WO2019193579A1 - Method for producing a solidifier for crude oil able to adsorb the gases and fumes generated during hydrocarbon and vegetable oil spills on any surface - Google Patents

Abstract

This invention relates to the manufacture of a solidifier for crude oil and vegetable oils that can coagulate same irrespective of the viscosity thereof provided that the density of said oils is less than that of water, adsorb the gases and fumes generated during spills, thereby protecting the environment and ensuring the safety of rescue teams or specialised emergency action forces. The solidifier is obtained using fibrous plant matter obtained from municipal solid waste, such as plants, used textiles, paper printed with dry inks and soot or carbon black or graphite from used batteries, which are subjected to processes for extracting the cellulose pulp, a nanotechnological process in which doped graphitic carbon coats the cellulose or reeds in monolayers upon application of mechanical exfoliation, micromechanics and electrostatic attraction and ultrasound (sonication), thus modifying the porous structure and texture, increasing the ability to retain hydrocarbons and, at the same time, increasing adhesion, the containment of the gases and fumes responsible for fires, explosions and damage to the ozone layer, while also allowing the crude oil encapsulated to be recovered by way of a mechanical process.

Description

 PROCESS OF OBTAINING THE SOLIDIFIER FOR OIL CAPABLE OF ADSORING ANY SURFACE, GASES AND VAPORS GENERATED IN THE SPILLS OF HYDROCARBONS AND VEGETABLE OILS.

Technology sector

This invention is framed in the field of chemical engineering applied in the petroleum industry, especially in exploration, extraction, refining, transport, storage in any area that handles both new and used fuels, to clean and handle the possible handling incidents

Object of the invention

The present invention relates to the manufacture of a solidifier of petroleum and vegetable oils, capable of coagulating on any surface, without interest its viscosity provided it has less density than water, adsorbs gases and vapors generated in the spills, providing protection to the environment environment and safety for relief agencies or specialized groups that attend emergencies; obtained from fibrous plant material from urban solid waste such as: vegetables, used textiles, printed paper, dry inks and soot or carbon black, graphite from discarded batteries, using state-of-the-art technique where materials are used to nano scale

Previous Technique:

Since oil was discovered and used, it is always prone to incidents and accidents such as outcrops, leaks, blasting of pipelines that result in spills on soils and bodies of water. Then, to control and / or clean this contamination, natural materials consisting of clays, sand, sawdust, earth, synthetic and chemical materials have been used in order to absorb them, eliminate them or transfer the contamination from one side to the other with elimination processes that go to the air by evaporation when the adsorbed material is volatized, they are also incinerated by transferring them to the layer of ozone; or they are abandonment in the open or in landfills, sanitary landfills or leaving them in water thinking that they are degraded with the support of bacteria and time.

Hydrocarbon absorbents and adsorbents are composed of a wide range of organic, inorganic and synthetic products designed to remove hydrocarbons from soil and water. Its composition and configuration depend on the material used.

Currently, mechanical equipment is used to collect oil spills, which require a complex and expensive process; There are other types of products on the market such as sorbents, absorbents such as sawdust, sand, peat, plastic barriers, containment dams, cardboard, paper, oleophilic cloth, which can play the same role as the solidifier. Products such as sawdust, peat and sand have problems for handling and transport because they are very heavy, they are slow to absorb the hydrocarbon once they get in contact, large quantities are required due to their adsorption capacity, cartons, this type of material adsorbs very little and once contaminated it becomes a greater volume of waste. There are also other types of products that can serve as a complement to the function of the absorbent, some of these are degreasers, detergents, cleaners, etc., Degreasers and cleaners do not fulfill the same function, really what they do is transfer the hydrocarbons and also Because they are not biodegradable, they contribute even more to water pollution. They are not applicable in water and present problems after being used because they become hazardous waste. Oil companies strongly recommend the non-large-scale use of adsorbents on land and at sea, as excessive volumes of hydrocarbon-contaminated waste are generated for later disposal.

There is also a variety of products on the market such as mobs, activated carbon, molecular sieves, volcanic ash, zeolites, chemical and polystyrene materials, materials that due to their properties and cost are not suitable for this specific type of treatment; In particular, Natural, synthetic absorbent and adsorbent material should be used sparingly and carefully to ensure that it is used at full capacity to minimize subsequent waste disposal problems. Most of the products available for oil spill response have separate results, very few are truly absorbent.

One of the new technologies of the 21st century “The era of nano-materials” Until 2004 the pioneers in using graphene in this way were the scientists AK Geim and KS Novoselov, in 2010 they were awarded the Nobel Prize. These scientists obtained individual graphene sheets. For this, they used the mechanical exfoliation method that is feasible thanks to the weak interaction forces between graphene sheets. Recently the field of nano materials has evolved rapidly, making its way through existing materials, one of the most important recently is "graphene". Graphene It is a nano-material that is formed by layers of a few thick carbon atoms. This material has gained special importance due to the wide spectrum of applications to which it can be applied, however, it has a great disadvantage, this is that it has not been obtained in sufficiently large quantities by an economic method that allows its use in a industrial. In order to obtain graphene, different techniques have been studied, which can be grouped as TOP-DOWN techniques, when manometric thickness graphene is obtained from a micrometric thickness material such as graphite, or BOTTOM-UP; TOP-DOWN The method of mechanical exfoliation is to take an adhesive tape to pass it through the graphite, and then with successive passes, part of that graphite is eliminated, obtaining after several rounds layers of graphene of very small thicknesses. This method is simple and cheap, but it has the disadvantages that it is a slow method since several passes have to be made to reduce the thickness, due to this it also does not have a very good performance since it is not a procedure with which Get graphene in large quantities. Generally, for micro-mechanical exfoliation processes, graphite is rubbed against a surface. This process is adequate in terms of the properties of the graphene that is obtained, however, it is a process that is very laborious and expensive in terms of labor and the time required to obtain just a few sheets of graphene.

 To obtain the solidifier; It allows us to update ourselves and be willing to adjust and design new processes, where techniques are obtained that help protect the environment, use materials and raw materials that we have abandoned in landfills, generating other pollution and that we intend to help recover using the technology of Latest generation using “nanotechnology” like this:

Methods used in the manufacture of the Solidifier:

 To obtain the petroleum solidifier capable of adsorbing on any surface, gases and vapors generated in the spills of hydrocarbons and vegetable oils, a combination of techniques have been used:

We take as a starting point the 3 patents lent by us: First patent: to obtain a sorbent (absorbent) 98-039158 from 07-10-98 before the Superintendence of industry and Commerce, the second: process to obtain an adsorbent product presented before WIPO (Switzerland) W02004 / 050267 and the third: process for decontamination by adsorption of vapors and liquids generated along the oil chain in the presence of water and soil, from spills, their management and final disposal applying cleaner technology, Presented to WIPO (Switzerland) WO2011036508 A1.

In addition, the following techniques are applied: a) Micromechanical Exfoliation. It is currently the most effective method to produce individual sheets of high quality graphene. This method consists of making a stamping on Si02 support, with highly oriented pyrolytic graphite plates (HOPG). Subsequently, successive detaches are carried out by careful pressure or rubbing by dividing graphene sheets, individual or double, from the stamped graphite, which leads to thicknesses not greater than 3 nm. The low density obtained by this procedure, only a few single or double sheets per substrate area, combined with the lack of precision when positioning these sheets in a controlled manner, limit the implementation of graphene in current devices.

b) Mechanical Exfoliation. It consists of dispersing graphite by mechanical exfoliation in a solvent such as dichlorobenzene, applying ultrasound for five minutes. This technique generates graphene sheets dispersed by the action of ultra sounds. A method similar to the one mentioned above was used to obtain graphene tapes with thicknesses on the nanometric scale. The main drawback is that when using long ultrasound times individual sheets of low lateral dimensions are formed, while structural defects occur. c) Chemical Exfoliation. It is based on the intercalation of molecules between graphite sheets. In this way, shorter times and ultrasound power are required, reaching larger dimensions with fewer defects in the sheets. Recent work done with ultrasound at low power on the interleaved graphite, with ternary potassium salts, K (THF) X C24 (x = 1-3), obtaining negatively charged graphene sheet solutions. One technique with the possibility of mass production of graphene is the direct epitaxial growth of graphene on an insulating substrate. It consists of heating silicon carbide solids, to produce a partial graffiti of the upper sheet. However, this technique is hindered by the control of the number of sheets produced. Another strategy is focused on generating graphene oxide (GO) sheets, which have no tendency to aggregate and can be deposited as individual sheets on the surface. The GO is prepared using the Hummers method which consists of the strong oxidation of graphite. Through this method, rough sheets with hydroxyl, epoxy and carboxylic groups are generated, mainly located in positions bordering the plane. These functional groups increase the hydrophilic character which reduces the inter-planar forces, thus facilitating exfoliation by gentle application of ultrasound. Subsequently it is required to apply a reduction process that generates graphene using the GO, through different physical and chemical reduction techniques. The reduced GO, whose advantage is that it can be deposited in specific surface areas in a wide range of substrates. Hydrazine and plasma-generated hydrogen have been used as reducing agents. In both cases this reduction is significant by partially returning the conductivity in three orders of greater magnitude than the GO, but far from what is expected for graphene. These low electrical conduction values are due to defects in the oxide reduction process. which essentially consist of carbon vacancies. The reduced GO has a non-metallic behavior with a conductance that decreases by three orders of magnitude at low measurement temperatures.

d) Sonication of graphite. Based on the dispersion of graphite in a liquid medium, which receives sound waves that make its particles shake. Then, by centrifugation, graphene is separated from graphite. Sonication is the act of applying sound energy (usually ultrasound) to agitate the particles in a sample, for various scientific or industrial purposes. Ultrasound, in turn, generates vibrations in the target material. If it contains liquids, millions of microscopic bubbles will be generated, which undergo very rapid expansion and collapse processes that can transmit their energy to other materials.

e) Doped graphene: doping is a technique performed during the obtaining of carbon nano structures where manometric particles of some other compatible element can be added for the desired modification of their properties.

f) Electrostatic attraction is the property of the matter responsible for electrostatic phenomena, whose effects appear in the form of attractions and repulsions among the bodies that possess it. The term static electricity refers to the accumulation of excess electrical charge (positive or negative) in a conductor or insulator. The effects of static electricity are familiar to most people because they can see, notice and even feel the sparks of the discharges that occur when the excess charge of the charged object is placed near a good electrical conductor (such as a conductor connected to a ground) or other object with an excess load, but with the opposite polarity.

e) Induced charge occurs when a charged object repels or attracts electrons from the surface of a second object. This creates a region in the second object that is with a greater positive charge, creating an attractive force between the objects. For example, when a balloon is rubbed, the balloon will remain attached to the wall due to the attractive force exerted by two surfaces with opposite charges (the wall surface gains an induced electrical charge because the free electrons from the wall surface are repelled by the electrons that the balloon has gained by rubbing; thus a positively charged surface on the wall is created by electrostatic induction, which will attract the negative surface of the globe).

g) Friction charge, is transferred to the large number of electrons because friction increases the contact of one material with the other. The innermost electrons of an atom are strongly bound to the nucleus, of opposite charge, but the outermost of many atoms are very weakly bound and can be easily removed. The force that holds the outer electrons in the atom varies from one substance to another. For example, electrons are retained more strongly in the resin than in wool, and if a resin cake is rubbed with a very dry wool fabric, the electrons in the wool are transferred to the resin. Therefore, the Resin cake is left with an excess of electrons and is negatively charged. In turn, the wool fabric is left with an electron deficiency and acquires a positive charge. Electron-deficient atoms are ions, positive ions because, by losing electrons (which have a negative charge), their net charge is positive.

h) Induction load, a body can be loaded by a simple procedure that begins with the approach to it of a rod of insulated material, loaded. Consider a non-charged conductive sphere, suspended from an insulating wire. When the negatively charged rod approaches it, the conduction electrons that are on the surface of the sphere migrate to the far side of it; as a result, the far side of the sphere is negatively charged and the near one is positively charged. The sphere oscillates approaching the rod, because the force of attraction between the near side of the rod and the rod itself is greater than that of repulsion between the far side and the rod. We see that it has a net electric force, even if the net charge in the spheres as a whole is zero. Induction load is not restricted to conductors, but may occur in all materials.

In the state of the art, no product similar to that of the application is known: from waste, crop leftovers, municipal solid waste (cellulose of paper and cardboard, cuttings of textiles and used clothing, graphite of used batteries, leftover toner ink and printer cartridges, fumes and greases (smock) that stick to curtains and facades or air measurement hoses or filters, laundry wastewater), which after being treated the inks are used as part of the catalyst that is used as raw material to obtain the solidifier, that meets the requirements of the market: that absorb quickly, that trap gases, that are biodegradable and capable of collecting less dense liquid substance than water, that can be recovered in a clean and safe way the spilled material, both of bodies of water and of the earth, which significantly reduces the impact on the environment of oil spills by having to dispose m nimas amounts as hazardous materials, protect the integrity of relief agencies, I provide a tool and methodology of prevention, care oil spill (PADH).

In the oil industry to deal with an incident with hydrocarbons they look for the ideal product, which have the following qualities: good wetting properties (To achieve satisfactory adsorption, hydrocarbons should wet the material and spread on its surface with preference to water), large Capillary action (Capillary action is particularly important with foam-based adsorbents. Foam with fine pores easily collect low viscosity hydrocarbons, although the pores clog quickly with thicker hydrocarbons), Cohesion / adhesion (Cohesion refers to attraction of a material to the material itself, thus opposing spreading on a solid surface, while adhesion refers to the attraction of one material to another), Surface area (A satisfactory adsorbent material must have a high relationship between surface area and volume, including available internal and external surfaces), Buoyancy (must present and maintain high buoyancy and remain afloat even when saturated with hydrocarbons and water.), Saturation, Hydrocarbon retention, Strength and durability, Fermentation, Availability, storage and transport, use on all terrain and surface, easy to apply, that is compatible with other cleaning techniques, easy to collect, that suits tasks of

"Maintenance" and other roles, easy Temporary storage and transport of material contaminated by hydrocarbons, that the disposal routes or final dissipations and that the solidifier is reusable, conforms to the requirements that environmental and exploitation and the most important can recover absorbed or encapsulated oil.

Consideration to consider

Once spilled, hydrocarbons begin to undergo weathering processes and their physical and chemical characteristics change over time. The processes of spreading, evaporation, dispersion and emulsification are important in the early stages of the spill, while photo oxidation, sedimentation and biodegradation are long-term processes that determine the final destination of hydrocarbons. The speed at which these processes occur depends on the climatic, meteorological conditions and characteristics of hydrocarbons such as specific gravity, volatility, viscosity and pour point. Evaporation and dispersion contribute to the removal of hydrocarbons from the sea surface, while emulsification causes their persistence and an increase in the volume of contaminant.

 We know from experience that even well-managed responses can produce large volumes of oily waste. Even the original volume of the spill is up to 10 times; Everything that touches hydrocarbons becomes waste and is classified as hazardous waste, which must be handled as indicated by regulations.

The personnel (Firefighters, Lifeguards, person and technical groups in care of incidents) that handle these spills are exposed to impregnate or absorb liquids through the skin and gases and vapors by inhalation, another source of irrigation is made up of containers and tanks Storage are large generated from dangerous atmospheres and can explode. Definitions to better understand the invention

• Solidifier: Solidification is a physical process that consists of changing the state of matter from liquid to solid.

 • Curdling is to bind a liquid so that it becomes solid or pasty; It is also coagulate, condense, solidify, freeze, harden.

 • Adsorbent: It is said of a body or a substance that adsorbs (attracts and retains particles from another body). It is also said of a substance, usually solid and porous, that has great capacity to retain on its surface another component present in liquid or gaseous streams.

 • Catalyst, any substance that modifies the speed of a chemical reaction. An important feature is that the catalyst mass is not modified during the chemical reaction, which differentiates it from a reagent, whose mass decreases throughout the reaction.

 • Electrostatic attraction: The electric charge is the property of the matter responsible for the phenomena whose effects appear in the form of attractions and repulsions among the bodies that hold it.

 • Nanotechnology: it is the study, design, creation, synthesis, manipulation and application of materials, devices and functional systems through the control of matter on a nano scale, and the exploitation of phenomena and properties of matter on a nano scale.

 • Exfoliation: is the division of a thing into sheets or scales

 • Graphene: It is a substance formed by pure carbon, with atoms arranged in a regular hexagonal pattern, similar to graphite, but on a sheet of an atom thick.

 • Nanonized: Reduction of a substrate to particle size of nanometers.

Detailed description of the invention:

Basically, the starting point of the invention includes the recovery of raw materials, the use of this material, the solid waste is transformed and its potential for reinstatement is returned to the materials as a raw material for the manufacture of new products, applying state-of-the-art techniques (nano -materials) to obtain graphite graphene from the used batteries, carbon black and dry inks that arise from the wastewater management of the washing processes or obtaining the pulps. .

The process for obtaining the solidifier is based on obtaining the raw material that is obtained from fibrous plant materials and the cellulose and the scream of the used batteries, dry inks and carbon black that is part of the catalyst are extracted; and they are described in 5 sections and one has its stages: (1) obtaining raw material (cellulose) and the obtaining the materials, (2) catalyst manufacturing (3) Homogenization and Mixing, (4) Quality control and (5) packaging;

(1) Obtaining raw material (cellulose).

First stage the selection of the raw material from solid waste, they are those derived from paper, cardboard, used clothes, textile waste, fibrous vegetable waste, wood, stems and banana leaves, fruit peels, ameros, and other derivatives of fibrous agricultural products, water hyacinth or buchón, sediments of inks and carbon black for the treatment of sewage, batteries (graphite) and printer toner;

Second stage, this raw material is divided into subgroups according to their origin as follows:

-Derivatives of paper, newspapers, cardboard, cardboard, folding, carbon paper.

-Derivatives of paper combined with plastic and aluminum, adhesives, milk packaging

(tetrapak).

- Textile derivatives: those that are of cotton origin, linen, coming from used garments and cuttings of the clothing industry.

-Derivatives of agricultural products: bagasse, fruit pods, leaves, wood, waste from cotton crops, wheat, barley, coconut, cassava etc., then proceed to make the cut, ground, defibrated and chopped, these steps are performed separately and simultaneously for each of the subdivisions of the raw material.

Generally, this part of the selection and classification is carried out in the corresponding collection center in each region.

Third stage the selected material is passed to a conveyor belt, it is verified that it does not contain foreign materials or different from those arranged for the next step.

Fourth stage the crushing is carried out, for its handling and lightening of the process the material sizes must be reduced to 3 to 5 square centimeters, said operation is carried out with the appropriate machinery according to the type of material as follows: Cut for derivatives of the paper, in strips of centimeter, with machine and taking special care with the sewing hooks, staples, tapes, plastic adhesives, all plasticized, cartons of tetra pack and / or any other foreign element. The grinding is done for materials such as paper combined with plastics, aluminum foil, adhesives, carbon paper, these materials are reduced to a size of 5 to 6 mm by means of an impact mill. The defibration is made with cutting and tearing machines for textile materials, these have been previously selected by hand and separated from foreign bodies such as buttons, brooches, staples, zippers etc., the sanforized fabrics are also separated and the elastics are removed. Chopping is done to materials derived from agricultural products, previously dried and separated by class, to be reduced to a size of 6 mm.

The fifth stage, basic in the process consists of maturation, which is carried out in a closed tank, which comprises: first the pulping, where the crushed and dried material is treated by adding enough water and chemical hydroxide liquor selected of sodium or sodium carbonate at a certain temperature. Second, the continuous shaking or stirring of the mixture that imparts characteristics to the product and third, the refining that consists of removing, through successive washes, the materials that affect the effectiveness of the adsorbent such as starches, sugars, gums, inks, as well as the objects have passed in the previous stages, at this stage the fibers are washed and if necessary they are treated with sodium silicate to reach a neutral pH, they are combed and their length is reduced. The pulp must contain a humidity of 10%.

Depending on the type of material, ripening is carried out according to the following conditions:

-For textiles 35 Kg / L of water, 5% chemical liquor, 85ºC temperature, pH = 8, internal pressure of the system 2.1 Kg / cm2 and a time of 240 minutes.

-For papers 20 Kg / L of water, 3% of chemical liquor, 60ºC of temperature, pH = 6, internal pressure of the system 1, 8 Kg / cm2 and a time of 60 minutes.

-For plant materials 25 Kg / L of water, 20% of chemical liquor, 135ºC of temperature, pH = 9, internal pressure of the system 2.9 Kg / cm2 and a time of 480 minutes.

The sixth stage is the drying of the material from the previous stage, with hot air circulation at a temperature between 180ºC and 230ºC for an approximate time of 120 minutes, then the dry material leaves the machine and is left at rest at room temperature for 60 minutes.

The seventh stage consists in the formulation of the final product, free of moisture where pulps (cellulose) from paper, textiles and vegetables are mixed in equal parts, and then passed to the carding machine first by a diameter of 4 mm and then by one of 2 mm.

The eighth stage: obtaining the catalyst, you must recover materials that are in the wastewater generated from the washing of paper pulp, filter side, toner and ink cartridges, carbon black from the sleeves and air filters and the graphite of the discarded batteries to which the following process is done to obtain doped graphene: The graphite bars of the batteries are passed to a ball mill and crushed to obtain a powder and then stir with the inks removed from the washing wastewater.

The wastewater generated in the washing of papers, textiles, toner, cartridges and filters and sleeves of the air extractors, is dry printing inks, carbon black, causing pollution to the water to be poured; which floating and must be removed in order not to pour them into the sewer and is done with a sonication process (it is the act of applying the energy of sound (usually ultrasound). Ultrasounds generate, in turn, vibrations in the target material If it contains liquids, millions of microscopic bubbles will be generated, which undergo very rapid expansion and collapse processes that can transmit their energy to other materials.

The semi-dry inks and the graphite powder are subjected to Nanonized processes (Reduction of a substrate to nanometer particle size) obtaining low quality graphene, which will be combined with lime, sodium bicarbonate, boric acid, borax, for Obtain the catalyst of the solidifier, which will be the additive or doping material.

The jealous is ready to go to the reactor.

(2) catalyst manufacturing:

A fundamental and key basis for obtaining the solidifier is made in the reactor and with the addition of the catalyst obtained from the graphite of the discarded batteries, printing inks in the process of obtaining pulps of the printed papers, the remaining inks of the toners and cartridges when washed, and carbon black which is removed from the magicians and air purification filters; When the wastewater from the pulp and washing processes is treated, particles appear that are removed from the aqueous medium with equipment moved by dry air, then passed through the sonicator, peristaltic pump, centrifuge and muffle or dryer.

The catalyst is obtained from the enlistment of the inks, carbon black and graphite is made separately by removing from its origin by graphite sonication processes. Based on the dispersion of graphite in a liquid medium, which receives sound waves that make its particles shake. Then, by centrifugation, graphene is separated from graphite; To the catalyst is added as additive material OR dopant in 2: 2 proporsion (lime, sodium bicarbonate, boric acid, borax) is mixed, applying ultrasound for fifteen minutes, then and the catalyst is obtained, which is moved by peristaltic pump, excess moisture is removed with centrifuge and dry heat to be applied in the reactor to obtain the solidifier . Adhering the doped graphene to the cellulose covers the reeds and helps improve the purposes.

(3) Homogenization and Mixing

Homogenization of the solidifier

Once the cellulose pulps and the catalyst in the form of doped graphene are received, the solidifier adaptation section in the Reactor is passed, where e! Micro mechanical exfoliation process, which consists of rubbing against a surface, the reeds and the catalyst until the material adheres and covers the reeds.

The cellulose is passed from the rest area to the reactor in pneumatic medium and plastic pipe 4 inches in diameter and 20 meters of lake; this route is provided with electro magnets that charge the fibers; This transition does improve electrical conductivity (Induced charge occurs when a charged object repels or attracts electrons from the surface of a second object) and is discharged into the reactor.

Mixture.

As different fibers have been processed, an equal mixture of 100: 1 (100 cellulose and 1 doped graphene) is made, the reactor that is rotating at 2,500 rpm is fed and ends at 3,700 rpm for a time of 15 minutes; where simultaneously the carding, combing and homogenizing materials are denied.

Carding and hairstyle.

Within the reactor there is a continuous movement, rubbing the cellulose with the blades and at the same time the process of micro-mechanical exfoliation of the doped graphene is denied, which leads to thicknesses not greater than 3 nm; said Process that is carried out in the reactor that agitates until it is formed into cylindrical branched fibers (reeds) of different calibers and lengths that can reach 0.01mm and a thickness of O. lmm; The stirring process inside the reactor is 2,700 rpm at 3,700 rpm, the what it does is add films that cover the reeds with mono layers of doped graphene, electrostatic attraction will be applied where the solidifying properties of this invention are given unique properties; The solidifier is passed through the pneumatic network, to the resting area where it is classified by density, the texture is measured, the moisture is stabilized and the porosity, adhesion, containment, retention, adsorption of petroleum and vegetable oils are measured, which must be 1 to 40 times its weight and the containment of gases and vapors.

Classifier by density.

The solidifier is transported by pneumatic means and taken to the sector where a density classification is carried out; the rods that do not meet the lengths, are passed back to reactors 3, 4 and 5 and the operation is repeated until it meets the specification.

(4) Quality control

Tests that are done to adjust processes and procedures that are done in batches:

1- Absorption capacity [gallons / square inch] of hydrocarbons

 2- Fiber diameter [myras]

 3- Lattice [myras] that is the average distance between fibers

 4- Porosity [number of pores / square inch]. From each fiber and the average is taken out.

 5- Channeling [number of ducts / cubic inch]. Number of channels to allow free flow of hydrocarbon.

 6- Recovery [liters or gallons / square inch], Indicates that both of the collected hydrocarbon can be reused.

 7- Flammability. To measure your tolerance to be a flame propagator.

Particle size analysis. The evolution of particle size, adhesion, adsorption has been analyzed by optical microscopy.

Due to the great diversity of hydrocarbon adsorbent materials that exist in the market, it is proposed to use the international standardized method ASTM F726-06 to evaluate its performance through its adsorption capacity and market requirement, (5) Packaging

Once the Solidifier is rested, it passes the quality control, it is vacuum packed in bags of 1, 3, 10 and 20 kilograms compressed, taking advantage of storage and transport space.

Solidifier Characteristics

With the processes mentioned above and the application of Nanonized processes, a unique solidifier was obtained in the market, with the characteristics of several products in one, which covers the needs of the oil industry as follows:

 When hydrocarbon spills occur, the processes of spreading, evaporation, dispersion and emulsification are important in the early stages of the spill, while photo oxidation, sedimentation and biodegradation are long-term processes that determine the final destination of hydrocarbons. It is advisable to use the solidifier that complies with:

• Good Absorption and Adsorption. It traps gases and adheres or adsorbs liquids by up to 96.5%.

 • Avoid recreation. It has the properties to contain, adsorbent, clean, collect and protect.

 • Good wetting properties (In order to achieve satisfactory adsorption, hydrocarbons should moisten the material and spread on its surface in preference to water),

 • Great Capillary Action (Capillary action is particularly important with foam-based adsorbents. Foam with fine pores easily collect low viscosity hydrocarbons, although the pores clog quickly with thicker hydrocarbons),

 • Cohesion / adhesion (Cohesion refers to the attraction of a material to the material itself, thereby opposing spreading on a solid surface, while adhesion refers to the attraction of one material to another),

• Surface area (A satisfactory adsorbent material must have a high relationship between surface area and volume, including available internal and external surfaces),

 • Buoyancy (must have and maintain high buoyancy and remain afloat even when saturated with hydrocarbons and water),

 • Saturation, hydrocarbon retention. Once the hydrocarbon is encapsulated, it does not produce leaching, keeping the hydrocarbon trapped or encapsulated all the time.

• Strength and durability, the Solidifier stored indoors, can last for plus 5 years without losing their properties.

 • Fermentation, when the hydrocarbon is removed from the solidifier, can be decomposed with composting processes, as it is a petroleum-free plant material.

 • Availability, as it is a product manufactured with fibrous and recycled plant materials, can be obtained in any city and the possessed are easy to replicate.

 • Storage and transport. The solidifier, being an understandable material, can be compressed to increase storage and facilitate transport; Then you can restore your appearance and by passing it by sprinkler,

 • It can be used on all land and surface, works on any surface being more effective in aqueous media.

 • Easy to apply, can be applied manually or with equipment. The equipment is a turbine, with hose to apply as a sprinkler

 «Compatible with other cleaning techniques, where traditional equipment can no longer remove contamination, the solidifier acts very effectively.

 • Easy Collection, can be collected with simple strainer, rake or with industrial vacuum cleaner.

 • That it adapts to “maintenance” tasks and other roles, apart from removing the oil in cleaning, is a good tool to restore impregnated areas in a short time, as it is also very practical when cleaning oiled animals or people .

 «Easy Temporary storage and transport to contaminated material. It is avoided to store oily water, since only hydrocarbons can be removed and not the water.,

• That the disposal routes or final dissipations are of use or reuse as raw material to manufacture other products.

 • That the solidifier once reused can be reused and drained for more than 10 times,

 • That meets the environmental requirements. It serves as a prevention system for possible oil spills and industrial safety tools.

• That absorbed or encapsulated oil can be recovered. By subjecting the impregnated solidifier to mechanical processes of compression or centrifugation, it releases up to 80% in hydrocarbons if it alters its composition.

Claims

1) Process of obtaining solidifier for oil capable of adsorbing on any surface, gases and vapors generated in the spills of hydrocarbons and vegetable oils CHARACTERIZED because it comprises the stages:

 a) Recovery of raw materials from urban solid waste (MSW), in process leftovers, organic fibrous processes and packaging, derived from agricultural products, buchón, papers, cartons, packages combined with printed with dry inks, graphite from batteries or batteries, used clothing, textile waste, we apply traditional techniques to obtain cellulose pulp, its size is reduced to 3-5 mm fragments, they are sterilized and / or sanitized by steam and dry heat, with equipment heat and steam generators, where they are released from bacteria; the papers and cartons are ground and the gums, glues and inks are removed in aqueous medium with caustic treatment; used batteries are opened, cathode or graphite is removed; to the toners or containers of ink printers, the inks, the carbon black and graphite are isolated or separated from the water, the recovery step is done by means of sonication of graphite.

b) Mechanical and chemical stages to the recovered cellulose as indicated in the previous stage, are passed to the maturation area where the mechanical operations of cutting, grinding, defibration, removal of foreign materials by agitation, washing and centrifugation are applied; and chemical, then independent pulping is done, for the different materials according to their origin, by wet methods with caustic soda, sodium silicate and calcium carbonate; sodium silicate is added so that the pH is neutral; then undergoes combing by card; Fiber length is standardized and dried until moisture is adjusted.

 c) Stage of obtaining the solidification graphite catalyst, with the product of the graphite bars insulation of the batteries, the inks, carbon black is made separately by removing from its source it is subjected to a micromechanical exfoliation stage, followed by mixing graphites from different sources, applying ultrasound for 35 minutes; obtaining an additive material for cellulose coatings with doped graphene. d) Formulation of the solidifier, taking from the different sources the cellulose pulp, mixed in equal parts, the nanonized catalyst, obtained by micromechanical exfoliation, is applied, mixing until homogeneous.

 e) Quality controls of the particle size by means of optical microscopy and / or scanning electron microscopy, the uniformity of the particle size, adhesion, adsorption, the way the particles are grouped is analyzed.

f) Packaging. 2) Process according to claim 1, CHARACTERIZED because in the further stage the catalyst is doped by treating it with boric acid and calcium carbonate, these reagents are mixed by applying ultrasound for 10-25 minutes, then pneumatically passed to a reactor , which agitates until cylindrical branched fibers (reeds) of different calibers and lengths that can reach 0.01 mm and a thickness of 0.1 mm are formed.

 3) Process according to the preceding claims CHARACTERIZED because in addition the catalyst is electrostatically charged by stirring treatment inside the reactor at revolutions between 1000-5000 rpm, thereby achieving to add films covering the reeds with monolayer of doped graphene, conferring thus the property of electrostatic attraction.

 4) Process according to the preceding claims CHARACTERIZED because the solidifier already formulated is passed through a pneumatic network, to a resting area where the density properties, its texture, moisture is stabilized and its porosity is measured , adhesion, containment, retention, adsorption of oil, vegetable oils; its containment of gases and vapors.

 5) Solidifier for petroleum capable of adsorbing on any surface, gases and vapors generated in the spills of hydrocarbons and oils obtained in accordance with the previous claims CHARACTERIZED because it comprises a) synchronized cellulose of plant residues, used textiles, printed paper, cardboard or the like from urban solid waste; b) a nanonized graphite solidification catalyst, with the product of graphite bars insulation of batteries, inks, waste toner, carbon black.

 6) Solidifier of claim 5 CHARACTERIZED because the catalyst is doped.

7) Solidifier of claim 6 CHARACTERIZED in that the catalyst is electrostatically charged by mono layers of doped graphene.

 8) The solidifier allows to recover the solidified substances with mechanical processes without altering the composition.

9) we claim the recovery of crude oil that reaches 96.5% of the EI that is currently being sold