free in production process, and raw material basis is provided for the scale application of amination graphene.
Description
Technical field
The invention belongs to the preparing technical fields of graphene, more specifically to a kind of the continuous of amination graphene
Metaplasia produces device and method.
Background technology
Graphene be one kind by carbon atom with sp2Hybridized orbit forms the flat film that hexangle type is in honeycomb lattice, thickness
For the thickness (0.35nm) of a carbon atomic layer, there is excellent mechanical property, electrical property and hot property.Graphene is extensive at present
For the composite modified of material, basis material is modified using the excellent properties of graphene, the performance of basis material can be made
It is significantly improved, therefore graphene nanocomposite material becomes current material circle research hot topic.
For the interface cohesion of guarantee graphene and basis material, need to modify graphene surface by small molecule,
To achieve the purpose that introduce group on the surface of graphene, such as amination graphene is exactly the table by chemical modification in graphene
Face introduces amino group.In the prior art, the preparation of amination graphene also rests on laboratory stage at present, not yet in fact
Existing industrialization large-scale production, problem urgently to be resolved hurrily are how industrially continuously and stably to produce the ammonia of high quality
Base graphite alkene.
Invention content
In view of the above-mentioned problems existing in the prior art, one of the objects of the present invention is to provide a kind of amination graphenes
Continuous production device, rationally distributed, succinct, production efficiency and high degree of automation, can not only realize function graphite
The industrialized production of alkene, and obtained amination graphene has the advantages that piece diameter is small, single layer rate is high, dispersion effect is good；This
The second purpose of invention is to provide the production method using the amination graphene continuous production device.
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
A kind of continuous production device of amination graphene, including sequentially connected acid treatment device, oxidation unit,
One washing Suction filtration device, the second washing Suction filtration device, decentralized processing device, the first homogenization processing unit, first micro- reaction dress
It sets, the first pipe reaction device, the second pipe reaction device, first filter redisperse device, the second micro-reaction device, third pipe
Formula reaction unit, the 4th pipe reaction device, second filter redisperse device, third suction filtration redisperse device, the first reaction production
Object storage tank, the second homogenization processing unit, third homogenization processing unit and the second reaction product storage tank, material delivery pipe
Static mixer is equipped in road；Wherein, it is equipped with high-shear emulsion machine and ultrasonic dispersers in the decentralized processing device, described point
Scattered processing unit is externally provided with outer circulation shear pump；The first homogenization processing unit, the second homogenization processing unit and third
Uniform the decentralized processing that processing unit is used for system；It is cut equipped with height in first micro-reaction device and the second micro-reaction device
Mulser, first micro-reaction device and the second micro-reaction device are cut for carrying out decentralized processing while material reaction；
Inside the first pipe reaction device, the second pipe reaction device, third pipe reaction device and the 4th pipe reaction device
Equipped with multilayer static mixer；Described first, which filters redisperse device, the second suction filtration redisperse device and third, filters redisperse
It is equipped with Suction filtration device in device, redisperse is carried out for addition solvent after the suction filtration and suction filtration of material.
A kind of continuous production method of amination graphene using above-mentioned apparatus, includes the following steps：
Step 1, after graphite being carried out sour processing by acid treatment device, oxidation reaction is carried out into oxidation unit, then
It washed, filtered by the first washing Suction filtration device, the second washing Suction filtration device is passed through after n,N-Dimethylformamide is added
It washed, filtered again, obtain graphite oxide slurry；
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device and carries out decentralized processing, then led to
Cross the further dispersion that the first homogenization processing unit carries out material；
Step 3, chloride reagent is slowly added in the material obtained to step 2, is then sent to first micro- reaction dress
Middle carry out mixed at high speed is set, acyl chloride reaction is proceeded by；
Step 4, the product that step 3 obtains is passed through the first pipe reaction device and the second pipe reaction device successively, after
It is continuous to carry out acyl chloride reaction；
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse device, N, N- dimethyl methyls is supplemented after suction filtration
Amide, and carry out the dispersion again of filter cake；
Step 6, amination reagent is slowly added in the product obtained to step 5, is then sent to second micro- reaction dress
Middle carry out mixed at high speed is set, ammoxidation is proceeded by；
Step 7, the product that step 6 obtains is passed through third pipe reaction device successively and the 4th pipe reaction device continues
Carry out ammoxidation；
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse device, N, N- dimethyl methyls is supplemented after suction filtration
Amide carries out the dispersion again of filter cake；It then passes to third and filters redisperse device, N, N- dimethyl formyls are supplemented after suction filtration
Amine carries out the dispersion again of filter cake；
Step 9, the product that step 8 obtains is passed sequentially through into the second homogenization processing after the first reaction product storage tank
Device and third homogenization processing unit carry out homogenization processing, and final product is passed through the second reaction product storage tank, obtains ammonia
Base graphite alkene.
In the step 1, graphite is added in acid solution, is impregnated at 0~20 DEG C, oxygen is delivered to after 0.5~4h
Makeup is set, and adds primary oxidant and pro-oxidant, controls 10~110 DEG C of temperature, and the first washing is delivered to after reacting 2~12h
Suction filtration device is washed by deionized water, is filtered three times, and n,N-Dimethylformamide is then added and is disperseed, by object
Material delivers into the second washing Suction filtration device, and after n,N-Dimethylformamide washing, filtering three times, graphite oxide is disperseed
In n,N-Dimethylformamide, graphite oxide slurry is obtained.
The graphite and the mass ratio of acid solution are 1：(1~3), the graphite, primary oxidant, pro-oxidant mass ratio be
1：(0.1~10)：(0.01~1), the acid solution are dilute hydrochloric acid, dilute sulfuric acid, dust technology, phosphoric acid,diluted, oxalic acid or formic acid, the master
Oxidant is potassium bichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate or molybdenum dioxide, and the pro-oxidant is hydroperoxidation
Object, dialkyl peroxide, diacyl peroxide, peroxy esters, peroxycarbonates or ketone peroxide.
In the step 2, to decentralized processing device in such a way that high-shear emulsion machine and ultrasonic dispersers are run simultaneously
In graphite oxide slurry handled, while by outer circulation shear pump to graphite oxide slurry into Mobile state mix, it is described
The rotating speed of high-shear emulsion machine be 3000~3500r/min, ultrasonic power be 1~15kw, device run time 30~
200min。
In the step 3, the mass ratio of chloride reagent and graphene oxide is 1:10~10:1, the chloride reagent
For phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride or sulfonic acid chloride.
In the step 6, amination reagent is 1 with graphene mass ratio:10~1:1, the amination reagent is second two
Amine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, o-phenylenediamine, m-phenylene diamine (MPD), to benzene two
Amine, lauryl amine or octadecylamine.
The homogenization pressure of the first homogenization processing unit is 50~80MPa, the second homogenization processing unit
Homogenization pressure is 80~110MPa, and the homogenization pressure of the third homogenization processing unit is 110~150MPa.
Reaction temperature in first micro-reaction device and the first pipe reaction device is controlled at -10~10 DEG C, described
Reaction temperature in second pipe reaction device is controlled at 40~150 DEG C.
Reaction temperature in second micro-reaction device and third pipe reaction device is controlled at -5~30 DEG C, and described the
Reaction temperature in four pipe reaction devices is controlled at 50~150 DEG C.
Compared with the prior art, beneficial effects of the present invention are：
The continuous production device of the amination graphene of the present invention, piece diameter after raw material is by pre-processing, homogenization is handled
Become smaller, narrow particle size distribution, single layer rate improves；By micro-reaction device equipped with highdensity plywood emulsifier unit, to be equipped with multilayer quiet
The pipe reaction device of state mixer makes reaction mass come into full contact with, reaction efficiency improves；Redisperse device collection is filtered to filter, divide
It dissipates in one, improves device efficiency；Material reaction complete after handled using homogenization, make graphene piece diameter size,
The indexs such as flake diameter distribution, single layer rate further increase, and the piece diameter and piece for making modified graphene is used for multiple times in a variety of dispersion means
Layer thickness smaller increases the proton number of reaction product.
The continuous preparation method of the amination graphene of the present invention, realizes industrialization, the scale of amination graphene
Change and prepare, the piece thickness, piece diameter when solving preparation of industrialization amination graphene are big, disperse the problems such as uneven, production
The piece diameter of modified amido graphite alkene is small, flake diameter distribution is narrow, single layer rate is high, pollution-free in production process, is amination graphene
Scale application provide raw material basis.
Description of the drawings
Fig. 1 is the continuous production device schematic diagram of the amination graphene of the present invention；
In figure：1, acid treatment device；2, oxidation unit；3, the first washing Suction filtration device；4, the second washing Suction filtration device；5,
Decentralized processing device；6, the first homogenization processing unit；7, the first micro-reaction device；8, the first pipe reaction device；9, second
Pipe reaction device；10, first redisperse device is filtered；11, the second micro-reaction device；12, third pipe reaction device；13,
4th pipe reaction device；14, second redisperse device is filtered；15, third filters redisperse device；16, the first reaction product
Storage tank；17, the second homogenization processing unit；18, third uniforms processing unit；19, the second reaction product storage tank；607,
First raw material high position adding set；1011, the second raw material high position adding set.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The continuous production device of a kind of amination graphene of the present embodiment, as shown in Figure 1, including sequentially connected acid
Processing unit 1, oxidation unit 2, first wash Suction filtration device 3, second and wash Suction filtration device 4, decentralized processing device 5, first
One, which changes processing unit 6, the first micro-reaction device 7, the first pipe reaction device 8, the second pipe reaction device 9, first, filters again
Dispersal device 10, the second micro-reaction device 11, third pipe reaction device 12, the 4th pipe reaction device 13, second filter again
Dispersal device 14, third filter redisperse device 15, the first reaction product storage tank 16, second homogenization processing unit 17, the
Three homogenization processing units 18 and the second reaction product storage tank 19, the first homogenization processing unit 6 and the first micro-reaction device 7
Between be equipped with the first raw material high position adding set 607, first suction filtration redisperse device 10 and the second micro-reaction device 11 between set
There is the second raw material high position adding set 1011, is equipped with static mixer in each material conveying pipe, makes the original of material and addition
Material is adequately mixed, and reaction efficiency is improved.A whole set of continuous production device is transported under the control of automatic control system
Row, may be implemented the large-scale production of modified function graphite alkene, solves the industrial applications demand of graphene.
Wherein：
Processing of the acidification treater 1 for acid to graphite, oxidation unit 2 are used for the oxidation reaction of graphite, acid processing dress
Set 1 and oxidation unit 2 be all normal pressure band stirring reaction kettle.
First washing Suction filtration device 3 and second is washed the washing deacidification after Suction filtration device 4 is used to react graphite oxidation, is taken out
Solvent is filtered off, is the reaction kettle with stirring, the bottom welding metal of kettle is sintered felt, realizes the function of suction filtration.
Decentralized processing device 5 is internally provided with high-shear emulsion machine and ultrasonic dispersers, and outside is equipped with outer circulation shear pump, uses
In the decentralized processing of piece diameter, the processing of the number of plies and system.
It is homogeneous that first homogenization processing unit 6, second, which uniforms processing unit 17 and third homogenization processing unit 18,
Machine, the second homogenization processing unit 17 are connected with third homogenization processing unit 18 by series system, realize classification homogenization
Processing, improves the utilization rate and service efficiency of equipment.
First raw material high position adding set 607 is to allow raw material can smoothly enter into using difference in height in high-order raw material storage tank
The discharge port of reaction system, the first raw material high position adding set 607 is connected with the feed inlet of the first micro-reaction device 7, and first is former
The high-order adding set 607 of material carries out flow control by the way of adding online by flowmeter.
It is equipped with high-shear emulsion machine in first micro-reaction device 7 and the second micro-reaction device 11, simultaneously for material reaction
Carry out decentralized processing.
First pipe reaction device 8, the second pipe reaction device 9, third pipe reaction device 12 and the 4th pipe reaction
Device 13 is the reaction tower for being internally provided with multilayer homogenizing plate, and homogenizing plate plays current balance function, while so that material is sufficiently mixed not
Rolling up and down can be formed, it is ensured that the material of advanced reaction tube also first goes out reaction tube, to ensure the reaction time of material.
First suction filtration redisperse device 10, second filters redisperse device 14 and third is filtered and is equipped in redisperse device 15
Suction filtration device carries out redisperse for addition solvent after the suction filtration and suction filtration of material.
In order to realize the control to reaction temperature, the first pipe reaction device 8, third pipe reaction device 12 respectively with even
Continuous circulating refrigerating device is connected；Second pipe reaction device 9, the 4th pipe reaction device 13 recycle heating combined equipment with continuous respectively
It is connected.Meanwhile first raw material high position adding set and the second raw material high position adding set be also connected with continuous circulating refrigerating device
Realize the control of temperature.
The outside of first reaction product storage tank 16 and the second reaction product storage tank 19 is equipped with circulating pump, plays storage object
Material, the effect of intermediate transition.
The continuous production of amination graphene is carried out using above-mentioned apparatus, the oxidation of graphite is carried out first, then by oxygen
Graphite carries out chloride and amination successively, obtains amination graphene, specifically includes following steps：
Step 1,10kg graphite powders are added in 30kg dilute sulfuric acids (mass fraction 50%), are impregnated at 0 DEG C, 4h
Oxidation unit 2 is delivered to by the speed for pumping with 100kg/h afterwards, and by online add-on system add 50kg primary oxidants and
5kg pro-oxidants, the adding speed of primary oxidant potassium permanganate is 5kg/h, the adding speed of pro-oxidant hydrogen peroxide is 2kg/
H, control temperature are delivered to the first washing Suction filtration device 3 by pump after reaction 12h, are carried out repeatedly by deionized water at 10 DEG C
Washing filters three times, and n,N-Dimethylformamide is then added and is disperseed, and material, which is delivered into the second washing, by pump takes out
Device 4 is filtered, after n,N-Dimethylformamide washing, filtering three times, graphite oxide is dispersed in n,N-Dimethylformamide
In, obtain graphite oxide slurry.
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device 5, using high-shear emulsion machine and
The mode that ultrasonic dispersers are run simultaneously handles the graphite oxide slurry in decentralized processing device 5, while by following outside
Ring shear pump mixes graphite oxide slurry into Mobile state, and the rotating speed of the high-shear emulsion machine is 3500r/min, ultrasonic work(
Rate is 12kw, device run time 100min.Treated, and slurry is delivered to the first homogenization processing dress with the speed of 200kg/h
The further dispersion for setting 6 carry out materials, under homogenization pressure 50MPa effects, material is further removed, piece diameter size,
Lamellar spacing becomes smaller.
Step 3, the temperature for the material and thionyl chloride that rate-determining steps 2 obtain is 0 DEG C, and chloride reagent thionyl chloride is led to
It crosses the first raw material high position adding set 607 to be slowly added in the material obtained to step 2, the adding speed of thionyl chloride is
10kg/h is immediately conveyed to carry out mixed at high speed in the first micro-reaction device 7 after mixing, proceeds by acyl chloride reaction, reaction
Time 6h；The rotating speed of high-shear emulsion machine is 3500r/min in device, and the mass ratio of chloride reagent and graphene oxide is 1：
1。
Step 4, the product that step 3 obtains is passed through the first pipe reaction device 8, reaction unit 8 carries out circularly cooling, temperature
Degree is maintained at 0 DEG C, reaction time 6h, and material enters from reaction unit lower end, passes through the multilayer homogenizing plate of device inner setting
Further material is mixed, is disperseed, while device top carries out pumping negative-pressure operation, the gas that reaction generates is allowed to enter gas washing
Device；Material reaches device upper end outlet and starts to discharge, and then reaches the second pipe reaction device 9, and reaction unit 9 is recycled
Heating, temperature are maintained at 120 DEG C, reaction time 6h, and material enters from device lower end, passes through the multilayer homogenizing plate inside device
Further material is mixed, is disperseed, similarly, device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter
Air-washer.
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse dress by the upper end of the second pipe reaction device 9
Set 10, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion.
Step 6, the temperature for the material and ethylenediamine that rate-determining steps 5 obtain is 10 DEG C, and amination reagent ethylenediamine is passed through
Second raw material high position adding set 1011 is slowly added in the material obtained to step 5, and the adding speed of ethylenediamine is 15kg/h,
It is immediately conveyed to carry out mixed at high speed in the second micro-reaction device 11 after mixing, proceeds by ammoxidation；Height is cut in device
The rotating speed of mulser is cut as 3500r/min, the mass ratio of amination reagent and graphene is 1：1.
Step 7, the product that step 6 obtains is passed through third pipe reaction device 12, device 12 carries out circularly cooling, temperature
Be maintained at 15 DEG C, reaction time 6h, material enters from reaction unit lower end, by the multilayer homogenizing plate of device inner setting into
Material is mixed, is disperseed by one step, while device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter gas washing dress
It sets；Material reaches device upper end outlet and starts to discharge, and then reaches the 4th pipe reaction device 13, and device 13 carries out cycle system
Heat, temperature are maintained at 120 DEG C, reaction time 6h, and material enters from device lower end, by the multilayer homogenizing plate inside device into
Material is mixed, is disperseed by one step, and similarly, device top carries out pumping negative-pressure operation, is allowed the gas that reaction generates to enter and is washed
Device of air.
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse dress by the upper end of the 4th pipe reaction device 13
Set 14, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion；Then material is delivered to by third by pump and filters redisperse device 15, n,N-Dimethylformamide is supplemented after suction filtration, into
The dispersion again of row filter cake.
Step 9, the product that step 8 obtains is passed sequentially through after the first reaction product storage tank 16 at the second homogenization
Reason device 17 and third homogenization processing unit 18 carry out homogenization processing, the homogenization pressure in the second homogenization processing unit 17
For 100MPa, it is 120MPa that third, which uniforms the homogenization pressure in processing unit 18, and final product is passed through the storage of the second reaction product
Batch can 19, obtains amination graphene.
Using above-mentioned gained amination graphene as test sample, to its lamellar spacing, piece diameter size, nitrogen element content into
Go measurement, to ensure that the accuracy of test is sampled test when being produced to the product (A~E) of different phase,
Specific test result is shown in Table 1.
The test result of 1 embodiment of table, 1 continuous production amination graphene different phase product
| GO pieces diameter (nm) | GO lamellar spacings (nm) | N content (%) | |
| A | 250 | 1.4 | 0 |
| B | 240 | 1.3 | 0 |
| C | 245 | 1.2 | 18.8 |
| D | 240 | 1.3 | 19.0 |
| E | 250 | 1.3 | 19.1 |
In upper table, product A is derived from enter step 3 reactions after step 2 is completed before, product B is derived from step 5 reaction completion
After enter step 6 reactions before, product C is derived from enter step 8 reactions after step 7 is completed before, product D be derived from step 8 complete with
After enter step 9 before, product E be derived from step 9 complete after.
As it can be seen from table 1 using the continuous producing apparatus and preparation method thereof of amination graphene provided by the invention,
It may be implemented industrialization, the consecutive production of amination graphene, the amination graphene piece diameter of production is small, lamella is thin, and produces
Quality is stablized, at the same nitrogen content is higher and content is relatively stablized, illustrate the amino graphene continuous production of the present invention
Stabilization of equipment performance is high, and production efficiency is high, while illustrating that the preparation method effect of the amination graphene of the present invention is good, can produce
Meet the amination graphene for composite material.
Embodiment 2
The present embodiment uses the continuous production that amination graphene is carried out with 1 identical device of embodiment, including
Following steps：
Step 1,10kg graphite powders are added in 10kg dilute hydrochloric acid (mass fraction 15%), are impregnated at 20 DEG C,
Oxidation unit 2 is delivered to by the speed for pumping with 100kg/h after 0.5h, and passes through online add-on system and adds the main oxidations of 100kg
Agent and 10kg pro-oxidants, the adding speed of primary oxidant potassium hyperchlorate is 5kg/h, the adding speed of pro-oxidant peroxy esters is
2kg/h, control temperature are delivered to the first washing Suction filtration device 3 by pump after reaction 10h, are carried out by deionized water at 80 DEG C
It washs, filtered three times repeatedly, n,N-Dimethylformamide is then added and is disperseed, material, which is delivered into second, by pump washes
Suction filtration device 4 is washed, after n,N-Dimethylformamide washing, filtering three times, graphite oxide is dispersed in N, N- dimethyl methyls
In amide, graphite oxide slurry is obtained.
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device 5, using high-shear emulsion machine and
The mode that ultrasonic dispersers are run simultaneously handles the graphite oxide slurry in decentralized processing device 5, while by following outside
Ring shear pump mixes graphite oxide slurry into Mobile state, and the rotating speed of the high-shear emulsion machine is 3000r/min, ultrasonic work(
Rate is 1kw, device run time 200min.Treated, and slurry is delivered to the first homogenization processing dress with the speed of 200kg/h
The further dispersion for setting 6 carry out materials, under homogenization pressure 70MPa effects, material is further removed, piece diameter size,
Lamellar spacing becomes smaller.
Step 3, the temperature for the material and phosphorus oxychloride that rate-determining steps 2 obtain is -10 DEG C, by chloride reagent phosphorus oxychloride
It is slowly added in the material obtained to step 2 by the first raw material high position adding set 607, the adding speed of phosphorus oxychloride is
10kg/h is immediately conveyed to carry out mixed at high speed in the first micro-reaction device 7 after mixing, proceeds by acyl chloride reaction, reaction
Time 10h；The rotating speed of high-shear emulsion machine is 3200r/min in device, and the mass ratio of chloride reagent and graphene oxide is
1：10.
Step 4, the product that step 3 obtains is passed through the first pipe reaction device 8, reaction unit 8 carries out circularly cooling, temperature
Degree is maintained at 10 DEG C, and the reaction time is that for 24 hours, material enters from reaction unit lower end, is flowed by the multilayer of device inner setting
Material is further mixed, is disperseed by plate, while device top carries out pumping negative-pressure operation, is allowed the gas that reaction generates to enter and is washed
Device of air；Material reaches device upper end outlet and starts to discharge, and then reaches the second pipe reaction device 9, and reaction unit 9 is followed
Ring heats, and temperature is maintained at 150 DEG C, reaction time 6h, and material enters from device lower end, is flowed by the multilayer inside device
Material is further mixed, is disperseed by plate, and similarly, device top carries out pumping negative-pressure operation, allow reaction generate gas into
Enter air-washer.
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse dress by the upper end of the second pipe reaction device 9
Set 10, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion.
Step 6, the temperature for the material and hexamethylene diamine that rate-determining steps 5 obtain is 30 DEG C, and amination reagent hexamethylene diamine is passed through
Second raw material high position adding set 1011 is slowly added in the material obtained to step 5, and the adding speed of hexamethylene diamine is 15kg/h,
It is immediately conveyed to carry out mixed at high speed in the second micro-reaction device 11 after mixing, proceeds by ammoxidation；Height is cut in device
The rotating speed of mulser is cut as 3500r/min, the mass ratio of amination reagent and graphene is 1：5.
Step 7, the product that step 6 obtains is passed through third pipe reaction device 12, device 12 carries out circularly cooling, temperature
Be maintained at 30 DEG C, reaction time 6h, material enters from reaction unit lower end, by the multilayer homogenizing plate of device inner setting into
Material is mixed, is disperseed by one step, while device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter gas washing dress
It sets；Material reaches device upper end outlet and starts to discharge, and then reaches the 4th pipe reaction device 13, and device 13 carries out cycle system
Heat, temperature are maintained at 50 DEG C, and the reaction time is that for 24 hours, material enters from device lower end, by the multilayer homogenizing plate inside device into
Material is mixed, is disperseed by one step, and similarly, device top carries out pumping negative-pressure operation, is allowed the gas that reaction generates to enter and is washed
Device of air.
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse dress by the upper end of the 4th pipe reaction device 13
Set 14, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion；Then material is delivered to by third by pump and filters redisperse device 15, n,N-Dimethylformamide is supplemented after suction filtration, into
The dispersion again of row filter cake.
Step 9, the product that step 8 obtains is passed sequentially through after the first reaction product storage tank 16 at the second homogenization
Reason device 17 and third homogenization processing unit 18 carry out homogenization processing, the homogenization pressure in the second homogenization processing unit 17
For 80MPa, it is 150MPa that third, which uniforms the homogenization pressure in processing unit 18, and final product is passed through the second reaction product storing
Tank 19, obtains amination graphene.
Using above-mentioned gained amination graphene as test sample, to its lamellar spacing, piece diameter size, nitrogen element content into
Measurement is gone, acquired results are：Piece diameter 250nm, lamellar spacing 1.4nm, N content 18.9% illustrate the amino graphite of production
Alkene piece diameter is small, lamella is thin, and the content of nitrogen is higher.
Embodiment 3
The present embodiment uses the continuous production that amination graphene is carried out with 1 identical device of embodiment, including
Following steps：
Step 1,10kg graphite powders are added in 20kg oxalic acid, are impregnated at 10 DEG C, after 2h by pump with
The speed of 100kg/h is delivered to oxidation unit 2, and adds 10kg primary oxidants and 1kg pro-oxidants by online add-on system,
The adding speed of primary oxidant potassium bichromate is 5kg/h, the adding speed of pro-oxidant peroxycarbonates is 2kg/h, control
Temperature is delivered to the first washing Suction filtration device 3 after reaction 8h at 60 DEG C by pump, by deionized water wash repeatedly, take out
Filter three times, is then added n,N-Dimethylformamide and is disperseed, material is delivered into the second washing Suction filtration device by pumping
4, after n,N-Dimethylformamide washing, filtering three times, graphite oxide is dispersed in n,N-Dimethylformamide, is obtained
Graphite oxide slurry.
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device 5, using high-shear emulsion machine and
The mode that ultrasonic dispersers are run simultaneously handles the graphite oxide slurry in decentralized processing device 5, while by following outside
Ring shear pump mixes graphite oxide slurry into Mobile state, and the rotating speed of the high-shear emulsion machine is 3200r/min, ultrasonic work(
Rate is 15kw, device run time 30min.Treated, and slurry is delivered to the first homogenization processing dress with the speed of 200kg/h
The further dispersion for setting 6 carry out materials, under homogenization pressure 80MPa effects, material is further removed, piece diameter size,
Lamellar spacing becomes smaller.
Step 3, the temperature for the material and phosphorus pentachloride that rate-determining steps 2 obtain is 10 DEG C, and phosphorus pentachloride is passed through the first original
Material high position adding set 607 is slowly added in the material obtained to step 2, and the adding speed of phosphorus pentachloride is 10kg/h, mixing
After be immediately conveyed to carry out mixed at high speed in the first micro-reaction device 7, proceed by acyl chloride reaction, reaction time 10h；Device
The rotating speed of middle high-shear emulsion machine is 3500r/min, and the mass ratio of chloride reagent and graphene oxide is 10：1.
Step 4, the product that step 3 obtains is passed through the first pipe reaction device 8, reaction unit 8 carries out circularly cooling, temperature
Degree is maintained at -10 DEG C, reaction time 20h, and material enters from reaction unit lower end, is flowed by the multilayer of device inner setting
Material is further mixed, is disperseed by plate, while device top carries out pumping negative-pressure operation, is allowed the gas that reaction generates to enter and is washed
Device of air；Material reaches device upper end outlet and starts to discharge, and then reaches the second pipe reaction device 9, and reaction unit 9 is followed
Ring heats, and temperature is maintained at 40 DEG C, reaction time 20h, and material enters from device lower end, is flowed by the multilayer inside device
Material is further mixed, is disperseed by plate, and similarly, device top carries out pumping negative-pressure operation, allow reaction generate gas into
Enter air-washer.
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse dress by the upper end of the second pipe reaction device 9
Set 10, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion.
Step 6, the temperature for the material and lauryl amine that rate-determining steps 5 obtain is -5 DEG C, and lauryl amine is passed through the second raw material height
Position adding set 1011 is slowly added in the material obtained to step 5, and the adding speed of lauryl amine is 15kg/h, after mixing immediately
It is delivered in the second micro-reaction device 11 and carries out mixed at high speed, proceed by ammoxidation；High-shear emulsion machine in device
Rotating speed is 3500r/min, and the mass ratio of amination reagent and graphene is 1：2.
Step 7, the product that step 6 obtains is passed through third pipe reaction device 12, device 12 carries out circularly cooling, temperature
Be maintained at 30 DEG C, reaction time 8h, material enters from reaction unit lower end, by the multilayer homogenizing plate of device inner setting into
Material is mixed, is disperseed by one step, while device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter gas washing dress
It sets；Material reaches device upper end outlet and starts to discharge, and then reaches the 4th pipe reaction device 13, and device 13 carries out cycle system
Heat, temperature are maintained at 150 DEG C, reaction time 10h, and material enters from device lower end, passes through the multilayer homogenizing plate inside device
Further material is mixed, is disperseed, similarly, device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter
Air-washer.
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse dress by the upper end of the 4th pipe reaction device 13
Set 14, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion；Then material is delivered to by third by pump and filters redisperse device 15, n,N-Dimethylformamide is supplemented after suction filtration, into
The dispersion again of row filter cake.
Step 9, the product that step 8 obtains is passed sequentially through after the first reaction product storage tank 16 at the second homogenization
Reason device 17 and third homogenization processing unit 18 carry out homogenization processing, the homogenization pressure in the second homogenization processing unit 17
For 110MPa, it is 110MPa that third, which uniforms the homogenization pressure in processing unit 18, and final product is passed through the storage of the second reaction product
Batch can 19, obtains amination graphene.
Using above-mentioned gained amination graphene as test sample, to its lamellar spacing, piece diameter size, nitrogen element content into
Measurement is gone, acquired results are：Piece diameter 270nm, lamellar spacing 1.4nm, N content 18.8% illustrate the amino graphite of production
Alkene piece diameter is small, lamella is thin, and the content of nitrogen is higher.
Embodiment 4
The present embodiment uses the continuous production that amination graphene is carried out with 1 described device of embodiment, including following step
Suddenly：
Step 1,10kg graphite powders are added in the 30kg concentrated sulfuric acids (mass fraction 98%), are impregnated at 5 DEG C, 1h
Oxidation unit 2 is delivered to by the speed for pumping with 100kg/h afterwards, and by online add-on system add 1kg primary oxidants and
0.1kg pro-oxidants, the adding speed of primary oxidant potassium permanganate is 5kg/h, the adding speed of pro-oxidant hydrogen peroxide is
2kg/h, control temperature are delivered to the first washing Suction filtration device 3 by pump after reaction 2h, are carried out by deionized water at 110 DEG C
It washs, filtered three times repeatedly, n,N-Dimethylformamide is then added and is disperseed, material, which is delivered into second, by pump washes
Suction filtration device 4 is washed, after n,N-Dimethylformamide washing, filtering three times, graphite oxide is dispersed in N, N- dimethyl methyls
In amide, graphite oxide slurry is obtained.
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device 5, using high-shear emulsion machine and
The mode that ultrasonic dispersers are run simultaneously handles the graphite oxide slurry in decentralized processing device 5, while by following outside
Ring shear pump mixes graphite oxide slurry into Mobile state, and the rotating speed of the high-shear emulsion machine is 3200r/min, ultrasonic work(
Rate is 6kw, device run time 60min.Treated, and slurry is delivered to the first homogenization processing unit with the speed of 200kg/h
6 carry out the further dispersion of material, and under homogenization pressure 60MPa effects, material is further removed, piece diameter size, piece
Layer thickness becomes smaller.
Step 3, the temperature for the material and sulfonic acid chloride that rate-determining steps 2 obtain is 5 DEG C, and chloride reagent sulfonic acid chloride is passed through the
One raw material high position adding set 607 is slowly added in the material obtained to step 2, and the adding speed of sulfonic acid chloride is 10kg/h, is mixed
It is immediately conveyed to carry out mixed at high speed in the first micro-reaction device 7 after conjunction, proceeds by acyl chloride reaction, reaction time 10h；Dress
The rotating speed of middle high-shear emulsion machine is set as 3500r/min, the mass ratio of sulfonic acid chloride and graphene oxide is 5：1.
Step 4, the product that step 3 obtains is passed through the first pipe reaction device 8, reaction unit 8 carries out circularly cooling, temperature
Degree is maintained at 0 DEG C, reaction time 6h, and material enters from reaction unit lower end, passes through the multilayer homogenizing plate of device inner setting
Further material is mixed, is disperseed, while device top carries out pumping negative-pressure operation, the gas that reaction generates is allowed to enter gas washing
Device；Material reaches device upper end outlet and starts to discharge, and then reaches the second pipe reaction device 9, and reaction unit 9 is recycled
Heating, temperature are maintained at 100 DEG C, reaction time 6h, and material enters from device lower end, passes through the multilayer homogenizing plate inside device
Further material is mixed, is disperseed, similarly, device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter
Air-washer.
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse dress by the upper end of the second pipe reaction device 9
Set 10, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion.
Step 6, the temperature for the material and octadecylamine that rate-determining steps 5 obtain is 20 DEG C, and amination reagent octadecylamine is passed through
Second raw material high position adding set 1011 is slowly added in the material obtained to step 5, and the adding speed of octadecylamine is 15kg/h,
It is immediately conveyed to carry out mixed at high speed in the second micro-reaction device 11 after mixing, proceeds by ammoxidation；Height is cut in device
The rotating speed of mulser is cut as 3500r/min, the mass ratio of amination reagent and graphene is 1：10.
Step 7, the product that step 6 obtains is passed through third pipe reaction device 12, device 12 carries out circularly cooling, temperature
Be maintained at 15 DEG C, reaction time 6h, material enters from reaction unit lower end, by the multilayer homogenizing plate of device inner setting into
Material is mixed, is disperseed by one step, while device top carries out pumping negative-pressure operation, and the gas that reaction generates is allowed to enter gas washing dress
It sets；Material reaches device upper end outlet and starts to discharge, and then reaches the 4th pipe reaction device 13, and device 13 carries out cycle system
Heat, temperature are maintained at 100 DEG C, reaction time 6h, and material enters from device lower end, by the multilayer homogenizing plate inside device into
Material is mixed, is disperseed by one step, and similarly, device top carries out pumping negative-pressure operation, is allowed the gas that reaction generates to enter and is washed
Device of air.
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse dress by the upper end of the 4th pipe reaction device 13
Set 14, the filtering accuracy of filter device is 1 μm in kettle, n,N-Dimethylformamide is supplemented after suction filtration, and carry out filter cake again
Dispersion；Then material is delivered to by third by pump and filters redisperse device 15, n,N-Dimethylformamide is supplemented after suction filtration, into
The dispersion again of row filter cake.
Step 9, the product that step 8 obtains is passed sequentially through after the first reaction product storage tank 16 at the second homogenization
Reason device 17 and third homogenization processing unit 18 carry out homogenization processing, the homogenization pressure in the second homogenization processing unit 17
For 90MPa, it is 130MPa that third, which uniforms the homogenization pressure in processing unit 18, and final product is passed through the second reaction product storing
Tank 19, obtains amination graphene.
Using above-mentioned gained amination graphene as test sample, to its lamellar spacing, piece diameter size, nitrogen element content into
Measurement is gone, acquired results are：Piece diameter 280nm, lamellar spacing 1.3nm, N content 18.9% illustrate the amino graphite of production
Alkene piece diameter is small, lamella is thin, and the content of nitrogen is higher.
Claims (10)
1. a kind of continuous production device of amination graphene, which is characterized in that including sequentially connected acid treatment device
(1), oxidation unit (2), the first washing Suction filtration device (3), the second washing Suction filtration device (4), decentralized processing device (5), first
Uniform processing unit (6), the first micro-reaction device (7), the first pipe reaction device (8), the second pipe reaction device (9),
First filters redisperse device (10), the second micro-reaction device (11), third pipe reaction device (12), the 4th pipe reaction dress
Set (13), second filter redisperse device (14), third filter redisperse device (15), the first reaction product storage tank (16),
Second homogenization processing unit (17), third homogenization processing unit (18) and the second reaction product storage tank (19), material is defeated
It send and is equipped with static mixer in pipeline；Wherein, high-shear emulsion machine and ultrasonic disperse are equipped in the decentralized processing device (5)
Device, the decentralized processing device (5) are externally provided with outer circulation shear pump；The first homogenization processing unit (6), the second homogenization
Processing unit (17) and third homogenization processing unit (18) are used for the decentralized processing of system；First micro-reaction device (7)
It is interior equipped with high-shear emulsion machine, first micro-reaction device (7) and the second micro-reaction device with the second micro-reaction device (11)
(11) it is used to carry out decentralized processing while material reaction；The first pipe reaction device (8), the second pipe reaction device
(9), third pipe reaction device (12) and the 4th pipe reaction device (13) are internally provided with multilayer static mixer；Described first
It filters to be equipped with to filter in redisperse device (10), the second suction filtration redisperse device (14) and third suction filtration redisperse device (15) and fill
It sets, redisperse is carried out for addition solvent after the suction filtration and suction filtration of material.
2. a kind of continuous production method of amination graphene using device as described in claim 1, which is characterized in that packet
Include following steps：
Step 1, after graphite being carried out sour processing by acid treatment device (1), oxidation reaction is carried out into oxidation unit (2), so
It washed, filtered by the first washing Suction filtration device (3) afterwards, the second washing suction filtration is passed through after n,N-Dimethylformamide is added
Device (4) is washed, is filtered again, obtains graphite oxide slurry；
Step 2, the graphite oxide slurry that step 1 obtains is delivered to decentralized processing device (5) and carries out decentralized processing, then passed through
First homogenization processing unit (6) carries out the further dispersion of material；
Step 3, chloride reagent is slowly added in the material obtained to step 2, is then sent to the first micro-reaction device (7)
Middle carry out mixed at high speed, proceeds by acyl chloride reaction；
Step 4, the product that step 3 obtains is passed through the first pipe reaction device (8) and the second pipe reaction device (9) successively,
Continue acyl chloride reaction；
Step 5, the product that step 4 obtains is passed through the first suction filtration redisperse device (10), N, N- dimethyl methyls is supplemented after suction filtration
Amide, and carry out the dispersion again of filter cake；
Step 6, amination reagent is slowly added in the product obtained to step 5, is then sent to the second micro-reaction device
(11) mixed at high speed is carried out in, proceeds by ammoxidation；
Step 7, the product that step 6 obtains is passed through third pipe reaction device (12) and the 4th pipe reaction device (13) successively
Continue ammoxidation；
Step 8, the product that step 7 obtains is passed through the second suction filtration redisperse device (14), N, N- dimethyl methyls is supplemented after suction filtration
Amide carries out the dispersion again of filter cake；It then passes to third and filters redisperse device (15), N, N- dimethyl methyls are supplemented after suction filtration
Amide carries out the dispersion again of filter cake；
Step 9, the product that step 8 obtains is passed sequentially through into the second homogenization processing after the first reaction product storage tank (16)
Device (17) and third homogenization processing unit (18) carry out homogenization processing, and final product is passed through the second reaction product storage tank
(19), amination graphene is obtained.
3. production method according to claim 2, which is characterized in that in the step 1, graphite is added in acid solution,
It is impregnated at 0~20 DEG C, oxidation unit (2) is delivered to after 0.5~4h, and add primary oxidant and pro-oxidant, controlled
10~110 DEG C of temperature is delivered to the first washing Suction filtration device (3) after reacting 2~12h, is washed, filtered by deionized water
Three times, n,N-Dimethylformamide is then added to be disperseed, material is delivered into the second washing Suction filtration device (4), is passed through
After filtering three times, graphite oxide is dispersed in n,N-Dimethylformamide for n,N-Dimethylformamide washing, obtains oxidation stone
Black slurry.
4. production method according to claim 3, which is characterized in that the graphite and the mass ratio of acid solution are 1：(1~
3), the graphite, primary oxidant, pro-oxidant mass ratio be 1：(0.1~10)：(0.01~1), the acid solution be hydrochloric acid,
Sulfuric acid, nitric acid, phosphoric acid, oxalic acid or formic acid, the primary oxidant be potassium bichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate or
Molybdenum dioxide, the pro-oxidant are hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxy esters, peroxidating
Carbonic ester or ketone peroxide.
5. production method according to claim 2, which is characterized in that in the step 2, using high-shear emulsion machine and surpass
The mode that sound disperser is run simultaneously handles the graphite oxide slurry in decentralized processing device (5), while by following outside
Ring shear pump mixes graphite oxide slurry into Mobile state, and the rotating speed of the high-shear emulsion machine is 3000~3500r/min, is surpassed
The power of sound is 1~15kw, 30~200min of device run time.
6. production method according to claim 2, which is characterized in that in the step 3, chloride reagent and graphite oxide
The mass ratio of alkene is 1:10~10:1, the chloride reagent be phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride or
Sulfonic acid chloride.
7. production method according to claim 2, which is characterized in that in the step 6, amination reagent and graphene matter
Amount is than being 1:10~1:1, the amination reagent is ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonyl
Diamines, decamethylene diamine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, lauryl amine or octadecylamine.
8. production method according to claim 2, which is characterized in that the homogeneous of the first homogenization processing unit (6)
Pressure is 50~80MPa, and the homogenization pressure of the second homogenization processing unit (17) is 80~110MPa, and the third is uniform
The homogenization pressure for changing processing unit (18) is 110~150MPa.
9. production method according to claim 2, which is characterized in that first micro-reaction device (7) and the first tubular type
Reaction temperature in reaction unit (8) is controlled at -10~10 DEG C, the reaction temperature control in the second pipe reaction device (9)
System is at 40~150 DEG C.
10. production method according to claim 2, which is characterized in that second micro-reaction device (11) and third pipe
Reaction temperature in formula reaction unit (12) is controlled at -5~30 DEG C, the reaction temperature in the 4th pipe reaction device (13)
Control is at 50~150 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876746A (en) * | 2019-03-18 | 2019-06-14 | 汤阴永新化学有限责任公司 | A kind of system and method for the micro- reaction synthetic rubber anti-scorching agent CTP of continuous flow |
| EP4296226A1 (en) | 2022-06-24 | 2023-12-27 | Espio, s.r.o. | The method of preparing functionalized reduced graphene oxide layer and the temperature sensor comprising such a layer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058398A (en) * | 2014-07-15 | 2014-09-24 | 福建江夏学院 | Modified graphene and preparation method thereof |
| CN104109187A (en) * | 2014-07-03 | 2014-10-22 | 北京大学 | Guanidyl-functionalized graphene material, and preparation method and application thereof |
| CN105348577A (en) * | 2015-12-03 | 2016-02-24 | 梅庆波 | Preparation method for oxidized graphene and bentonite modified rubber |
| CN106633715A (en) * | 2016-10-20 | 2017-05-10 | 青海大学 | Graphene modified carbon black/calcium carbonate/polycaprolactone composite conductive polymeric material and preparation method thereof |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
-
2018
- 2018-09-13 CN CN201811068471.0A patent/CN108793148B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109187A (en) * | 2014-07-03 | 2014-10-22 | 北京大学 | Guanidyl-functionalized graphene material, and preparation method and application thereof |
| CN104058398A (en) * | 2014-07-15 | 2014-09-24 | 福建江夏学院 | Modified graphene and preparation method thereof |
| CN105348577A (en) * | 2015-12-03 | 2016-02-24 | 梅庆波 | Preparation method for oxidized graphene and bentonite modified rubber |
| CN106633715A (en) * | 2016-10-20 | 2017-05-10 | 青海大学 | Graphene modified carbon black/calcium carbonate/polycaprolactone composite conductive polymeric material and preparation method thereof |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876746A (en) * | 2019-03-18 | 2019-06-14 | 汤阴永新化学有限责任公司 | A kind of system and method for the micro- reaction synthetic rubber anti-scorching agent CTP of continuous flow |
| EP4296226A1 (en) | 2022-06-24 | 2023-12-27 | Espio, s.r.o. | The method of preparing functionalized reduced graphene oxide layer and the temperature sensor comprising such a layer |
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