WO2021024240A1 - Procédé et système d'exploitation pour la production à haut rendement de matériaux nanostructurés à base de carbone à fonctionnalité variable - Google Patents

Procédé et système d'exploitation pour la production à haut rendement de matériaux nanostructurés à base de carbone à fonctionnalité variable Download PDF

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WO2021024240A1
WO2021024240A1 PCT/IB2020/059446 IB2020059446W WO2021024240A1 WO 2021024240 A1 WO2021024240 A1 WO 2021024240A1 IB 2020059446 W IB2020059446 W IB 2020059446W WO 2021024240 A1 WO2021024240 A1 WO 2021024240A1
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graphene oxide
temperature
water
reaction
purification
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Spanish (es)
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Dania HERNANDEZ SÁNCHEZ
Isaac MATA CRUZ
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Energeia Fusion, S.A. De C.V.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C01B32/196—Purification
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C09K17/48—Organic compounds mixed with inorganic active ingredients, e.g. polymerisation catalysts

Definitions

  • the present invention describes a method and operating system or assembly for the production of carbon-based nanostructured materials, such as graphene oxide and reduced graphene oxide with variable functionalization that can be used in multiple applications in all types of industries.
  • the properties that make it unique are: its large surface area (2630 m 2 / g), high mechanical resistance with a Young's modulus of -1100 Gpa, it is biocompatible and does not oxidize; It is an excellent electrical conductor, with a charge mobility of 200,000 cm 2 V 1 s 1 and thermal, with a thermal conductivity of 3000-5000 W / m / K, this is due to the electrons that interact with the graphene network they can move through the hexagonal cells, at a speed three hundred times less than the speed of light, much higher than the usual speed of electrons in an ordinary conductor.
  • graphene One of the most interesting characteristics of graphene has to do with its electrical conductivity. It is known that one way to classify materials is according to how well they conduct electricity: insulators, conductors, and semiconductors. But graphene shares characteristics between conductors and semiconductors. On the other hand, graphene is a very reactive molecule, this means that it has the ability to chemically react with other substances to modify or form new compounds, so it can be used, for example, as an additive to increase mechanical, electrical and thermal in polymers or non-ferrous materials, such as cement; as an additive to provide anticorrosive and antimicrobial properties to coatings; as a component in electrodes for fuel cells, supercapacitors, lithium ion batteries and photovoltaic cells.
  • CVD chemical vapor deposition
  • monolayer or bilayer graphene One method of obtaining graphene is chemical vapor deposition (CVD) and is known as monolayer or bilayer graphene. It should be noted that although it is the method with which the highest quality graphene is obtained, its disadvantages are substantial, since it is an extremely expensive and complex method, it requires sophisticated equipment and facilities, its production capacity is low and graphene obtained with this method is more suitable for electronic, optical, etc. applications, but not suitable for applications that require mixing or creating composites with other materials.
  • Low-layer graphene is a type of graphene made up of up to five layers of carbon. It should be noted that, by having a greater number of carbon layers, its properties with respect to monolayer or bilayer graphene are lower, but still important. This type of graphene is obtained by exfoliation of graphite in the liquid phase, which is a relatively simpler method, with lower cost and with greater production capacity; However, however, toxic and difficult to eliminate solvents are used for its synthesis, so the use of the graphene obtained is limited, in particular for the jump to the industrial scale, in which they are required tons, not grams. Surfactants or organic molecules with lower toxicity but low performance and low reproducibility are also used.
  • Graphene oxide comprises graphene monolayers stabilized by the electrostatic repulsion produced by the negative charge that they acquire in dispersion, due to the ionization of the functional groups that it has on its surface after the chemical treatment it receives for oxidation and exfoliation.
  • the properties of graphene oxide, with respect to monolayer, bilayer or few-layer graphene are completely different and, therefore, suitable for other types of applications.
  • the reduced graphene oxide arises from the total or partial elimination of the oxygenated groups previously anchored to the carbon network, thus obtaining a material with properties shared between graphene oxide and graphene.
  • the methods for the reduction of graphene oxide are diverse, among which the chemical, thermal and photothermal methods stand out. However, special equipment, toxic chemical reagents and controlled atmospheres are often used that make it difficult to handle.
  • a 9: 1 mixture of concentrated sulfuric acid (H 2 S0 4 ) and phosphoric acid (H 3 P0 4 ) was prepared. Subsequently, 3 grams of graphite and 18 grams of potassium permanganate (KMn0 4 ) were added, generating a slight exotherm of 35-40 ° C. The reaction was then heated to 50 ° C and mixed for 12 hours. Subsequently, the reaction was cooled to room temperature and placed in ice, adding 3 ml of 30% H 2 0 2 . The mixture was then screened using 300 ⁇ m stainless steel mesh and filtered with polyester fibers. The filtrate was centrifuged at 4000 rpm for 4 hours, discarding the supernatant.
  • the recovered solid was washed with 200 ml of water, the mixture was sieved using 300 ⁇ m stainless steel meshes and filtered with polyester fibers. The filtrate was centrifuged at 4000 rpm for 4 hours, discarding the supernatant.
  • the recovered solid was washed with 200 ml of 30% HCl, the mixture was sieved using 300 ⁇ m stainless steel mesh and filtered with polyester fibers. The filtrate was centrifuged at 4000 rpm for 4 hours, discarding the supernatant.
  • the recovered solid was washed with 200 ml of ethanol, the mixture was sieved using 300 pm stainless steel mesh and filtered with polyester fibers.
  • the filtrate was centrifuged at 4000 rpm for 4 hours, discarding the supernatant. At the end of the washings, the material was coagulated with 200 ml of ether and the resulting suspension was filtered on PTFE membranes with pore size of 0.45 pm and the recovered solid was dried under vacuum at room temperature. Finally, the amount of material obtained was 5.8 grams.
  • the present invention developed a method and replicable operating system or assembly for the large-scale production of graphene oxide and reduced graphene oxide, in less time, minimal risk, low cost and high quality, for multiple applications and economically viable at an industrial level.
  • the optimization of each stage occurs based on the equipment and devices implemented for a production line with which there are risk prevention and control measures, industrial-scale production capacity, reduction of times and quality control is favored and replicability, both of the process and the product.
  • the invention is divided into four large modules differentiated by their function.
  • the oxidation-exfoliation and reaction containment stages are carried out, in the second module the purifications of the material are carried out, in the third the discharge of the residual leachate generated by the process is carried out and finally in the fourth module the finished product.
  • the particularities of each module will be described later.
  • Document US 2018/0230014 Al discloses a method for the production of graphite oxide, graphene oxide and graphene, at an industrial and cost efficient level.
  • This document indicates that the first step, before oxidation, is to grind the graphite at 100-150 pm, followed by its purification by flotation at 90 ° C. Subsequently, the pre-purified graphite is oxidized by inorganic oxidizing agents such as potassium permanganate, sodium nitrate and sulfuric acid. The oxidized graphite is exfoliated using external forces such as sonication, to finally be reduced to graphene.
  • the product of the claimed method is nanoscale graphene oxide sheets or platelets with a thickness less than 100 nm.
  • the disclosed method also represents a model for low graphene oxide productions, this is justified because the resulting amount of graphene oxide can be inferred by the initial amount of graphite, where the invention refers to the grinding of 30 grams of graphite for subsequent oxidation. Therefore, it is not a method that can be used for the use of graphene oxide at industrial levels.
  • US patent 9,758,379 B2 mentions a process for preparing oxidized graphite to obtain exfoliated graphene.
  • the process uses considerably less chlorate than previously known systems and is carried out by heating oxidized graphite at temperatures of 250 ° C to 2000 ° C.
  • the method claimed in said patent represents in the same way, a method for low production of oxidized graphite, this considering that the quantity of oxidized graphite produced can be estimated by the quantity of graphite to be oxidized.
  • the method claimed in US patent 9,758,379 B2 refers to the grinding of 30 grams of graphite for its oxidation; therefore, its production capacity is reduced.
  • Document MX / a / 2016/007399 describes a method of partial reduction of graphene oxide using mild reducers at room temperature.
  • the method comprises: (a) oxidation of graphite nanoplatelets to obtain graphene oxide, preferably by oxidation by the Hummers method; and exfoliating the resulting graphene oxide through ultrasonic means; (b) reduction of graphene oxide in aqueous medium with a mild reducing agent at room temperature and basic pH; and (c) drying the graphene oxide at room temperature; and where, in a preferred embodiment, the reduction involves the use of mild reducers such as fructose and ascorbic acid in aqueous medium at pH 10, at temperatures between 20 ° C and 35 ° C, in ratios of 1:10 and 1:20 (graphene oxide-reducing agent), using reduction times from 10 minutes to 144 hours.
  • mild reducers such as fructose and ascorbic acid in aqueous medium at pH 10, at temperatures between 20 ° C and 35 ° C,
  • document MX / a / 2016/007399 reports a graphene oxide production capacity of only 5.8 grams, using oxidation times of 7 to 19 hours with temperature ranges from 30 ° C to 85 ° C.
  • document MX / a / 2016/007399 uses vacuum filtration systems, which are expensive systems, with low capacity and filtration speed (ml / h).
  • hydrazine is used, which is a highly toxic and possibly carcinogenic reagent. Reduction times of approximately 75 minutes and production capacity in the order of milligrams (54 mg).
  • Document MX / a / 2017/010798 describes a method of functionalization of graphene oxide of controllable size by ultrasound, in bath conditions of temperature of 15 ° C, power of 40% amplitude for times of 10 to 100 minutes, with branched or linear amines in the presence of an organic solvent of interest such as 1,2-dichlorobenzene or toluene; where functionalization involves the use of substances such as dodecylamine, octadecylamine and heptadeca-9-amine dissolved in ethanol, methane, propanol, butanol or isopropanol in volume ratios of 1: 3 to 2: 1 under stirring.
  • an organic solvent of interest such as 1,2-dichlorobenzene or toluene
  • said functionalization has the purpose of imparting affinity to graphene oxide in organic solvents where it normally would not have it.
  • said document is directed to a functionalization method and not to solve the problems of production of graphene oxide and reduced graphene oxide to which the present invention relates.
  • MX / a / 2011/012432 discloses a highly oxidized graphene oxide and methods for its production in various modalities; In general, the methods include mixing a graphite source with a solution containing at least one oxidant and at least one protective agent to form the graphene oxide.
  • the document points out that graphene oxide synthesized by the methods described herein is of high structural quality, is more oxidized and maintains a higher proportion of aromatic rings and aromatic domains than graphene oxide prepared in the absence of at least less of a protection agent. Said document further mentions that the methods for the reduction of graphene oxide to chemically converted graphene are also disclosed; chemically converted graphene is significantly more electrically conductive than chemically converted graphene prepared from other graphene sources.
  • the problems to be solved by the present invention are: reduction of operational risks, process time and production costs; obtaining standardized products according to replicable methods and well-established quality parameters, as well as reducing complexity for their massive and safe production, to have high availability for their industrial application, as well as allowing the programmed functionalization of graphene oxide obtained.
  • the present invention refers to an improved method to increase the production and reduction of graphene oxide, comprising: chemically reacting graphite with a standard particle size and KMn0 4 in the presence of H 2 S0 4 / H 3 P0 4 ; controlling the start temperature in an automated rotary mixing system (SMRA); control the temperature of a refrigeration recirculator and set increasing heating ramps of the reaction temperature in si tu and ex si tu from 0 ° C to 50 ° C in a 5 to 12 hour oxidation-exfoliation interval within the SMRA ; contain the reaction with H 2 0 2 at a constant temperature; control the temperature of an external refrigeration recirculator and control the in situ response of the mixture by infrared monitoring; purifying the obtained graphene oxide paste in the presence of H 2 0, HC1 and CH CH 2 OH by means of standardized purification steps; control the final finish of graphene oxide with variable functionalization to obtain it in the form of paste, powder and reduced graphene oxide,
  • SMRA
  • the present invention also refers to an operative system or assembly for the production of graphene oxide
  • an oxidation-exfoliation and reaction containment module formed by a modified balloon flask with internal ribs that operates inserted into an automated rotary mixing system (SMRA) connected to both an external cooling recirculator and a water line derived from a purification system and an infrared sensor for temperature monitoring;
  • SMRA automated rotary mixing system
  • a purification module made up of purification systems with a mechanized cover
  • bases and frames with filters mounted on anti-spill platforms connected to a module for direct discharge of residual leachate
  • a finishing module formed by a chamber with forced extraction inside which is arranged a mechanical convection oven for vacuum drying.
  • the present invention refers to formulations containing graphene oxide and / or reduced graphene oxide obtained by the method of the present invention as an improver and / or additive for coatings, paints, waterproofing agents, inks, concrete, cement, asphalt, as raw material and / or nanofiller in chemical technical applications, among others.
  • primer with base alkyd, alkyd-based enamel, vinyl-acrylic-based paints, acrylic-styrene-based paints, aromatic polyurethane-based paints, aliphatic polyurethane-based paints, water-based polyurethane paints, alkyd traffic paint, chlorinated rubber
  • primer primer base
  • epoxy base with waterproofing agents, inks, conductive paints, concrete additive, cement additive, asphalt additive, among others.
  • graphene oxide or reduced graphene oxide in their formulation in said products, they are given high performance since they provide them with improved properties; for example, without being limiting, anticorrosive, flame retardant, antimicrobial, waterproofing, longer lasting, with greater adherence and greater resistance to UV radiation, increased Marshall resistance and indirect tension resistance, increased hardness and resistance to penetration without reducing elasticity, among others.
  • FIGS 1, 2A-2B and 3 illustrate a system of modules A), B), C) and D) by means of which the method of the present invention is carried out, module A) being an oxidation-exfoliation module and containment, module B) a purification module, module C) a residual leachate discharge module and module D) a module for product finishing.
  • Figures 4a and 4b correspond to representative images of diffraction patterns by high resolution transmission electron microscopy.
  • Figures 4c and 4d show the Raman spectrum of the graphene oxide obtained by the invention, before and after being reduced, respectively.
  • the invention developed the installation of an operating system or assembly for the large-scale production of carbon-based nanostructured materials, known as: graphene oxide and reduced graphene oxide.
  • the system or assembly is characterized by an oxidation-exfoliation and containment module, a purification module, a residual leachate discharge module and a product finishing module.
  • oxidation-exfoliation and containment module characterized by an oxidation-exfoliation and containment module, a purification module, a residual leachate discharge module and a product finishing module.
  • a series of systematized stages are developed that allow: high production capacity, minimal operational risk, low cost and versatility, since the production of different types of graphene oxide of excellent quality is achieved, with variable and replicable functionalizations, with greater production capacity in less time and greater operational safety, completely replacing known methods and tools.
  • the initial methodology of the invention was based on the improved Hummers method, however, due to its low production efficiency, high operational risk, and no feasibility to bring the use of graphene oxide produced to industrial levels, through the present invention, multiple modifications were made, both methodological and technical, implementing variations in chemical reagents, proportions, temperatures, times, stages, processes and devices used for different activities to its original conception, giving them properties to create a unique industrial process for the production, diversification, efficient and safe of different types of graphene oxide and reduced graphene oxide. With the modifications included in the present invention, it was possible to increase the production per reaction from grams to kilograms, with reduction of production times, with high quality of the material, with greater safety and standard replicability between production batches.
  • the present invention developed a replicable operating method and system or assembly for large-scale production of graphene oxide and reduced graphene oxide, in less time, minimal risk, low cost and high quality for multiple applications and economically. industrially viable.
  • the optimization of each stage occurs in function of the equipment and devices implemented for a production line with which there are risk prevention and control measures, industrial-scale production capacity, reduction of times and favoring quality control and replicability of both the process and the product.
  • the invention is divided into four large modules differentiated by their function.
  • the oxidation-exfoliation and reaction containment stages are carried out
  • the purifications of the material are carried out
  • the discharge of the residual leachate generated by the process is carried out
  • the fourth product finishing module the activities related to the drying and reduction of graphene oxide are carried out. The particularities of each module will be described later.
  • the claimed method for the production of carbon-based nanostructured materials takes as a reference the Hummers method, however, the modifications of the present invention do so Totally different from said method and any other known method since, as will be seen later, multiple methodological and technical modifications were made to said Hummers method, implementing variations in chemical reagents, proportions, temperatures, times, stages, processes and devices. used for activities other than their original conception, giving them properties to create a unique industrial process for the production, diversification, efficient and safe of different types of graphene oxide and reduced graphene oxide.
  • the invention calls for an operating system or assembly that represents a novel installation for the formation of a complete production line, allowing the phases of each stage to be separated clearly and safely by modules, where in figure 1 the module (A) is an oxidation, exfoliation and containment module, in figure 2A the module (B) is a purification module, in figure 2C module C) is a residual leachate discharge module and in figure D) it is a module of finished product.
  • the oxidation, exfoliation and reaction containment module (A) comprises a water filtration system (1) comprising three filters of activated carbon and ultraviolet light, which distributes the filtered water through a tube (a) towards a system of automated rotary mixing (SMRA) (2), through a tube (b) that comes out of a water container (3) located in the upper part of the SMRA; the filtration system Water (1) also distributes the filtered water through a tube (c) towards an ice-producing device (4) or similar and finally, distributes the filtered water through a tube (d) to a second filtration system by reverse osmosis made up of three filters (5) that provide the water required for the graphene oxide purification stages.
  • SMRA automated rotary mixing
  • the SMRA (2) comprises a balloon flask (6) with a capacity of 20 liters (which may be of a smaller or larger capacity; requiring, where appropriate, a change in the proportions of reagents within the ranges established in the present invention ) modified with internal ribs to favor the mixing of the reagents by means of internal turbulence, a vertical condenser (7) whose design was modified to create a lateral feed inlet (8) for the dosage of reagents in an indirect way, that is to say that once the flask is installed in the SMRA (2), the operator to dose the reagents or chemicals can feed them through the side inlet (8) through a funnel (9) that enters at 45 degrees with respect to the longitudinal axis vertical condenser (7) with a path of 90 to 100 cm from the external part of the safety cabin (11) of the SMRA (2) and that reaches the inner center of the balloon flask (6), without being totally exposed in form d Direct to the gases generated by the chemical reaction inside the
  • the vertical condenser (7) which can be for example Graham, Friedrichs, Dimroth, Liebig, Allihn or some other commercially available type, is connected to a refrigeration recirculator (12), the purpose of which is, by means of the operation to low temperatures, avoid leaks of the gases generated by the chemical reaction and contain them within the SMRA (2), in order to provide greater safety to the operator and obviate the need for an extraction hood such as that used in known techniques, and in which the operator is completely exposed to the gases generated during the reaction, in addition to reducing the space or work area, the method of the present invention being limited to only one or two modules to operate simultaneously.
  • they use tap water at room temperature as coolant in continuous flow through rosary-type condensers, resulting in 12-15 hours of non-recirculating water flow, not reusable and that does not guarantee the absence of gas leaks.
  • Temperature changes are monitored internally through the SMRA's own control panel (2) that detects the ex situ temperature of the reaction and the second external path through an infrared sensor (13), which allows temperature measurement in situ of the reaction.
  • FIG. 2A illustrates the graphene oxide purification module B) and Figure 2C the residual leachate discharge module.
  • independent filtration systems (14) were adapted for each stage.
  • the base of these systems is made of containers made of a material with high chemical resistance with a holding capacity of hundreds of liters. These containers were designed with a mechanized cover (15) to avoid product contamination.
  • racks (16) were manufactured with filters made of polyester, for example, to be placed on top of each container.
  • An outlet (17) with opening and closing valves (18) was designed for each purification system to discharge leachate to the waste collection area.
  • the complete filtration purification system is mounted on anti-spill platforms (19).
  • a discharge line or tube (20) is connected, which is hidden under the floor and empties into Module C) for directly discharging leachates.
  • the opening and closing valves (18) are opened synchronously with the opening and closing valves (23) that reach the high-density polyethylene containers (21). for filling through a pipe (20).
  • Module C comprises the containers (21) which are supported on anti-spill platforms (22).
  • the pipes (20) of the leachate discharge lines from the purification systems controlled by the opening and closing valves (18) reach the containers (21).
  • the filling of the containers (21) is carried out by means of the synchronized opening of the valves (18) of the purification systems and the valves (23) of the containers (21) of the leachate discharge module.
  • the disposition of the purification and leachate flow modules have been designed in such a way that they do not depend on electrical energy and for safety terms, they are arranged so as not to retain more than 50% of their maximum capacity inside.
  • Module D comprises a chamber with forced extraction (24) inside which is arranged a mechanical convection oven for vacuum drying (25) and an aluminum container with a lid (26).
  • the nature and size of the particle is fundamental for the type of graphene oxide, as well as for the oxidation-exfoliation time.
  • graphical materials were classified according to various criteria.
  • Amorphous graphite refined amorphous
  • synthetic graphite refined synthetic
  • crystalline graphite even the combination of graphites to obtain different qualities of graphenic material, depending on its production methodology.
  • the particle size was selected through an automated screening process. With the method of the present invention, a high degree of quality, replicability and functionalization is achieved, for which it is required that the selection and initial preparation of graphical materials are perfectly controlled. Stage 2. Pre-oxidation.
  • module A (see figure 1) of oxidation -exfoliation and containment of the production line was ensured, which comprises a water filtration system (1) comprising three activated carbon filters and light ultraviolet, with four branches leading to an automated rotary mixing system (SMRA) (2), a water container (3), an ice-making device (4) or similar, and a three-filter water system by reverse osmosis (5), the water from the latter system being used in the process.
  • SMRA automated rotary mixing system
  • the SMRA (2) comprises a modified balloon flask (6) with internal ribs that was fitted and secured within the SMRA (2).
  • Said modified balloon flask (6) was placed or arranged inside a container (10), which was filled with water to immerse the balloon flask (6).
  • the temperature of the water in the container (10) was controlled in a range of 0 to 10 ° C.
  • the low vacuum function was activated in a range of 250-500 bar, to fill it with a mixture of the oxidizing agent (H 2 S0 4 ) and the protective agent (H 3 P0 4 ) in previously measured quantities , according to the type of graphene oxide to be produced.
  • the vertical condenser and the SMRA were hermetically sealed, so that the gases and / or vapors emitted inside the balloon flask (6) were kept inside the SMRA and by the vertical condenser (7) through which it passes a refrigerant that is recirculated by the recirculation cooler (12) which was programmed at a temperature of -10 ° C and recirculated to the SMRA (2).
  • the vacuum function was deactivated and the mixing function was activated from 20 to 30 revolutions per minute. minute (rpm) for 5 to 10 minutes for a first exothermic control.
  • the safety cap or seal found at the feed inlet (8) was removed to proceed with the dosage of the permanganate powders.
  • the reaction between the first two oxidizing agents H 2 S0 4 and KMn0 4 ) produces manganese heptoxide (MN 2 0 7 ), which is highly volatile and can explode on contact with air, water or even with a bang. Therefore, the physical barrier represented by the SMRA (2) is important for controlling the temperature from the recirculating cooler (12) to the vertical condenser (7), so as not to allow the gases generated by the acid reaction and oxidizer come out of the SMRA (2) and therefore, the operator is not exposed to them.
  • step 1 The conditions established in step 1 were appropriately adjusted and then the temperature range of the reaction during step 2 was controlled at 10-20 ° C; However, in case of sudden increases in temperature, part of the ice produced by the ice-producing equipment (4) must be used and it must be added to the water container (10), of which A certain volume of hot water must be drained and replaced by ice in a controlled manner, until the in situ temperature is adjusted between 10-20 ° C by infrared monitoring (infrared sensor (13)). At the end of reagent administration, mixing at 20-30 rpm was maintained for 10 minutes.
  • the mixing speed was reduced to 10 rpm and controlled temperature increases were made from 20 to 25 ° C in 10 minutes, from 25 to 30 ° C with 15 minutes mixing, from 30 to 35 ° C with mixing. 15 minutes, 35-40 ° C with mixing for 30 minutes and 40-50 ° C with mixing for 5-12 hours depending on the type of graphene oxide to be synthesized.
  • the technology of the SMRA (2) offers automatic stop of the temperature with sustained mixing and also allows to automatically detect variations in the volume of the heating water container (10), so that the filtered water tank (3) connected to the SMRA ( 2) Automatically compensates for the volume of water evaporated during the 5-12 hours of the process.
  • the heating function of the SMRA (2) was automatically deactivated while the mixing function was maintained, thus allowing a slow descent to room temperature. Subsequently, the water from the SMRA (2) was partially drained and replaced by ice received from the ice generator (4) until an ex situ and in situ temperature of ⁇ 0 ° C and ⁇ 10 ° C, respectively, was achieved to control a fourth exotherm generated by H 2 0 2 . The stability of the temperature was corroborated using the infrared sensor (13) before and during the addition of the next reagent (H 2 0 2 ).
  • the safety cap or seal (8) was removed, the long tube funnel (9) was inserted through which the H 2 0 2 was slowly and dripped .
  • KMn0 4 like H 2 0 2 are strong oxidants that, when in contact, cause an oxide-reduction reaction, in which KMn0 4 that could have remained unreacted, oxidizes hydrogen peroxide releasing oxygen and causing a fourth exotherm, Therefore, at the end of dosing the H 2 0 2 , the funnel (9) was removed and the safety cap or seal (8) was placed immediately. The mixing must remain active from 3 to 5 hours at 10 rpm to complement the reaction. Subsequently, the balloon flask (6) was disassembled from the SMRA (2) and prepared for the purification step. Stage 5. Purification.
  • Step 6 Graphene oxide paste finish.
  • the paste recovered from the fourth purification system was recovered without additional treatments to purification 4.
  • the properties of this graphene oxide depend on the production and application process.
  • Step 7 Finishing graphene oxide powder.
  • the graphene oxide paste that was recovered from purification system 4 was transferred to the forced extraction chamber (24) and dried at 50-80 ° C inside a mechanical convection oven (25) for 24-48 hrs.
  • the drying time is dependent on the mass and the desired percentage of humidity.
  • the graphene oxide powder obtained following the method and operating the operating system or assembly of the invention is used as a precursor for the production of reduced graphene oxide.
  • Phase 1 Pre-drying: Inside the chamber with forced extraction (24), the graphene oxide paste was pre-dried at 80 ° C for 24 hours inside the mechanical convection oven (25).
  • Phase 3 Programming The graphene oxide powder dried at room temperature was extracted from the mechanical convection oven and the temperature (25) was programmed at 260 ° C and an aluminum container with a lid (26) was preheated inside.
  • Phase 4 Reduction The dried graphene oxide was immediately deposited and covered inside the preheated aluminum container (26) and kept inside the mechanical convection oven (25) at 260 ° C for 90-120 seconds.
  • Phase 5 After 90-120 seconds, the aluminum container (26) was extracted from the mechanical convection oven (25) with the reduced graphene oxide inside and was placed inside the chamber with forced extraction (24 ), without removing the lid of the container to prevent the material from reacting violently on contact with oxygen, until it cools.
  • Table 2 summarizes the generic methodological and process stages described above, considering that the type and quality of each product will depend on the particular modifications of each method, in terms of type of graphite and reagent concentrations.
  • graphene oxides are given by their laminar, non-conductive and hydrophilic structure, thanks to the anchoring on their surface of different percentages of functional groups carboxyl, epoxide, alcohol and other chemical elements, which increase the distance between their monolayers, the They stabilize by electrostatic repulsion, decrease their interaction energy and therefore make them easier to exfoliate and hybridize with other compounds to form new materials.
  • Stage 1 Preparation of equipment and selection of reagents according to the characteristics of the material to be synthesized.
  • the initial operating conditions of the system or operating assembly were adjusted, turning on and programming the refrigeration recirculator at -10 ° C and filling the SMRA water container with water and ice, adjusting the temperature to ⁇ 10 ° C.
  • the adapted balloon flask with internal ribs was adjusted for internal turbulence generation that ensures homogeneous mixing in the SMRA within the safety cabinet of the equipment, at an inclination of ⁇ 45 °.
  • the flask was immersed in the water container until it was covered by 50%.
  • the SMRA vacuum system was activated and an 8.8: 1 ratio of H 2 SO 4 / H 3 PO 4 (2400: 270 ml) was poured into the balloon flask. From the SMRA control panel, the SMRA rotation was adjusted to 20 rpm for 5 minutes.
  • a funnel was introduced to dose the KMn0 4 (300 g, 1.0 eq.) Onto the H 2 SO 4 / H 3 PO 4 mixture at a temperature of ⁇ 10 ° C, with mixing at ⁇ 20 rpm, for 30 minutes.
  • the temperature of the reaction was continuously monitored during the dosage, to control that the internal temperature of the mixture was ⁇ 15 ° C.
  • the mixing was programmed at ⁇ 10 rpm and an ascending heating ramp of reaction temperature was started, raising to 30 ° C and stabilizing for 30 minutes.
  • the temperature was set to 40 ° C and stabilized for 30 minutes.
  • the temperature of the reaction during the heating ramps must be strictly controlled and monitored with the infrared sensor. If temperatures higher than those programmed were identified for each stabilization point of the heating ramp, the water container was slightly drained and the volume was replaced with ice until the reaction temperature was controlled at the programmed temperature.
  • the reaction was contained with H 2 0 2 , by means of a water exchange from the SMRA, by ice inside the container until the temperature in si tu of the reaction was adjusted to ⁇ 15 ° C , ensuring thermal stability for 1 hour by infrared monitoring.
  • a funnel was introduced to drip 30 ml of 50% H 2 0 2 . From the SMRA control panel, mixing was programmed for 3-5 hours at 10 rpm with automatic equipment shutdown.
  • the inner ribbed balloon flask containing the oxidized material was disassembled from the SMRA and the first purification started.
  • Purification 1 Immediately after disassembling the flask, 3 kilograms of graphene oxide paste were recovered and a dilution was made with filtered water by reverse osmosis, ratio 1: 1.7 at room temperature, inside a container at ⁇ 4 ° C. The product was mixed and kept at rest in a chamber with forced extraction for 5 hours until the exotherm and the release of gases stopped. Once at room temperature, the graphene oxide paste was poured onto the filter Polyester adapted in the frames placed on the purification systems 1 to eliminate the non-oxidized material and / or residual products. Purification 2.
  • the mixture remained at rest for 5 hours, to later be diluted with water filtered by reverse osmosis in a 1: 1.7 ratio to begin to raise the pH of the graphene oxide.
  • the product was poured onto the adapted polyester filter in the racks placed on the purification systems 3 for its last filtration. 1.5 kilos of graphene oxide paste were recovered and diluted in filtered water by reverse osmosis at a 1: 5 ratio.
  • the diluted product was filtered on the polyester filter adapted in the frames placed on the purification systems 4.
  • Stage 1 Preparation of equipment and selection of reagents according to the characteristics of the material to be synthesized.
  • the initial operating conditions of the operating system or assembly were adjusted by turning on and programming the cooling recirculator at -10 ° C and filling the SMRA water container with water and ice, adjusting the temperature to ⁇ 10 ° C.
  • Stage 2 Pre-oxidation.
  • the flask was immersed in the water container, until it was covered by 50%.
  • the SMRA vacuum system was activated and an 8.8: 1 ratio of H 2 SO 4 / H 3 PO 4 (4800: 540 ml) was poured into the balloon flask. From the SMRA control panel, the SMRA rotation was adjusted to 20 rpm for 5 minutes.
  • a funnel was introduced to dose the KMn0 4 (600 g, 2.0 eq.) Onto the mix H 2 SO 4 / H 3 PO 4 at ⁇ 0 ° C, with mixing at ⁇ 20 rpm, for 30 minutes.
  • the temperature of the reaction during the dosage was continuously monitored with the infrared sensor, controlling that the internal temperature of the mixture was ⁇ 15 ° C.
  • a funnel was introduced to dose the refined amorphous graphite (300 g, 1.0 eq.) With size of particle of ⁇ 50 pm on the mixture H 2 S0 4 / H 3 P0 4 / KMn0 4 .
  • the reaction temperature during the metering of the refined amorphous graphite was continuously monitored with the infrared sensor, controlling that the internal temperature of the mixture was ⁇ 18 ° C. If temperatures above 18 ° C are identified, the water container must be drained and the volume must be replaced with ice until the reaction temperature is controlled at 18 ° C.
  • mixing was programmed at ⁇ 10 rpm from the SMRA control panel, and an ascending heating ramp of reaction temperature was started, raising to 20 ° C and stabilizing for 30 minutes.
  • the temperature was set to 30 ° C and stabilized for 30 minutes.
  • the temperature was set at 40 ° C from the SMRA control panel set at ⁇ 10 rpm, and stabilized for 30 minutes.
  • the reaction temperature during the heating ramps was strictly controlled and monitored with the infrared sensor.
  • the reaction was contained with H 2 0 2 .
  • part of the water was drained from the SMRA water container and the in situ temperature of the reaction was adjusted with ice to ⁇ 10 ° C, ensuring thermal stability for 1 hour by infrared monitoring.
  • a funnel was introduced to drip, 120 ml of 50% H 2 0 2 .
  • Mixing was programmed for 3 hours at 10 rpm from the SMRA control panel with automatic equipment shutdown. Stage 5. Purification.
  • the inner ribbed balloon flask containing the oxidized material was disassembled from the SMRA and the first purification started.
  • Purification 1 Immediately after disassembling the flask, 3 kilos of graphene oxide paste were recovered and a dilution was made with filtered water by reverse osmosis, ratio 1: 1.7 at room temperature, inside a container at ⁇ 4 ° C. The product was mixed and kept at rest in a chamber with forced extraction for 5 hours until the exotherm and the release of gases stopped. Once at room temperature, the graphene oxide was poured onto the polyester filter adapted to the frames placed on the purification systems 1 to eliminate the non-oxidized material and residual products of the chemical reaction. Purification 2.
  • the mixture remained at rest for 5 hours, to later be diluted with water filtered by reverse osmosis in a 1: 1.7 ratio to begin to raise the pH of the graphene oxide.
  • the product was poured onto the polyester filter adapted to the racks placed on the purification systems 3 for its final filtering. 1.5 kilos of graphene oxide paste were recovered and diluted in filtered water by reverse osmosis at a 1: 5 ratio. The diluted product was filtered on the polyester filter adapted in the frames placed on the purification systems 4.
  • Stage 1 Preparation of equipment and selection of reagents according to the characteristics of the material to be synthesized.
  • the initial operating conditions of the operating system or assembly were adjusted, turning on and programming the refrigeration recirculator at -10 ° C and filling the SMRA water container with water and ice by adjusting the temperature to ⁇ 10 ° C.
  • the adapted balloon flask with internal ribs for internal turbulence generation that ensures homogeneous mixing was fitted in the SMRA inside the safety cabinet of the equipment, at an inclination of ⁇ 45 °.
  • the balloon flask was immersed in the water container up to 50%.
  • the SMRA vacuum system was activated and an 8.8: 1 ratio of H 2 SO 4 / H 3 PO 4 (4800: 540 milliliters) was poured into the balloon flask. Adjust the rotation of the SMRA at 20 rpm for 5 minutes.
  • a funnel was introduced to dose the KMn0 4 (600 g, 1.0 eq.) Onto the H 2 SO 4 / H 3 PO 4 mixture at a temperature of ⁇ 10 ° C with mixing at ⁇ 20 rpm for 30 minutes.
  • the temperature of the reaction during the dosage was continuously monitored with the infrared sensor, controlling that the internal temperature of the mixture was ⁇ 15 ° C.
  • a funnel was introduced to dose the refined amorphous graphite (600 g, 1.0 eq.) With a particle size of ⁇ 50 pm on the EfiSCfi / EfiPCVKMnCfi mixture.
  • the reaction temperature during the dosing of the refined amorphous graphite was continuously monitored with the infrared sensor, controlling that the internal temperature of the mixture was ⁇ 18 ° C. If temperatures are identified above 18 ° C, the water container would be drained slightly and the volume would be readjusted with ice until the reaction temperature was controlled at 18 ° C.
  • the temperature was increased again to 50 ° C from the SMRA control panel programmed at ⁇ 10 rpm, and it stabilized for 30 minutes and then mixing was programmed for 4.0 hours at 50 ° C, ensuring automatic filling for the replacement of the water evaporated during the process, turning off the container or container of water and sustained mixing of the product until gradually reducing the reaction temperature to ⁇ 26 ° C.
  • the reaction was contained with H 2 0 2 .
  • part of the water at room temperature was drained from the SMRA water container and the in situ temperature of the reaction was adjusted with ice to ⁇ 15 ° C, ensuring thermal stability for 1 hour by infrared monitoring.
  • a funnel was introduced to drip, 60 ml of 50% H 2 0 2 . Mixing for 3-5 hours at 10 rpm with automatic equipment stop was programmed from the SMRA control panel.
  • the inner ribbed balloon flask containing the oxidized material was disassembled from the SMRA and the first purification started.
  • Purification 1 Immediately after disassembling the flask, ⁇ 6 kg of graphene oxide paste was recovered and a dilution was made with filtered water by reverse osmosis, ratio 1: 1.7 at room temperature, inside a container at ⁇ 4 ° C . The product was mixed and kept at rest in a chamber with forced extraction for 5 hours until the exotherm and the release of gases stopped. Once at room temperature, the graphene oxide was poured onto the polyester filter adapted to the frames placed on the purification systems 1 to eliminate the non-oxidized material and residual products of the chemical reaction. Purification 2.
  • the mixture remained at rest for 5 hours to later dilute with water filtered by reverse osmosis in a 1: 1.7 ratio to begin to raise the pH of the graphene oxide.
  • the product was poured on the polyester filter adapted in the frames placed on the purification systems 3 for its last filtration.
  • ⁇ 3 kilos of graphene oxide paste was recovered and diluted in filtered water by reverse osmosis at a ratio of 1: 5.
  • the diluted product was filtered on the polyester filter adapted in the frames placed on the purification systems 4.
  • ⁇ 2.5 kilograms of the graphene oxide paste was recovered which was used as a precursor of reduced graphene oxide.
  • Phase 1 The stage for the reduction of graphene oxide was divided into 5 Phases: Phase 1. Drying: The graphene oxide paste (2.5 kg) recovered from purification system 4 was placed inside a mechanical convection oven for drying at 80 ° C for 24 hours. Phase 2. Rehydration. A fraction of the pre-dried graphene oxide (1.5 kg) was homogeneously rehydrated at a 1: 1-1: 3 ratio with (C 2 H 5 ) 2 0 until a new paste was formed, which would later be dried under vacuum and room temperature. for 1 hour. Phase 3. Programming: The temperature of the mechanical convection oven was set at 260 ° C and an aluminum container with a lid was preheated inside for 30 minutes. Phase 4.
  • the material recovered in the aluminum deposit was transformed to reduced graphene oxide.
  • the reduction of the material consisted of the detachment of functional groups from its surface and self-repair of the graphene structure. Of detachment From the functional groups, a weight loss of approximately 20% of the parent graphene oxide resulted, where ⁇ 82% of the reduced graphene oxide are carbon atoms and -16% are oxygen atoms.
  • the partial repair of the graphene lattice structure makes it an amphiphilic semiconductor material with a density of 0.059 g / cm 3 and an exfoliated particle size of - 3 pm.
  • the structural changes of the reduced graphene oxide with respect to the graphene oxide used as a precursor can be identified by changes in its UV-visible absorption spectrum that changes with respect to its precursor graphene oxide at: 275 nm (graphene oxide: B max : 242/305 nm) and changes in the Raman spectrum to: I D 1339 cm (graphene oxide: 1348) I G 1580 cm (graphene oxide: 1602) and definition of the signal at 2682 cm.
  • the images correspond to two representative images of the characterization by high-resolution transmission electron microscopy (HRTEM, for its acronym in English).
  • the white circle in figure 4b shows the repair of the structure of the graphene network, a result of the detachment of functional groups after the reduction of graphene oxide.
  • Figures 4c and 4d correspond to a characteristic Raman spectrum where the evident spectral changes of graphene oxide are appreciated before and after being reduced.
  • the variations in the intensity of the D band are related to the disappearance of the oxygenated groups anchored on the graphene oxide, as well as the decrease in the size of the particles resulting from the reduction process.
  • the definition of the 2D band is also associated with the repair of the graphene lattice structure after reduction of the graphene oxide.
  • the graphene oxide and reduced graphene oxide produced by the method and system or operative assembly of the present invention can be used in the formulation or production of new high performance coatings, such as paints, inks and waterproofing agents and additives.
  • the present invention provides anticorrosive, flame retardant, antimicrobial, impermeability, increased durability, adhesion and blocking properties against electromagnetic radiation.
  • some of the uses, without being limiting, of the present invention and modalities of coatings are paints and waterproofing agents, as well as inks and additives for concrete and asphalt, without being limiting of other uses and modalities that may be developed as they are obvious.
  • using the graphene oxide or reduced graphene oxide produced by the method and operative assembly or system of the present invention using the graphene oxide or reduced graphene oxide produced by the method and operative assembly or system of the present invention.
  • the type of functionalized graphene oxide that was used for the production of the first alkyd was in a water-based paste presentation with 30-40% humidity and pH 3.5- 4.5 at a ratio of 0.005% to 0.10% per kilogram of material.
  • all the liquid raw materials (resins and solvents) were weighed and incorporated into a mill, subsequently grinding began and the pigments were incorporated.
  • the graphene oxide paste was added in a proportion of 0.005% to 0.10% per kilogram of the primer to be produced. The grinding was maintained for approximately 50 minutes reaching a maximum temperature of 100 ° C.
  • the primer was allowed to cool and was discharged into a disperser. When the product temperature is less than 50 ° C, the drying agent was added and dispersed for 5 minutes. Subsequently, the trays were emptied for storage.
  • the type of graphene oxide that was used was in a paste presentation, water-based with 30-40% humidity and pH 3.5-4.5 at a proportion by weight percentage in the range of 0.005% to 0.10% per kilogram of material.
  • the liquid raw materials were weighed: resins and solvents (Xylol and naphtha gas), they were incorporated into a mill and the grinding began, adding the pigments.
  • graphene oxide was added in a proportion of 0.005% to 0.10% per kilogram of the enamel to be produced. Once added, the grinding was maintained for 50 to 60 minutes reaching a maximum temperature of 100 ° C. After time, the enamel was allowed to cool and was discharged into a disperser. With a temperature lower than 50 ° C, the desiccant was added and dispersed for 5 minutes, finally it was emptied into buckets for storage.
  • the type of functionalized graphene oxide that was used was a water-based paste with 30-40% humidity and pH 3.5- 4.5.
  • the required amounts of graphene oxide were in a range of 0.005% to 0.10% per kilogram of material.
  • For the preparation of the vinyl-acrylic paint as a first stage all the liquid raw materials were weighed and mixed in a disperser and dispersion began, subsequently and without stopping dispersing, the titanium dioxide and material loads were added. . After 10 minutes of continuous dispersion, the graphene oxide was added according to the amount of paint to be produced and it was kept in dispersion for 20 minutes.
  • the disperser was stopped and the thickener (cellulosic thickener) was added and dispersed for approximately 60 minutes at this point, reaching a maximum temperature of 45 ° C. Finally the dispersion was stopped, the resin was added and dispersed for 5 minutes. At the end of the process, the modified paint was allowed to cool for 24 hours, it was given a light mixing for 2-3 minutes, to finally be packaged.
  • the thickener cellulosic thickener
  • the type of reduced graphene oxide used was in powder form.
  • the required amounts of reduced graphene oxide were in a range of 0.1% to 0.3% per kilogram of material.
  • the titanium dioxide and material loads were added.
  • the graphene oxide was added according to the amount of paint to be produced and it was kept in dispersion for 20 minutes.
  • the disperser was stopped and the thickener (cellulosic thickener) was added and dispersed for approximately 60 minutes at this point, reaching a maximum temperature of 45 ° C.
  • the dispersion was stopped, the resin was added and dispersed for 5 minutes.
  • the modified paint was allowed to cool for 24 hours, it was given a light mixing for 2-3 minutes to finally be packaged.
  • Formulation of paints with acrylic-styrene base and graphene oxide for the incorporation of graphene oxide in acrylic-styrene paint to confer antimicrobial properties, to substantially increase its durability, resistance to UV radiation and wear (for example, greater than 18,000 cycles).
  • the type of functionalized graphene oxide that was used was a water-based paste with 30-40% humidity and pH 3.5- 4.5.
  • the amounts used were by weight percentage of the paint in the range of 0.005% to 0.10% per kilogram of material.
  • all the liquid raw materials were weighed and mixed in a disperser. During the dispersion, the titanium dioxide, material fillers and pigments were added. After 10 minutes of continuously dispersing, the graphene oxide was added and dispersed for 20 minutes. At 20 minutes, the dispersion was stopped, the thickener was added and dispersed for approximately 60 minutes. At this stage the paint reached a temperature of approximately 45 ° C.
  • the dispersion was stopped, the acrylic-styrene resin was added and dispersed for 5 minutes; after the time, the stirring was stopped and it was allowed to cool for 24 hours. Finally, the paint was lightly agitated for 2 to 3 minutes, to later be packaged.
  • the type of functionalized graphene oxide that was used was in powder form, with 10-30% humidity and pH 6.4- 7.4. A proportion of 0.001% to 0.05% of graphene oxide was used, per kilogram of material.
  • the polyurethane binder polyurethane precursor-prepolymer
  • the solvents were added. During milling, the pigments were incorporated little by little.
  • the graphene oxide powder corresponding to the amount of polyurethane to be produced was added. Grinding was maintained for 30 minutes reaching a maximum temperature of 75 ° C. After 30 minutes the milling was stopped and it was allowed to cool down to a temperature below 56 ° C to add the remaining fraction of the Polyurethane prepolymer, mixing for 5 minutes. Finishing this last mixing, the aromatic polyurethane was hot cast.
  • the type of functionalized graphene oxide for the chlorinated rubber alkyd traffic paint that was used was in powder form with 10-30% humidity and pH 3.5- 4.5.
  • All liquid raw materials (resins and solvents) were weighed and incorporated into a mill. The grinding was started continuously and the pigments were incorporated little by little.
  • graphene oxide was added in a range of proportions from 0.005% to 0.10% per kilogram of paint. to produce. The grinding was maintained for 50 to 60 minutes, during which time it reached a maximum temperature of approximately 100 ° C. Over time, the paint was allowed to cool and was discharged into a disperser until it reached a temperature below 50 ° C. At this time the blotter and chlorinated rubber were added, dispersing for 5 minutes to finally empty it for storage.
  • Epoxy-based primer formulation and graphene oxide Process for incorporating graphene oxide into a two-component anticorrosive epoxy primer for use on metallic surfaces in marine environments.
  • the type of functionalized graphene oxide that was used to make the first anticorrosive epoxy was presented as a water-based paste with 30-40% humidity and pH 3.5- 4.5.
  • the liquid raw materials epoxy resin and solvents
  • the pigments were gradually incorporated and after 20 minutes the graphene oxide paste was added in percentages by weight in the range of 0.005% to 0.10% per kilogram of the first epoxy to be produced.
  • the grinding was maintained for approximately 60 minutes, reaching a maximum temperature of 100 ° C.
  • the mixture was allowed to cool and was discharged into a disperser.
  • the drying agent was added, dispersing for 5 minutes, to finally empty the first epoxy with graphene oxide to its storage containers.
  • the ink made with graphene oxide obtained by means of the present invention is of high performance, easy application and ultra fast drying, with great thermal resistance, anti-abrasive, anticorrosive, resistance to UV radiation, with excellent adhesion and covering power.
  • the ink For the production of the ink, cellulose butyric ester was used as a base resin, all the liquid raw materials (resins and solvents) were weighed and incorporated into a mill, then grinding began and titanium dioxide was added. (pigment), after 10 min of continuous grinding, the graphene material corresponding to the amount of ink to be produced (g of GO paste / Kg of ink) was added, with a concentration of between 0.001% and 0.005% of graphene oxide powder with a pH of 7.5. Subsequently, the grinding was maintained for approximately 30 min, the maximum temperature reached in this procedure was approximately 70 ° C. After time, the ink was allowed to cool and was discharged. With a temperature lower than 50 ° C, the final container was emptied.
  • the type of functionalized graphene oxide for the preparation of the waterproofing that was used was in a water-based paste presentation, with 30-40% humidity and pH 3.5- 4.5.
  • all liquid raw materials were weighed and mixed in a disperser and dispersion was started. Without stopping dispersing, the material and pigment loads were added.
  • the graphene oxide paste was added in percentages by weight in the range of 0.005% to 0.10% per kilogram of the waterproofing agent to be produced.
  • the mixing now with the graphene oxide was kept for 20 minutes.
  • the disperser was stopped to add the thickener and they dispersed again for approximately 50 more minutes. In this stage the paint reached a temperature of approximately 45 to 50 ° C.
  • the dispersion was stopped to incorporate the resin, it was again dispersed for 5 minutes and allowed to cool to room temperature to be packaged.
  • the type of graphene oxide for the preparation of the concrete admixture that was used was in a paste presentation, water-based with 30-40% humidity and pH 3.5- 4.5.
  • the preparation of the admixture for concrete is water-based pH 7.0- 8.0 in which 2.5- 3.5 grams of graphene oxide paste were dispersed per liter of admixture that was dispersed by propellers at 100-500 RPM for 10 minutes.
  • the various aggregates that integrated the concrete were mixed in a conventional way: cement, gravel, sand, water and line additives, once the concrete mixture was ready, the concrete additive with graphene oxide was incorporated directly into the mixing zone in such a way that the concentration adjustment corresponds to 0.5 to 1.5 grams of graphene oxide per ton of cement.
  • the conventional parameters for the application of concrete were continued.
  • the proportion for the additivation of the cement with the graphene oxide powder was in a range of 0.5 to 1.5 grams of graphene oxide per ton of cement and its addition can be carried out in two stages of the process, both at the end of the cooling of the clinker. or in the final grinding. In such a way that the resulting cement is already reinforced with graphene oxide.
  • the type of functionalized graphene oxide used for the preparation of the asphalt additive was presented as a water-based paste with 30-40% humidity and pH 3.5- 4.5.
  • a dose of 20 to 50 milliliters of asphalt additive with 5 to 10 grams of graphene oxide was required.
  • the first step was to preheat 20 to 50 milliliters of the dispersing medium, either oily or polymeric, at a temperature below 155 ° C and slowly add the graphene oxide paste, mixing until homogenized.
  • the second step consisted of heating a ton of asphalt cement from 140 to 155 ° C, at this temperature, the asphalt additive reinforced with graphene oxide was incorporated until homogenized.
  • the third step was to incorporate the missing aggregates (sand and gravel) into the asphalt mix. In such a way that 5 to 10 grams of functionalized graphene oxide are applied per ton of asphalt cement.

Abstract

L'invention concerne un procédé et un système ou un ensemble d'exploitation complet évolutif, réplicable et à bas coût pour la production de matériaux nanostructurés à base de carbone connus comme: l'oxyde de graphène et l'oxyde de graphène réduit à fonctionnalisation variable pour un usage industriel à partir de l'oxydation et l'exfoliation chimique de graphites de nature différente (amorphe raffiné, synthétique raffiné, cristallin ou des combinaisons de celles-ci) et de taille différente (≤50-100 µm), par exposition à H2SO4, H3PO4, KMnO4, H2O2; purification par HCl et CH3CH2OH et réduction par (C2H5)2O. L'invention concerne un système ou un ensemble d'exploitation complet de production au moyen: d'un module d'oxydation-exfoliation et retenue, un module de purification, un module de décharge de lixiviats et un module d'achèvement du produit.
PCT/IB2020/059446 2019-08-08 2020-10-08 Procédé et système d'exploitation pour la production à haut rendement de matériaux nanostructurés à base de carbone à fonctionnalité variable WO2021024240A1 (fr)

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