Purification of hydrocarbons

Abstract

To provide a method for purifying hydrocarbons.SOLUTION: The method includes flowing an aqueous phase 108 comprising water into a first end of a mixing zone 110 of a reactor 102 along a first direction. Organic phase 114 is mixed with aqueous phase 108 via counter-current flow by flowing organic phase 114 into a second end of mixing zone 110 opposite the first end. The organic phase 114 includes oils, fats, greases, or combinations thereof from plant and / or animal sources. The flow of the organic phase 114 is along a second direction opposite to the first direction, and the organic phase 114 comprises at least contaminants comprising halides, phosphorus, sulfur, alkali metals, metalloids, heavy metals, or any combination thereof. The mixing region 110 is heated. The purified organic phase 114 is extracted from the purification zone of the reactor 102. Waste is extracted from the waste area of the reactor 102.SELECTED DRAWING: Figure 4

Description

Detailed Description of the Invention

[0001] [Field] Aspects of the present disclosure relate generally to systems and methods for refining hydrocarbons, and more particularly to systems and methods for refining fats and oils.

[0002] [background]

[0002] The refining of hydrocarbons, e.g., fats, oils, and / or greases, is carried out in a variety of industries, including food, cosmetics, waxes, biofuels, and other oleochemicals. Typically, hydrocarbons are refined using one or more steps to solubilize contaminants in the water stream by using water washing in a separatory centrifuge, acid refining, and / or caustic refining. The contaminants are then further adsorbed and / or filtered out using adsorbent filtration, such as "bleaching earth," silica, diatomaceous earth, or carbon black. Unfortunately, each of these processes is costly, and each subsequent step increases capital and operating costs, along with waste disposal and product loss. High-shear mixing, cavitation, filtration capacity, chelating agents, and enzymes have been introduced in attempts to reduce waste disposal and product loss. These efforts have improved efficiency and yield, but capital and operating costs have remained constant.

[0003]

[0003] One process that reduces waste disposal and product loss is the Colgate-Emery process. The Colgate-Emery process is a continuous countercurrent process typically operated at 250-260°C and 725 psig, where oil is fed to the bottom of a dividing column and demineralized water is fed to the top. Unfortunately, the Colgate-Emery process liberates glycerin from glycerides and produces large amounts of free fatty acids, both of which are often undesirable in downstream refining. The process also must operate below glycerin cracking temperatures, e.g., 290°C, and requires long residence times, e.g., 2-3 hours, to enable gravity separation. Furthermore, the Colgate-Emery process requires large equipment, which means that large volumes of oil must be processed to be economically viable, making it cost-prohibitive for the production of alternative fuels. Therefore, there is a need in the art for improved systems and methods for refining hydrocarbons, particularly for refining fats and oils from plant and / or animal sources.

[0004] [overview] The present disclosure provides a method for purifying hydrocarbons. The method includes flowing an aqueous phase along a first direction into a first end of a mixing zone of a reactor. The organic phase is mixed with the aqueous phase in a countercurrent flow manner by flowing an organic phase into a second end of the mixing zone opposite the first end. The organic phase flows along a second direction opposite the first direction. The organic phase contains at least contaminants. The mixing zone is heated. A purified organic phase is extracted from the purification zone of the reactor. A waste product is extracted from the waste zone of the reactor.

[0005] The present disclosure also provides a method for purifying hydrocarbons, the method including flowing an aqueous phase into a first mixing zone of a first reactor; flowing an organic phase into the first mixing zone, thereby mixing the organic phase with the aqueous phase; separating the purified organic phase from waste products; and conducting the purified organic phase from the first reactor to a second mixing zone of a second reactor.

[0006] The present disclosure also provides a method for purifying hydrocarbons. The method includes flowing an aqueous phase containing water along a first direction into a first end of a mixing zone of a reactor. Flowing an organic phase into a second end of the mixing zone opposite the first end, thereby mixing the organic phase with the aqueous phase in a countercurrent flow. The organic phase includes oil, fat, grease, or a combination thereof. The flow of the organic phase is along a second direction opposite the first direction, and the organic phase includes at least contaminants including halides, phosphorus, sulfur, alkali metals, metalloids, heavy metals, or any combination thereof. The mixing zone is heated. A purified organic phase is extracted from the purification zone of the reactor. A waste product is extracted from the waste zone of the reactor. The waste product is directed to a recuperator.

[0007]

[0007] A more particular description of the present disclosure briefly summarized above, so that the above-mentioned features of the present disclosure can be understood in detail, can be had by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered as limiting its scope, since the present disclosure may admit of other equally effective embodiments. [Brief explanation of the drawings]

[0008] [Figure 1A] 1A-1C are schematic diagrams of a countercurrent liquid-liquid extraction column according to one embodiment of the present disclosure. [Figure 1B] 1A-1C are schematic diagrams of a countercurrent liquid-liquid extraction column according to one embodiment of the present disclosure. [Figure 2A] 2A and 2B are schematic diagrams of an agitated countercurrent liquid-liquid extraction column according to one embodiment of the present disclosure, respectively. [Figure 2B] 2A and 2B are schematic diagrams of an agitated countercurrent liquid-liquid extraction column according to one embodiment of the present disclosure. [Figure 3]FIG. 1 is a schematic diagram of a countercurrent mixer-settler system according to one aspect of the present disclosure. [Figure 4] FIG. 1 is a schematic diagram of a countercurrent liquid-liquid extraction column with a recuperator, according to one embodiment of the present disclosure.

[0009]

[0012] For ease of understanding, the same reference numerals have been used, where possible, to indicate identical elements common to the figures. The figures are not drawn to scale and may be simplified for clarity. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

[0010] [Detailed Description of the Invention]

[0013] The description of various aspects of the present disclosure has been presented for illustrative purposes and is not intended to be exhaustive or to be limited to the disclosed aspects. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described aspects. The terms used herein were selected to best explain the principles of the aspects, practical applications or technical improvements to technology found in the market, or to enable others skilled in the art to understand the aspects disclosed herein.

[0011]

[0014] Aspects of the present disclosure generally relate to systems and methods for purifying hydrocarbons. In one embodiment, the systems and methods for purifying hydrocarbons include a hydrocarbon purification system. In one embodiment, the hydrocarbon purification system can include a countercurrent liquid-liquid extraction column, as described in detail below with reference to Figures 1A-3. The countercurrent liquid-liquid extraction column can include a fixed column, as shown in Figures 1A, 1B, and 3, and an agitated column, as shown in Figures 2A and 2B. The fixed column may not include a dynamic mechanism for inducing turbulent fluid flow, such as a mixer. The fixed column can use fixed flow paths to introduce the organic and aqueous phases at opposite ends of the reactor to promote contact between the organic and aqueous phases. In one embodiment, the fixed column can include packing, such as structured packing or multiple sieve trays, that can improve contact between the aqueous and organic phases.

[0012]

[0015] Referring now to FIG. 1A, a countercurrent liquid-liquid extraction column 100 is shown. The countercurrent liquid-liquid extraction column 100 includes a reactor 102. The reactor 102 comprises a vessel, storage container, or column compartment configured to hold about 1 to about 20 times the flow rate of the fluid stream 114, e.g., about 1 to about 5 times, about 5 to about 10 times, about 10 to about 15 times, or about 15 to about 20 times the flow rate of the fluid stream 114. In one embodiment, the reactor 102 can be a tubular plug flow reactor (PFR), a continuous stirred tank reactor (CSTR), or any combination of these reactor types, e.g., a PFR followed by a CSTR, a CSTR followed by a PFR, or a PFR followed by a CSTR followed by a PFR. Different reactor configurations provide various mixing, heat transfer, and residence times. In one embodiment, reactor 102 can operate at a temperature of about 50°C to about 500°C, e.g., about 50°C to about 100°C, about 100°C to about 150°C, about 150°C to about 200°C, about 200°C to about 250°C, or about 250°C to about 300°C, about 300°C to about 350°C, about 350°C to about 400°C, about 400°C to about 450°C, or about 450°C to about 500°C. In at least one embodiment, reactor 102 can include one or more heating devices, e.g., heat exchangers, to regulate the temperature of reactor 102. The heating devices can be internal and / or external to reactor 102.

[0013]

[0016] In one embodiment, the reactor 102 may be heated, cooled, or otherwise maintained at a constant temperature. For example, the reactor 102 may be maintained at a constant temperature of about 100° C. In one embodiment, the reactor 102 may have a temperature profile. As used herein, a "temperature profile" refers to a range of temperatures that vary throughout the reactor 102. For example, a first region of the reactor 102 may operate at a first temperature of about 100° C. to about 125° C., while a second region of the reactor 102 may operate at a second temperature of about 200° C. to about 250° C., as described in further detail below with reference to FIG. 4. Without being bound by theory, the temperature profile of the reactor 102 may enhance one or more of the reactivity and / or solubility properties of contaminants at different points in the reactor 102.

[0014]

[0017] In one embodiment, reactor 102 may operate at a pressure of from about 50 pounds per square inch gauge (psig) to about 900 psig, e.g., from about 50 psig to about 100 psig, from about 100 psig to about 200 psig, from about 200 psig to about 300 psig, from about 300 psig to about 400 psig, from about 400 psig to about 500 psig, from about 500 psig to about 600 psig, from about 600 psig to about 700 psig, from about 700 psig to about 800 psig, or from about 800 psig to about 900 psig. In one embodiment, steam 106 may be introduced at a pressure sufficient to cause turbulence, e.g., mixing, of the fluid within reactor 102. For example, steam can be introduced at a fluid flow rate of about 150 barrels per day (bpd) to about 5,000 bpd, e.g., about 150 bpd to about 500 bpd, about 500 bpd to about 1000 bpd, about 500 bpd to about 1500 bpd, about 1000 bpd to about 1500 bpd, about 1500 bpd to about 2000 bpd, about 2000 bpd to about 3000 bpd, about 3000 bpd to about 4000 bpd, or about 4000 bpd to about 5000 bpd.

[0015]

[0018] In one embodiment, steam 106 can be introduced into reactor 102 via lines 104a-104d. In one embodiment, steam 106 can be introduced at a temperature of about 150°C to about 270°C, e.g., about 150°C to about 200°C, about 200°C to about 250°C, or about 250°C to about 270°C. Without being bound by theory, each of lines 104a-104d can independently introduce steam 106 at different temperatures. For example, line 104a can introduce steam 106 at a first temperature of about 100°C to about 125°C, and line 104b can introduce steam 106 at a second temperature of about 200°C to about 250°C. In one embodiment, each of lines 104a-104d can independently introduce steam based on the temperature profile of reactor 102.

[0016]

[0019] The reactor 102 receives an aqueous phase 108 at a first end of the mixing zone 110 via a reactor line 112. In one embodiment, the line 112 can have a diameter of about 20 mm to about 150 mm, e.g., about 20 mm to about 40 mm, about 40 mm to about 60 mm, about 60 mm to about 80 mm, about 80 mm to about 100 mm, about 100 mm to about 120 mm, or about 120 mm to about 150 mm. The aqueous phase 108 can include a polar solvent, such as water, an alcohol, e.g., methanol, ethanol, propanol, or any combination thereof. For example, the aqueous phase 108 is water. As a further example, the aqueous phase 108 is or includes ethanol. The aqueous phase 108 can be introduced via the line 112 using a distributor 115. In one embodiment, the distributor 115 can introduce from 1% by weight (wt%) to about 100% by weight of the aqueous phase 108, e.g., from about 1% by weight to about 40% by weight, from about 20% by weight to about 40% by weight, from about 5% by weight to about 20% by weight, from about 5% by weight to about 10% by weight, from about 40% by weight to about 80% by weight, from about 50% by weight to about 70% by weight, or from about 60% by weight to about 100% by weight. In one embodiment, the distributor can generate droplets of the aqueous phase having a size or diameter of from about 1 mm to about 15 mm, e.g., from about 1 mm to about 5 mm, from about 5 mm to about 10 mm, or from about 10 mm to about 15 mm. Without being bound by theory, a droplet size of from about 1 mm to about 15 mm of the aqueous phase can increase the overall capacity of the reactor 102 to purify one or more hydrocarbons.

[0017]

[0020] Aqueous phase 108 can include from about 50 parts per million (ppm) to about 20,000 ppm, e.g., from about 50 ppm to about 1,000 ppm, from about 1,000 ppm to about 4,000 ppm, from about 4,000 ppm to about 6,000 ppm, from about 6,000 ppm to about 8,000 ppm, from about 8,000 ppm to about 10,000 ppm, or from about 10,000 ppm to about 20,000 ppm. In one embodiment, the one or more additives can be introduced into aqueous phase 108 in line 112, line 142, line 124, line 130, mixing region 110, or a combination thereof. The additives can be or include a hydrolyzing agent, an acid, a base, a salt, glycerin, a chelating agent, a polar solvent, a non-polar solvent, or any combination thereof. For example, the additive can include one or more hydrolysis agents. The hydrolysis agent can be or include any chemical capable of hydrolyzing hydrocarbons, such as fats, oils, or greases. For example, the hydrolysis agent can be or include citric acid, sulfuric acid, phosphoric acid, salts thereof, or any combination thereof. As a further example, the hydrolysis agent can be or include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, or any combination thereof. Without being bound by theory, the additive can react with triglycerides to separate the fatty acids of the triglycerides from the glycerin backbone, allowing for the purification of the fatty acids in the triglycerides. Furthermore, without being bound by theory, the additive can hydrolyze phospholipids and other contaminants more easily than fatty acids, allowing for the selective hydrolysis of phospholipids at lower temperatures and with shorter residence times than those required for the fatty acid splitting of triglycerides, reducing the production of free fatty acids in reactor 102. Additionally, without being bound by theory, the additive may increase the density and / or molecular weight of the aqueous phase 108 , thereby promoting faster separation of the organic phase 114 and the aqueous phase 108 .

[0018]

[0021] The aqueous phase 108 can be introduced into the reactor 102 at a temperature of about 20°C to about 200°C, e.g., about 20°C to about 50°C, about 50°C to about 100°C, about 100°C to about 150°C, or about 150°C to about 200°C. The aqueous phase 108 can be heated by a heating device (not shown), such as a heat exchanger, to form a heated aqueous phase. The heating device can be internal and / or external to the aqueous phase 108 and / or line 112. It should be understood that the aqueous phase 108 can be heated by any known process or device, including heat recovery from other processes described herein, to optimize overall thermal efficiency. For example, the aqueous phase 108 can be heated by steam 106 (not shown). In one embodiment, aqueous phase 108 can be introduced into reactor 102 at a pressure of from about 25 psig to about 1000 psig, e.g., from about 25 psig to about 100 psig, from about 100 psig to about 200 psig, from about 200 psig to about 300 psig, from about 300 psig to about 400 psig, from about 400 psig to about 500 psig, from about 500 psig to about 600 psig, from about 600 psig to about 700 psig, from about 700 psig to about 800 psig, from about 800 psig to about 900 psig, or from about 900 psig to about 1000 psig.

[0019]

[0022] Reactor 102 receives organic phase 114 via line 116 at a second end of mixing zone 110, the second end being opposite the first end of mixing zone 110. Organic phase 114 flows from the second end toward the first end such that organic phase 114 flows opposite the aqueous phase. As used herein, "opposite side" refers to a flow direction of the organic phase in mixing zone 110 relative to the flow of the aqueous phase in mixing zone 110 that is between about 135° and about 225°, e.g., between about 125° and about 150°, between about 150° and about 175°, between about 175° and about 185° (e.g., about 180°), between about 175° and about 200°, or between about 200° and about 225°. In one embodiment, the line 116 can include a diameter of about 20 mm to about 150 mm, e.g., about 20 mm to about 40 mm, about 40 mm to about 60 mm, about 60 mm to about 80 mm, about 80 mm to about 100 mm, about 100 mm to about 120 mm, or about 120 mm to about 150 mm.

[0020]

[0023] The organic phase 114 can be introduced into the reactor 102 at a temperature of about 50°C to about 250°C, e.g., about 50°C to about 100°C, about 100°C to about 150°C, about 150°C to about 200°C, or about 200°C to about 250°C. The organic phase 114 can be heated by a heating device (not shown), such as a heat exchanger, to form a heated aqueous phase. The heating device can be internal and / or external to the organic phase 114 and / or line 116. It should be understood that the organic phase 114 can be heated by any known process or device, including heat recovery from other processes described herein, to optimize overall thermal efficiency. For example, the organic phase 114 can be heated by steam 106 (not shown). In one embodiment, the organic phase 114 can be introduced into reactor 102 at a pressure of from about 25 psig to about 1000 psig, e.g., from about 25 psig to about 100 psig, from about 100 psig to about 200 psig, from about 200 psig to about 300 psig, from about 300 psig to about 400 psig, from about 400 psig to about 500 psig, from about 500 psig to about 600 psig, from about 600 psig to about 700 psig, from about 700 psig to about 800 psig, from about 800 psig to about 900 psig, or from about 900 psig to about 1000 psig.

[0021]

[0024] The organic phase 114 can include non-polar fluids, such as petroleum-based feedstocks, such as crude petroleum oil, shale oil, petroleum refinery intermediate streams (such as vacuum tower bottoms (VTB)), pyrolysis oil, recycled plastics, coal liquids, used motor oil, and mixtures thereof. Alternatively, the organic phase 114 can be a renewable feedstock, such as vegetable oil. Suitable vegetable oils include canola oil, carinata oil, castor oil, jatropha oil, palm oil, pongamia oil, soybean oil, tung oil, and / or corn oil (such as from distillers grains), soapstock, waste vegetable oil, yellow grease (from cooking oils), brown grease (from grease traps and wastewater treatment), highly acidic oils (also called acidic oils), animal tallow, algal oil, microbial oil, terpene and other pine-related by-products from tall oil, or other biosynthetic oils (such as those derived from pyrolysis, esterification, oligomerization, or polymerization), and mixtures thereof. In one embodiment, the organic phase 114 may be plant-based, animal-based, insect-based, microbial-based, or any combination thereof.

[0022]

[0025] Organic phase 114 can also include from about 50 ppm to about 20,000 ppm, e.g., from 50 ppm to about 1,000 ppm, from about 1,000 ppm to about 4,000 ppm, from about 4,000 ppm to about 6,000 ppm, from about 6,000 ppm to about 8,000 ppm, from about 8,000 ppm to about 10,000 ppm, or from about 10,000 ppm to about 20,000 ppm. In one embodiment, the one or more additives can be introduced into organic phase 114 in line 116, line 1146, line 128, line 140, mixing zone 110, or a combination thereof.

[0023]

[0026] In at least one embodiment, the organic phase 114 has a concentration of from about 1 parts per million (ppm) to about 5000 ppm, e.g., from about 1 ppm to about 100 ppm, from about 100 ppm to about 200 ppm, from about 200 ppm to about 300 ppm, from about 300 ppm to about 400 ppm, from about 400 ppm to about 500 ppm, from about 500 ppm to about 600 ppm, from about 600 ppm to about 700 ppm, from about 700 ppm to about 800 ppm, from about 800 ppm to about 900 ppm, or 00 ppm, about 900 ppm to about 1000 ppm, about 1000 ppm to about 1100 ppm, about 1100 ppm to about 1200 ppm, about 1200 ppm to about 1300 ppm, about 1300 ppm to about 1400 ppm, about 1400 ppm to about 1500 ppm, about 1500 ppm to about 300 ppm, or about 3000 ppm to about 5000 ppm of one or more contaminants, e.g., organic materials and / or inorganic materials. For example, inorganic materials can include halides such as chlorine-containing compounds including chlorine, chloride, chlorate, chlorite, chlorite salts, or any combination thereof (e.g., F, Cl, Br, I), phosphorus and phosphorus-containing compounds and species, sulfur and sulfur-containing compounds and species, arsenic and arsenic-containing compounds and species, alkali metals and metalloids (e.g., B, Na, K, Si), heavy metals (Pb, Hg, Sb, Sn, Tl), and other metals (e.g., Ca, Fe, Mg, Ni, V, Zn, As, Al, Pb, Ba, Mn, Cr, Cu). As further examples, the organic material can include asphaltenes, polymers (such as polyesters and / or polypropylenes), high molecular weight organic compounds or waxes (e.g., those containing more than 50 carbon atoms, more than 60 carbon atoms, and / or those having a boiling point greater than 600°C), coke, coke precursors, nitrogen-containing compounds (e.g., amines, amides, imines, enamines, nitrates, nitrites, proteins, amino acids, or any combination thereof), fatty acids (e.g., triglycerides, diglycerides, monoglycerides, or any combination thereof), organic salts, organic soaps, or any combination thereof.

[0024]

[0027] The organic phase 114 can be introduced via line 116 using a distributor 118. In one embodiment, distributor 118 can introduce an organic phase at a rate of 500 to about 50,000 bpd, e.g., about 500 bpd to about 1,000 bpd, about 1,000 bpd to about 10,000 bpd, about 10,000 bpd to about 30,000 bpd, or about 30,000 bpd to about 50,000 bpd. Without being bound by theory, distributor 118 can disperse the flow of organic phase 114 to provide a uniform distribution throughout mixing region 110. In one embodiment, the distributor can generate droplets of organic phase that are about 1 mm to about 15 mm, e.g., about 1 mm to about 5 mm, about 5 mm to about 10 mm, or about 10 mm to about 15 mm. Without being bound by theory, a droplet size of about 1 mm to about 15 mm in the organic phase can increase the overall capacity of reactor 102 to purify one or more hydrocarbons.

[0025]

[0028] In one embodiment, the organic phase 114 and the aqueous phase 108 can be introduced into the mixing zone 110 of the reactor 102 to provide a water-to-oil weight ratio in the mixing zone 110 of about 1:100 to about 3:1, e.g., about 1:10 to about 1:1. In one embodiment, the organic phase 114 and the aqueous phase 108 can be introduced via countercurrent fluid flow to create turbulent flow conditions. In one embodiment, the organic phase 114 can be introduced into the mixing zone 110 such that the organic phase 114 is the continuous phase, e.g., greater than 50% of the volume of the mixing zone, and the aqueous phase 108 is the dispersed phase, e.g., less than 50% of the volume of the mixing zone 110. Without being bound by theory, the continuous organic phase can increase the residence time of the reaction, increasing the time it takes for the aqueous phase to separate from the organic phase and allowing for more efficient heating in the mixing zone. Alternatively, in one embodiment, the organic phase 114 can be introduced into the mixing region such that the organic phase 114 is the dispersed phase, e.g., less than 50% of the volume of the mixing region 110, and the aqueous phase 108 is the continuous phase, e.g., more than 50% of the volume of the mixing region 110. Without being bound by theory, a continuous phase that is an aqueous phase may result in faster separation of the organic and aqueous phases and / or reduced residence time compared to when the continuous phase is an aqueous phase.

[0026]

[0029] For example, turbulent flow conditions can include turbulence exhibiting a Reynolds number (Re) of about 1000 to about 5000, e.g., about 1000 Re to about 2000 Re, about 2000 Re to about 3000 Re, about 3000 Re to about 4000 Re, or about 4000 Re to about 5000 Re. Without being bound by theory, countercurrent fluid flow to create turbulent conditions can optimize mixing and maximize heat transfer between the aqueous and organic phases.

[0027]

[0030] In one embodiment, the organic phase 114 and the aqueous phase 108 can be mixed in a mixing zone 110, where the refined hydrocarbon 120 can rise to a refined zone 122 of the reactor 102. The refined hydrocarbon 120 can be or can include a purified oil in which about 90% to about 100% of the contaminants have been removed from the oil, compared to the organic phase 114, e.g., about 90% to about 92%, about 92% to about 94%, about 94% to about 96%, about 96% to about 98%, or about 98% to about 100% of the contaminants have been removed from the oil. For example, the refined hydrocarbon 120 can have about a 95% reduction in the contaminant content of the oil, e.g., phosphorus, salt, mineral, and / or metal content, compared to the organic phase 114. By way of further example, the organic phase 114 can include from about 100 ppm to about 2000 ppm phosphorus, and the refined hydrocarbon 120 can include from about 1 ppm to about 50 ppm, e.g., from 1 ppm to about 10 ppm, from about 10 ppm to about 20 ppm, from about 20 ppm to about 30 ppm, from about 30 ppm to about 40 ppm, or from about 40 ppm to about 50 ppm phosphorus. In one embodiment, the refined hydrocarbon 120 can include less than 0.2% carbon residue, less than 0.1% asphaltenes, less than 0.05% ash, and / or less than 20 ppm total metals. In another embodiment, refined hydrocarbon 120 can include less than 0.1 ppm to about 3000 ppm nitrogen, less than 0.1 ppm to about 1000 ppm chlorine, less than 0.1 ppm to about 1500 ppm calcium, less than 0.1 ppm to about 800 ppm iron, less than 0.1 ppm to about 600 ppm potassium, and less than 0.1 ppm to about 800 ppm sodium.

[0028]

[0031] In one embodiment, the organic phase 114 and the aqueous phase 108 can be mixed in a mixing zone where the waste 124 can fall or be introduced into the waste region 126. The waste 124 can include the aqueous phase 108 with contaminants from the organic phase 114. In one embodiment, the waste 124 can include from about 50 ppm to about 30,000 ppm, e.g., from about 50 ppm to about 500 ppm, from about 500 ppm to about 1000 ppm, from about 1000 ppm to about 10,000 ppm, or from about 10,000 ppm to about 30,000 ppm of phosphorus, salts, metal content, and / or minerals. In one embodiment, the waste 124 can be free or substantially free of the organic phase 114. For example, the waste 124 may contain about 0.01% v / v to about 1% v / v of the organic phase 114, e.g., about 0.01% v / v to about 0.05% v / v, about 0.05% v / v to about 0.1% v / v, about 0.1% v / v to about 0.5% v / v, or about 0.5% v / v to about 1% v / v.

[0029]

[0032] In one embodiment, the refined hydrocarbons 120 and the waste material 124 may be separated in the mixing region 110 based on density. For example, the refined hydrocarbons may have a density of 1 g / cm 3 Less than, for example, 0.9 g / cm 3 Less than 0.8g / cm 3 Less than 0.7g / cm 3 Less than 0.6g / cm 3 Less than or equal to 0.5g / cm 3 The waste material 124 may have a density of less than about 0.5 g / cm 3 For example, about 0 / 5g / cm 3 , about 1g / cm 3 , about 1.1g / cm 3 , about 1.2g / cm 3 , about 1.3g / cm 3 , approximately 1.4 g / cm 3 , or about 1.5 g / cm 3The waste density may be greater than the refined hydrocarbon density. In one embodiment, the refined hydrocarbon 120 may rise above the waste 124 due to gravity and the waste 124 being denser than the refined hydrocarbon 120. Additionally, the rate at which the aqueous phase 108 and organic phase 114 separate may depend on the droplet size of each organic and aqueous phase 108 (e.g., from about 100 microns to about 20 mm, e.g., from about 100 microns to about 1 mm, from about 1 mm to about 10 mm, or from about 10 mm to about 20 mm), the agitation (e.g., pulsation, rotation, or vibration (frequency, amplitude, rpm, etc.)), the coalescing media (random packing, structured packing, coalescing elements, hydrophilic, hydrophobic, dispersed phase, or continuous phase), the temperature (e.g., from about 100° C. to about 200° C., e.g., from about 100° C. to about 200° C., e.g., from about 100° C. to about 200° C.), and the rate at which the aqueous phase 108 and organic phase 114 separate may depend on factors such as the droplet size of each organic and aqueous phase 108 (e.g., from about 100 microns to about 1 mm, from about 1 mm to about 10 mm, or from about 10 mm to about 20 mm), the agitation (e.g., pulsation, rotation, or vibration (frequency, amplitude, rpm, etc.)), the coalescing media (random packing, structured packing, coalescing elements, hydrophilic, hydrophobic, dispersed phase, or continuous phase), the temperature (e.g., from about 100° C. to about 200° C., e.g., from about 100° C. to about 200° C.), and the amount of the aqueous to about 150°C, or about 150°C to about 200°C), density (e.g., a larger density difference may promote faster separation), and viscosity (e.g., about 0.1 centipoise (cP) to about 1.8 cP (e.g., about 0.1 cP to about 0.5 cP, about 0.5 cP to about 1 cP, or about 1 cP to about 1.8 cP) for the aqueous phase and about 5 cP to about 1,000 cP (e.g., about 5 cP to about 100 cP, about 100 cP to about 500 cP, or about 500 cP to about 1,000 cP) for the organic phase).

[0030]

[0033] The refined hydrocarbons 120 may be extracted via line 128. In one embodiment, a filter (not shown) may be disposed in line 128. The filter (not shown) may remove contaminants that may remain in the refined oil 120 or may prevent the contaminants from being introduced into further processing, as described below. In one embodiment, the filter (not shown) may include a ceramic cloth membrane filter.

[0031]

[0034] The refined hydrocarbons 120 can be extracted at a temperature of about 200°C to about 300°C, e.g., about 200°C to about 220°C, about 220°C to about 240°C, about 240°C to about 260°C, about 260°C to about 280°C, or about 280°C to about 300°C. The refined hydrocarbons 120 can be directed to a first coalescer 138a. The first coalescer 138a can include a mechanical and / or electrostatic coalescer suitable for separating the residual aqueous phase 114, if any, from the refined oil 120. The refined oil 120 exits the first coalescer 138a via line 140 and can be further processed (not shown) into chemicals or fuels, depending on the type of refined hydrocarbon and product objective. Renewable oils and petroleum can be hydrothermally cracked through a fast reactor system to produce synthetic crude oil, which can then be hydrotreated to produce transportation fuels or chemicals. Alternatively, renewable oils can be converted to biodiesel via esterification or hydrotreating, hydroisomerization, and hydrocracking to renewable fuels and chemicals through conventional refining processes.

[0032]

[0035] In at least one embodiment, the residual aqueous phase 114 recovered by the first coalescer 138a can be directed to the mixing zone 110 of the reactor 102 via line 142. Alternatively, the residual aqueous phase 114 recovered by the first coalescer 138a can be directed to the purification zone 122 and / or waste zone 126 of the reactor 102.

[0033]

[0036] Waste 124 may be extracted via line 130. In one embodiment, a filter (not shown) may be disposed in line 130. In one embodiment, a filter (not shown) may be disposed in either line 426 and / or 416, with reference to FIG. 4 . The filter (not shown) may remove contaminants that may remain in waste 124 or may prevent the contaminants from being introduced into further processing, as described below. In one embodiment, the filter (not shown) may include a ceramic cloth membrane filter.

[0034]

[0037] The waste 124 can be extracted at a temperature of about 200°C to about 300°C, e.g., about 200°C to about 220°C, about 220°C to about 240°C, about 240°C to about 260°C, about 260°C to about 280°C, or about 280°C to about 300°C. The waste 124 can be directed to a second coalescer 138b. The second coalescer 138b can include a mechanical and / or electrostatic coalescer suitable for separating the residual organic phase 108, if any, from the waste 124. The waste 124 can exit the second coalescer 138b via line 144 and can be further treated, reused, or processed for by-product recovery, landfill, or recycling. The waste 124 can be treated to remove one or more salts extracted from the organic phase 114 from the waste 124 so that the waste 124 can be recycled as the aqueous phase 108, as described in detail below with reference to Figure 4. In one embodiment, a countercurrent liquid-liquid extraction column 100 shown in Figures 1A and 1B can be used for rapid hydrolysis, and pure glycerin can be extracted into the waste 124 and recovered by a conventional distillation process. In one embodiment, the waste 124 can include water and additive ions, such as phosphate and / or citrate ions, which can be recovered and reused as a nutrient source for growing crops or algae.

[0035]

[0038] In at least one embodiment, the residual organic phase 108 recovered by the second coalescer 138b can be directed to the mixing region 110 of the reactor 102 via line 146. Alternatively, the residual organic phase 108 recovered by the second coalescer 138b can be directed to the purification region 122 and / or the waste region 126 of the reactor 102.

[0036]

[0039] In one embodiment, coalescers, e.g., mechanical and / or electrostatic coalescers, can be located in reactor 102, e.g., purification region 122, mixing region 110, and / or waste region 126. Although only two coalescers are shown in Figure 1A, any number of coalescers can be implemented, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more coalescers.

[0037]

[0040] Referring now to FIG. 1B, a schematic diagram of an extraction column 100 having packing material 132 is shown. Packing material 132 can include structured packing or multiple sieve trays. For example, packing material 132 can include a polymeric material, a ceramic material, a metallic material, and / or a glass material. In one embodiment, one or more packing materials 132a-132b can be disposed within extraction column 100. For example, first packing material 132a can be disposed in reactor mixing region 110 adjacent to purification region 122, and second packing material 132b can be disposed in reactor mixing region 110 adjacent to waste region 126. Although only two packing materials 132a-132b are shown, any number of packing materials can be disposed in reactor mixing region 110. For example, one, two, three, four, five, or more packing materials can be disposed in reactor mixing region 110. Without being bound by theory, the filler 132 may be arranged in the mixing region 110 based on one or more of void fraction, surface area, unit volume, random packing arrangement, structured packing arrangement, trays, continuous phase, dispersed phase, viscosity, and / or surface tension.

[0038]

[0041] The packing material can restrict the flow of one or more of the aqueous phase 108 and / or organic phase 114, such that the upward flow of the organic phase 114 cannot exceed the rate at which the aqueous phase 108 flows down the extraction column 100. Additionally, the rate at which the aqueous phase 108 flows down the extraction column 100 can vary based on the droplet size, agitation, coalescing media, temperature, density, and viscosity of the aqueous phase 108. Without being bound by theory, restricting the flow of the aqueous phase 108 and / or organic phase 114 may result in additional mixing during countercurrent flow, increasing the amount of contaminants removed from the organic phase 114.

[0039]

[0042] In one embodiment, extraction column 100 can include pump 134. Pump 134 can include any pump capable of generating pulsation in extraction column 100 via line 136. Although only one pump 134 is shown, any number of pumps 134, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more pumps, can be incorporated to provide sufficient pulsation to waste region 126, mixing region 110, and / or purification region 122. Without being bound by theory, pulsation can provide better agitation and interaction between aqueous phase 108 and organic phase 114 during countercurrent flow through reactor 102 compared to conventional cocurrent flow through reactor 102.

[0040]

[0043] Referring now to FIG. 2A, a schematic diagram of an agitated extraction column 200 is shown. The agitated extraction column 200 can include any of the extraction columns 100, as described in detail above with reference to FIGS. 1A and 1B. The agitated extraction column 200 can include an actuator 202. The actuator 202 can include any component suitable for generating force, torque, or displacement of another component within the agitated extraction column 200. For example, the actuator 202 can include an electric actuator, a pneumatic actuator, a hydraulic actuator, or a servomotor. In one embodiment, the actuator 202 actuates a drive shaft 204. The drive shaft 204 can include metal, wood, ceramic, glass, or a polymer. For example, the drive shaft 204 can include a metal rod, such as titanium or stainless steel. Without being bound by theory, the drive shaft 204 can agitate or mix the fluids within the mixing region 110 without oxidizing or reacting the aqueous phase 108 and / or the organic phase 114.

[0041]

[0044] The drive shaft 204 can extend from a first side of the reactor 102 toward a second side of the reactor 102. The drive shaft 204 can rotate about an axis, e.g., a longitudinal axis. In one embodiment, the drive shaft 204 can rotate about the longitudinal axis, and the plurality of displacement components 206a-j can agitate the aqueous phase 108 and the organic phase 114, which flow countercurrently through the mixing region 110. Each displacement component of the plurality of displacement components 206a-j can be any suitable device suitable for displacing fluids within the mixing region 110. For example, each displacement component of the plurality of displacement components 206a-j can independently be or include an impeller, paddle, propeller, agitator, spinner, blade, or any combination thereof. In one embodiment, each displacement component of the plurality of displacement components 206a-j can independently be or include a metal, wood, ceramic, glass, or polymer. For example, each displacement element of the plurality of displacement elements 206a-206j can comprise a metal rod, such as titanium or stainless steel. Although ten displacement elements 206a-206j are shown, any number of displacement elements can be implemented in the stirred extraction column 200, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more displacement elements.

[0042]

[0045] Drive shaft 204 can be configured to rotate plurality of displacement components 206a-206j at a speed of about 5 RPM to about 1200 RPM, e.g., about 5 RPM to about 100 RPM, about 100 RPM to about 500 RPM, about 500 RPM to about 1000 RPM, or about 1000 RPM to about 1200 RPM. Without being bound by theory, rotating plurality of displacement components 206a-206j at a speed of about 30 RPM to about 300 RPM can enhance interaction between aqueous phase 108 and organic phase 114 while allowing separation into waste region 126 and purification region 122.

[0043]

[0046] In one embodiment, reactor 102 can include a plurality of baffles 208a-208k disposed on a wall of reactor 102. Each baffle in the plurality of baffles 208a-208k can separate each of the plurality of displacement components 206a-206j. Without being bound by theory, separating each of the plurality of displacement components 206a-206j with each of the plurality of baffles 208a-208k can result in improved mass transfer between aqueous phase 108 and organic phase 114 due to increased agitation in mixing region 110.

[0044]

[0047] Referring now to FIG. 2B, a schematic diagram of an agitated extraction column 200 is shown. The agitated extraction column 200 can include any of the extraction columns 100, as described in detail above with reference to FIGS. 1A and 1B. The agitated extraction column 200 can include an oscillator 210. The oscillator 210 can include any component suitable for vibrating other components within the agitated extraction column 200. In one embodiment, the oscillator can be coupled to a central shaft 212, and the oscillator 210 can vibrate the central shaft longitudinally. The central shaft 212 can include one or more types of material, such as metal, wood, ceramic, glass, polymer, or any combination thereof. For example, the central shaft 212 can include a metal rod, such as titanium or stainless steel. Without being bound by theory, the central shaft 212 can vibrate within the mixing region 110 based on the oscillator 210 without oxidizing or reacting the aqueous phase 108 and / or organic phase 114. The central shaft 212 can extend from a first side of the reactor 102 toward a second side of the reactor 102 .

[0045]

[0048] In one embodiment, the stirred extraction column 200 includes a plurality of porous elements 214a-214i. Each porous element of the plurality of porous elements 214a-214i can comprise metal, wood, ceramic, glass, or a polymer. For example, each porous element of the plurality of porous elements 214a-214i can independently be or include a ceramic porous element and / or a metal porous element. Although only nine porous elements 214a-214i are shown, any number of porous elements can be implemented in the stirred extraction column 200, e.g., 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more porous elements.

[0046]

[0049] In one embodiment, each of the plurality of porous plates can have an average pore size of about 3 mm to about 50 mm, e.g., about 3 mm to about 10 mm, about 10 mm to about 20 mm, about 20 mm to about 30 mm, about 30 mm to about 40 mm, or about 40 mm to about 50 mm. Without being bound by theory, smaller pore size may increase agitation within mixing region 110 and enhance interactions between aqueous phase 108 and organic phase 114.

[0047]

[0050] In one embodiment, the plurality of porous components 214a-214i may be vibrated longitudinally by the oscillator 210 at a frequency of about 0.5 Hz to about 60 Hz, e.g., about 0.5 Hz to about 5 Hz, about 5 Hz to about 20 Hz, about 20 Hz to about 40 Hz, or about 40 Hz to about 60 Hz. In one embodiment, the plurality of porous components 214a-214i may be vibrated longitudinally by the oscillator 210 at a distance of about 10 mm to about 150 mm, e.g., about 10 mm to about 50 mm, about 50 mm to about 100 mm, or about 100 mm to about 150 mm. Without being bound by theory, oscillator 210 vibrating multiple porous elements 214a-214i at a greater frequency and / or distance can enhance the interaction between aqueous phase 108 and organic phase 114, simultaneously enabling separation into waste region 126 and purification region 122.

[0048]

[0051] Referring now to FIG. 3, a schematic diagram of a countercurrent mixer-settler system 300 is shown. The countercurrent mixer-settler system 300 can include a first reactor 102a. The first reactor 102a can include any of the reactors 102 described above with reference to FIGS. 1A and 1B. In one embodiment, the first reactor 102a receives an aqueous phase 108 from a distributor 115 via line 112. The aqueous phase 108 enters a first mixing zone 110a of the first reactor 102a. The first mixing zone 110a can include a first actuator 202a, a first drive shaft 204a, and a first displacement element 206a. The organic phase 114 enters the first mixing zone 110a via line 302. The aqueous phase 108 and organic phase 114 exit the first mixing zone 110a and separate based on gravity, droplet size, agitation, coalescing media, temperature, density, and viscosity, as described above, to form a first purification zone 122a and a first waste zone 126a.

[0049]

[0052] The refined hydrocarbons 120 are extracted from the first purification zone 122a, while the waste 124 in the first waste zone 126a flows through line 304 to the second reactor 102b. The second reactor 102b can include any of the reactors 102 described above with reference to FIGS. 1A and 1B. In one embodiment, the second reactor 102b receives the aqueous phase 108 from the first waste zone 126a via line 304. The aqueous phase 108 enters a second mixing zone 110b of the second reactor 102b. The second mixing zone 110b can include a second actuator 202b, a second drive shaft 204b, and a second displacement component 206b. The organic phase 114 enters the second mixing zone 110b via line 306. The aqueous phase 108 and organic phase 114 exit the second mixing zone 110b and separate based on gravity, droplet size, agitation, coalescing media, temperature, density, and viscosity, as described above, to form the second purification zone 122b and the second waste zone 126b. The purified hydrocarbons from the second purification zone 122b can be directed to the first mixing zone 110a via line 302.

[0050]

[0053] In one embodiment, the waste 124 from the second waste region 126b can be directed to a third mixing region 110c via line 308 of a third reactor 102c. The third reactor 102c can include any of the reactors 102 described above with reference to Figures 1A and 1B. In one embodiment, the third reactor 102c receives the aqueous phase 108 from the second waste region 126b via line 308. The third mixing region 110c can include a third actuator 202c, a third drive shaft 204c, and a third displacement component 206c. The organic phase 114 enters the third mixing region 110c via line 116. The aqueous phase 108 and organic phase 114 exit the third mixing zone 110c and separate based on gravity, droplet size, agitation, coalescing media, temperature, density, and viscosity, as described above, to form a third purification zone 122c and a third waste zone 126c. The purified hydrocarbons from the third purification zone 122c can be directed to the second mixing zone 110b via line 306. The waste 124 from the third waste zone 126c can be extracted from the countercurrent mixer-settler system 300 via line 130.

[0051]

[0054] Although only three reactors 102a, 102b, and 102c are shown, countercurrent mixer-settler system 300 can include any number of reactors suitable for purifying one or more organic phases, such as two reactors, three reactors, four reactors, five reactors, six reactors, seven reactors, eight reactors, nine reactors, ten reactors, or more than ten reactors. Without being bound by theory, the organic phase flowing through each reactor of the plurality of reactors is progressively purified, with purified hydrocarbons exiting the first reactor 102a of the plurality and waste 124 exiting the last reactor of the plurality of reactors.

[0052]

[0055] In at least one embodiment, reactors 102a, 102b, and 102c can include one or more heating devices, such as integral coils, recuperative heat exchangers, and / or primary heat exchangers, to regulate the temperature of reactor 102. The heating devices can be internal and / or external to reactor 102. Additionally, in at least one embodiment, reactors 102a, 102b, and 102c can each independently include one or more direct steam injections (not shown). Without wishing to be bound by theory, the temperatures of organic phase 114 and aqueous phase 108 can be adjusted to facilitate heat transfer between successive mixing zones, such that each of organic phase 114 and aqueous phase 108 acts as a heat exchanger within the mixing zone. Additionally, without wishing to be bound by theory, each mixing zone can be independently operated at a different temperature, from about 50°C to about 300°C, to facilitate the refining of one or more hydrocarbons, such as oils, fats, greases, or any combination thereof.

[0053]

[0056] Referring now to FIG. 4, a schematic diagram of a countercurrent liquid-liquid extraction column 400 is shown. The countercurrent liquid-liquid extraction column 400 includes a reactor 102, which may include any of the reactors 102 described in detail above with reference to FIGS. 1A and 1B. In one embodiment, the reactor 102 includes a temperature profile, which includes a first temperature "T1" and a second temperature "T2." In one embodiment, each of T1 and T2 may independently be from about 50°C to about 300°C, e.g., from about 50°C to about 100°C, from about 100°C to about 150°C, from about 150°C to about 200°C, from about 200°C to about 250°C, or from about 250°C to about 300°C. In one embodiment, T1 may be greater than T2. ​​In one embodiment, T2 may be greater than T1. Without being bound by theory, when T2 is greater than T1, increased hydrocarbon refinery may occur.

[0054]

[0057] In one embodiment, a temperature profile including T1 and T2 can be established using an external heater (not shown). A portion of the volume within the mixing zone 110 can be extracted from a first zone of the mixing zone 110, e.g., T1 or T2. The portion can be directed to a heat exchanger (not shown) external to the reactor 102. The heat exchanger (not shown) can heat the portion of the volume received from the mixing zone and reintroduce the heated portion of the volume into a second zone of the mixing zone 110, e.g., T1 or T2. For example, a temperature profile can be established by extracting a portion of the volume within the mixing zone 110 from a first zone, such as T2, heating the portion using an external heat exchanger (not shown), and directing the heated portion into the second zone of the mixing zone 110. Without being bound by theory, the temperature profile can help reduce the pressure in the reactor 102 and lower the temperature throughout the reactor to prevent impurities or coking from impurities.

[0055]

[0058] In one embodiment, a portion of the volume within the mixing zone 110 can be extracted from the first region of the mixing zone 110 and directed to an external vessel, e.g., a storage vessel, a transfer line, a tank, a holder, a valve, or a combination thereof. The external vessel can be heated by a heat exchanger (not shown) external to the reactor 102. The external vessel can hold a portion of the volume such that there is a residence time of about 1 second to about 30 days, e.g., about 1 second to about 60 seconds, about 60 seconds to about 1 hour, about 1 hour to about 24 hours, about 24 hours to about 7 days, or about 7 days to about 30 days. The external vessel can transfer a portion of the volume to the mixing zone 110, and transferring the portion of the volume of the mixing zone 110 can include cooling the portion of the volume. For example, the portion of the volume of the mixing zone 110 can be cooled using a cooling system, e.g., a water chiller, a chiller, a refrigeration system, or the like. In one embodiment, the cooling system can cool a portion of the volume to a temperature of about 5° C. to about 250° C., e.g., about 5° C. to about 20° C., about 20° C. to about 50° C., about 50° C. to about 100° C., about 100° C. to about 150° C., about 150° C. to about 200° C., or about 200° C. to about 250° C. Without being bound by theory, cooling a portion of the volume of the mixing zone within the outer vessel prior to reintroduction into the mixing zone 110 can reduce the pressure and / or temperature of the reactor 102 to prevent the formation of impurities or coking from the impurities within the reactor 102.

[0056]

[0059] In one embodiment, the aqueous phase 108 is introduced into the mixing zone 110 of the reactor 102 via line 112. In one embodiment, the line 112 can have a diameter of about 20 mm to about 150 mm, e.g., about 20 mm to about 40 mm, about 40 mm to about 60 mm, about 60 mm to about 80 mm, about 80 mm to about 100 mm, about 100 mm to about 120 mm, or about 120 mm to about 150 mm. In one embodiment, the aqueous phase 108 can be introduced into the mixing zone 110 of the reactor using one or more pumps (not shown). The aqueous phase 108 can be introduced into the mixing zone 110 at a temperature of about 20°C to about 80°C, e.g., about 20°C to about 40°C, about 40°C to about 60°C, or about 60°C to about 80°C.

[0057]

[0060] Simultaneously, organic phase 114 can be introduced into countercurrent liquid-liquid extraction column 400 via line 402 using one or more pumps (not shown) at a temperature of about 80°C to about 100°C, e.g., about 80°C to about 90°C, about 90°C to about 95°C, or about 95°C to about 100°C. Without being bound by theory, heating the organic phase before contacting it with the aqueous phase may reduce phospholipid loss from the organic phase. Line 402 can direct organic phase 114 through valve 404. Valve 404 can include a T-valve. The T-valve can direct a portion of waste 124 exiting reactor 102 toward organic phase 114 into organic phase 114 via line 406. In one embodiment, the temperature of the portion of waste in line 406 can be about 80°C to about 100°C, e.g., about 80°C to about 90°C, about 90°C to about 95°C, or about 95°C to about 100°C. In one embodiment, T-valve 404 can generate a mixture by introducing waste 124 such that line 408 contains about 70% v / v to about 90% v / v organic phase 114 and about 10% v / v to about 30% v / v waste 124.

[0058]

[0061] In one embodiment, line 408 can direct the organic phase 114 to a recuperator 410. Additionally, waste 124 can exit the reactor 102 via waste region 126 and be directed to a compressor 424 via line 130. In one embodiment, line 130 can include one or more filters and / or filtration systems, as described in detail above. For example, line 130 can include a micro-crossflow filtration system. Without being bound by theory, line 130 with a filter and / or filtration system can purify waste 124 so that it can be recycled to the reactor 102 as a purified aqueous phase. The compressor 424 can compress waste 124 to a pressure above the pressure of the reactor 102, for example, from about 10 psi to about 50 psi, e.g., from about 10 psi to about 20 psi, from about 20 psi to about 30 psi, from about 30 psi to about 40 psi, or from about 40 psi to about 50 psi. The compacted waste material can be directed to recuperator 410 via line 426 .

[0059]

[0062] In one embodiment, recuperator 410 can receive the compressed waste product via line 426 and the organic phase 114 via line 408, and recuperator 410 directs the fluids using one or more revalves and / or gates that can direct and / or bypass the fluids. In one embodiment, recuperator 410 can direct organic phase 114 and / or a mixture of the organic phase and the waste product to mixing zone 110 via line 412. Alternatively, or simultaneously, recuperator 410 can direct the waste product and / or a mixture of the organic phase and the waste product to line 414, exit countercurrent liquid-liquid extraction column 400 via line 416, and / or to cooling unit 418 via line 420. Without being bound by theory, recuperator 410 may reduce phospholipid losses that can occur when the incoming oil is preheated by the waste product 124 that has just exited reactor 102.

[0060]

[0063] In one embodiment, cooling unit 418 can cool organic phase 114 and / or the mixture of organic phase 114 and waste material 124 to a temperature of about 70° C. to about 90° C., e.g., about 70° C. to about 80° C., about 80° C. to about 85° C., or about 85° C. to about 90° C. The cooled organic phase 114 and / or the mixture can be introduced into mixing zone 110 via line 422.

[0061]

[0064] Without being bound by theory, the recuperator 410 and cooling unit 418 may result in an overall net water usage reduction for the countercurrent fluid flow. By using a recuperator to recycle the waste 124, the aqueous phase 108 may be reused and recycled to extract impurities from the organic phase 114 multiple times before being removed from the countercurrent liquid-liquid extraction column 400. Furthermore, the waste 124 exiting the waste region 126 of the reactor 102 may have an elevated temperature of about 100° C. to about 300° C., which may provide effective heat transfer to the organic phase 114 before entering the mixing region 110 of the reactor 102. Therefore, a reduction of about 5% to about 50% of the aqueous phase 108 introduced via line 112 may occur. For example, about 1% to about 40% of the water volume in mixing region 110 can originate as aqueous phase 108 via line 112, while about 60% to about 99% of the water volume in mixing region 110 can originate from recuperator 410 via line 412 and / or line 422.

[0062]

[0065] In one embodiment, each of lines 112, 402, 406, 408, 412, 414, 416, 420, 422, and 426 can independently include a diameter of about 20 mm to about 150 mm, e.g., about 20 mm to about 40 mm, about 40 mm to about 60 mm, about 60 mm to about 80 mm, about 80 mm to about 100 mm, about 100 mm to about 120 mm, or about 120 mm to about 150 mm.

[0063] [Example]

[0066] Tests were conducted in a 1-liter stainless steel Parr reactor equipped with a magnetically coupled stirrer. The reactor was externally heated by an electric heating coil. The reactor was instrumented with a thermocouple and a 500 psig pressure transducer and monitored by an Allen Bradley CompactLogix™ programmable logic controller, which also controlled the heating coil. The reactor was vented at the start of each test and allowed to fill with steam before closing the vent.

[0064]

[0067] Tests were conducted at various temperatures and durations, as shown in Table 1 below. Each test included crude degummed organic soybean oil, distilled water, and approximately 1000 ppm citric acid. The crude degummed soybean oil had a starting free fatty acid content of 1.3 wt % and phosphorus of 1329 ppm. The "Liq Water" column in the table is an estimate of the water content of the reaction mixture, taking into account the water vapor filling the reactor headspace.

[0065] [Table 1]

[0066]

[0068] Phosphorus levels below 1 ppm were achieved at all temperatures above 237.8°C, and even at temperatures as low as 218.9°C when 3.4 g of citric acid was present. Without being bound by theory, the higher the temperature, the less phosphorus. Furthermore, increasing the residence time from 3 to 11 minutes significantly reduced phosphorus.

[0067]

[0069] Three additional tests were conducted using the same methodology as above. Test 1 utilized crude soybean oil from a primary source, while Tests 2 and 3 utilized crude degummed soybean oil (CDSBO) obtained from a secondary source. The reaction conditions were also the same for all three batches: approximately 238°C at a pressure of approximately 450 psig for approximately 10-12 minutes. Approximately 30% of the water was in the liquid phase, with the remainder in the reactor headspace.

[0068]

[0070] After each test, the reactor was rapidly cooled, and the reactor contents were poured into a separatory funnel and allowed to settle at approximately 77°C for approximately 2-3 hours. The water separated at the bottom of the separatory funnel and was discarded. The rag layer, along with several grams of recovered oil, was transferred to a graduated vial. The rag layer was allowed to settle, and the rag and oil were measured using the vial's scale. The oil remaining in the separatory funnel was dried and weighed. This weight was added to the oil measurement above the rag in the graduated vial and is recorded below as "recovered oil." Additionally, residual oil was wiped from the reactor and agitator using paper towels of known starting weight. The paper towels were reweighed, and the additional weight was recorded in Table 2 as "reactor residue." The data is presented below; see Table 2.

[0069] [Table 2]

[0070] [Embodiment]

[0071] Aspects of the present disclosure further relate to any one or more of the following embodiments E1-E27.

[0071]

[0072] E1. A method for purifying hydrocarbons, the method comprising the steps of: flowing an aqueous phase along a first direction into a first end of a mixing zone of a reactor; mixing an organic phase with the aqueous phase in a countercurrent manner by flowing an organic phase into a second end of the mixing zone opposite the first end, wherein the flow of the organic phase is along a second direction opposite the first direction, the organic phase containing at least contaminants; heating the mixing zone; extracting a purified organic phase from the purification zone of the reactor; and extracting waste from the waste zone of the reactor.

[0072]

[0073] E2. The method of embodiment E1, further comprising heating the mixing region to a temperature of from about 50°C to about 300°C.

[0073]

[0074] E3. The method of embodiment E1 or E2, further comprising heating a first region of the mixing region to a first temperature of about 100°C to about 125°C, and heating a second region of the mixing region to a second temperature of about 200°C to about 250°C.

[0074]

[0075] E4. The method of any one of embodiments E1-E3, further comprising heating the mixing zone by introducing steam.

[0075]

[0076] E5. The method of any one of embodiments E1-E4, further comprising heating the mixing zone with a heat exchanger.

[0076]

[0077] E6. The method of any one of embodiments E1-E5, wherein the contaminants comprise one or more organic materials and / or one or more inorganic materials.

[0077]

[0078] E7. The method of embodiment E6, wherein the organic material comprises asphaltenes, polymers, high molecular weight organic compounds, waves, coke, coke precursors, nitrogen-containing compounds, fatty acids, organic salts, organic soaps, or any combination thereof.

[0078]

[0079] E8. The method of embodiment E6, wherein the inorganic material comprises a halide, phosphorus, sulfur, an alkali metal, a metalloid, a heavy metal, an inorganic salt, an inorganic soap, or any combination thereof.

[0079]

[0080] E9. The method of any one of embodiments E1-E8, wherein the mixed region comprises a filler.

[0080]

[0081] E10. The method of any one of embodiments E1-E9, wherein the step of mixing the organic phase with the aqueous phase further comprises rotating a displacement component within the mixing region with an actuator, and wherein the mixing region comprises the actuator.

[0081]

[0082] E11. The method of any one of embodiments E1-E10, wherein mixing the organic phase with the aqueous phase further comprises vibrating a porous element in the mixing region with an oscillator.

[0082]

[0083] E12. The method of any one of embodiments E1-E11, further comprising removing a residual aqueous phase from the purified organic phase using a first coalescer.

[0083]

[0084] E13. The method of embodiment E12, further comprising removing a residual organic phase from the waste using a second coalescer.

[0084]

[0085] E14. A method for purifying hydrocarbons, comprising the steps of: flowing an aqueous phase to a first mixing zone of a first reactor; mixing an organic phase with the aqueous phase by flowing the organic phase through the first mixing zone; separating the purified organic phase from waste products; and directing the purified organic phase from the first reactor to a second mixing zone of a second reactor.

[0085]

[0086] E15. The method of embodiment E14, further comprising: flowing the aqueous phase along a first direction to a first end of the first mixing region; and mixing the organic phase with the aqueous phase via countercurrent flow by flowing the organic phase to a second end of the first mixing region opposite the first end, wherein the flow of the organic phase is along a second direction opposite the first direction.

[0086]

[0087] E16. The method of embodiment E14 or E15, further comprising heating the first mixing region to a temperature of from about 50°C to about 300°C.

[0087]

[0088] E17. The method of any one of embodiments E14-E16, further comprising heating the first mixing zone by introducing steam.

[0088]

[0089] E18. The method of any one of embodiments E14-E17, wherein mixing the organic phase with the aqueous phase further comprises rotating a displacement component within the first mixing region with an actuator.

[0089]

[0090] E19. A method for purifying hydrocarbons, comprising the steps of: flowing an aqueous phase comprising water along a first direction into a first end of a mixing zone of a reactor; mixing an organic phase with the aqueous phase via countercurrent flow by flowing the organic phase into a second end of the mixing zone opposite the first end, wherein the organic phase comprises oil, fat, grease, or combinations thereof, and the flow of the organic phase is along a second direction opposite the first direction, wherein the organic phase comprises one or more contaminants comprising halides, phosphorus, sulfur, alkali metals, metalloids, heavy metals, or any combination thereof; heating the mixing zone; extracting the purified organic phase from the purification zone of the reactor; and directing waste to a recuperator.

[0090]

[0091] E20. The method of embodiment E19, further comprising heating the mixing region.

[0091]

[0092] E21. The method of embodiment E19 or E20, further comprising mixing the organic phase with recuperator waste to produce a mixture to be introduced into the reactor.

[0092]

[0093] E22. The method of embodiment E21, further comprising cooling the mixture using a cooling unit.

[0093]

[0094] E23. The method of embodiment E22, further comprising introducing the cooled mixture into a reactor.

[0094]

[0095] E24. The method of any one of embodiments E19-E23, further comprising heating a region of the mixing zone with an external heat exchanger.

[0095]

[0096] E25. The method of embodiment E24, further comprising the steps of: extracting a portion of the volume within the mixing zone; directing the portion of the volume to an external vessel; heating the external vessel using an external heat exchanger; and directing the portion of the volume within the external vessel to the mixing zone of the reactor, wherein transferring the portion of the volume comprises cooling the portion of the volume using a cooling system.

[0096]

[0097] E26. The method of any one of embodiments E19-E25, wherein the organic phase comprises the dispersed phase and the aqueous phase comprises the continuous phase.

[0097]

[0098] E27. The method of any one of embodiments E19-E26, wherein the organic phase comprises the continuous phase and the aqueous phase comprises the dispersed phase.

[0098]

[0099] E28. The method of any one of embodiments E19-E27, wherein the aqueous phase comprises an additive, and the additive is a hydrolyzing agent.

[0099]

[0100] Overall, the disclosed systems and methods provide a hydrocarbon refining method that utilizes countercurrent liquid-liquid extraction to increase mixing between the aqueous and organic phases, thereby improving the purity of the refined hydrocarbons without the need for glycerol production, reducing the total amount of water used in the refining process, and lowering operating costs. By implementing countercurrent fluid flow, contaminants are removed from the oil during the countercurrent fluid flow, reducing and / or eliminating the need for centrifugation. Furthermore, the aqueous and organic phases can be introduced into at least one reactor, where the aqueous and organic phases are subjected to a temperature profile that increases extraction of contaminants in the organic phase. The hydrocarbon refining method can reduce capital and operating costs because the system requires fewer storage tanks and / or reactors than conventional hydrocarbon refining systems. Furthermore, the aqueous phase can be reintroduced into the reactor via a recycle device, further reducing operating costs compared to conventional hydrocarbon refining systems.

[0100]

[0101] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments may be devised without departing from the basic scope thereof, the scope of which is determined by the claims that follow. All documents set forth herein, including priority documents and / or testing procedures to the extent not inconsistent herewith, are incorporated herein by reference. While forms of the disclosure have been illustrated and described, as is apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, no limitation of the present disclosure is intended. Similarly, the term "comprising" is considered synonymous with the term "including" for purposes of U.S. law. Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements can also be preceded by the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is," and vice versa. As used herein, the term "about" refers to a ±10% variation from the nominal value. It is understood that such a variation can be included in any value provided herein.

[0101]

[0102] Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It is understood that ranges including any two combinations of values ​​are contemplated, for example, any lower limit with any upper limit, any two lower limits, and / or any two upper limits, unless otherwise indicated. Particular lower limits, upper limits, and ranges are set forth in one or more claims below.

Claims

1. 1. A method for purifying hydrocarbons, comprising: flowing the aqueous phase along a first direction into a first end of a mixing zone of the reactor; mixing the organic phase with the aqueous phase via countercurrent flow by flowing the organic phase into a second end of the mixing zone opposite the first end, wherein the flow of the organic phase is along a second direction opposite the first direction, and the organic phase includes at least contaminants; heating the mixing region; extracting a purified organic phase from the purification zone of the reactor; and extracting waste material from a waste region of said reactor. A method comprising:

2. The method of claim 1 further comprising heating the mixing zone to a temperature of from about 50°C to about 300°C.

3. heating a first region of the mixing zone to a first temperature of about 100°C to about 125°C; and heating a second region of the mixing zone to a second temperature of about 200°C to about 250°C. The method of claim 1 further comprising:

4. The method of claim 1 further comprising the step of heating the mixing zone by introducing steam.

5. The method of claim 1 further comprising heating the mixing zone with a heat exchanger.

6. The method of claim 1 , wherein the contaminants comprise organic or inorganic materials.

7. 7. The method of claim 6, wherein the organic material comprises asphaltenes, polymers, high molecular weight organic compounds, waves, coke, coke precursors, nitrogen-containing compounds, fatty acids, organic salts, organic soaps, or any combination thereof.

8. 7. The method of claim 6, wherein the inorganic material comprises a halide, phosphorus, sulfur, an alkali metal, a metalloid, a heavy metal, an inorganic salt, an inorganic soap, or any combination thereof.

9. The method of claim 1 , wherein the mixed region comprises a filler material.

10. 10. The method of claim 1, wherein the step of mixing the organic phase with the aqueous phase further comprises rotating a displacement component within the mixing region with an actuator, the mixing region comprising the actuator.

11. 10. The method of claim 1, wherein the step of mixing the organic phase with the aqueous phase further comprises vibrating a porous element within the mixing region with an oscillator.

12. 10. The method of claim 1, further comprising removing a residual aqueous phase from the purified organic phase using a first coalescer.

13. 13. The method of claim 12, further comprising removing a residual organic phase from the waste using a second coalescer.

14. 1. A method for purifying hydrocarbons, comprising: flowing the aqueous phase into a first mixing zone of a first reactor; mixing the organic phase with the aqueous phase by flowing the organic phase through the first mixing zone; Separating the purified organic phase from the waste product; and directing the purified organic phase from the first reactor to a second mixing zone of a second reactor. A method comprising:

15. flowing the aqueous phase along a first direction to a first end of the first mixing region; and mixing the organic phase with the aqueous phase via countercurrent flow by flowing the organic phase into a second end of the first mixing zone opposite the first end, the flow of the organic phase being along a second direction opposite the first direction. The method of claim 12 further comprising:

16. The method of claim 14, further comprising heating the first mixing zone to a temperature of from about 50°C to about 300°C.

17. 15. The method of claim 14, further comprising the step of heating the first mixing zone by introducing steam.

18. 15. The method of claim 14, wherein mixing the organic phase with the aqueous phase further comprises rotating a displacement component within the first mixing region with an actuator.

19. 1. A method for purifying hydrocarbons, comprising: flowing an aqueous phase comprising water along a first direction into a first end of a mixing zone of the reactor; mixing the organic phase with the aqueous phase via countercurrent flow by flowing the organic phase into a second end of the mixing zone opposite the first end, wherein the organic phase comprises an oil, a fat, a grease, or a combination thereof, the flow of the organic phase is along a second direction opposite the first direction, and the organic phase comprises at least contaminants comprising halides, phosphorus, sulfur, alkali metals, metalloids, heavy metals, or any combination thereof; heating the mixing region; extracting a purified organic phase from the purification zone of the reactor; extracting waste material from a waste region of the reactor; and directing said waste material to a recuperator. A method comprising:

20. 20. The method of claim 19 further comprising the step of heating the mixing region.

21. 20. The method of claim 19, further comprising mixing the organic phase with the waste product of the recuperator to produce a mixture to be introduced into the reactor.

22. 22. The method of claim 21, further comprising producing a cooled mixture by cooling the mixture using a cooling unit.

23. 23. The method of claim 22, further comprising introducing the cooled mixture into the reactor.

24. 20. The method of claim 19, further comprising heating a first region of the mixing zone with an external heat exchanger.

25. extracting a portion of a volume within the mixed region; directing a portion of the volume into an outer container; heating the external vessel using the external heat exchanger; and directing a portion of the volume within the outer vessel to the mixing region of the reactor, wherein transferring the portion of the volume includes cooling the portion of the volume using a refrigeration system.

25. The method of claim 24, further comprising:

26. 20. The method of claim 19, wherein the organic phase comprises a dispersed phase and the aqueous phase comprises a continuous phase.

27. 20. The method of claim 19, wherein the organic phase comprises a continuous phase and the aqueous phase comprises a dispersed phase.

28. 20. The method of claim 19, wherein the aqueous phase comprises an additive, the additive being a hydrolysis agent.

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