Granular solid material and method for purifying the water produced in the oil industry

Abstract

The present invention relates to a water-insoluble granular solid material having three Hansen solubility spheres and comprising one or more components selected from: a) a resin, b) a wax and c) a synthetic polymer. The invention further relates to a method for purifying the water produced in the oil industry comprising contacting the granular solid material with the water produced. The invention further relates to a purification unit to perform the method comprising: a) a container including: i. an inlet for the produced water, ii. an injector for introducing and dispersing the water produced in, iii. an inner container with respect to the container a), formed by a metal grate so as to arrange the granular solid material, iv. a gas inlet that is connected to a diffuser to diffuse these gases for bubbling, v. a gas outlet to entrain the recovered oil, and vi. an outlet for the purified produced water; and b) a condenser to separate the recovered oil and recirculate the gases.

Description

[0001] A GRANULATED SOLID MATERIAL AND A PROCESS FOR PURIFYING WATER PRODUCED IN THE PETROLEUM INDUSTRY

[0002] DESCRIPTION

[0003] FIELD OF INVENTION

[0004] The present invention falls within the chemical sector, specifically in the technical field of processes for separating crude oil from produced water.

[0005] STATE OF THE ART

[0006] Due to the importance of the oil industry in ensuring a continuous energy supply for the development of nations, it has been extracting oil at an uninterrupted rate of over 4 billion metric tons annually for the past decade (https: / / es.statista.com). This is equivalent to approximately 80 million barrels of crude oil per day. Extraction involves the generation of large quantities of water contaminated with petroleum residue in the form of small emulsified droplets, referred to in this technological field as "produced water." It is estimated that the amount of produced water is twice the amount of crude oil extracted, with this quantity increasing as the oil well becomes depleted and more water needs to be injected to extract the remaining oil. The concentration of oil in the produced water ranges from 300 ppm to 1,000 ppm, amounts that should not be underestimated.Although much of the water produced is reused for reinjection into oil wells, the remainder must be discharged either onto the land or into the sea after treatment. According to data provided by the Norwegian Ministry of Petroleum and Energy, 126.5 million cubic meters were discharged into the North Sea in 2021. 3 of water produced with a forecast for the next 5 years that will exceed 130 million m³ 3 annual (https: / / www.norskpetroleum.no / en / ).

[0007] The water produced from oil droplets is associated with a complex, highly stable oil-in-water emulsion that requires special treatment to remove the droplets and recover its beneficial properties. Besides the hydrocarbons and greases from residual oil present in the produced water, it typically contains very high levels of salts, especially sodium chloride, sand, hydrogen sulfide, and even, in some cases, radioactive materials. However, it is the oil in the form of stable emulsions that is the most difficult to remove and can have the greatest environmental impact.

[0008] Oil companies and researchers have tested numerous methods for decontaminating produced water, which will be discussed later, without yet achieving optimal results. The problem of produced water must be addressed to reduce its environmental impact, but oil emulsions, because they are not easily broken down, mean that traditional methods, such as membranes, do not achieve a fully satisfactory and continuous result. This is because oil, due to its organic nature, affects the membranes themselves and causes them to become clogged. Similarly, methods such as oxidation or the use of algae are not practical for the actual quantities of water produced.

[0009] Despite the urgent need for oil for global uses, and the necessity of maintaining its production at constant levels to ensure that global fuel prices do not become unstable—and thus prevent a consequent increase in the prices of goods and services dependent on the production of oil and its derivatives, as well as the costs of transporting goods—oil companies are rushing to increase oil production to take advantage of crude oil prices. This raises the rates of wastewater production, and without thorough and radical treatment, it exacerbates the environmental pollution resulting from the discharge of oil-laden water, which leads to the clogging of soil pores. Inadequate solutions are therefore adopted, affecting both plants and animals, as is the case in the oil fields of Iraq.

[0010] The case of offshore oil platforms is the most extreme, since, on the one hand, space on the platforms is limited for treating produced water, and on the other hand, the treated produced water discharged into the sea must have the best possible purification characteristics to avoid affecting marine flora and fauna. The International Maritime Organization (IMO) recommends that countries have national and regional legislation for the discharge of waste into the sea. The Nigeria Environmental Guidelines and Standards for the Petroleum Industry (EGASPIN) establish that the maximum amount of oil / grease in produced water to be discharged into the sea is 40 ppm in deep waters and 30 ppm offshore and on the continental shelf (EGASPIN 4.2.1, 2001).

[0011] In Australia, it is established that treated water discharged into the open sea must contain a daily average of 30 ppm and an instantaneous maximum of 50 ppm.

[0012] In the North Sea, discharges are regulated by the Oslo-Paris Commission's waste treatment guidelines (OSPAR 2001 and confirmed in OSPAR 2012), which establish a recommended monthly average of 30 ppm of oil in the produced water that is discharged into the sea.

[0013] In the United States, the Environmental Protection Agency stipulates an average amount of oil in the water produced of 29 ppm per month for the outer continental shelf and a maximum of 42 ppm for daily discharge.

[0014] The C-NOPB 2002 recommendations for offshore waste management in Atlantic Canada set a monthly average of 30 ppm, effective from 2007. Meanwhile, Norwegian authorities, in agreement with operators of the Norwegian continental shelf, have established an environmental target of zero harmful discharges into the North Sea. As of 2022, zero discharges of chemicals related to oil production and other industries had been achieved in the North Sea, but this has not yet been the case for residual oil from produced water, as the technology to achieve this target does not yet exist.

[0015] It is important to note that offshore oil production regulations in most countries require that technology-based limits be consistent with the best available cost-effective treatment technology. As more efficient technology becomes available, regulations may become even more restrictive to achieve the goal of zero residual oil emissions.

[0016] Numerous produced water treatment processes have been described in the technical literature, although none of them have become fully satisfactory, especially with regard to the quality requirements for treated produced water that are intended to be established in the near future.

[0017] The treatment of produced water to remove residual oil typically consists of primary separation, secondary separation, and in some cases, final cleaning. Produced water enters primary treatment with up to 1,000 ppm of oil and exits with between 100 ppm and 200 ppm. In secondary treatment, the produced water enters with the same 100-200 ppm and exits with an oil concentration between 10 ppm and 40 ppm. After this secondary treatment, current regulations in most oil-producing regions could be met, but the future trend, as established by Norway for oil platforms, is toward zero harmful discharges. This is impossible with current technology. Current cleaning treatments can cost-effectively achieve up to about 15 ppm of residual oil, far short of the desired target.

[0018] Primary treatment can be carried out using skimming tanks, API oil separators, corrugated plate interceptors (CPIs), and coalescence. Secondary treatment may employ hydrocyclones, gas-induced flotation (GIF), dissolved gas flotation (DGF), compact flotation units (CFUs), or membranes, among other technologies. Final cleaning or refining treatment uses nutshell filters or dual-media filters (https: / / whatispiping.com / produced-water-treatment / ).

[0019] Thus, hydrocyclones require energy to pressurize the inlet, without solids separation, fouling problems, and higher maintenance costs.

[0020] Corrugated plate interceptors are inefficient due to the time required for the retention of fine oil particles and their maintenance.

[0021] Dissolved air flotation involves dissolving pressurized air in the produced water and then depressurizing it to atmospheric pressure. This releases air bubbles that adhere to the droplets, causing them to float. This technique has the drawbacks of requiring a large volume of air, long retention times for separation, and a high volume of skimming. Another disadvantage is that, if high temperatures are present, high pressure is needed to dissolve the gas in the water.

[0022] Hydrophilic membrane (FM) filtration is susceptible to fouling due to colloidal scale formation, requiring elaborate multi-stage pretreatment, a large base surface area, and complex treatment system designs. High energy consumption is required due to the high power per unit area of ​​membrane. Antiscalants and other pretreatment chemicals require handling and storage.

[0023] Microfiltration (MF) requires high energy, has low efficiency for divalent and monovalent salts and viruses, and iron fouling can be a problem. Ultrafiltration (UF) also requires high energy, iron fouling can be a problem, as can membrane fouling, lower efficiency for low molecular weight organic compounds, and salt rejects may contain radioactive materials.

[0024] Nanofiltration also requires high energy, is less efficient for monovalent salts and low molecular weight organic compounds, and like ultrafiltration, salt rejects can contain radioactive materials.

[0025] The catalytic method for treating produced water requires high temperature and pressure, which favors emulsification.

[0026] The method of preventing precipitation in produced water by injecting hydrate inhibitors at the bottom of the well makes the water look better, but the priority is to separate the crude oil droplets.

[0027] The use of media formed by alternating hydrophilic and hydrophobic fibers are old methods, convenient for the purification of liquids from some organic materials such as petroleum, but the interactions between crude oil droplets and water present complex correlations.

[0028] Ceramic membranes develop internal scale buildup, making their use inadvisable. Oxidation treats small quantities that are not proportional to the enormous quantities of water involved.

[0029] Something similar happens with methods that use microalgae or activated carbon: the quantities of water to be treated are so large that there is no possible proportionality.

[0030] In addition to traditional wastewater separation processes, there are numerous laboratory attempts and methods characterized by promising ideas, but which are not without their pros and cons if implemented on a real-world industrial scale. We will briefly discuss some of these methods.

[0031] The method using melamine sponges with silica granules as an absorbent has the drawback that the manufacturing process for these sponges is complex. Furthermore, the crude oil is removed from the water produced through absorption by the sponge, which complicates its subsequent separation from the sponge, its recovery, and its commercial viability.

[0032] One method currently being explored in computer simulations involves flooding the oil well with a thickening polymer, which would slow down some of the water flow and improve oil extraction. The necessary polymer concentrations are on the order of thousands of parts per million, which is quite excessive. Furthermore, this method is not specifically designed to remove oil droplets from the produced water, which would be preferable.

[0033] Other separation processes that rely on the use of cotton and lotus plants are for limited operations such as oil spills at sea. Porous cotton fabrics are used to remove oil from spills. Furthermore, the subsequent treatment of oil-saturated cotton involves burning it, which generates another type of environmental pollution.

[0034] Carbon- and graphene-based membrane methods are also proposed, but the percentage of crude oil recovered—a crucial piece of information for assessing treatment effectiveness—is not mentioned. Another alternative is the use of cationic double-chain fatty acid surfactants such as esterquat. This method has limited application and achieves only 81.31% to 83.75% oil recovery.

[0035] Another absorption method involves using sawdust at an ideal temperature of 27 degrees Celsius. This is not feasible at sea or in large quantities of water. Furthermore, this method does not indicate the percentage of oil separated. Sawdust absorbs oil well, but it does not offer a good separation rate of up to 70%, and the oil is difficult to separate afterward. Saturated sawdust could be burned to produce energy, but this would simply shift one pollution problem to another. Sawdust is useful for cleaning stains from essentially dry surfaces, but it is of little use when mixed with produced water.

[0036] It is also proposed to use beds of superhydrophilic Al₂O₃ particles both to remove oil from produced water and to remove traces of water from oil. If the pore width in the layers is around 0.3 µm, they are useful for removing oil from oil-in-water (O / W) emulsions, and if the pore width is approximately 40 µm, they are useful for removing water from water-in-oil (W / O) emulsions. However, the problem with produced water is that it is not composed of a single emulsion, but rather of multiple, highly complex emulsions, and this system would not work.

[0037] The carbon steel method is suitable for the treatment of produced water, but it has the disadvantage that the manufacturing cost in addition to the crude oil removal percentage is not optimal.

[0038] The use of aluminum polychloride is also proposed as a method for treating produced water, studying the effects of salinity and temperature, and suggesting an increase in temperature to improve crude oil separation. However, this is logical, since increased temperature enhances molecular movement, and it has been shown that emulsification begins at just 47 degrees Celsius, which is detrimental to crude oil separation. Ultimately, both traditional industrial processes and the more recent, still laboratory-based, attempts to purify produced water suffer from significant shortcomings.Among the methods that exhibit low performance are those that are not scalable to an industrial level (for many laboratory applications), or are very expensive, and some even fail to recover crude oil for later sale to cover purification costs, or in solving one environmental problem, create a new one, and so on. Therefore, a simple procedure is needed that is easy to implement in industry, scalable to large-scale production, highly efficient in purifying produced water, and so economical that it doesn't even increase the cost of crude oil extraction, but rather becomes a means of profiting from the crude oil recovered from the produced water.

[0039] DESCRIPTION OF THE INVENTION

[0040] The term “produced water” refers to water contaminated with traces of oil, in the form of small droplets in the form of a complex emulsion, and which comes from the oil extraction process.

[0041] The present invention comprises contacting the produced water with a granular solid material to destabilize the emulsions, causing the oil droplets to agglomerate, coalesce, and separate by creaming, forming a homogeneous oil phase that floats on the produced water. This oil is recovered and can be sold. The produced water is essentially free of oil droplets.

[0042] The present invention relates, firstly, to a water-insoluble, granular solid material exhibiting three Hansen solubility spheres and comprising one or more components selected from a resin, a wax, and a synthetic polymer, and combinations thereof, such that: a) the resin is selected, without limitation, from mastic resin, rosin resin, dammar resin, myrrh resin, frankincense resin, amber, benzoin resin, pine resin, copal resin, labdanum resin, frankincense resin, natural rubber, elemi resin, turpentine resin, acacia gum resin, guar gum resin, shellac resin, copaiba resin, guaiac resin, guarana resin, gum arabic resin, tamarind resin, and combinations thereof; b) the wax is selected, without limitation, from candelilla wax, carnauba wax, beeswax, white beeswax, jojoba wax, wax of husk, castor wax, cottonseed wax,hemp wax, macadamia wax, baobab wax, sandalwood wax, wheat bran wax, spermaceti, palm wax, rice wax, soybean wax, sunflower wax, cocoloba wax, chamomile wax, shellac, copal wax, peppermint wax, rosehip wax, sacha inchi wax, red algae wax, quinine wax, chicle wax, and fir wax, and combinations thereof; and c) the synthetic polymer is selected not exclusively from polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyamide, polyvinyl chloride, polycarbonate, polyamide-imide, polyacrylonitrile, polymethacrylate, polyurethane, epoxy polymer, polyacetal, polyvinyl acetate, phenol-formaldehyde polymer, unsaturated polyester, urethane-formaldehyde polymer, polyimide, synthetic rubber, butyl rubber, nitrile rubber, silicone rubber, polylactic acid, acid polyglycolic acid, aliphatic polyester, polyphosphorylcholine, polyphenyl sulfide, polyarylenic acid, polytetrafluoroethylene,polyethersulfone, chlorofulfond polyethylene, asphalt, bitumen, tar, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and polyethylene terephthalate copolymer, and combinations thereof.

[0043] The combinations of substances a), b) and c) can be combinations of two components, for example, a) and b), or combinations of three components, i.e., a), b) and c), such that one or more of a), b) and / or c) may be present.

[0044] Hansen's solubility parameters are related to the cohesive energy of the constituent molecules and consist of the dispersion parameter (do), the polarity parameter (dp), and the hydrogen bonding parameter (ΔH). Details on the experimental determination of Hansen's solubility parameters, the concept of the solubility sphere, the radius of the spheres, and their application to numerous physical phenomena of solubilization and surface interactions are described in the book "Hansen Solubility Parameters: A User's Handbook," CRC Press, 2007. Only materials of very complex chemical composition, including nonpolar molecules along with polar molecules and molecules of intermediate polarity, can exhibit up to three solubility spheres. These three spheres are called the lipophilic sphere, the lipophilic-hydrophilic sphere, and the hydrophilic sphere. Few materials can exhibit three solubility spheres.The three solubility spheres are characterized by the following parameters: lipophilic sphere:.

[0045] • The dispersion parameter, do, has values ​​between 15.0 and 18.0 MPa 1 / 2 , and more preferably between 16.0 and 17.0 MPa 1 / 2

[0046] • The polarity parameter, dp, has values ​​between 0.0 and 8.0 MPa 1 / 2 , and more preferably between 3.0 and 6.0 MPa 1 / 2 .

[0047] • The hydrogen bonding parameter, dn, has values ​​between 0.0 and 5.0 MPa 1 / 2 , and more preferably between 0 and 3.0 MPa 1 / 2 . lipophilic - hydrophilic sphere:

[0048] • The dispersion parameter, do, has values ​​between 15.0 and 23.0 MPa 1 / 2 , and more preferably between 19.0 and 21.0 MPa 1 / 2 .

[0049] • The polarity parameter, dp, has values ​​between 5.0 and 14.0 MPa 1 / 2 , more preferably between 7.0 and 11.0 MPa 1 / 2, and more preferably between 8.0 and 9.5 MPa 1 / 2 .

[0050] • The hydrogen bonding parameter, dn, ranges from 8.0 to 15.0 MPa 1 / 2 , more preferably between 11.0 and 14.0 MPa 1 / 2 , and even more preferably 12.0 and 13.0 MPa 1 / 2 . hydrophilic sphere:

[0051] • The dispersion parameter, do, has values ​​between 15 and 19 MPa 1 / 2 , and more preferably between 16 and 17 MPa 1 / 2 .

[0052] • The polarity parameter, dp, has values ​​between 4.0 and 15.0 MPa 1 / 2 , and more preferably between 6.0 and 11.0 MPa 1 / 2 .

[0053] • The hydrogen bonding parameter, dn, has values ​​between 20.0 and 35.0 MPa 1 / 2 , and more preferably between 25.0 and 29.0 MPa 1 / 2 .

[0054] The mastic used as a representative example in the present invention is a resin obtained by making incisions in the bark of the mastic tree (Pistacia lentiscus). The mastic tree grows naturally in coastal areas of Mediterranean and neighboring countries. It has traditionally been used for therapeutic purposes, as a varnish to protect oil paintings, in food to produce chewing gum and dietary supplements, and as an ingredient in cosmetics.

[0055] Natural resins are usually obtained by making incisions in tree trunks, such as mastic trees or pine trees; they are exudates. In contrast, waxes are part of the plant, typically coating leaves and fruits, and do not come off after incisions.

[0056] The chemical composition of mastic resins is very complex and has not yet been fully elucidated. Numerous compounds have been found, including natural polymers; triterpenes (with a tetracyclic skeleton of euphane and damrano, and with a pentacyclic skeleton of oleane and lupane, such as lentisk acid, isosomal acid, oleanolic acid, tirucaroll, etc.); monoterpenic hydrocarbons, oxygenated monoterpenes, and sesquiterpenes; and polyphenols and phytosterols, among other compounds.

[0057] The water-insoluble granular solid material of the invention may further comprise one or more inert components. An inert component is defined in this context as a component that does not inherently possess the properties to purify the produced water or that forms part of the core of the granular solid material without contact with the surface. This component, if present, is in a solid physical state and serves as a filler and / or provides structure and mechanical and / or thermal resistance to the assembly.

[0058] Examples of inert components are: quartz, feldspar, mica, basalt, limestone, dolomite, bauxite, calcined alumina, silicon carbide, natural garnet, natural corundum, natural pozzolans, fly ash, granulated blast furnace slag, silica fume, hematite, magnetite, synthetic iron oxide, soda-lime glass, borosilicate glass, fused silica glass.

[0059] Recycled glass can also be used, as illustrated in example 15 of the invention.

[0060] The proportion of inert component in the water-insoluble granulated solid material may be between 0% and 95%, and preferably between 10% and 50% by weight, with respect to the total weight of the granulated solid material.

[0061] Examples of granulated solid material may include: glass granules, such as recycled glass, coated with a layer of varnish, such as mastic varnish; silica sand granules coated with a layer of varnish, such as mastic varnish; mastic varnish granules and acrylic copolymer; mastic varnish granules and neoprene; mastic varnish granules and polyvinyl chloride (PVC); and mastic varnish granules and polyethylene.

[0062] The granulated solid material defined above can be obtained using any of the following methods listed below:

[0063] When using natural resins, the granulated solid material can be obtained by: a) Traditional method, which includes extraction through incisions in the tree trunk, drying and solidification into irregular fragments, and a final granulation stage through mechanical crushing followed by sieving. This method is preferred for resins such as mastic. b) Spray drying method, which consists of dissolving the resin in a suitable solvent such as turpentine, filtering to remove insoluble residues, and then spray drying to obtain granules of controlled size. Spray drying towers are used, and this method is recommended for resins such as rosin.

[0064] In the case of using natural waxes, the granulated solid material can be obtained through the following stages: a) Melting of the raw wax and purification by hot filtration b) Formation of beads: it is dropped into a granulation tower in the form of a drop onto cold bands or chilled water solidifying into the form of small balls.

[0065] In the case of using synthetic polymers, the granulated solid material can be obtained by one of the following techniques:

[0066] 1. Extrusion and pelletizing comprising the following steps: a) The molten polymer, such as polyethylene, polypropylene, polystyrene, or polyethylene terephthalate, is mixed in an extruder. b) The extruder expels a continuous strand of molten polymer. c) The strand is cooled in a water bath. d) It is cut into cylindrical or spherical pellets.

[0067] 2. Underwater pelletizing comprising the following steps: a) The molten polymer is passed through a perforated plate b) A rotating blade cuts the droplets which fall into cold water and solidify instantly. When the granulated solid material comprises a homogeneous mixture of resins, waxes, synthetic polymers and / or inert components, the procedure can be carried out by: a) Joint dissolution of the resins, waxes and / or synthetic polymers in a solvent and subsequent atomization by spray drying b) Joint melting of the resins, waxes and / or synthetic polymers and granulating the resulting melt by forming beads in a granulation tower, extrusion and pelletizing, or underwater pelletizing.

[0068] When the granulated solid material consists of a coated inert core, the core being surrounded by resins, waxes or synthetic polymers alone or mixtures thereof, the procedure comprises the following steps:

[0069] 1. Formation of the inert core using one of the following techniques: a) Crushing and classification by mechanical fragmentation of a massive material in the form of rock, block, or ingot. b) Flux granulation, which involves melting the material and passing it through jets or pouring it onto rotating discs or fluidized beds, forming droplets that solidify. This is suitable for soda-lime glass or borosilicate glass microspheres. c) Atomization in a process similar to spray drying but for molten materials: The liquid is sprayed and solidifies instantly. This process is preferred for fused silica spheres. d) Cutting into cylindrical or spherical granules.

[0070] 2. Coating the inert core with resins, waxes, synthetic polymers or combinations thereof.

[0071] The preferred procedure for the case where the granulated solid material is in the form of a coated inert core comprises the following steps: a) Melting the coating material or dissolving it in a solvent to obtain a fluid material; b) Rotating the inert core in the drum of a coating machine; c) Spraying the coating material onto the rotating inert cores and applying hot air to aid in solidifying the coating material. According to a preferred embodiment of the invention, the granulated solid material defined above comprises mastic.

[0072] According to a preferred embodiment of the invention, the granulated solid material defined above comprises mastic and at least one inert material, for example mastic coating at least one inert material.

[0073] According to a preferred embodiment of the invention, the granulated solid material defined above is mastic.

[0074] The present invention also relates to a process for purifying water produced in the petroleum industry, comprising bringing the above-defined granulated solid material into contact with the produced water, thereby obtaining clean water.

[0075] According to the procedure of the invention, the contact of the granulated solid material with the water must be an intimate contact.

[0076] Depending on the specific implementation, the contact can be carried out using any of the usual techniques in the industry such as direct mixing and subsequent separation by filtration or centrifugation, or by flow of the produced water over a fixed bed made up of the granulated solid material.

[0077] The contact time between the granulated solid material and the produced water can be between 30 seconds and 3 minutes, for example, 1 minute, and preferably between 30 seconds and 1 minute.

[0078] In the procedure of the invention, the operating temperature, i.e., the temperature at which it is carried out, is between 0 °C and 100 °C, preferably between 15 °C and 95 °C, more preferably between 25 °C and 75 °C, and even more preferably between 40 °C and 50 °C, which is the temperature at which the water produced after being separated from the oil in the extraction from the subsoil is usually found.

[0079] The concentration of granulated solid material (e.g., mastic) in the stirred-tank process of the invention may be between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm relative to the treated water. In the fixed-bed process of the invention, the circulation rate of the treated water must be such that the Reynolds number is between Re = 1 and Re = 10. 7 , preferably between Re = 1 and Re = 10 5 , more preferably between Re = 10 and Re = 2400, and even more preferably between Re = 50 and Re = 500

[0080] Optionally, one or more additives can be added.

[0081] The additives are of two types: a) Additives that are added to the produced water b) Additives that are added to the granulated solid material.

[0082] Additives added to produced water can be, for example: a) common salt b) a salt soluble in produced water c) a hydrocarbon in a liquid state at the operating temperature, such as xylene or cyclohexane d) a substance that increases the ionic strength of water e) a substance in which petroleum is partially or totally soluble.

[0083] When the additive is a hydrocarbon in a liquid state at the operating temperature, it can be any alkane, alkene, or alkyne from C5 to C20, whether linear or branched, cyclic aliphatic or cyclic aromatic. Alternatively, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, and other analogues can also be used, although this list is not exhaustive.

[0084] According to specific implementations, the additive added to the produced water is selected from: a) common salt, b) a salt soluble in the produced water, and c) a substance that increases the ionic strength of the water. Its concentration is between 0 g / L and 200 g / L, preferably between 100 g / L and 180 g / L, and more preferably between 75 g / L and 125 g / L of produced water. If the additive is a salt soluble in the produced water, the concentration mentioned includes the salt naturally present in the produced water at the well outlet.

[0085] The additives added to the granulated solid material can be, for example: a) a hydrocarbon in a liquid state at the operating temperature, such as xylene or cyclohexane; b) a substance in which petroleum is partially or totally soluble.

[0086] When the additive is a hydrocarbon in a liquid state at the operating temperature, it can be any of those mentioned above.

[0087] The amount of additive or additives that can be added to the granulated solid material (e.g., mastic) is in a proportion with respect to the mass of granulated solid material (e.g., mastic) plus additive, between 0% and 75%, more preferably between 10% and 50%, and even more preferably between 15% and 30%. That is, 0% means that it does not contain any additives.

[0088] According to particular realizations, the additive that is added to the granulated solid material is a hydrocarbon in a liquid state at the operating temperature, and the concentration of granulated solid material, preferably mastic, plus liquid hydrocarbon is between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm with respect to the produced water.

[0089] An example of a hydrocarbon used as an additive is xylene, preferably as a mixture of its ortho, meta, and para isomers. Another example of a hydrocarbon used as an additive is cyclohexane.

[0090] When using a mixture of granulated solid material, such as mastic, and xylene, or of granulated solid material and cyclohexane, the amount of xylene or cyclohexane can range from 5 to 75% by weight of the total mixture; for example, from 15 to 30% by weight of the mixture of granulated solid material, such as mastic, and xylene or cyclohexane. For example, a treatment can be carried out with 100 ppm of a mixture consisting of 75 ppm of mastic, with the commercial particle size distribution, and 25 ppm of xylene. The particle size distribution should be such that, approximating the granulated solid material particles to equivalent spheres of equal surface area, the specific surface area is between 0.5 m² and 0.5 m². 2 / kg and 30m 2 / kg, more specifically between 2.0 m 2 / kg and 20m 2 / kg, and even more preferably between 2.0 m 2 / kg and 5.0 m 2 / kg.

[0091] According to particular embodiments, the procedure comprises the following steps: a) mixing the granulated solid material, and optionally the additives, with the produced water, b) keeping in contact for a time between 20 seconds and 3 minutes, and c) recovering the granulated solid material.

[0092] According to additional specific embodiments, the process comprises: a) mixing the granulated solid material, and optionally the additives, with the produced water containing the oil droplets in a continuously fed, stirred tank; b) continuously conveying the mixture from the previous stage to a settling tank where the recovered crude oil is continuously extracted from the top and the produced water and granulated solid material are continuously extracted from the bottom; c) continuously separating the granulated solid material from the produced water.

[0093] The granulated solid material can be recovered in stage c) by various techniques, such as filtration, centrifugation or any other industrial technique.

[0094] The granulated solid material can be cleaned after its recovery in stage c) with a stream of steam or natural gas and reincorporated into stage a).

[0095] The invention's procedure can be carried out in three operating modes: batch, semi-continuous, or continuous. Likewise, any type of contact commonly used in industry is possible, including stirred tank, plug flow, combinations of both, and single or multiple contacts. However, the continuous method is preferred, using several batteries in parallel, each consisting of several purification units also in parallel, as described in the section "Unit for the Continuous Method" and represented by Figure 1, Figure 2, and Table 1.

[0096] According to particular embodiments, the procedure is carried out in batches, is discontinuous, and comprises the following stages: a) mixing in an agitated tank the granulated solid material, and optionally the additives, with the produced water, b) letting it stand so that the creaming takes place, then separating the recovered crude oil from the top of the tank, and the purified produced water along with the granulated solid material from the bottom, and c) recovering the granulated solid material.

[0097] The granulated solid material can be recovered in stage c) by various techniques, such as filtration, centrifugation or any other industrial technique.

[0098] The granulated solid material can also be cleaned after its recovery in stage c) with a stream of steam or natural gas and reincorporated into the next batch in stage a).

[0099] According to specific implementations, the process is a continuous process comprising the following stages: a) mixing the granulated solid material, and optionally the additives, with the produced water in a continuously fed, agitated tank; b) continuously conveying the mixture from the previous stage to a settling tank where the recovered crude oil is continuously extracted from the top and the produced water and granulated solid material are continuously extracted from the bottom; c) continuously separating the granulated solid material from the produced water.

[0100] The granulated solid material can be recovered in stage c) continuously by various techniques, such as filtration, centrifugation or any other industrial technique.

[0101] It can also be cleaned with a stream of steam or natural gas and reincorporated into the next batch in step a).

[0102] According to specific embodiments, the procedure is carried out continuously and comprises: 1) placing the granulated solid material in a fixed bed reactor,

[0103] 2) introduce the produced water into the reactor,

[0104] 3) to make the produced water flow between the granules of the granulated solid material in the reactor, breaking the emulsion of the crude oil droplets contained in the produced water,

[0105] 4) separate the oil droplets obtained mixed with the gaseous carrier fluid,

[0106] 5) recover the granulated solid material,

[0107] 6) recover the clean water produced, and

[0108] 7) recover the crude oil.

[0109] In the case of carrying out the procedure in continuous mode, the granulated solid material is recovered in stage c) continuously by filtration or centrifugation.

[0110] The granulated solid material can be cleaned with a stream of steam or natural gas and reincorporated into the next batch in step a).

[0111] The entrainment of crude oil can be carried out using a gaseous carrier fluid, which can be air or a gaseous hydrocarbon, such as gas or steam, at the operating temperature. The gaseous carrier fluid is introduced into the reactor from the bottom.

[0112] According to more specific implementations, the continuous process involves adding common salt and / or xylene (or another liquid hydrocarbon at the operating temperature, as an extraction enhancer) to the untreated produced water. The liquid can be any of those mentioned above.

[0113] Untreated produced water can enter the reactor under pressure from the desalters during the oil extraction stage. In standard oil extraction techniques, the term "desalters" refers to the initial, primary stage of separating the produced water (which is saline) from the crude oil, not to an operation that removes salt from the produced water. Optionally, the gaseous carrier stream is a gaseous hydrocarbon, such as natural gas, which is enriched with oil droplets in the reactor, collected for storage, and later use.

[0114] Optionally, the gaseous carrier fluid stream is a gaseous hydrocarbon, such as natural gas, which in the reactor is enriched in oil with the oil droplets obtained, is condensed and collected separately: on one side, the crude oil, and on the other side, the exhausted gaseous fluid at the operating temperature.

[0115] Optionally, the procedure involves recirculating some of the clean produced water back into the fresh produced water inlet stream to be reintroduced into the reactor.

[0116] The process may also include a purification stage of the granulated solid material used to separate any remaining traces of oil. In this case, the process involves completely emptying the reactor of produced water and introducing a gaseous fluid, such as a gaseous hydrocarbon, which will carry away the small traces of oil, preferably natural gas. Alternatively, other liquid organic solvents can be used, but they are not recommended due to their more difficult handling and the unnecessary additional cost. Natural gas is preferable to air because of its affinity for oil, its ability to penetrate all the spaces between the grains of the granulated solid material, such as mastic, and because it is a free or very low-cost raw material that comes from the same oil wells where the crude oil is being extracted.

[0117] In this respect, the continuous process of the invention has the additional advantage of preventing the natural gas used as a gaseous fluid from being burned directly in flares. Thus, its use as a means of cleaning the granulated solid material provides an extra benefit.

[0118] Preferably, since the cleaning process for granular solid material requires a downtime, to ensure the plant continues operating uninterrupted, at least two purification units are used. While one is being cleaned, the other operates normally. This procedure reduces oil concentrations in the produced water from around 300 ppm to less than 0.1 ppm, virtually eliminating any trace of crude oil.

[0119] The process requires very small doses, even less than 100 ppm, of the granulated solid material or the granulated solid material plus an additive, such as xylene, and can be reused for at least 10 purification cycles. Raw material and operating costs are very low, making the process highly profitable due to its low cost and greater efficiency compared to other known processes in this technological field. This process can achieve the goal of zero oil emissions into the environment.

[0120] Mastic and other similar natural resins, apart from their ability to remove crude oil droplets very effectively, offer a number of advantages:

[0121] 1) Relatively cheap compared to other materials.

[0122] 2) Available.

[0123] 3) Non-toxic and environmentally friendly.

[0124] 4) Its chemical structure is similar to hydrocarbons as organic compounds.

[0125] 5) Demulsifier, because it resembles the resins used in the production of expensive demulsifiers that help separate water from crude oil.

[0126] 6) Natural resource that can be reproduced and planted from trees and not synthesized.

[0127] 7) Easy to transport, package and use.

[0128] 8) They do not affect the properties of the oil that is isolated from the produced water.

[0129] 9) In particular, mastic, as it is produced in many African, Asian and European countries, cannot be monopolized, so competition prevents a single agent from controlling prices.

[0130] The present invention further provides a produced water purification unit not previously known among chemical industry equipment. It combines a fixed bed filled with granules of solid material, such as mastic, suspended within a hybrid reactor, a hybrid between a perfect-mix and a plug-flow design, with the additional capabilities of accelerating the creaming of oil extracted from the produced water by means of air, natural gas, or another gaseous hydrocarbon at the operating temperature, and subsequent beneficiation of that crude oil. More particularly, the produced water purification unit comprises: a) a vessel including: i. an inlet for the produced water,

[0131] i. an injector for introducing and dispersing the produced water into: iii. an inner container with respect to container a), formed by a metal grid for disposing of the solid material, such as mastic; iv. a gas inlet that is connected to a diffuser for bubbling, v. a gas outlet for carrying away the recovered oil, and vi. an outlet for the purified produced water; b) a condenser for separating the recovered oil and recirculating the gases; c) optionally means for recirculating produced water arranged at the outlet of the purified produced water for reprocessing.

[0132] The purification unit meets all the requirements regarding flow rate, temperature, pressure, construction materials, etc., and operating parameters required for its industrial implementation. Figure 1 shows an example schematic of a prototype purification unit according to the invention, and Table 1 provides a legend for its various constituent elements.

[0133] Table 1.- Legend of the unit for continuous purification of water produced with mastic (Image in Figure 1)

[0134] Figure 2 shows an explanatory flow diagram of how the aforementioned continuous processed water purification unit operates according to an embodiment of the invention, applicable to industry. The untreated water (201), or water to which additives such as common salt and / or xylene (or another extraction-enhancing hydrocarbon) have been added, is introduced into the purification unit into an internal chamber formed by a fine metal mesh (204) containing granulated solid material (203). The mesh allows the entry and exit of water and gases but prevents the exit of the granulated solid material. The untreated water enters the unit under the pressure of the water exiting the desalination plants during the previous groundwater extraction stage, thus eliminating the need for pumps and additional energy costs.The injector (202) distributes the produced water among the granulated solid material, causing the multiple emulsion of crude oil droplets (212) to break down and coalesce into slightly larger droplets (211). These droplets are represented in the figure as black dots and are still contained within the produced water. The process is enhanced by the action of the carrier fluid—air, natural gas, or any gaseous hydrocarbon at the operating temperature—which is introduced through the bottom of the unit (204). The bubbles (210) formed by a diffuser (209) carry the oil droplets (212) to the reactor outlet (213), where they exit mixed with the air, natural gas, or gaseous hydrocarbon at the operating temperature.This reactor outlet line, carrying the carrier fluid (213), passes through a valve (216) that either directs it through a second line (215) for the sale of natural gas or gaseous hydrocarbons at the operating temperature, enriched with petroleum; or directs it through a third line (217) to the condenser (218). In the condenser (218), the crude oil (219) is collected and sent to storage for later sale through a fourth line (219), and the exhausted air, natural gas, or gaseous hydrocarbons at the operating temperature are collected through a fifth line (207). A fresh stream of carrier gas, either air, natural gas, or gaseous hydrocarbon at operating temperature, enters through a sixth conduit (206) and mixes with the exhausted carrier gas that is recirculated through the fifth conduit (207), to form the carrier gas stream of conduit (205) that feeds the diffuser (209).To prevent the entrainment gas flow from pipe (206) from entering the fifth pipe (207), a non-return valve (208) is installed. The treated treated water exits the unit through a seventh pipe (214) for storage and subsequent use, or is discharged freely. Optionally, to improve the unit's efficiency, part of the flow from the seventh pipe (214) can be recirculated through the recirculation pipe (220) to the fresh treated water inlet pipe (201).

[0135] In the case of mash, being non-porous, it does not absorb oil, but it causes the emulsion droplets to coalesce into larger droplets. Even so, small amounts of these droplets remain adsorbed on its surface during the operation. Some droplets may also become trapped in the spaces between the grains. In any case, the mash tends to lose effectiveness. Therefore, after the appropriate operating time, the mash is cleaned of these remaining oil residues. To do this, the unit is completely emptied of produced water, and steam, natural gas, or any gaseous hydrocarbon is introduced through the same inlet (205). This will carry away any small traces of oil that may be present on the mash surface, which will then exit through the reactor's outlet pipe (213) carrying the carrier fluid.Other liquid organic solvents could be used, but they are not recommended due to their more difficult application and the unnecessary additional cost. Natural gas is preferable to air because of its affinity for petroleum, its ability to penetrate all the spaces between the mastic kernels, and because it is a free or very low-cost raw material sourced from the same oil wells where the crude oil is extracted. In many cases, this natural gas is burned directly in flares. Using it to clean the mastic provides an added benefit. Since the mastic cleaning process requires downtime, to ensure the facility continues operating uninterrupted, it is necessary to have at least two, or preferably more than two, banks of purification units. While one bank is being cleaned, the other must operate normally.

[0136] The present invention also relates to the use of water-insoluble granulated solid material having three Hansen solubility spheres, as defined above, for the recovery of produced water in the petroleum industry, and preferably to the use of mastic as a granulated solid material for the recovery of produced water in the petroleum industry.

[0137] As a specific object, the invention relates to a produced water recovery process comprising bringing granulated mastic into intimate contact with produced water containing droplets of crude oil.

[0138] This section of the memory up to the beginning of the section describing the figures refers exclusively to this object of the invention.

[0139] According to particular embodiments, the invention relates to a process that consists of bringing granulated mastic into intimate contact with produced water containing droplets of crude oil.

[0140] According to these embodiments relating to the use of mastic, the operating temperature is between 0 °C and 100 °C, preferably between 25 °C and 75 °C, and more preferably between 40 °C and 50 °C.

[0141] According to these embodiments, additives can be added, which may be, but are not exclusive to: common salt; xylene; any salt soluble in the produced water; any hydrocarbon in a liquid state at the operating temperature between 0 °C and 100 °C, preferably between 25 °C and 75 °C, and more preferably between 40 °C and 50 °C; any substance that increases the ionic strength of water; any substance in which petroleum is partially or totally soluble.

[0142] The mastic can be of any geographical origin, but it must meet the following requirements: a) It must present three solubility spheres according to the Hansen solubility parameter model b) The lipophilic sphere must meet the following characteristics: i. The dispersion parameter, 5 D , it must present values ​​between 15.0 and 18.0 MPa 1 / 3 , and more preferably between 16.0 and 17.0 MPa 1 / 3

[0143] i. The polarity parameter, 5 P , must present values ​​between 0.0 and 8.0 MPa 1 / 3 , and more preferably between 3.0 and 6.0 MPa 1 / 3 iii. The hydrogen bonding parameter, 5 H , must present values ​​between 0.0 and 5.0 MPa 1 / 3 , and more preferably between 0 and 3.0 MPa 1 / 3 c) The lipophilic-hydrophilic sphere must meet the following characteristics: iv. The dispersion parameter, 5 D , must present values ​​between 15.0 and 23.0 MPa 1 / 3, and more preferably between 19.0 and 21.0 MPa 1 / 3 . v. The polarity parameter, 5 P , must present values ​​between 5.0 and 14.0 MPa 1 / 3 , more preferably between 7.0 and 11.0 MPa 1 / 3 , and more preferably between 8.0 and 9.5 MPa 1 / 3 . vi. The hydrogen bonding parameter, 5 H , will range between 8.0 and 15.0 MPa 1 / 3 , more preferably between 11.0 and 14.0 MPa 1 / 3 , and even more preferably 12.0 and 13.0 MPa 1 / 3 d) The hydrophilic sphere must meet the following characteristics: vii. The dispersion parameter, 5 D , it must present values ​​between 15 and 19 MPa 1 / 3 , and more preferably between 16 and 17 MPa 1 / 3 . viii. The polarity parameter, 5 P , must present values ​​between 4.0 and 15.0 MPa 1 / 3 , and more preferably between 6.0 and 11.0 MPa 1 / 3 ix. The hydrogen bonding parameter, 5 H , must present values ​​between 20.0 and 35.0 MPa1 / 3 , and more preferably between 25.0 and 29.0 MPa 1 / 3 e) It should be slightly soluble in water, but preferably insoluble in water. f) The density should be between 1000 kg / m³ 3 and 1600 kg / m 3 but preferably between 1050 kg / m 3 and 1400 kg / m 3 g) The particle size distribution must be such that, approximating the particles to equivalent spheres of equal surface area, the specific area is between 0.5 m 2 / kg and 30m 2 / kg, more specifically between 2.0 m 2 / kg and 20m 2 / kg, and even more preferably between 2.0 m 2 / kg and 5.0 m 2 / kg.

[0144] Xylene or any other liquid hydrocarbon at the operating temperature may be optionally added to the mastic, in a proportion relative to the mass of mastic plus the xylene or liquid hydrocarbon at the operating temperature, between 0% and 75%, more preferably between 0% and 50%, and even more preferably between 15% and 30%. The concentration of common salt or any water-soluble salt, including the salt naturally present in the water produced at the well outlet, is between 0 g / L and 200 g / L, preferably between 100 g / L and 180 g / L, and even more preferably between 75 g / L and 125 g / L.

[0145] More specifically, the batch or discontinuous process consists of the following steps: d) Mixing the mash, and optionally the additives, in a stirred tank with the produced water containing the oil droplets. e) Allowing the mixture to settle for creaming, then separating the recovered crude oil from the top of the tank, and the purified produced water from the bottom, along with the mash, which can be recovered by filtration, centrifugation, or any other industrial technique, cleaned with a stream of steam or natural gas, and reincorporated into the next batch in step a).

[0146] More specifically, the continuous process consists of the following stages: d) Mixing in a continuously fed, agitated tank of the mash, and optionally the additives, with the produced water containing the oil droplets. e) The mixture from the previous stage is continuously conveyed to a settling tank where the recovered crude oil is continuously extracted from the top, and the produced water and mash are continuously extracted from the bottom. f) The mash is continuously separated from the produced water by filtration, centrifugation, or any other industrial technique and recirculated to stage a) of mixing, after being cleaned with a stream of steam or natural gas.

[0147] The concentration of mastic plus xylene or other liquid hydrocarbon at the operating temperature, in the batch or discontinuous process, may be between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm.

[0148] The concentration of mastic plus xylene or other liquid hydrocarbon at the operating temperature, in the continuous process, is between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm. A further object of the invention, according to particular embodiments relating to the use of mastic, is a produced water purification and oil recovery unit consisting of: a) A vessel that includes:

[0149] ...an inlet for the water produced

[0150] ...an injector that introduces and disperses the water produced in:

[0151] a) An inner container formed by a metal grid containing mastic; iv. a gas inlet leading to a gas diffuser for bubbling; v. a gas outlet carrying the recovered oil; and vi. an outlet for the purified produced water. b) A condenser to separate the recovered oil and recirculate the gases. c) Optionally, a recirculation at the outlet of the purified produced water for reprocessing if necessary.

[0152] The produced water purification and oil recovery unit defined in the preceding paragraph operates according to the following steps: a) Produced water enters the unit from the outlet water isolators during the subsurface extraction stage. b) The injector distributes the produced water among the seedling grains, breaking down the multiple emulsion of crude oil droplets and coalescing them into larger droplets. c) Air, natural gas, or any gaseous hydrocarbon is introduced at an operating temperature between 0°C and 100°C, preferably between 25°C and 75°C, and even more preferably between 40°C and 50°C, to form bubbles with the diffuser and entrain the larger droplets formed in the previous step. d) The air, natural gas, or any gaseous hydrocarbon exits at the operating temperature mentioned in point c) above, enriched with the dissolved oil.e) Optionally, direct beneficiation of natural gas or gaseous hydrocarbon at the operating temperature mentioned in point c) above, enriched with oil. f) Optionally, condensation of the oil in the condenser for separation and beneficiation, and recycling of the air, natural gas, or gaseous hydrocarbon at the operating temperature mentioned in point c) above for reuse in the unit according to operation f). g) Use of a non-return valve at the condenser outlet to prevent fresh air, natural gas, or gaseous hydrocarbon at the operating temperature mentioned in point c) above, entering the unit, from entering the condenser. h) Optionally, recycling of treated produced water to improve the performance of the produced water treatment and oil recovery unit.

[0153] An additional object of the invention, according to particular embodiments relating to the use of mastic, is a continuous process that includes using batteries of produced water purification and oil recovery units, consisting of the following: h) The untreated produced water is optionally mixed with the additives, as mentioned above, i) Several produced water purification units are connected in parallel in the form of a battery (5). j) At least two batteries of units are connected in parallel, where while one or more batteries are in purification mode, the rest are in cleaning mode, so that situations such as the following can occur: k) When a battery is in water purification mode, unprocessed produced water and air or natural gas or other gaseous hydrocarbon enter the battery at the operating temperature between 0°C and 100°C, preferably between 25°C and 75°C, and more preferably between 40°C and 50°C,l) When a battery is in seedbed cleaning and regeneration mode, the unprocessed produced water and air at the operating temperature mentioned in point k) enter the battery. m) When a battery is in water purification mode, air, or natural gas or gaseous hydrocarbon, with or without enriching crude oil, exits through (13), depending on whether it has been passed through the condenser of the battery's purification units. n) When a battery is in seedbed cleaning and regeneration mode, natural gas or gaseous hydrocarbon, with or without enriching crude oil, exits, depending on whether it has been passed through the condenser of the battery's purification units. o) The oil recovered in the condenser exits and is taken to storage.for subsequent packaging and marketing. p) The produced water is discharged and stored until it is used or disposed of. q) The produced water in the storage tank will have a residual crude oil concentration value that is the average between the initial value of the purification process and the final value of the purification process just before switching to mash regeneration mode. r) If xylene or another liquid hydrocarbon is used as an additive at the operating temperature mentioned above in k), it is discharged along with the oil and natural gas. s) Common salt or water-soluble salt is discharged along with the produced water.

[0154] BRIEF DESCRIPTION OF THE FIGURES

[0155] Figure 1.- Example diagram of a continuous purification unit, prototype according to the invention. It consists of a gas and air outlet stream (101), gas and air outlet stream valve (102), thermocouple orifice inlet (103), produced water jet inlet (104), reactor vessel (105), gas and air heater (106), insulation layer (107), mastic grains (108), gas and air jet (109), gas and air flow meters (110), AP meter (111), device body container (112), Pt100 thermocouple (113), purified water outlet (114), produced water inlet (115), gas inlet (116), water pump (117), produced water storage (118), 5 bar pressure gauge (119), pure water outlet stream (120), produced water inlet stream (121), gas outlet pipe (122), digital air and gas temperature regulator (123), digital temperature regulator of the reactor vessel (124),reactor temperature voltage controller (125), air and gas temperature voltage controller (126), water recycling valve (127), gas and air recycling valves (128), AP pump signal light on (129), air and gas heater power indicator light (130), power switch (131), power cable (132), relays (134), air compressor (135) and gas supply (136).

[0156] Figure 2.- Flow diagram of the continuous processed water purification unit. The untreated water produced (201), or water to which additives such as common salt and / or xylene (or another extraction-enhancing hydrocarbon) have been previously added, is introduced into the purification unit into an internal chamber formed by a fine metal mesh (204) containing the mastic seeds (203). The operating process of this purification unit has been explained previously based on the function of the injector (202).

[0157] Figure 3.- Schematic of the steps for batch purification of the water produced using as an example mastic as a granulated solid material according to the invention.

[0158] Figure 4. Standard line of oil concentration, Cp, expressed in ppm versus absorbance at a wavelength of 311 nm in tetrachloroethane. It allows spectrophotometric analysis of the residual oil concentration in the produced water after extraction in a test tube using equal volumes of produced water and tetrachloroethane as the extraction agent.

[0159] Figure 5.- Flow diagram of the industrial-scale batch treatment of produced water. In stage 1, the reactor, which is a stirred tank (504), is charged with produced water entering through a produced water line (501). Additives (503), if used, are added, and finally the mastic (502). The supernatant layer of crude oil is separated by the crude oil outlet stream (505) and stored for later packaging and sale. The mixture of produced water with the granulated solid material and the optionally added common salt is discharged from the bottom via the water outlet stream (506) and conveyed to a granulated solid material separation unit (507).The extract exiting through an extract line (508) consists of the purified produced water plus optionally added common salt, and the raffinate (509) consists of the granulated solid material with small traces of petroleum that must be removed in the regenerator (510). The regeneration fluid is introduced into the regenerator (510) through line (511) (regenerator fluid inlet line). The regeneration fluid, carrying any petroleum residue contained in the granulated solid material, exits through line (512) (regenerator fluid outlet line). The regenerated granulated solid material is recirculated through the recirculation line (513) back to the stirred tank (504), which must be operating in stage 1.

[0160] Figure 6.- Flow diagram of the produced water treatment process according to a continuous stirred tank model. Produced water is continuously introduced into tank (602) via pipe (601). Optional additives are introduced into the produced water via pipe (604) (additive inlet pipe), and granulated solid material from the regeneration stage (610) is introduced via the recirculation stream (603). The treated produced water, mixed with the granulated solid material and optional additives, passes to the settling tank (605). The continuously recovered oil is removed via the oil outlet stream (606), and if xylene or another liquid hydrocarbon is used as an additive at the operating temperature, it will also be discharged via the oil outlet stream (606) dissolved with the oil.The treated produced water, along with the granulated solid material and common salt, is collected at the base of the settling tank (605) and conveyed to a granulated solid material separation unit (607). The treated produced water and common salt are discharged through pipe (608) (treated water and salt outlet pipe). The granulated solid material is then conveyed through pipe (609) (granulated solid material stream) to the granulated solid material regenerator (610), which can operate by introducing steam, natural gas from the oil being extracted from the wells, or any hydrocarbon or hydrocarbon mixture in a gaseous state at the operating temperature via pipe (611) (steam line). Waste from the granulated solid material regenerator (610), carried by the natural gas or gaseous hydrocarbons, is removed through pipe (612) (waste line).

[0161] Figure 7.- Flow diagram of the purification of the produced water according to a continuous process with a battery of produced water purification units.

[0162] Figure 8.- Residual oil concentration, Cp (ppm) after treatment of produced water with 10 types of mastic as medium-sized granulated solid materials versus mastic concentration, Cm (ppm). The most efficient mastices are numbers 10, 3, and 2, with residual produced water concentrations in the produced water after treatment always below 2 ppm.

[0163] Figure 9.- Residual oil concentration, Cp (ppm) after treatment of produced water with 10 types of mastic as medium-sized granulated solid materials versus the concentration of xylene as an additive, Cx, expressed as a % of the mastic plus xylene concentration, Cm. The concentration Cm is equal to 100 ppm. The minimum residual oil concentration value is in all cases when Cx = 25%, that is, when it is 25 ppm.

[0164] Figure 10.- Residual oil concentration, Cp (ppm) after treatment of produced water with 10 types of mastic as granulated solid materials versus specific area expressed in m² 2 / kg. The concentration of residual oil decreases in all cases when the specific surface area of ​​the grains increases, remaining almost constant from about 4 m 2 / kg.

[0165] Figure 11.- Residual oil concentration, Cp (ppm) after treatment of produced water with 10 types of mastic as medium-sized granulated solid materials versus salt concentration as an additive, Cs (ppm). The salt concentration includes the naturally occurring salt in the produced water plus the added salt. The optimum concentration is 160 g / l in all cases.

[0166] Figure 12.- Solubility spheres of mastic 3. a) Three-dimensional representation, b) Two-dimensional representation of the polarity solubility parameter, do (MPa 1 / 2 ), versus the hydrogen bond solubility parameter, dn (MPa 1 / 2 ); c) two-dimensional representation of the dispersion solubility parameter, do (MPA 1 / 2 ) versus the polarity solubility parameter, dp, (MPa 1 / 2 ); d) two-dimensional representation of the polarity solubility parameter, dp (MPa 1 / 2), versus the hydrogen bond solubility parameter, dn (MPa 1 / 2 Each solvent used in the test is represented by a square dot. The size of the dot is proportional to the molar volume. Dark dots represent solvents with which the mastic interacts because it dissolves, disperses, or forms a gel. White dots indicate that the mastic does not interact with that solvent. The estimated absolute error in the radius of each sphere is also represented with finer lines. The centers of the lipophilic, lipophilic-hydrophilic, and hydrophilic spheres are indicated by the labels L, LH, and H, respectively.

[0167] Figure 13.- Two-dimensional representation of the polarity solubility parameter, dp (MPa 1 / 2 ), versus the hydrogen bond solubility parameter, dn (MPa 1 / 2), where the centers of the lipophilic spheres, L, for the seedbeds are represented. White dots represent seedbeds with acceptable performance in removing oil from the produced water, gray dots represent high-performance seedbeds, and black dots represent maximum-performance seedbeds.

[0168] Figure 14.- Two-dimensional representation of the polarity solubility parameter, dp (MPa 1 / 2 ), versus the hydrogen bond solubility parameter, OH (MPa 1 / 2 ), where the centers of the lipophilic-hydrophilic spheres, LH, for the masts are represented. White dots represent masts with acceptable performance in removing oil from the produced water, gray dots represent high-performance masts, and black dots represent those with maximum performance.

[0169] Figure 15.- Two-dimensional representation of the polarity solubility parameter, dp (MPa 1 / 2 ), versus the hydrogen bond solubility parameter, dn (MPa 1 / 2), where the centers of the hydrophilic spheres, H, for the seedbeds are represented. White dots represent seedbeds with acceptable performance in removing oil from the produced water, gray dots represent high-performance seedbeds, and black dots represent maximum-performance seedbeds.

[0170] Figure 16. Residual oil concentration in the produced water, Cp (ppm), treated with the continuous method, using the produced water purification unit according to the invention, versus process time expressed in minutes. The mastic used is size 10 in three particle sizes. The purification process is more effective as the particle size decreases. As time progresses, the residual oil concentration increases in all three cases according to a quadratic function. At minute 1, the residual oil concentration is in the range of 0.1 ppm - 0.4 ppm, and at 10 minutes it is in the range of 1.5 ppm - 2.1 ppm. In any case, the purification efficiency of the produced water with the continuous method, using the purification unit according to the invention, is exceptionally good.

[0171] EXAMPLES

[0172] EXAMPLE 1

[0173] Crude oil and synthetic produced water. The crude oil used comes from the Rumaila oil field (Basra, Iraq). It is a medium-light crude oil with the characteristics shown in Table 2.

[0174] Table 2.- Characteristics of the crude oil used

[0175] Because the produced water obtained directly from the crude oil extraction process in the oil field fluctuates from batch to batch, and because importing large quantities from an oil field located thousands of kilometers away is not straightforward, the decision was made to synthesize produced water in the laboratory with consistent characteristics. The procedure involves adding and mixing 150 ppm of crude oil to an 80,000 ppm sodium chloride solution using a magnetic stirrer. This sodium chloride concentration is the typical average value found in the water produced in the Rumaila field. The mixing vessel is kept in a water bath at 50 °C to simulate the actual conditions under which produced water is formed in the industrial facilities of the oil field. Stirring is maintained for two hours or more until all the crude oil is completely emulsified in the water.Optionally, in cases where the effect of salinity on the purification of the produced water is studied, once generated, the extra amount of sodium chloride to be tested is dissolved.

[0176] Tested seedbeds

[0177] Ten types of mastic from different geographical locations were tested as granular solid material. Table 3 shows the origin of the mastic, as well as its density and water solubility. In all cases, the mastic is denser than water, which is a technological advantage for its use in fixed-bed packed columns. Water solubility is also a parameter of interest, as it is necessary for the mastic to be as insoluble as possible, since it must come into contact with the produced water and not dissolve in it. In the case of mastic types 6 and 7, there is some solubility with the formation of a viscous gel over the long term. This could be a disadvantage, although they were tested nonetheless, since they are generally very poorly soluble.The remaining mastic is completely insoluble in water, so it is not expected that it will be consumed by dissolution when it comes into contact with the produced water, or when treated with steam to regenerate it after the oil recovery process.

[0178] Table 3.- Origin of the tested seedlings, density and solubility in water

[0179] The present invention is not limited exclusively to these specific seedbeds, but extends to any other type of seedbed from any geographical origin. The ones tested are merely illustrative examples.

[0180] EXAMPLE 2

[0181] Laboratory procedure for separating crude oil from produced water

[0182] Under agitation, 15 mg of mastic containing 50 mg of xylene are mixed with 100 ml of produced water synthesized according to Example 1, to which 2 grams of sodium chloride have also been added. Contact is maintained for only 1 minute, at which point the crude oil emulsion breaks down. After settling, or centrifugation to accelerate the process, the crude oil droplets coalesce and separate as a supernatant phase on the produced water, which becomes clear and transparent (See Figure 3). The procedure, therefore, does not consist of the absorption of the oil into the mastic, as might initially be suspected. Rather, and this is the most surprising and unexpected aspect, the presence of the mastic causes the multiple emulsions formed by the oil to break down, separating the pure crude oil, which floats as a supernatant on the produced water. The mastic thus acts as a demulsifying agent, not as an absorbent.

[0183] To analytically determine, using spectrophotometry, the residual concentration of crude oil remaining in the treated produced water (prepared according to the procedure described above), this residual oil is extracted using an equal volume of tetrachloroethane and purified produced water. For example, for every 5 ml of treated and therefore purified produced water, 5 ml of tetrachloroethane are used. The tetrachloroethane extract is then placed in a spectrophotometer, and its absorbance is measured at a wavelength of 311 nm.

[0184] This laboratory purification procedure is easily scalable to an industrial level using any of the standard contact methods employed in the chemical industry. The novel and surprising aspect of this procedure, therefore, is the use of mastic as a granular solid material and adjuvants such as xylene and sodium chloride as a means of separating crude oil from the produced water. This application of mastic as a demulsifier has never been described before and is completely unexpected.

[0185] Analytical determination of the concentration of oil in the produced water

[0186] The method chosen for determining the concentration of oil in the produced water, and which is common in the art, is spectrophotometric. The produced water, after undergoing the purification treatment described in the invention, is subjected to an extraction process with an equal volume of tetrachloroethane. The extract, which contains the remaining crude oil in the produced water, is analyzed in a spectrophotometer at a wavelength of 311 nm. The oil concentration, C o , is calculated using Equation 1: Cp=105.39 Equation 1 where A is the absorbance and C pis the concentration of crude oil present in the produced water, expressed in ppm (parts per million). Equation 1 is the standard curve resulting from measuring the absorbance of known oil concentrations and fitting the values ​​using the least squares method. The experimental values ​​of the standard curve are shown in Table 4. They are also represented graphically in Figure 4, and the perfect alignment of the experimental points is visually verified. The coefficient of determination obtained was:

[0187] R2= 0.9999 Equation 2

[0188] This value of the coefficient of determination so close to unity means that the fit is excellent and that the spectrophotometric method is suitable for determining the concentration of crude oil in the produced water.

[0189] Table 4.- Experimental values ​​for the standard line of crude oil concentration versus absorbance at 311 nm

[0190] The following are some examples of processes to illustrate the multiple possibilities, but the present invention is not limited exclusively to them.

[0191] EXAMPLE 3

[0192] Batch Process with Stirred Tank Model Figure 5 shows the flow diagram. The process, being batch, requires more than one stage, in this case two. In stage 1, the reactor, which is a stirred tank (504), is loaded with the produced water (501), the additives (503) are added, if used, and finally the mastic (502).

[0193] Additives are optional and can be common salt and xylene (or any other liquid hydrocarbon at the working temperature between 15 °C and 95 °C, more preferably between 25 °C and 75 °C and even more preferably between 45 °C and 50 °C, which is the temperature at which the water produced after being separated from the oil in the extraction from the subsoil is usually found)

[0194] Intense agitation is carried out for at least 1 minute, and the mixture is allowed to settle until the demulsified oil forms a clear supernatant layer and the produced water below it appears clear. This time may vary depending on the specific nature of the crude oil being processed. The supernatant layer of crude oil is separated by the crude oil outlet stream (505) and stored for subsequent packaging and sale. If xylene, cyclohexane, or another liquid hydrocarbon has been used as an additive at the operating temperature, it will accompany the oil in the crude oil outlet stream (505). Since xylene, cyclohexane, or the liquid hydrocarbons optionally used as additives to improve oil recovery are common components of the oil, further removal of the crude oil collected by the crude oil outlet stream (505) is not necessary.Furthermore, they make the oil somewhat lighter and therefore give it a higher market value. The mixture of water produced with the granulated solid material and the optionally added common salt is discharged from the bottom via the water outlet stream (506) and fed into a granulated solid material separation unit (507). This unit can be a filter of any type commonly used in industry or a centrifuge of the type also commonly used in industry. The extract (508) consists of the purified produced water plus the optionally added common salt, and the raffinate (509) consists of the granulated solid material with small traces of oil that must be removed in the regenerator (510). A regeneration fluid is introduced into the regenerator (510) via pipe (511).Since the granulated solid material is highly insoluble in water and has a high melting point, it is possible to use steam in the regeneration process, which, through steam stripping, would leave the mastic free of oil. It is also possible, and more preferable, to use natural gas as the regeneration fluid, derived from the gas used to remove the oil during extraction. In this way, instead of burning it in a flare without any benefit, it would be used to regenerate the granulated solid material. The regeneration fluid, carrying any remaining oil residue from the granulated solid material, exits through pipe (512). The regenerated granulated solid material is then recirculated via recirculation stream (513) back to the stirred tank (504), which must be operating in stage 1.

[0195] This procedure requires very large agitated tanks and a long time for the oil surface layer to form. The advantage is that it requires less monitoring.

[0196] EXAMPLE 5

[0197] Continuous process with stirred tank model

[0198] Figure 6 shows an illustrative example of a continuous process with a stirred tank model. Produced water is continuously introduced into tank (602) through pipe (601) (produced water pipe). Optional additives are introduced through pipe (604) (additive inlet pipe), and granulated solid material from the regeneration stage (610) is introduced through pipe (603) (solid material inlet pipe). Since the contact time can be very brief, as little as one minute, as demonstrated in laboratory tests, the tank size is considerably reduced because it needs to replenish its volume quickly. The treated produced water, mixed with the granulated solid material and optional additives, then passes to the settling tank (605). Although the stirred tank is small, the settling tank must have a large volume and surface area.The residence time will be determined by the terminal velocity of the droplets, which, according to Stokes' Law, depends primarily on the square of their diameter. If the surface area of ​​the settling tank is sufficiently large, the processing capacity for produced water can be very high. The continuously recovered oil is removed through the oil outlet pipe (606), and if xylene or another liquid hydrocarbon is used as an additive at the operating temperature, it will also be dissolved in the oil. The treated produced water, along with the granular solid material and common salt, is collected at the base of the settling tank (605) and conveyed to a granular solid separation unit (607). The granular solid separation unit can be any type of filter commonly used in industry or a centrifuge of the type also commonly used in industry. The treated produced water and common salt exit through pipe (608).The granulated solid material is conveyed through pipe (609) to the granulated solid material regenerator (610), which can operate by introducing steam, natural gas from the oil being extracted from the wells, or any hydrocarbon or hydrocarbon mixture in a gaseous state at the operating temperature through pipe (611). This temperature must be between 15 °C and 95 °C, more preferably between 25 °C and 75 °C, and even more preferably between 45 °C and 50 °C. The residues carried by the natural gas or gaseous hydrocarbons are removed from the granulated solid material regenerator (610) through pipe (612).

[0199] EXAMPLE 6

[0200] Continuous process with batteries of water purification units

[0201] Figure 7 shows an example of a continuous process employing produced water purification units (Figure 2) according to the present invention. Produced water flows from the produced water-oil separation device (701) to an intermediate tank (702). In the mixer (704), it is mixed with optional additives previously stored in storage tanks (703). The additives can be common salt, xylene, or any liquid hydrocarbon at the operating temperature. Figure 7 depicts two produced water purification units (705) according to the present invention (Figure 2). Each unit consists of two or more produced water purification units. The produced water flows alternately to these units depending on their operational status. When one unit is purifying, the other is regenerating the mash.

[0202] Unprocessed water enters the battery through pipe (706), and air (when in purification mode) or steam, natural gas, or other gaseous hydrocarbon at the operating temperature (when in mash regeneration mode) enters through pipe (712). Optionally, the natural gas, if it has not passed through the oil condenser as shown in Figure 2, may contain oil and would therefore be a hydrocarbon-enriched natural gas of significant economic interest. The operating temperature is between 0 °C and 100 °C, more preferably between 25 °C and 75 °C, and even more preferably between 45 °C and 50 °C.Equipment (711) is an air supply device and can be either a compressor or a blower. Air is injected from the air supply device (711) into the battery in purification mode. Steam, natural gas, or gaseous hydrocarbon at operating temperature is supplied from the source of steam, natural gas, or gaseous hydrocarbon (713) when the battery is in mash regeneration mode. Steam, air, or natural gas or gaseous hydrocarbon, with or without crude oil for enrichment depending on the operating mode, exits through pipe (713).Through pipeline (707) (recovered oil outlet pipeline) the oil recovered in the condenser is taken to its storage in the tank (708), to be subsequently packaged and marketed, and through pipeline (709) (produced water outlet pipeline) the produced water is taken to its storage in the tank (710) waiting to be used or disposed of.

[0203] After successive operations, the water produced from the storage tank will have a residual crude oil concentration, Cp, that is an average value between the initial value of the process and the final value of the process just before switching to the mash regeneration mode.

[0204] If xylene, cyclohexane or another liquid hydrocarbon is used as an additive at the working temperature, it exits together with the oil through line (707) (additive outlet line) and together with the natural gas through line (713) (natural gas outlet line), and if common salt is used as an additive, it exits through the stream of line (709) (common salt outlet line) together with the produced water.

[0205] EXAMPLE 7

[0206] Influence of mastic type and concentration on crude oil removal. Samples of produced water were processed in the same way as in Example 2, with a crude oil content of 150 ppm. Ten types of mastic were used as granular solid material at concentrations of 50, 100, 150, 200, and 250 ppm. Table 5 shows the results obtained, using a medium particle size distribution as in the example. It is surprising that even with mastic quantities as small as 50 ppm, the crude oil concentration in the produced water was reduced in all cases from 150 ppm to less than 4 ppm. Table 5 presents these results as the residual crude oil concentration in the produced water and as the percentage of crude oil removed. In all cases, the removal rate exceeded 98%.The granulometry of the seedlings determined according to the methodology of example 9 and as specified in Table 7 has been of medium type with Sauter equivalent diameters, d32, between 0,780 mm and 1,584 mm, and with specific areas, a, between 2.12 m. 2 / kg and 5.82 m 2 / kg.

[0207] Table 5.- Concentration of crude oil, Cp, in the produced water expressed in ppm and % removed after processing it with the different types of mastic at different concentrations, Cm.

[0208] Mastic concentration, C m , ppm

[0209] 0 50 100 150 200 250

[0210] Cp, % Cp, % Cp, % Cp, % Cp, % Cp, % ppm Delim, ppm Delim, ppm Delim, ppm Delim, ppm Delim, ppm Delim.

[0211] Mastic 1 150 0.00 4.53 96.98 4.14 97.24 3.71 97.53 3.41 97.72 3.08 97.95

[0212] Mastic 2 150 0.00 1 .85 98.76 1 .57 98.95 1 .16 99.23 1 .28 99.15 1 .21 99.19

[0213] Almaciga s 150 0.00 1 .62 98.92 1 .18 99.21 1 .01 99.33 0.96 99.36 0.94 99.37

[0214] Masthead 4 150 0.00 5.36 96.42 4.32 97.12 4.12 97.25 3.75 97.50 3.37 97.75

[0215] Almaciga s 150 0.00 3.55 97.63 2.99 98.00 2.89 98.07 2.31 98.46 2.00 98.67

[0216] Almaciga s 150 0.00 9.57 93.62 7.37 95.09 5.28 96.48 4.84 96.78 4.41 97.06

[0217] Almáciga 7 150 0.00 9.75 93.50 7.87 94.75 5.41 96.40 5.07 96.62 4.63 96.92

[0218] Almaciga s 150 0.00 4.05 97.30 3.20 97.86 3.12 97.92 3.01 97.99 2.87 98.09

[0219] Almáciga 9 150 0.00 1 .75 98.83 1 .07 99.28 0.98 99.35 0.92 99.39 0.85 99.43

[0220] Warehouse150 Q 0Q 1 34 99 1 1 Q 8g gg 41 0 85 gg 43 0 78 99 48 0 55 99 63

[0221] It is also observed that the effectiveness in removing crude oil, while extremely high in all cases, depends slightly on the type of seedling. Seedlings 10, 9, 3, and 8 stand out as the most effective. In contrast, the worst results occur with seedling types 7 and 8. These differences are likely due to the fact that seedling is a natural product that responds to variations related to the climate of the growing areas and soil characteristics. Even though they originate from the same tree species, the genetic variability of cultivars from different countries plays a significant role. The composition of seedling is so complex that it is difficult, if not nearly impossible, to find a simple explanation for its behavior and ability to demulsify oil emulsions in the produced water.Similarly, this same complexity in composition will be found in other natural resins and waxes that meet the density, water solubility and solubility parameters properties of the present invention as described in the description section of the invention.

[0222] Figure 8 shows that, except for seedbeds 6 and 7, which have the lowest extraction yield, extraction is practically at its maximum starting at 100 ppm of seedbed material and remains approximately constant, independent of the seedbed concentration used. Therefore, a seedbed concentration of 100 ppm can be considered optimal from both a technological and cost perspective.

[0223] EXAMPLE 8

[0224] Influence of adding xylene to mastic

[0225] To facilitate the separation of crude oil from the produced water, extractions were carried out by adding the hydrocarbon xylene (a typical commercial product with ortho, meta, and para isomers) to the mastic. In all trials, the total concentration of the mastic-xylene mixture was maintained at 100 ppm, but with xylene percentages of 0%, 25%, 50%, and 75% relative to the total weight of the mastic-xylene mixture, and therefore, 100%, 75%, 50%, and 25% mastic. Since the xylene isomers have almost indistinguishable chemical and physical properties, it is not expected that varying isomeric mixtures of commercial xylene will exhibit appreciable differences in their performance during crude oil extraction from the produced water. On the other hand, it is not feasible to use pure isomers of xylene due to their high cost, while the commercial mixture of isomers is, by far, very economical.Table 6 shows the results obtained, and Figure 9 shows that the presence of 25% xylene in the mash leads to improved crude oil extraction from the produced water. Masts 10, 9, 3, and 2 exhibit the best performance, with the residual crude oil concentration in the treated produced water even lower than 1 ppm. In all cases, an increase in xylene above 25% leads to an increase in the crude oil concentration in the treated produced water, thus worsening the oil recovery process. The mash particle size distribution, determined according to the methodology in Example 9 and specified in Table 7, was medium, with Sauter equivalent diameters (d32) between 0.780 mm and 1.584 mm, and specific areas (a) between 2.12 m². 2 / kg and 5.82 m 2 / kg.

[0226] Table 6.- Concentration of crude oil, Cp, in the produced water expressed in ppm and % removed after processing it with 100 ppm of mixtures made up of the indicated % of xylene and the remainder mastic

[0227] EXAMPLE 9

[0228] Influence of particle size

[0229] The grain size distributions of all the seedling trays were determined using photographic image processing. The grains were photographed with a Canon EOS 1300D camera and a Sigma DC 18-250mm f / 3.5-6.3 Macro HSM telephoto lens against a matte black surface. The photographs have a resolution of 5180 x 3456 pixels. Specific software was programmed in Microsoft VB.NET using Visual Studio 2012 as the IDE. This software, using computer vision, allows for the identification of each seedling grain individually and the determination of its equivalent diameter, surface area, volume, and mass. It also calculates the total surface area, total mass, and arithmetic mean equivalent diameter for the entire size distribution. a , the geometric mean equivalent diameter, d gThe Sauter diameter, d32, and the specific area, a. It has been observed that the parameters Sauter diameter, d32, and the specific area, a, and more preferably the specific area, are the parameters that best represent the granulometric distributions and their relationship with the effectiveness of the seedbeds.

[0230] Table 7 shows the concentration of residual oil in the produced water, as well as the percentage of removal after treatment with 100 ppm of the 10 seedbeds in their three granulometries, fine, medium and coarse, defined for each seedbed according to its Sauter diameter, d32, and the specific area, a.

[0231] Table 7.- Sauter equivalent diameter, d23, specific area, a, crude oil concentration, C p , in the water produced and % removed after processing with 100 ppm with the different types of mastic In the

[0232] Figure 10 shows the concentration of crude oil remaining in the water produced after extraction with the 10 seedbeds in fine, medium and coarse granulometries, as a function of the specific area expressed in m² 2 / kg, which preferentially correlates particle size better with the oil extraction efficiency of the produced water. It is observed again that the mastic sizes 10, 8, 3, and even 2 are the most effective in all particle size ranges. From 3 to 5 m 2 / kg of specific surface area, increasing it barely implies a greater yield in the extraction of crude oil from the produced water, so particle sizes around these values, medium particle sizes, can be considered optimal. Furthermore, a medium particle size is more advantageous than a fine one for use in fixed-bed packed columns, as it is easier to prevent carryover in continuous extraction processes. It can be concluded that the particle size (for example, the particle size of mastic) should be such that, approximating the particles to equivalent spheres of equal surface area, the specific surface area, a, is between 0.5 m² and 0.5 m². 2 / kg and 30 m 2 / kg, more preferably between 2.0 m 2 / kg and 20 m 2 / kg, and even more preferably between 2.0 m 2 / kg and 5.0 m 2 / kg.

[0233] On the other hand, it is surprising and unexpected that such low specific surface areas are so effective at removing crude oil from produced water. By comparison, activated carbon, widely used in absorption and desorption processes, has specific surface areas around 50,000 m². 2 / kg and 2,500,000 m 2 / kg, thousands and even hundreds of thousands of times greater than mastic, a solid resin with hardly any pores.

[0234] EXAMPLE 10

[0235] Influence of salt concentration

[0236] The water produced during oil extraction contains a high concentration of common salt, on the order of 80 g / L, as is the case in the Rumaila supergiant oil field (Iraq). Common salt is an readily available and very inexpensive byproduct of oil extraction, making it a viable additive to improve crude oil extraction using mastic. Table 8 shows the crude oil recovery results after adding common salt to increase the concentration from 80 g / L to successively higher amounts of 100, 120, 160, and 200 g / L. Figure 11 graphically illustrates the effect of adding common salt. It shows some improvement in extraction, especially in the lower-yielding mastic pits. In pits 10 and 9, the most efficient, a salt concentration of 100 g / L results in a slight decrease in extraction efficiency, although higher concentrations improve the process.

[0237] Any salt can be used, but common salt is by far the preferred one, and it can be established that the preferred concentration of common salt is between 0 g / l and 200 g / l, preferably between 100 g / l and 180 g / l, and even more preferably between 75 g / l and 125 g / l of produced water

[0238] Table 8.- Concentration of crude oil, Cp, in the produced water expressed in ppm and % removed after processing it with 100 ppm with the different types of mastic and fine granulometry at different concentrations of common salt

[0239] Concentration of common salt, C s , g / l

[0240] EXAMPLE 11

[0241] Performance of the granulated solid material in relation to Hansen's solubility parameters, HSP. Table 9 shows the Hansen solubility parameters of the three solubility spheres of the 10 mastic seeds, as well as their solubility radii, determined by comparison with a battery of solvents, according to the technique described in the book “Hansen Solubility Parameters. A User's Handbook”, CRC Press, 2007.

[0242] Table 9.- Solubility parameters of lipophilic, L, lipophilic-hydrophilic, LH, and hydrophilic, H spheres, as well as the radii of the spheres, Ro, of the 10 seedbeds. Units in MPa 1 / 2 .

[0243] Figure 12 shows, as an example, graphical representations of the three solubility spheres of mastic 3. a) Three-dimensional representation, b) two-dimensional representation of do versus dn, c) two-dimensional representation of do versus dp, and d) two-dimensional representation of dp versus dn.

[0244] Figure 13, Figure 14, and Figure 15 show the Hansen solubility parameters of the centers of the solubility spheres of the 10 seedlings in a two-dimensional representation of the polarity solubility parameter, dp, versus the solubility parameter, dn.

[0245] It is observed that the centers of the seedling cells in the lipophilic sphere, Figure 13, are very similar for all seedling cells. In light of these results, the seedling cells suitable for purifying the produced water should have a dp in the lipophilic sphere between 0.0 and 8.0 MPa 1 / 2 , and more preferably between 3.0 and 6.0 MPa 1 / 2, while the OH values ​​will range between 0 and 5.0 MPa 1 / 2 , and more preferably between 0.0 and 3.0 MPa 1 / 2 Furthermore, the dispersion parameters, OD, must have values ​​between 15.0 and 18.0 MPa 1 / 2 , and more preferably between 16.0 and 17.0 MPa 1 / 2 (Table 9).

[0246] As shown in Figure 14, the seedbeds selected for purifying the produced water must have a dp between 4.0 and 15.0 MPa in the hydrophilic sphere 1 / 2 , and more preferably between 6.0 and 11.0 MPa 1 / 2 , while the OH values ​​will range between 20.0 and 35.0 MPa 1 / 2 , and more preferably between 25.0 and 29.0 MPa 1 / 2 Furthermore, the dispersion parameters, OD, must have values ​​between 15.0 and 19.0 MPa 1 / 2 , and more preferably between 16.0 and 17.0 MPa 1 / 2 (Table 9).

[0247] The lipophilic-hydrophilic spheres of the seedling trays, Figure 15, exhibit a clear pattern in this case that distinguishes those trays with acceptable yield, trays 6 and 7, from those with high and very high yield, which are the rest. Therefore, in light of these results, the lipophilic-hydrophilic spheres of the seedling trays should have a dp between 5.0 and 14.0 MPa 1 / 2 , more preferably between 7.0 and 11.0 MPa 1 / 2 , and more preferably between 8.0 and 9.5 MPa 1 / 2 The hydrogen bond parameters, OH, will range between 8.0 and 15.0 MPa 1 / 2 , more preferably between 11.0 and 14.0 MPa 1 / 2 , and even more preferably 12.0 and 13.0 MPa 1 / 2 Finally, the dispersion parameters, OD, must have values ​​between 15.0 and 23.0 MPa 1 / 2 , and more preferably between 19.0 and 21.0 MPa 1 / 2 (Table 9).

[0248] Resins such as mastic and other natural waxes of complex and poorly understood composition, usable as granulated solid materials, are effective for demulsifying the multiple emulsions in water produced for purification purposes, provided they have three solubility spheres with centers and radii similar to those defined above. Composite materials that also exhibit three solubility spheres with centers and radii similar to those defined above will be equally effective in purifying water produced by demulsifying its multiple emulsions.

[0249] EXAMPLE 12

[0250] Experimental Results of the Continuous Method To illustrate the performance of the water purification unit produced according to the invention, mastic 10 was used. The reactor of the purification unit is a cylinder 7.1 cm in diameter and 19.5 cm high. Three dynamic tests were carried out, one for each type of particle size. The masses used and the fraction of voids remaining in the chamber with the metal grid are shown in Table 10. The flow rate of water produced was 500 ml / minute, which implies a Reynolds number for the entire reactor, excluding the part occupied by the grid with the mastic, of Re = 159, i.e., laminar flow.

[0251] Table 10.- Masses and void fraction of mash 10 in the dynamic test o , , . « Void fraction s

[0252] Particle size. Sample mass, g.

[0253] Thick 100 40.4

[0254] Average 120 18.1

[0255] Fine 130 0.9

[0256] A heat exchanger was used to heat the air, and a heater was used to heat the produced water to achieve the ideal temperature, simulating the natural outlet temperature of 40°C–50°C from the water and salt buffer used for treatment. This means that, at an industrial level, a separate heat source is not required because the produced water reaches the purification unit at the desired temperature of 40°C–50°C, which is the preferred temperature range. This also represents an additional economic benefit.

[0257] Table 11 shows the results obtained. As time passes, the effectiveness decreases in all particle sizes, but even so, after 10 minutes of treatment, the removal percentage is very high, better than in any procedure known to date in the industry.

[0258] Table 11.- Residual crude oil concentration, Cp, and percentage removed after treatment with mastic 10 for three particle sizes

[0259] Fine Medium Coarse

[0260] , minutes Cp, ppm % Delim. Cp, ppm % Delim. Cp, ppm % Delim.

[0261] 0 0.08 99.94 0.24 99.84 0.28 99.81

[0262] 1 0.11 99.93 0.31 99.80 0.38 99.75

[0263] 2 0.12 99.92 0.36 99.76 0.44 99.70 3 0.21 99.86 0.40 99.73 0.51 99.66

[0264] 4 0.37 99.75 0.55 99.63 0.71 99.53

[0265] 5 0.52 99.66 0.66 99.56 0.74 99.51

[0266] 6 0.53 99.65 0.75 99.50 0.92 99.39

[0267] 7 0.72 99.52 0.83 99.44 1 .13 99.25

[0268] 8 0.91 99.40 1 .11 99.26 1 .29 99.14

[0269] 9 1 ,22 99,18 1 ,50 99,00 1 ,89 98,74

[0270] 10 1 ,46 99,02 1 ,83 98,78 2,06 98,63

[0271] Figure 16 shows the values ​​of Cp versus continuous process time and have been fitted to a second-degree polynomial, with excellent values ​​of the coefficient of determination R 2 .

[0272] With these results and for the specific case of seedbed 10, by switching the purification unit batteries from purification mode to cleaning mode every 5 minutes and vice versa, it is possible to have purified produced water effluents with less than 1 ppm of residual oil.

[0273] This would improve even the most demanding quality standards for water emissions produced both on land and on oil platforms.

[0274] EXAMPLE 13

[0275] Examples of the use of composites and additives

[0276] It is worth noting that any type of mastic can be used for the treatment of produced water, including those not described in this document. Granular solid materials with Hansen's solubility parameters (HSP) similar to mastic are also suitable. In the following examples, the produced water from the Rumaila oil field (Iraq) is used as a reference, although this is not an exclusive criterion. Therefore, when the concentration of common salt is expressed, the added common salt and the final concentration are indicated, which includes the 80 g / L naturally present in the Rumaila produced water. When granular solid material is indicated, it is understood that mastic is also included.

[0277] In batch water purification processes such as embodiment number 4 “Batch process with agitated tank model”, continuous processes according to embodiment number 5 “Continuous process with agitated tank model”, or similar common industrial processes, the concentration of granulated solid material shall be between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm.

[0278] In continuous water purification processes such as example number 6 “Continuous process with batteries of water purification units” the void fraction of the granulated solid material (e.g., mastic) in the grid container will be between 0.5% and 80%, more preferably between 10% and 40%, and even more preferably between 15% and 20%.

[0279] The circulation regime of the water produced by the purification unit according to Figure 2 must be such that the Reynolds number is between Re = 1 and Re = 10 7 , preferably between Re = 1 and Re = 10 5 , more preferably between Re = 10 up to Re = 2400, and even more preferably between Re = 50 up to Re = 500.

[0280] The working pressure of the gases above the ambient pressure in the purification unit according to Figure 2 will be between 1 bar and 5 bar, and more preferably between 1 bar and 2 bar.

[0281] The working pressure of the water produced above the ambient pressure in the purification unit according to Figure 2 will be between 1 bar and 5 bar, and more preferably between 1 bar and 2 bar.

[0282] The operating temperature may be between 0 °C and 100 °C, preferably between 25 °C and 75 °C, and even more preferably between 40 °C and 50 °C.

[0283] EXAMPLE 14

[0284] Procedure for dissolving mastic in solvents to form a coating varnish for inert cores

[0285] It has been known for centuries that mastic can be dissolved in turpentine to form a solution for varnishing oil paintings on canvas. Unlike other varnishes, mastic varnish provided high transparency, good protection of the underlying oil paint, and did not crack when used on canvas due to its flexibility. These varnishes have also been used to protect wood from atmospheric agents, nourish it, and maintain its mechanical properties of flexibility and strength. The object of the present invention is to coat solid inert cores with an outer layer of mastic and optionally other materials to form a composite that is useful as granular material in the purification of treated wastewater.

[0286] Since turpentine essence may be too expensive for use in the present invention, other alternative solvents, including turpentine essence and water as references, have been tested in the manner described below.

[0287] Five grams of mastic are ground into a fine material with a particle size of less than 0.1 mm. In a sealed jar, the 5 grams of mastic are combined with 20 grams of solvent. The mixture is shaken vigorously to form a suspension, and this shaking is repeated at regular intervals for 72 hours. The procedure is carried out in a sealed container to prevent solvent evaporation over such a long period. After this time, a clear, yellow solution is obtained, along with a residual sediment containing the remains of inactive plant material and dirt present in the natural product extracted from the exudates of the mastic tree. Finally, the solution is filtered, and the sediment is discarded. The intensity of the yellow color of the clear solution is proportional to the degree of mastic dissolution achieved.

[0288] The solvents tested are shown in Table 12. The qualitative composition, supplier, and mastic dissolution efficiency are specified on a scale from 0 (water) to 5 (turpentine). Eurotex universal solvent was found to have similar efficiency to turpentine. From an industrial perspective, the use of a solvent like Eurotex universal solvent is more advisable because its price is significantly lower and its composition is not as variable as that of turpentine.

[0289] Table 12.- Efficiency of mastic extraction using solvents to form a coating varnish for inert cores

[0290] Epoxy solvent can have a composition, for example, like the following:

[0291] 2-butoxyethanol 15-25%, diacetone alcohol 10-20%, isobutyl ketone 10-20%, and butanol 5-10%. C8-C10 aromatic hydrocarbons (CAS: 64742-95-6) q.s. 100%

[0292] The universal solvent can have a composition, for example, like the following:

[0293] Universal Solvent: 4-10% Methanol, 10-20% methyl acetate, remainder up to 100% toluene.

[0294] Pure turpentine solvent can have a composition, for example, like the following:

[0295] Pure turpentine: Saturated hydrocarbons C6-C13 (CAS: 64742-48-9) >90% Turpentine essence < 10%

[0296] EXAMPLE 15

[0297] Recycled glass granules coated with a layer of mastic varnish

[0298] A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as the solvent.

[0299] 25 grams of recycled glass granules with diameters between 0.6 and 1.25 mm are weighed out. Under continuous stirring, 5 grams of mastic varnish 10 are added using a spray. Stirring is maintained until the mixture dries by applying a stream of hot air. The glass granules, thus coated with an outer layer of mastic varnish 10, are used to purify produced water with a petroleum content of 150 ppm and a salt content of 80,000 ppm. The petroleum removal achieved is 99.1%.

[0300] EXAMPLE 16

[0301] Silica sand granules coated with a layer of mastic varnish

[0302] A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as the solvent.

[0303] Weigh out 25 grams of silica sand with granules between 0.4 and 0.8 mm in diameter. Add 5 grams of mastic varnish 10 under continuous stirring, using a spray. Stirring is maintained until the mixture dries by applying a stream of hot air.

[0304] Silica granules coated with an outer layer of mastic 10 are used to purify produced water with an oil content of 150 ppm and a salt content of 80,000 ppm. The oil removal achieved is 99.6% for the recycled glass granules and 99.3% for the silica sand granules.

[0305] EXAMPLE 17

[0306] Mastic varnish and acrylic copolymer

[0307] A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as the solvent.

[0308] In a reactor, 60 grams of ethyl acetate are introduced. At room temperature and under stirring, 40 grams of a finely divided butyl acyllate / methyl methacrylate / acrylic acid copolymer are added until completely dispersed. The reactor is closed to prevent solvent evaporation, and stirring continues until no lumps remain (approximately 1 hour).

[0309] Mix 4.5 grams of the previously prepared mastic varnish with 0.5 grams of the copolymer solution and coat recycled glass granules as described in Example 15. The coating on the granules exhibits greater adhesion to the glass and improved mechanical strength compared to when mastic alone is used. Following the procedure in Example 15, a petroleum removal rate of 98.8% is achieved.

[0310] EXAMPLE 18

[0311] Mast and neoprene varnish A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as a solvent.

[0312] In a reactor, 42.9 grams of xylene, 11.4 grams of ethyl acetate, and 1.7 grams of butanone are introduced. At room temperature and under stirring, 12 grams of finely divided material are added until completely dissolved. Then, finely divided neoprene is added gradually to avoid lumps, and mixing is continued for 1 to 3 hours until completely homogeneous.

[0313] Mix 4.6 grams of the previously prepared mastic varnish with 0.4 grams of the previous neoprene preparation, and proceed to coat silica sand granules as per example 15. The coating layer on the granules provides greater impact and water resistance than when made with mastic alone.

[0314] Following the procedure in example 16, a 99.5% oil removal rate is achieved.

[0315] EXAMPLE 19

[0316] Mastic varnish and polyvinyl chloride (PVC)

[0317] A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as the solvent.

[0318] In a reactor, 50 grams of tetrahydrofuran, 15 grams of cyclohexanone, and 10 grams of butanone are introduced. At room temperature and under stirring, 25 grams of finely divided PVC are added until completely dispersed. The reactor is closed to prevent solvent evaporation, and stirring continues until no PVC lumps remain (approximately 1 hour).

[0319] Mix 4 grams of the previously prepared mastic varnish with 1 gram of the PVC solution, and proceed to coat recycled glass granules as shown in the example.

[0320] 15. The coating layer of the granules has greater mechanical resistance than when it is made only with mastic.

[0321] Similarly, 4 grams of the previously prepared mastic varnish are mixed with 1 gram of PVC solution, and silica granules are coated as shown in the example.

[0322] 16. The coating layer of the granules has greater mechanical resistance than when it is made only with mastic.

[0323] Following the procedures outlined in Examples 15 and 16, the produced water is treated. The oil removal achieved is 98.9% for recycled glass granules and 99.3% for silica sand granules. EXAMPLE 20

[0324] Mastic varnish and polyethylene

[0325] A varnish is prepared according to example 14 using mastic 10 and Eurotex universal solvent as the solvent.

[0326] On the other hand, 25 grams of finely divided polyethylene are dissolved in limonene at a temperature of 60 °C (about 15 minutes of stirring)

[0327] 45 grams of previously prepared mastic varnish are mixed with 4.5 grams of the polyethylene solution in limonene. Then, 0.5 grams of silane are added to improve adhesion to glass and silica.

[0328] With 5 grams of the above mixture, 25 grams of recycled glass are coated as per example 15. After treating purified water, the oil removal reaches 99.0%. Similarly, with 5 grams of the above mixture, another 25 grams of silica sand granules are coated as indicated in example 16. The oil removal is 99.5%.

Claims

CLAIMS 1. A water-insoluble, granular solid material exhibiting three Hansen solubility spheres and comprising one or more components selected from: a) a resin, selected from mastic resin, rosin resin, dammar resin, myrrh resin, frankincense resin, amber, benzoin resin, pine resin, copal resin, labdanum resin, frankincense resin, natural rubber, elemi resin, turpentine resin, acacia gum resin, guar gum resin, shellac resin, copaiba resin, guaiac resin, guarana resin, gum arabic resin, and tamarind resin, and combinations thereof, b) a wax, selected from candelilla wax, carnauba wax, beeswax, alba beeswax, jojoba wax, cascarilla wax, castor wax, cottonseed wax, hemp wax, macadamia wax, baobab wax, sandalwood, wheat bran wax, spermaceti, palm wax, rice wax, soy wax, sunflower wax, cocoloba wax,chamomile wax, shellac, copal wax, mint wax, rosehip wax, sacha inchi wax, red algae wax, quinine wax, chicle wax, and fir wax, and combinations thereof, c) a synthetic polymer, selected from polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyamide, polyvinyl chloride, polycarbonate, polyamide-imide, polyacrylonitrile, polymethacrylate, polyurethane, epoxy polymer, polyacetal, polyvinyl acetate, phenol-formaldehyde polymer, unsaturated polyester, urethane-formaldehyde polymer, polyimide, synthetic rubber, butyl rubber, nitrile rubber, silicone rubber, polylactic acid, polyglycolic acid, aliphatic polyester, polyphosphorylcholine, polyphenyl sulfide, polyarylenic acid, polytetrafluoroethylene, polyethersulfone, chlorofluoroethylene, asphalt, bitumen, tar, copolymer of styrene-butadiene, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl-acetate copolymer,and polyethylene terephthalate copolymer and combinations thereof and combinations of two or more of a), b) and c)., 2. A granulated solid material according to claim 1, the three Hansen solubility spheres of which have the following properties: lipophilic sphere: • The dispersion parameter, do, has values ​​between 15.0 and 18.0 MPa 1 / 2 , and more preferably between 16.0 and 17.0 MPa 1 / 2 • The polarity parameter, dp, has values ​​between 0.0 and 8.0 MPa 1 / 2 , and more preferably between 3.0 and 6.0 MPa 1 / 2 . • The hydrogen bonding parameter, dn, has values ​​between 0.0 and 5.0 MPa 1 / 2 , and more preferably between 0 and 3.0 MPa 1 / 2 . lipophilic - hydrophilic sphere: • The dispersion parameter, do, has values ​​between 15.0 and 23.0 MPa 1 / 2 , and more preferably between 19.0 and 21.0 MPa 1 / 2 . • The polarity parameter, dp, has values ​​between 5.0 and 14.0 MPa 1 / 2 , more preferably between 7.0 and 11.0 MPa 1 / 2 , and more preferably between 8.0 and 9.5 MPa 1 / 2 . • The hydrogen bonding parameter, dn, ranges from 8.0 to 15.0 MPa 1 / 2 , more preferably between 11.0 and 14.0 MPa 1 / 2 , and even more preferably 12.0 and 13.0 MPa 1 / 2 . hydrophilic sphere: • The dispersion parameter, do, has values ​​between 15 and 19 MPa 1 / 2 , and more preferably between 16 and 17 MPa 1 / 2 . • The polarity parameter, dp, has values ​​between 4.0 and 15.0 MPa 1 / 2 , and more preferably between 6.0 and 11.0 MPa 1 / 2 . • The hydrogen bonding parameter, dn, has values ​​between 20.0 and 35.0 MPa 1 / 2 , and more preferably between 25.0 and 29.0 MPa 1 / 2 .

3. A granulated solid material according to claim 1 or 2, further comprising one or more inert materials.

4. A granulated solid material according to any one of claims 1 to 3, which is configured as a core of inert material covered by the remaining components.

5. A process for purifying water produced in the petroleum industry comprising bringing the granulated solid material defined in any one of claims 1 to 4 into contact with the produced water, obtaining clean water.

6. A process according to claim 5, wherein the contact between the granulated solid material and the water is carried out by a technique selected from: a) direct mixing and subsequent separation by filtration or centrifugation, b) flow of the produced water over a fixed bed made up of the granulated solid material.

7. A process according to claim 5 or 6, comprising the addition of one or more additives.

8. A process according to claim 7, wherein the additives are selected from one or more of: a) common salt b) a salt soluble in the produced water c) a hydrocarbon in a liquid state at the operating temperature d) a substance that increases the ionic strength of water e) a substance in which petroleum is partially or totally soluble.

9. A process according to claim 8, wherein the additive is selected from: a) common salt, b) a salt soluble in the produced water, and c) a substance that increases the ionic strength of water and whose concentration is between 0 g / l and 200 g / l, preferably between 100 g / l and 180 g / l, and more preferably between 75 g / l and 125 g / l of produced water.

10. The process according to claim 8, wherein the additive is a hydrocarbon in a liquid state at the operating temperature that is added to the granulated solid material; the concentration of granulated solid material plus liquid hydrocarbon is between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm with respect to the sum of the granulated solid material plus the additive.

11. The process according to any one of the preceding claims 5 to 10, carried out in batch or discontinuous stages and comprising the following steps: a) mixing in a stirred tank of the granulated solid material, and optionally of the additives, with the produced water, b) allow to rest for the cremation to occur, then separate the recovered crude oil from the top of the tank, and the purified produced water along with the granulated solid material from below and c) recover the granulated solid material.

12. The process according to claim 11, wherein the granulated solid material is recovered in step c) by filtration or centrifugation.

13. The process according to claim 12, wherein the granulated solid material is cleaned with a stream of steam or natural gas and reincorporated into the next batch in step a).

14. The process according to any one of claims 5 to 13, which is a continuous process comprising the following steps: a) mixing the granulated solid material, and optionally the additives, with the produced water containing the oil droplets in a continuously fed, stirred tank; b) continuously conveying the mixture from the previous step to a settling tank where the recovered crude oil is continuously extracted from the top and the produced water and granulated solid material are continuously extracted from the bottom; c) continuously separating the granulated solid material from the produced water.

15. The process according to any one of the preceding claims 5 to 13, which is carried out continuously and comprises: 1) Place the granulated solid material in a fixed bed reactor, 2) introduce the produced water into the reactor, 3) to make the produced water flow between the granules of the granulated solid material in the reactor, breaking the emulsion of the crude oil droplets contained in the produced water, 4) separate the oil droplets obtained mixed with the previously introduced gaseous carrier fluid into the reactor, 5) recover the granulated solid material, 6) recover the clean water produced, and 7) recover the crude oil.

16. The process according to claim 15, wherein the granulated solid material is recovered in step c) continuously by filtration or centrifugation.

17. The process according to claim 16, wherein the granulated solid material is cleaned with a stream of steam or natural gas and reincorporated into the next batch in step a).

18. A method according to any one of the preceding claims 5 to 13, wherein one or more of the following conditions are met: - the contact time between the granulated solid material and the produced water is between 30 seconds and 3 minutes, preferably between 30 seconds and 1 minute, - the operating temperature is between 0 °C and 100 °C, preferably between 15 °C and 95 °C, more preferably between 25 °C and 75 °C, and even more preferably between 40 °C and 50 °C, or in the process of the invention with a fixed bed: - the concentration of granulated solid material is between 20 ppm and 300 ppm, more preferably between 50 ppm and 150 ppm, and even more preferably between 75 ppm and 125 ppm, - is carried out continuously with batteries of water purification units, so that the void fraction of the granulated solid material in the grid container is between 0.5% and 80%, more preferably between 10% and 40%, and even more preferably between 15% and 20%, - the circulation regime of the water produced by the purification unit is such that the Reynolds number is between Re = 1 and Re = 10 7 , preferably between Re = 1 and Re = 10 5 , more preferably between Re = 10 and Re = 2400, and even more preferably between Re = 50 and Re = 500, - The working pressure of the gases above ambient pressure is between 1 bar and 5 bar, and more preferably between 1 bar and 2 bar. - The working pressure of the water produced above the ambient pressure is between 1 bar and 5 bar, and more preferably between 1 bar and 2 bar.

19. Purification unit for carrying out the procedure defined in any one of claims 5 to 18, comprising: a) a container that includes: i. an inlet for the produced water i. an injector to introduce and disperse the produced water into: iii. an inner container with respect to container a), formed by a metal grid to arrange the granulated solid material iv. a gas inlet that is connected to a diffuser of these gases to bubble, v. a gas outlet to carry away the recovered oil, and vi. an outlet for the purified produced water b) a condenser to separate the recovered oil and recirculate the gases.

20. Purification unit according to claim 19, further comprising means for recirculating produced water arranged at the outlet of the purified produced water for reprocessing.

21. Use of the water-insoluble solid granulated material having three Hansen solubility spheres, as defined in any one of claims 1 to 4, for the recovery of produced water

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