Pretreatment methods for biofuel raw materials

Abstract

In one aspect, a method is disclosed, the method comprising contacting a composition with an aqueous solution to produce a mixture, wherein the composition comprises one or more of animal fats, animal oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases and used edible oils, about 5 wt.-% or more of free fatty acids, about 10 wppm or more of total metals, about 8 wppm or more of phosphorus, about 20 wppm or more of nitrogen, and the aqueous solution comprises ((NH4)2H2EDTA, (NH4)4EDTA, the monoammonium salt of diethylenetriaminepentaacetic acid, the diammonium salt of diethylenetriaminepentaacetic acid, the triammonium salt of diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid, The method further comprises centrifuging the mixture to produce a first treated composition, wherein the first treated composition has less total metals and less phosphorus than the composition.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 059,749, filed on July 31, 2020, the entire contents of which are incorporated herein by reference for any and all purposes.

[0003] field

[0004] The present technology generally relates to the treatment of compositions useful as biorenewable feedstocks to be hydroprocessed. More specifically, and not by way of limitation, the present technology provides a method for upgrading low-value and waste fat, oil and grease compositions to produce treated compositions having reduced total metal and phosphorus amounts.

[0005] Overview

[0006] In one aspect, the present technology provides a method comprising contacting a composition with an aqueous solution to produce a mixture, wherein the composition comprises one or more of animal fats, animal oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases, and used edible oils, about 5 wt.% or more of free fatty acids, about 10 wppm or more of total metals, about 8 wppm or more of phosphorus, about 20 wppm or more of nitrogen, and the aqueous solution comprises ethylenediaminetetraacetic acid diammonium hydrogen phosphate ("(NH4)2H2EDTA"; CAS#20824-56-0), ethylenediaminetetraacetic acid tetraammonium ("(NH4)4EDTA"; CAS#22473-78-5), the monoammonium salt of diethylenetriaminepentaacetic acid, the diammonium salt of diethylenetriaminepentaacetic acid, and diethylenetriamine. A combination of citric acid and tetrasodium ethylenediaminetetraacetic acid ("Na4EDTA"; CAS#13235-36-4), a combination of citric acid and disodium ethylenediaminetetraacetic acid ("Na2H2EDTA"; CAS#139-33-3), a combination of citric acid and monosodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and disodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and trisodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and tetrasodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and pentasodium of diethylenetriaminepentaacetic acid ("Na5DTPA"; CAS#140-01-2), or a combination of any two or more thereof. The method further comprises centrifuging the mixture to produce a first treated composition, wherein the first treated composition has less total metals and less phosphorus than the composition.

[0007] BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 is a schematic diagram of an illustrative embodiment of the method of the present technology discussed in this disclosure.

[0009] Details

[0010] Various embodiments will be described below. It should be noted that the specific embodiments are not intended to be exhaustive descriptions or limitations on the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment, but can be practiced with any other one or more embodiments.

[0011] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If the purpose of the term is not clear to one of ordinary skill in the art, "about" means plus or minus up to 10% of the particular term, taking into account the context in which it is used - for example, "about 10% by weight" should be understood as "9% to 11% by weight". It should be understood that when "about" precedes a term, the term should be interpreted as disclosing "about" the term as well as the term not modified by "about" - for example, "about 10 wt.%" discloses "9% to 11% by weight" and discloses "10% by weight".

[0012] The phrase "and / or" used in this disclosure will be understood to refer to any one of the members recited individually or in combination with any two or more - for example, "A, B and / or C" means "A, B, C, A and B, A and C, or B and C."

[0013] Unless otherwise indicated herein or clearly contradictory in context, as used herein and in the appended claims, in the context of describing elements (especially in the context of the following claims), singular articles such as "a" and "an" and "the" and similar indicators should be interpreted as covering the singular and plural. Unless otherwise indicated herein, the description of the range of values ​​herein is intended only as a simplified method of individually quoting each individual value falling within the range, and each individual value is incorporated into the specification as if it is described separately in this article. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradictory in other aspects with the context. Unless otherwise stated, the use of any and all examples or exemplary language (e.g., "for example") provided herein is intended only to better illustrate the embodiment, without limiting the scope of the claims. Any language in the specification should not be interpreted as indicating any unclaimed element as necessary.

[0014] As used herein, hydroprocessing describes various types of catalytic reactions occurring in the presence of hydrogen, but is not limited thereto. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing (HDW), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending on the catalyst type, reactor configuration, reactor conditions, and feedstock composition, a variety of reactions from pure heating (i.e., no catalyst is required) to catalysis may occur. In the case of describing the primary functions of a particular hydroprocessing unit (e.g., an HDO reaction system), it should be understood that the HDO reaction is only one of the primary reactions occurring, and other reactions may also occur.

[0015] Pyrolysis is understood to mean the thermochemical decomposition of carbonaceous materials in the absence of diatomic oxygen or diatomic hydrogen during the thermochemical reaction. The selective use of catalysts in pyrolysis is generally referred to as catalytic cracking, which is encompassed by the term as pyrolysis and is not to be confused with hydrocracking.

[0016] Hydrotreating (HT) involves the removal of elements from Groups 3, 5, 6 and / or 7 of the Periodic Table from organic compounds. Hydrotreating may also include hydrodemetallization (HDM) reactions. Thus, hydrotreating includes the removal of heteroatoms such as oxygen, nitrogen, sulfur and any combination of two or more thereof by hydroprocessing. For example, hydrodeoxygenation (HDO) is understood to be the removal of oxygen by a catalytic hydroprocessing reaction to produce water as a byproduct; similarly, hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) describe the removal of the indicated elements, respectively, by hydroprocessing.

[0017] Hydrogenation comprises adding hydrogen in organic molecules, and molecule is not decomposed into multiple subunits.It is two non-limiting examples of hydrogenation that hydrogen is added to carbon-carbon or carbon-oxygen double bonds to produce singly-bound bonds.Partial hydrogenation and selective hydrogenation are terms used to refer to the hydrogenation reaction that causes unsaturated raw materials to be partially saturated.For example, the vegetable oil with high-percentage polyunsaturated fatty acids (for example, linoleic acid) can experience partial hydrogenation to provide the product of hydrotreatment, wherein polyunsaturated fatty acids are converted into monounsaturated fatty acids (for example, oleic acid) and do not increase the percentage of undesirable saturated fatty acids (for example, stearic acid).Although hydrogenation is different from hydrotreating, hydroisomerization and hydrocracking, hydrogenation may occur in these other reactions.

[0018] Hydrocracking (HC) refers to the breaking of the carbon-carbon bonds of a molecule in the presence of hydrogen to form at least two molecules. Such a reaction is usually followed by a subsequent hydrogenation of the resulting double bonds.

[0019] Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds in the presence of hydrogen to form isomers. Hydrocracking is a competing reaction for most HI catalyzed reactions, and it is understood that the HC reaction pathway is included as a minor reaction when the term HI is used. Hydrodewaxing (HDW) is a special form of hydrocracking and hydroisomerization aimed at improving the low temperature properties of hydrocarbon fluids.

[0020] It will be understood that if a composition comprises "C x -C y Hydrocarbons", such as C7-C 12 By normal paraffins, it is meant that the composition comprises one or more paraffins having a carbon number in the range of x to y.

[0021] With respect to a composition, the phrase "at least a portion" means from about 1% to about 100% of the composition.

[0022] "Diesel fuel" generally refers to fuels having a boiling point in the range of about 150°C to about 360°C (the "diesel boiling range").

[0023] Generally, "gasoline" refers to a fuel for spark-ignition engines having a boiling point in the range of about 30°C to about 200°C.

[0024] As used herein, "biodiesel" refers to fatty acid C1-C4 fatty esters produced by esterification and / or transesterification reactions between C1-C4 alkyl alcohols and free fatty acids and / or fatty acid glycerides, as described in U.S. Patent Publication No. 2016 / 0145536, which is incorporated herein by reference.

[0025] As used herein, "petroleum diesel" refers to diesel fuel produced from crude oil, such as produced in a crude oil refining facility, including hydrotreated straight run diesel, hydrotreated fluid catalytic cracked light cycle oil, hydrocracked coker light gasoline, hydrocracked FCC heavy cycle oil, and combinations thereof. Similarly, a "petroleum-derived" compound or composition refers to a compound or composition produced directly from crude oil, or a compound or composition produced from components and / or feedstocks that are ultimately produced from crude oil rather than biorenewable feedstocks.

[0026] It should be understood that the "volume percent" or "volume %" of a component in a composition or the volume ratio of different components in a composition is determined based on the initial volume of each individual component at 60°F, not the final volume of the components after combination.

[0027] Throughout this disclosure, various publications, patents, and published patent specifications are referenced by identifying the cited documents. Arabic numerals indicating the referenced documents are also included in this disclosure, and their complete bibliographic details are provided before the claims. The disclosures of these publications, patents, and published patent specifications are hereby incorporated into this disclosure by reference.

[0028] This technology

[0029] The hydrodeoxygenation (HDO) of fats, oils and greases (FOG) is a key step in the production of renewable diesel. FOG feedstocks of commercial interest include by-products from the refining and food processing industries, such as inedible tallow and used cooking oils. FOG feedstocks also include by-products from the palm oil and bioethanol industries, such as palm residue oil and distilled corn oil. These feeds are characterized by high free fatty acid (FFA) content, typically above 5wt.%, relatively high metal and phosphorus content (typically above 20wppm total), and basicity values ​​above 200mg / kg.

[0030] This byproduct FOG feed is also considered more sustainable. Based on the methodology used by the California Air Resources Board, the lifecycle greenhouse gas emissions of renewable diesel from used cooking oil are less than 30 grams of CO2 equivalent per megajoule of combustion energy provided (gCO 2e / MJ). In comparison, petroleum diesel has 100gCO 2e / MJ, renewable diesel produced from refined oil (such as refined, bleached and deodorized vegetable oil) is 50gCO 2e / MJ. Life cycle greenhouse gas emissions value is also called carbon intensity or CI.

[0031] Current FOG pretreatment methods for producing renewable diesel strive to achieve contaminant reduction levels for optimal HDO reactor performance. Typical performance issues associated with feed contaminants include fouling of the reactor catalyst bed with phosphorus- and metal-rich deposits, and catalyst deactivation by metals, phosphorus, and / or silicon.

[0032] The prior art discloses various "degumming" processes for removing phosphorus compounds from fats and oils. Most of these phosphorus compounds exist as phospholipids. The general structure of a phospholipid is that of a triglyceride in which one of the fatty acids is replaced by a phosphate substance, as shown by phosphatidic acid shown in formula (I) below.

[0033]

[0034] Due to the surfactant properties of phospholipids, when phospholipids come into contact with water, the lipids migrate to the oil / water interface. This so-called "hydration" step is an effective means of removing most phospholipids from fats and oils. However, a class of phospholipids known as non-hydratable phospholipids (NHPs) remain soluble in oil after hydration. NHPs are usually in the form of divalent metal salts of phosphatidic acid and are represented schematically by the following formula II, where M 2+ It is a divalent metal such as calcium or magnesium.

[0035]

[0036] Prior art teaches that effective removal of phosphorus and metals requires conversion of non-hydratable phospholipids (NHPs) present in fats and oils. Prior art also discloses that phosphoric acid or citric acid can split the ionic bond between the divalent metal and the phosphate group of NHP, thereby releasing phospholipids from the oil phase to the oil / water interface. Prior art also teaches that citric acid and phosphoric acid can also be used as chelating agents, wherein the divalent metal can be coordinated with the acid to mitigate further interaction between the phosphate group and the divalent metal, and also enhance the migration of the chelated divalent metal to the aqueous phase. Prior art also teaches the use of a disc stack centrifuge to continuously separate acid degummed oil from the heavy phase (water and oil / water interface).

[0037] The prior art further teaches that ethylenediaminetetraacetic acid (EDTA) is an effective chelator for multivalent metals, with a higher ability to form water-soluble complexes with the metal ions than most other common chelators. However, EDTA has poor solubility in water and generally needs to be introduced as a metal salt (e.g., as a sodium salt of EDTA) for applications requiring transfer of metals to the aqueous phase. As shown in the comparative examples of the present disclosure, treatment of high FFA FOG feeds using these EDTA salts results in soap formation (e.g., sodium oleate) and subsequent retention of the metal cations in the oil phase.

[0038] Therefore, there remains an unmet need for a feed pretreatment process for high FFA FOG feedstocks utilizing more effective chelating agents. The present technology addresses this need.

[0039] The present technology relates to a method for treating FOG feedstocks, for example, for producing biomass-based diesel fuels and fuel blends. The present technology is particularly advantageous as a pretreatment method for renewable diesel production, where the very low levels of metal and phosphorus contaminants produced by the method provide optimal performance for such production of renewable diesel.

[0040] Thus, in one aspect, the present technology provides a method comprising contacting a composition with an aqueous solution to produce a mixture, wherein the composition comprises one or more of animal fats, animal oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, and used edible oils, about 5 wt.% or more of free fatty acids, about 10 wppm or more of total metals, about 8 wppm or more of phosphorus, about 20 wppm or more of nitrogen, and the aqueous solution comprises ethylenediaminetetraacetic acid diammonium hydrogen phosphate ("(NH4)2H2EDTA"; CAS#20824-56-0), ethylenediaminetetraacetic acid tetraammonium ("(NH4)4EDTA"; CAS#22473-78-5), diethylenetriaminepentaacetic acid monoammonium salt, diethylenetriaminepentaacetic acid diammonium salt, and diethylenetriaminepentaacetic acid monoammonium salt. The invention can be used in combination with citric acid and diethylenetriaminepentaacetic acid, triammonium salt of ethylenediaminepentaacetic acid, tetraammonium salt of diethylenetriaminepentaacetic acid, pentaammonium salt of diethylenetriaminepentaacetic acid ("(NH4)5DTPA"), a combination of citric acid and tetrasodium of ethylenediaminetetraacetic acid ("Na4EDTA"; CAS#13235-36-4), a combination of citric acid and disodium of ethylenediaminetetraacetic acid ("Na2H2EDTA"; CAS#139-33-3), a combination of citric acid and monosodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and disodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and trisodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and tetrasodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and pentasodium of diethylenetriaminepentaacetic acid ("Na5DTPA"; CAS#140-01-2), or a combination of any two or more thereof. In any embodiments disclosed herein, the aqueous solution can have a pH of about 4 to about 6; thus, in any embodiments disclosed herein, the aqueous solution can have a pH of about 6.0, about 5.5, about 5.0, about 4.5, about 4.0, or any range including and / or between any two of these values, or any range below any of these values. In any embodiments disclosed herein, the contacting can include high shear mixing of the composition and the aqueous solution.

[0041] The method also includes centrifuging the mixture to produce a first treated composition, wherein the first treated composition has less total metal and less phosphorus than the composition. The total metal amount of the first treated composition of any embodiment disclosed herein may be about 20% or less of the total metal amount in the composition (e.g., when the composition has 20wppm of total metal, the first treated composition has 4wppm or less of total metal). The phosphorus amount of the first treated composition of any embodiment disclosed herein may be about 20% or less of the phosphorus amount in the composition. In any embodiment disclosed herein, centrifugation may include the use of a disc centrifuge, a decanter centrifuge and / or a three-phase centrifuge. Other methods, systems and equipment for separating centrifugal mixtures may be included. These include methods, systems and equipment (e.g., settling tanks) and are known to those of ordinary skill in the art.

[0042] In the embodiments disclosed herein, the volume ratio of the composition to the aqueous solution during contacting can be about 10: 1 to about 100: 1. Thus, in any of the embodiments disclosed herein, the volume ratio of the composition to the aqueous solution can be about 10: 1, about 11: 1, about 12: 1, about 13: 1, about 14: 1, about 15: 1, about 16: 1, about 17: 1, about 18: 1, about 19: 1, about 20: 1, about 22: 1, about 24: 1, about 26: 1, about 28: 1, about 30: 1, about 35: 1, about 40: 1, about 45: 1, about 50: 1, about 55: 1, about 60: 1, about 65: 1, about 70: 1, about 75: 1, about 80: 1, about 85: 1, about 90: 1, about 95: 1, about 100: 1, or any range including and / or between any two of these values.

[0043] In any of the embodiments disclosed herein, contacting can occur at a temperature of about 140° F. to about 300° F. Thus, in any of the embodiments disclosed herein, contacting can occur at a temperature of about 140° F., about 145° F., about 150° F., about 155° F., about 160° F., about 165° F., about 170° F., about 175° F., about 180° F., about 185° F., about 190° F., about 195° F., about 200° F., about 205° F., about 210° F., about 215° F., about 225° F., about 230° F., about 231° F., about 232° F., about 233° F., about 234° F., about 236° F., about 237° F., about 238° F., about 239° F., about 240° F., about 241° F., about 242° F., about 243° F., about 244° F., about 245° F., about 246° F., about 247° F., about 248° F., about 249° F., about 250° F., about 251° F., about 252° F. F, about 225°F, about 230°F, about 240°F, about 245°F, about 250°F, about 255°F, about 260°F, about 265°F, about 270°F, about 275°F, about 280°F, about 285°F, about 290°F, about 295°F, about 300°F, or any range of temperatures including and / or between any two of these values.

[0044] In any embodiments disclosed herein, the aqueous solution may contain about 10 wt.% to about 60 wt.% of (NH4)2H2EDTA, (NH4)4EDTA, (NH4)5DTPA, Na4EDTA, Na2H2EDTA, Na5DTPA, or a combination of any two or more thereof. Thus, in any embodiments herein, the aqueous solution may contain (NH4)2H2EDTA, (NH4)4EDTA, (NH4)5DTPA, Na4EDTA, Na2H2EDTA, Na5DTPA, or a combination of any two or more thereof, in an amount of about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%, about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, about 45 wt.%, about 50 wt.%, about 55 wt.%, about 60 wt.%, or any range including and / or between any two of these values.

[0045] In any of the embodiments disclosed herein, the weight ratio of the composition to (NH4)2H2EDTA (i.e., (NH4)2H2EDTA in the aqueous solution prior to contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to (NH4)2H2EDTA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1, about 105:1, about 110:1, about 112:1, about 113:1, about 114:1, about 115:1, about 116:1, about 117:1, about 118:1, about 119:1, about 120:1, about 121:1, about 122:1, about 123:1, about 124:1 : 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and (NH4)2H2EDTA, and the molar ratio of citric acid to (NH4)2H2EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and (NH4)2H2EDTA, and the molar ratio of phosphoric acid to (NH4)2H2EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0046] In any of the embodiments disclosed herein, the weight ratio of the composition to (NH4)4EDTA during contacting (i.e., (NH4)4EDTA in the aqueous solution prior to contacting) can be about 50:1 to about 500:1; thus, the weight ratio of the composition to (NH4)4EDTA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and (NH4)4EDTA, and the molar ratio of citric acid to (NH4)4EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and (NH4)4EDTA, and the molar ratio of phosphoric acid to (NH4)4EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0047] In any of the embodiments disclosed herein, during contacting, the weight ratio of the composition to the monoammonium salt of diethylenetriaminepentaacetic acid (i.e., the monoammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution prior to contacting) can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the monoammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 96:1, about 98:1, about 100:1, about 101:1, about 102:1, about 103:1, about 104:1, about 105:1, about 106:1, about 107:1, about 108:1, about 109:1, about 110:1, about 111:1, about 112:1, about 113:1, about 114:1, about 115:1, about 116:1, about 117:1, about 118:1, about 119:1, about 120:1, about 121:1, about 122:1 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and the monoammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of citric acid to (NH4)5DTPA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the monoammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the monoammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0048] In any of the embodiments disclosed herein, the weight ratio of the composition to the diammonium salt of diethylenetriaminepentaacetic acid (i.e., the diammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the diammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1, about 110:1, about 120:1, about 130:1, about 140:1, about 150:1, about 160:1, about 170:1, about 180:1, about 190:1, about 200:1, about 210:1, about 220:1, about 230:1, about 240:1, about 250:1, about 260:1, about 270:1, about 280:1, about 290:1, about 300:1, about 310:1, about 320:1 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and the diammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of citric acid to the diammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the diammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the diammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0049] In any of the embodiments disclosed herein, the weight ratio of the composition to the triammonium salt of diethylenetriaminepentaacetic acid (i.e., the triammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the triammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and the triammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of citric acid to the triammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the triammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the triammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0050] In any of the embodiments disclosed herein, the weight ratio of the composition to the tetraammonium salt of diethylenetriaminepentaacetic acid (i.e., the tetraammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the tetraammonium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and the tetraammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of citric acid to the tetraammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the tetraammonium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the tetraammonium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0051] In any of the embodiments disclosed herein, the weight ratio of the composition to (NH4)5DTPA during contacting (i.e., (NH4)5DTPA in the aqueous solution prior to contacting) can be about 50:1 to about 500:1; thus, the weight ratio of the composition to (NH4)5DTPA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include citric acid and (NH4)5DTPA, and the molar ratio of citric acid to (NH4)5DTPA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and (NH4)5DTPA, and the molar ratio of phosphoric acid to (NH4)5DTPA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0052] In any of the embodiments disclosed herein, the weight ratio of the composition to Na4EDTA (i.e., Na4EDTA in the aqueous solution prior to contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to Na4EDTA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... In some embodiments, the aqueous solution may have a molar ratio of citric acid to Na4EDTA of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and Na4EDTA, and the molar ratio of phosphoric acid to Na4EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0053] In any of the embodiments disclosed herein, the weight ratio of the composition to Na2H2EDTA (i.e., Na2H2EDTA in the aqueous solution prior to contacting) during contacting is about 50:1 to about 500:1; thus, the weight ratio of the composition to Na2H2EDTA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1. : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the molar ratio of citric acid to Na2H2EDTA included in the aqueous solution can be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and Na2H2EDTA, and the molar ratio of phosphoric acid to Na2H2EDTA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0054] In any of the embodiments disclosed herein, the weight ratio of the composition to the monosodium salt of diethylenetriaminepentaacetic acid (i.e., the monosodium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the monosodium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may comprise a molar ratio of citric acid to monosodium salt of diethylenetriaminepentaacetic acid of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the monosodium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the monosodium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0055] In any of the embodiments disclosed herein, the weight ratio of the composition to the disodium salt of diethylenetriaminepentaacetic acid (i.e., the disodium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the disodium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1, about 100:1 : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may comprise a molar ratio of citric acid to the disodium salt of diethylenetriaminepentaacetic acid of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the disodium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the disodium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0056] In any of the embodiments disclosed herein, the weight ratio of the composition to the trisodium salt of diethylenetriaminepentaacetic acid (i.e., the trisodium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the trisodium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may comprise a molar ratio of citric acid to trisodium salt of diethylenetriaminepentaacetic acid of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and the trisodium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to the trisodium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0057] In any of the embodiments disclosed herein, the weight ratio of the composition to the tetrasodium salt of diethylenetriaminepentaacetic acid (i.e., the tetrasodium salt of diethylenetriaminepentaacetic acid in the aqueous solution before contacting) during contacting can be about 50:1 to about 500:1; thus, the weight ratio of the composition to the tetrasodium salt of diethylenetriaminepentaacetic acid in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may comprise a molar ratio of citric acid to tetrasodium salt of diethylenetriaminepentaacetic acid of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and tetrasodium salt of diethylenetriaminepentaacetic acid, and the molar ratio of phosphoric acid to tetrasodium salt of diethylenetriaminepentaacetic acid may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0058] In any of the embodiments disclosed herein, the weight ratio of the composition to Na5DTPA during contacting (i.e., Na5DTPA in the aqueous solution prior to contacting) can be about 50:1 to about 500:1; thus, the weight ratio of the composition to Na5DTPA in the aqueous solution can be about 50:1, about 55:1, about 60:1, about 65:1, about 70:1, about 75:1, about 80:1, about 85:1, about 90:1, about 95:1, about 10 ... : 1, about 120: 1, about 140: 1, about 160: 1, about 180: 1, about 200: 1, about 220: 1, about 240: 1, about 260: 1, about 280: 1, about 300: 1, about 320: 1, about 340: 1, about 360: 1, about 380: 1, about 400: 1, about 420: 1, about 440: 1, about 460: 1, about 480: 1, about 500: 1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may comprise a molar ratio of citric acid to Na5DTPA of about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values. In any embodiments disclosed herein, the aqueous solution may include phosphoric acid and Na5DTPA, and the molar ratio of phosphoric acid to Na5DTPA may be about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, or any range including and / or between any two of these values.

[0059] In any embodiment disclosed herein, caustic solution can be added to the mixture before centrifugation and after contact. For example, in any embodiment herein, caustic solution can include hydroxide aqueous solution, bicarbonate aqueous solution, disulfide aqueous solution, alcohol salt aqueous solution (such as methanol salt aqueous solution), alkaline resin dissolved and / or suspended in aqueous solution, methanol salt solution or a combination of two or more thereof. In any embodiment herein, caustic solution can include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium bicarbonate, ammonium bisulfite, sodium methylate, potassium methylate or any two or more thereof. For example, in any embodiment herein, caustic solution can be a caustic solution of about 10wt.% to about 60wt.% (for example, a hydroxide aqueous solution of about 10wt.% to about 60wt.%). In any embodiment herein, before centrifugation, water can be added to the mixture (for example, in the case where caustic solution is added to the mixture, water can be added before or after adding caustic solution).

[0060] In any embodiment disclosed herein, in addition to producing the first processed composition, the centrifugal mixture may include producing water-soluble waste. The water-soluble waste may have a pH lower than about 7.0. The pH that the water-soluble waste has may be about 6.5, about 6.0, about 5.5, about 5.0, about 4.5, about 4.0, about 3.5, about 3.0, about 2.5, about 2.0, or any range including and / or between any two of these values ​​or any range lower than any one of these values. For example, in any embodiment herein, the pH that the water-soluble waste may have is about 3.5 to about 6.0 or about 4.0 to about 5.0. The water-soluble waste may be optionally treated; the water-soluble waste may be treated to reach specific disposal permit requirements, including but not limited to metal content, biological oxygen demand (BOD) and / or chemical oxygen demand (COD). Such treatment of water-soluble waste may include, but is not limited to, microbial degradation (see, e.g., U.S. Pat. No. 9,120,686), carbon adsorption (see, e.g., U.S. Pat. No. 6,315,906), and / or treatment with strong oxidants such as ozone (see, e.g., U.S. Pat. No. 6,126,842) and / or chlorine dioxide (see, e.g., U.S. Pat. No. 8,663,473).

[0061] In any embodiment disclosed herein, the method further comprises combining the first treated composition with an adsorption medium to form a slurry, wherein the slurry comprises the resulting adsorption medium and the second treated composition, and separating the second treated composition from the slurry. The adsorption medium (also referred to herein as "adsorbent medium") may include, but is not limited to, silica (e.g., silica hydrogel, silica hydrogel particles), diatomaceous earth, activated carbon, bleaching clay (also referred to as bleaching earth), perlite, cellulose media, alumina, silica aluminate, natural fibers, natural flakes, synthetic fibers, or any combination of two or more thereof. However, in any embodiment disclosed herein, the method of the present technology may or may not include the use of bleaching clay. The total metal amount of the second treated composition of any embodiment disclosed herein is about 20% or less of the total metal amount in the composition (e.g., when the composition has 20wppm of total metal, the second treated composition has 4wppm or less of total metal). The phosphorus amount of the second treated composition of any embodiment disclosed herein may be about 20% or less of the phosphorus amount in the composition.

[0062] In any embodiment disclosed herein, the adsorption medium may include both silica and diatomaceous earth. In any embodiment disclosed herein, the silica may be silica particles, wherein the silica particles may have an average particle size of about 10 microns (μm) to about 50 microns by laser diffraction analysis. Therefore, in any embodiment disclosed herein including silica particles as the adsorption medium, the average particle size of the silica particles by laser diffraction analysis may be, but is not limited to, about 10 microns, about 11 microns, about 12 microns, about 13 microns, about 14 microns, about 15 microns, about 16 microns, about 17 microns, about 18 microns, about 19 microns, about 20 microns, about 21 microns, about 22 microns, about 23 microns, about 24 microns, about 25 microns, about 26 microns, about 27 microns, about 28 microns, about 29 microns, about 30 microns, about 35 microns, about 40 microns, about 45 microns, about 50 microns, and any range including and / or between any two of these values ​​and lower than any of these values. In any embodiment disclosed herein that includes silica particles as an adsorption medium, the silica particles may include amorphous silica particles, wherein the amorphous silica particles may be synthetic amorphous silica, natural amorphous silica, or a combination thereof. In any embodiment disclosed herein where the adsorption medium includes both silica and diatomaceous earth ("DE"), the weight ratio of DE to silica in the slurry (DE:silicon dioxide) is from about 0.1:1 to about 1.5:1; thus, the weight ratio of DE:silicon dioxide of any embodiment disclosed herein may be about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, and any range including and / or between any two of these ratios. Thus, in any embodiments disclosed herein wherein the adsorption medium comprises both silica particles and diatomaceous earth, the weight ratio of diatomaceous earth to silica particles (DE:silicon dioxide) in the slurry is about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, or any range including and / or between any two of these ratios.

[0063] In any of the embodiments disclosed herein that include silica particles as the adsorption medium, the silica particles may have a BET surface area of ​​about 200 m 2 / g to about 1000m 2 / g. The BET surface area can be determined by a variety of methods, including the method described in ASTM-D3663-03 (2008), which is incorporated herein by reference in its entirety for any and all purposes. The BET surface area of ​​the silica particles may include, but is not limited to, about 200 m 2 / g, about 210m 2 / g, about 220m 2 / g, about 230m 2 / g, about 240m 2 / g, about 250m 2 / g, about 260m 2 / g, about 270m 2 / g, about 280m 2 / g, about 290m 2 / g, about 300m 2 / g, about 320m 2 / g, about 340m 2 / g, about 360m 2 / g, about 380m 2 / g, about 400m 2 / g, about 450m 2 / g, about 500m 2 / g, about 550m 2 / g, about 600m 2 / g, about 650m 2 / g, about 700m 2 / g, about 750m 2 / g, about 800m 2 / g, about 850m 2 / g, about 900m 2 / g, about 950m 2 / g, about 1000m 2 / g, or any range including and / or between any two of these values.

[0064] In any embodiment disclosed herein including silica particles as an adsorption medium, when the silica particles are present in an aqueous dispersion at 15 wt.%, they may have an aqueous solution having a pH of about 2.0 to about 6.0. Suitable aqueous solution pH values ​​for silica particles may include, but are not limited to, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, or any range including and / or between any two of these values. For example, in any embodiment herein, the silica particles may have an aqueous pH of about 2.0 to about 3.5, about 2.0 to about 3.0, about 2.5 to about 3.0, and any range including and / or between any two of these values ​​and less than any one of these values. The compacted bulk density of the silica particles may also be about 100 g / L to about 1000 g / L according to standard bulk density measurement techniques, such as ASTM D6393-08 Test E. The compacted density of the silica particles may include, but is not limited to, about 100 g / L, about 200 g / L, about 300 g / L, about 400 g / L, about 500 g / L, about 600 g / L, about 700 g / L, about 800 g / L, about 900 g / L, about 1000 g / L, and any range including and / or between any two of these values ​​and below any one of these values. For example, in any embodiment herein, the compacted bulk density of the silica particles may be about 500 g / L.

[0065] In any embodiment disclosed herein that includes silica particles as an adsorption medium, the silica particles can be combined with the first treated composition at about 0.1% (weight of silica particles to weight of the first treated composition) to about 0.8%. The weight of the silica particles to the weight of the first treated composition can be about 0.1% (w / w), about 0.15% (w / w), about 0.2% (w / w), about 0.25% (w / w), about 0.3% (w / w), about 0.35% (w / w), about 0.4% (w / w), about 0.45% (w / w), about 0.5% (w / w), about 0.55% (w / w), about 0.6% (w / w), about 0.65% (w / w), about 0.7% (w / w), about 0.75% (w / w), about 0.8% (w / w), or any range including and / or between any two of these values. For example, in any of the embodiments herein, the weight of the silica particles relative to the weight of the first treated composition can be from about 0.1% (w / w) to about 0.8% (w / w), from about 0.2% (w / w) to about 0.6% (w / w), and from about 0.3% (w / w) to about 0.4% (w / w).

[0066] In any of the embodiments disclosed herein, the adsorption medium can be combined with the first treated composition at a temperature of about 150°F to about 200°F. The combination with the adsorption medium can be carried out at a temperature including, but not limited to, about 150°F, about 155°F, about 160°F, about 165°F, about 170°F, about 175°F, about 180°F, about 185°F, about 190°F, about 195°F, about 200°F, or any range including and / or between any two of these values. For example, in any of the embodiments herein, the temperature can be in the range of about 160°F to about 190°F; in any of the embodiments herein, the temperature can be in the range of about 175°F to about 185°F.

[0067] In any embodiment disclosed herein, the slurry may be subjected to an absolute pressure of about 100 Torr to about 500 Torr to drive off moisture. The absolute pressure may include, but is not limited to, about 100 Torr, about 150 Torr, about 200 Torr, about 250 Torr, about 300 Torr, about 350 Torr, about 400 Torr, about 450 Torr, about 500 Torr, or any range including and / or between any two of these values.

[0068] In any embodiment disclosed herein, the first processed composition and adsorption medium combination to produce slurry can include a residence time of about 10 minutes to about 90 minutes. Suitable residence time can include but is not limited to about 10 minutes, about 11 minutes, about 12 minutes, about 13 minutes, about 14 minutes, about 15 minutes, about 16 minutes, about 17 minutes, about 18 minutes, about 19 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, about 60 minutes, about 65 minutes, about 70 minutes, about 75 minutes, about 80 minutes, about 85 minutes, about 90min, or include and / or any scope between any two of these values. For example, in any embodiment herein, the residence time can be about 20 minutes to about 50 minutes. The combination of the first processed composition and adsorption medium as described in any embodiment herein can be carried out in a continuous flow operation tank.

[0069] Once the slurry is obtained, in any embodiment disclosed herein, separating the second treated composition from the slurry may include removing the resulting adsorption medium from the slurry to provide a second treated composition. In any embodiment disclosed herein, removing the adsorption medium from the slurry may include filtering the slurry with one or more filters. For example, in any embodiment herein, one or more filters may include pressure filtration (e.g., vertical and / or horizontal leaf filters), filter presses, cartridge filters, compression filters, membrane plate presses, disc filters, drum filters, or any two or more combinations thereof. One or more filters may include filters pre-coated with DE, cellulose, perlite, or any two or more combinations thereof. For example, in any embodiment herein, one or more filters may include pressurized leaf filters pre-coated with DE.

[0070] As disclosed above about the method for the present technology, composition comprises animal fat, animal oil, vegetable fat, vegetable oil, vegetable fat, vegetable oil, grease, used edible oil or any two or more combinations thereof.Vegetable oil and / or vegetable oil may include but are not limited to babassu oil (babassu oil), castor oil, soybean oil, inedible corn oil, mustard oil (canola oil), coconut oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, palm residue oil, jatropha oil (jatropha oil), palm kernel oil, sunflower oil, castor oil, camellia oil, archaeal oil (archaeal oil) and any two or more mixtures thereof.According to pretreatment level and residual phosphorus and metal content, these materials can be divided into crude grade, degumming grade and RBD grade (refining, bleaching and deodorizing).However, any one of these grades can be used for the present technology. The animal fat and / or oil used above may include, but are not limited to, inedible tallow, edible tallow, industrial tallow, floating tallow (floatation tallow), lard, poultry fat (e.g., chicken fat), poultry oil, fish fat, fish oil, and mixtures thereof. Grease may include, but are not limited to, yellow grease, brown grease, used edible oil, waste vegetable oil, restaurant grease, waste oil in the captured grease of urban areas (e.g., water treatment facilities) and industrial packaged food operations and mixtures of any two or more thereof. For example, in any embodiment herein, the composition may include yellow grease, brown grease, floating grease, poultry fat, inedible corn oil, used edible oil, inedible tallow, floating oil, palm residue oil or mixtures of any two or more thereof.

[0071] The composition comprises about 8wppm or more of total metals, as measured by inductively coupled plasma (ICP) spectroscopy (such as ICP-AES (atomic emission spectroscopy) and ICP-OES (optical emission spectroscopy)) (such as AOCS recommended operating procedure Ca 17-01). Such metals may include, but are not limited to, As, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, Sr, Zn, or any combination of two or more thereof. For example, in any embodiment herein, the total metals may include Ca, Fe, K, Mg and Na. The amount of total metals present in the composition of any embodiment disclosed herein may include about 10wppm to about 1000wppm of total metals. Thus, the amount of total metals in the composition of any embodiment disclosed herein can be about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 105 wppm, about 110 wppm, about 115 wppm, about 120 wppm, about 125 wppm, about 130 wppm, about 135 wppm, about 140 wppm, about 145 wppm, about 150 wppm, about 155 wppm, about 160 wppm wppm, about 150wppm, about 160wppm, about 170wppm, about 175wppm, about 180wppm, about 185wppm, about 190wppm, about 195wppm, about 200wppm, about 225wppm, about 250wppm, about 275wppm, about 300wppm, about 325wppm, about 350wppm, about 375wppm, about 400wppm, about 425wppm, about 450wppm, about 475wppm, about 500wppm, about 550wppm, about 600wppm, about 650wppm, about 700wppm, about 750wppm, about 800wppm, about 850wppm, about 900wppm, about 1000wppm, or any range including and / or between any two of these values.For example, a suitable amount of total metals in the composition can be from about 10 wppm to about 1000 wppm, from 10 wppm to 1000 wppm, from about 10 wppm to about 800 wppm, from 10 wppm to 800 wppm, from about 10 wppm to about 600 ppm, from 10 wppm to 600 ppm, from about 10 wppm to about 400 wppm, from 10 ppm to 400 wppm, from about 10 wppm to about 200 wppm, from 10 wppm to 200 wppm, from about 10 wppm to about 100 wppm, from 10 wppm to 100 wppm, from about 10 wppm to about 50 wppm, or from 0 wppm to 50 wppm.

[0072] The composition comprises about 8 wppm or more phosphorus measured as elemental phosphorus. The amount of phosphorus in the composition of any embodiment disclosed herein can be about 8 wppm, about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 110 wppm, about 120 wppm, about 130 wppm, about 150 wppm, about 170 wppm, about 190 wppm, about 200 wppm, about 300 wppm, about 400 wppm, about 500 wppm, about 600 wppm, about 700 wppm, about 800 wppm, or any range including and / or between any two of these values ​​or any range above any of these values.

[0073] In any embodiment disclosed herein, composition can include about 10wppm or more chlorine measured with elemental chlorine (Cl atom).The amount of chlorine can be about 10wppm, about 11wppm, about 12wppm, about 13wppm, about 14wppm, about 15wppm, about 16wppm, about 17wppm, about 18wppm, about 19wppm, about 20wppm, about 25wppm, about 30wppm, about 35wppm, about 40wppm, about 45wppm, about 50wppm, about 55wppm, about 60wppm, about 65wppm, about 70wppm, about 75wppm, about 80wppm, about 85wppm, about 90wppm, about 95wppm, about 100wppm, or include and / or any range between any two of these values ​​higher than any range of any one of these values.

[0074] In any embodiment disclosed herein, the composition may include about 10 wppm or more sulfur measured as elemental sulfur (e.g., by AOAC method 923.01). The amount of sulfur may include, but is not limited to, at least about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 110 wppm, about 120 wppm, about 130 wppm, about 150 wppm, about 170 wppm, about 190 wppm, about 200 wppm, or any range including and / or between any two of these values ​​or any range exceeding any one of these values.

[0075] The composition comprises about 10 wppm or more nitrogen measured as elemental nitrogen (e.g., by ASTM D4629-17). The amount of nitrogen in the composition of any embodiment disclosed herein can be, but is not limited to, about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 110 wppm, about 120 wppm, about 130 wppm, about 150 wppm, about 170 wppm, about 180 wppm, about 190 wppm, about 201 wppm, about 210 wppm, about 220 wppm, about 230 wppm, about 240 wppm, about 250 wppm, about 260 wppm, about 270 wppm In some embodiments, the present invention relates to a range of the present invention to a range of about 150 wppm to about 200 wppm, about 250 wppm to about 300 wppm, about 350 wppm, about 400 wppm, about 450 wppm, about 500 wppm, about 550 wppm, about 600 wppm, about 650 wppm, about 700 wppm, about 750 wppm, about 800 wppm, about 850 wppm, about 900 wppm, about 950 wppm, about 1000 wppm, about 1100 wppm, or any range including and / or between any two of these values ​​or any range exceeding any of these values.

[0076] The composition comprises about 5 wt.% or more free fatty acids ("FFA"), based on the total weight of the composition, as measured by standard analytical techniques, such as AOCS Ca 5a-40. Thus, in any of the embodiments disclosed herein, the amount of FFA in the composition can be about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%, about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, about 40 wt.%, about 45 wt.%, about 50 wt.%, about 55 wt.%, about 60 wt.%, about 70 wt.%, about 75 wt.%, or any range including and / or between any two of these values. For example, in any embodiment disclosed herein, the amount of FFA in the composition may be about 5 wt.% to about 15 wt.%. In any embodiment disclosed herein, the amount of FFA in the composition may be about 5 wt.% to about 10 wt.%.

[0077] The acid value that the composition in any embodiment disclosed herein can have is about 10mg KOH / g to about 150mg KOH / g.Suitable acid value amount can include but is not limited to about 10mg KOH / g to about 150mg KOH / g, about 10mg KOH / g to about 100mg KOH / g, about 10mg KOH / g to about 50mg KOH / g, about 10mg KOH / g to about 25mg KOH / g, about 10mg KOH / g to about 20mg KOH / g, about 10mg KOH / g to about 15mg KOH / g, and including and / or between any two of these values ​​and exceeding any scope of any one of these values.For example, in any embodiment herein, the acid value of composition can be about 10mg KOH / g to about 30mg KOH / g.In other embodiments, the acid value of composition can be about 10mg KOH / g to about 20mg KOH / g.

[0078] The composition can also include a polymer. Such a polymer can be a dissolved polymer, a soluble polymer, a granular polymer, or a mixture of any two or more thereof. The granular polymer can have a weight average diameter of about 0.01 μm to about 1 millimeter (mm); therefore, the granular polymer can have a weight average diameter of about 0.01 μm, about 0.1 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 80 μm, about 100 μm, about 200 μm, about 300 μm, about 500 μm, about 750 μm, about 1 mm, or any range including and / or between any two of these values. The granular polymer can have a weight average diameter of less than about 0.01 μm. The polymer can be synthetic or natural. A partial list of synthetic polymers is shown in Table 1.

[0079] Table 1. Examples of polymers

[0080]

[0081] In any of the embodiments disclosed herein, the synthetic polymer may include thermoplastic acrylonitrile-butadiene-styrene, polyacrylate rubber, ethylene-acrylate rubber, polyester urethane, bromo-isobutylene-isoprene rubber, polybutadiene rubber, chloro-isobutylene isoprene rubber, polychloroprene, chlorosulfonated polyethylene, epichlorohydrin, ethylene-propylene rubber, ethylene-propylene rubber, ethylene-propylene-diene monomer, polyether polyurethane, tetrafluoroethylene / propylene rubber, perfluorocarbon elastomer, fluoroelastomer, fluorosilicone, fluorocarbon rubber, high density polyethylene, hydrogenated nitrile, polyisoprene, isobutylene-isoprene The present invention relates to a kind of polymers, for example, polyvinyl chloride, polyvinylidene chloride, polyurethane, styrene-butadiene, styrene-ethylene-butylene-styrene copolymer, polysiloxane, vinyl methyl silicone, acrylonitrile-butadiene carboxyl monomer, styrene-butadiene carboxyl monomer, thermoplastic polyether-ester, styrene-butadiene block copolymer, styrene-butadiene carboxyl block copolymer, polyester, polyamide, polyacetal, polylactic acid or any two or more thereof. For example, in any embodiment herein, polymers may include but are not limited to polyethylene, chlorosulfonated polyethylene, low density polyethylene, high density polyethylene, polyethylene terephthalate, polylactic acid or any two or more thereof. Natural polymers may include proteins, oligopeptides, polysaccharides and lignin.

[0082] In any of the embodiments disclosed herein, the amount of polymer in the composition can be about 0.05 wppm, about 0.1 wppm, about 0.5 wppm, about 0.1 wppm, about 5 wppm, about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 100 wppm, about 105 wppm, about 110 wppm, about 111 wppm, about 112 wppm, about 113 wppm, about 114 wppm, about 115 wppm, about 116 wppm, about 117 wppm, about 118 wppm, about 119 wppm, about 120 wppm, about 121 wppm, about 122 wppm, about 123 wppm, about 124 wppm, about 125 wppm ppm, about 100wppm, about 105wppm, about 110wppm, about 115wppm, about 120wppm, about 125wppm, about 130wppm, about 135wppm, about 140wppm, about 145wppm, about 150wppm, about 155wppm, about 160wppm, about 165wppm, about 170wppm, about 175wppm, about 180wppm, about 185wppm, about 190wppm, about 195wppm, about 200wppm, about 225wppm, about 250wppm, about 275wppm, about 300wppm, about 325wppm, about 350wppm, about 375wppm, about 400wppm, about 425wppm, about 450wppm, about 475wppm, about 500wppm, about 550wppm, about 600wppm, about 650wppm, about 700wppm, about 750wppm, about 800wppm, about 850wppm, about 900wppm, about 1000wppm, about 1500wppm, about 2000wppm, about 2500wppm, about 3000wppm In some embodiments, the composition may include any one of the following: about 100wppm, about 200wppm, about 300wppm, about 400wppm, about 500wppm, about 5000wppm, about 5500wppm, about 6000wppm, about 6500wppm, about 7000wppm, about 7500wppm, about 8000wppm, about 8500wppm, about 9000wppm, about 9500wppm, about 10,000wppm, about 10,500wppm, about 11,000wppm, and including and / or between any two of these values ​​and higher than any scope of any one of these values. In any embodiment herein, the composition may not include detectable polymer. " detectable " used herein refers to detecting on commercial detection instruments known in the art.

[0083] The composition of any embodiment disclosed herein may comprise about 15 mg or more of sediment per 100 mL of the composition. The sedimentation is determined according to the method described in AOCS Ca 3d-02, except that the method is performed at 65°C instead of 20°C.

[0084] In any of the embodiments disclosed herein, the composition may have an alkalinity value of about 200 mg / kg to about 6000 mg / kg as measured by AOCS Test Method Cc 17-95. Thus, in any of the embodiments disclosed herein, the composition may have an alkalinity value of about 200 mg / kg to about 6000 mg / kg as measured by AOCS Test Method Cc 17-95. The basicity value measured for 17-95 is about 200 mg / kg, about 300 mg / kg, about 400 mg / kg, about 500 mg / kg, about 600 mg / kg, about 700 mg / kg, about 800 mg / kg, about 900 mg / kg, about 1,000 mg / kg, about 1,200 mg / kg, about 1,400 mg / kg, about 1,600 mg / kg, about 1,800 mg / kg, about 2,000 mg / kg, about 2,500 mg / kg, about 3,000 mg / kg, about 3,500 mg / kg, about 4,000 mg / kg, about 4,500 mg / kg, about 5,000 mg / kg, about 5,500 mg / kg, about 6,000 mg / kg, or any range including and / or between any two of these values.

[0085] Before the composition is contacted with the aqueous solution, the composition may or may not be pretreated. Such pretreatment may include, but is not limited to, FFA stripping, bleaching, deodorization, washing, glycerol decomposition, degumming, alkalinity reduction, or any combination of two or more thereof. Glycerol decomposition generally involves reducing the amount of FFA by the reaction of the composition with glycerol, such as described in U.S. Patent No. 7,087,771, which is incorporated herein by reference. The product of the reaction may include monoglycerides, diglycerides, triglycerides, or a mixture of two or more thereof. For example, a representative reaction for converting FFA into monoglycerides may be as follows:

[0086]

[0087] Thus, glycerol hydrolysis can reduce the FFA content to about 15 wt.% or less, such as a range of about 5 wt.% to about 15 wt.% (about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%, about 15 wt.%, or any range including and / or between any two of these values). For example, in any embodiment of the present technology, the FFA content of the composition can be reduced to about 10 wt.% or less by pretreating the composition (e.g., by glycerol hydrolysis) before contacting the composition with an aqueous solution; as another example, in any embodiment of the present technology, the FFA content can be reduced to a value in the range of about 5 wt.% to about 10 wt.% by pretreating the composition by glycerol hydrolysis before contacting the composition with an aqueous solution.

[0088] One type of degumming is acid degumming, which includes contacting the composition with concentrated aqueous acid before contacting the composition with an aqueous solution. Exemplary acid degumming processes are described in U.S. Patent No. 9,404,064, which is incorporated herein by reference. Exemplary acids may include phosphoric acid, citric acid and maleic acid. Acid degumming can reduce metals such as calcium and magnesium and reduce phosphorus. Similarly, alkalinity reduction is usually carried out by adding acid (referring to any acid, such as citric acid) to a composition with high alkalinity. Acid has the effect of neutralizing saponification and / or chelated metal ions. The process equipment used for acid degumming and / or alkalinity reduction may include a high shear mixer, a circulating mixer, a decanter centrifuge and / or a disc centrifuge.

[0089] Thus, alkalinity reduction can reduce the concentration of metals, particularly Fe, Ca, K, and Na, in the composition prior to contacting the composition with an aqueous solution. In any embodiment herein, alkalinity reduction can include contacting the composition with steam to heat the composition to provide a steam-heated composition, combining the steam-heated composition with an acid (e.g., citric acid) to provide an acid-contacted composition, mixing the acid-contacted composition with water and then stirring to provide a mixture including uniformly dispersed droplets, and then separating a sludge phase, an aqueous phase, and an oil phase in a three-phase centrifuge, wherein the oil phase is a "pretreatment composition" having a reduced total metal content and reduced alkalinity (compared to the composition), wherein the "pretreatment composition" is used in the method (e.g., in any embodiment herein, the method can include contacting the "pretreatment composition" with an aqueous solution to produce a mixture. The steam-heated composition can be at about 15 0 ° F to about 200 ° F temperature. The amount of acid (e.g., citric acid) combined with the steam heated composition can be about 0.2 wt.% to about 10.0 wt.% (based on the mass of the composition). The amount of water combined with the acid contacted composition can be about 0.2 wt.% to about 10.0 wt.% (based on the mass of the composition). Stirring can include the use of an agitator, a recirculation loop, any other mixing method, or a combination of any two or more thereof. The total time of stirring (e.g., total mixing time) can be about 2 to 90 minutes. The pretreatment composition can include a reduced amount of metal based on the total amount of metal in the composition before the alkalinity is reduced. The alkalinity reduction can provide a total metal content of about 40% to about 99% lower than the composition before such alkalinity reduction.

[0090] In any of the embodiments disclosed herein, the methods of the present technology may or may not include bleaching with bleaching clay. Bleaching generally involves contacting the degumming composition with an adsorbent clay and filtering the spent clay through a pressurized leaf filter. Bleaching clays (e.g., Fuller's earth, ) can effectively remove chromophores containing nitrogen compounds (such as chlorophyll) and other polar substances. However, at relatively high FFA concentrations typical of the original FOG composition of the present technology, metals such as Fe, Mg and Ca are leached from the clay and further contaminate the composition.

[0091] As previously discussed, in any embodiments disclosed herein, the first treated composition and / or the second treated composition can have a total metal amount of about 20% or less of the total metal amount in the composition (e.g., when the composition has 20 wppm of total metal, the second treated composition has 4 wppm or less of total metal). Thus, in any embodiments disclosed herein, the first treated composition and / or the second treated composition can have a total metal amount of about 20% of the composition, about 15% of the composition, about 10% of the composition, about 5% of the composition, about 1% of the composition, about 0.1% of the composition, about 0.01% of the composition, or any range including and / or between any two of these values, or any range less than any of these values. In any embodiments disclosed herein, the first treated composition and / or the second treated composition can have an amount of phosphorus of about 20% of the composition, about 15% of the composition, about 10% of the composition, about 5% of the composition, about 1% of the composition, about 0.1% of the composition, about 0.01% of the composition, or any range including and / or between any two of these values, or any range less than any of these values.

[0092] The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain reduced amounts of phosphorus, total metals, sulfur, nitrogen and / or chlorine, while containing free fatty acids in an amount approximately the same as the amount of free fatty acids in the composition. The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain about 5 wt.% to about 10 wt.% free fatty acids. The amount of free fatty acids in the first treated composition and / or the second treated composition of any embodiment disclosed herein may be, but is not limited to, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, or any range including and / or between any two of these values.

[0093] The first treated composition and / or the second treated composition of any embodiment disclosed herein may have an acid value of about 10 mg KOH / g to about 150 mg KOH / g. Suitable acid value amounts may include, but are not limited to, about 10 mg KOH / g to about 150 mg KOH / g, about 10 mg KOH / g to about 100 mg KOH / g, about 10 mg KOH / g to about 50 mg KOH / g, about 10 mg KOH / g to about 25 mg KOH / g, about 10 mg KOH / g to about 20 mg KOH / g, about 10 mg KOH / g to about 15 mg KOH / g, or any range including and / or between any two of these values. For example, in any of the embodiments herein, the acid value of the first treated composition and / or the second treated composition can be from about 10 mg KOH / g to about 30 mg KOH / g, and can be about 10 mg KOH / g, about 11 mg KOH / g, about 12 mg KOH / g, about 13 mg KOH / g, about 14 mg KOH / g, about 15 mg KOH / g, about 16 mg KOH / g, about 17 mg KOH / g, about 18 mg KOH / g, about 19 mg KOH / g, about 20 mg KOH / g, about 21 mg KOH / g, about 22 mg KOH / g, about 23 mg KOH / g, about 24 mg KOH / g, about 25 mg KOH / g, about 26 mg KOH / g, about 27 mg KOH / g, about 28 mg KOH / g, about 29 mg KOH / g, about 30 mg KOH / g, or any range including and / or between any two of these values.

[0094] The first processed composition of any embodiment disclosed herein and / or the second processed composition may include less than about 10wppm of total metal. The first processed composition of any embodiment disclosed herein and / or the second processed composition may include less than about 9wppm, about 8wppm, about 7wppm, about 6wppm, about 5wppm, about 4wppm, about 3wppm, about 2wppm, about 1wppm, about 0.9wppm, about 0.8wppm, about 0.7wppm, about 0.6wppm, about 0.5wppm, about 0.4wppm, about 0.3wppm, about 0.2wppm, about 0.1wppm, or include and / or any scope between any two of these values, or less than any scope of any one of these values. For example, in any embodiment herein, the first processed composition and / or the second processed composition may include less than about 5wppm of total metal.

[0095] The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain less than about 8 wppm phosphorus; therefore, the amount of phosphorus in the first treated composition and / or the second treated composition of any embodiment disclosed herein can be about 7 wppm, about 6 wppm, about 5 wppm, about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm, or any range including and / or between any two of these values ​​or any range less than any one of these values.

[0096] The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain less than about 10 wppm of chlorine; the amount of chlorine in the first treated composition and / or the second treated composition of any embodiment disclosed herein can be about 9 wppm, about 8 wppm, about 7 wppm, about 6 wppm, about 5 wppm, about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm, or any range including and / or between any two of these values ​​or any range less than any one of these values.

[0097] The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain less than about 5wppm of sulfur. The amount of sulfur in the first treated composition and / or the second treated composition of any embodiment disclosed herein may be about 4wppm, about 3wppm, about 2wppm, about 1wppm, about 0.9wppm, about 0.8wppm, about 0.7wppm, about 0.6wppm, about 0.5wppm, about 0.4wppm, about 0.3wppm, about 0.2wppm, about 0.1wppm, or any range including and / or between any two of these values ​​or any range less than any one of these values.

[0098] The first treated composition and / or the second treated composition of any embodiment disclosed herein may contain less than about 250 wppm of nitrogen. The amount of nitrogen in the first treated composition and / or the second treated composition of any embodiment disclosed herein may be about 240 wppm, about 230 wppm, about 220 wppm, about 210 wppm, about 200 wppm, about 190 wppm, about 180 wppm, about 170 wppm, about 160 wppm, about 150 wppm, about 140 wppm, about 130 wppm, about 120 wppm, about 110 wppm, about 100 wppm, about 95 wppm , about 90 wppm, about 85 wppm, about 80 wppm, about 75 wppm, about 70 wppm, about 65 wppm, about 60 wppm, about 50 wppm, about 45 wppm, about 40 wppm, about 35 wppm, about 30 wppm, about 25 wppm, about 20 wppm, about 15 wppm, about 10 wppm, about 5 wppm, about 1 wppm, or any range including and / or between any two of these values ​​or any range less than any of these values.

[0099] The first treated composition and / or the second treated composition of any embodiment disclosed herein may include less than about 15 mg of sediment per 100 mL of treated composition. Therefore, the amount of sediment per 100 mL of the first treated composition and / or the second treated composition of any embodiment disclosed herein may be about 15 mg, about 14 mg, about 13 mg, about 12 mg, about 11 mg, about 10 mg, about 9 mg, about 8 mg, about 7 mg, about 6 mg, about 5 mg, about 4 mg, about 3 mg, about 2 mg, about 1 mg, about 0.1 mg, about 0.01 mg, or any range including and / or between any two of these values, or less than any one of these values.

[0100] The first treated composition and / or the second treated composition of any embodiment disclosed herein can include about 1 wppm or less of sodium fatty acid.

[0101] The method of the present technology may also include subjecting the first treated composition and / or the second treated composition of any embodiment disclosed herein to hydroprocessing. Hydroprocessing as used herein describes various types of catalytic reactions occurring in the presence of hydrogen, but is not limited thereto. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing (HDW), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending on the catalyst type, reactor configuration, reactor conditions, and feedstock composition, a variety of reactions from pure heat (i.e., no catalyst is required) to catalysis may occur.

[0102] To further help understand this technology, refer to Figure 1 Non-limiting examples of methods of the present technology are discussed. Figure 1 In the process shown, a FOG feed 101 comprising monoglycerides, diglycerides and triglycerides and at least 5 wt.% FFA is contacted with an aqueous solution 102 (comprising (NH4)2H2EDTA, (NH4)4EDTA, a combination of citric acid and Na4EDTA, a combination of citric acid and Na2H2EDTA, or a combination of any two or more thereof) in a mixer 10.

[0103] The FOG feed 101 has a basicity in the range of 200 to 20,000 mg / kg, a total metal content of about 10 wppm, and a phosphorus content of about 10 wppm or more. In any embodiments disclosed herein, the FOG feed 101 may have a molar ratio of phosphorus to multivalent metal ions (e.g., Fe, Ca, Mg, and Cu) of 0.1:1 to 2:1, 0.3:1 to 1.7:1, 0.5:1 to 1.2:1, 0.6:1 to 1.0:1, or 0.7:1 to 0.9:1.

[0104] For FOG feeds with alkalinity values ​​above 1000 mg / kg, aqueous solutions with pH values ​​less than 7 are preferred. The aqueous solutions of any embodiment disclosed herein may have a pH value of 4 to 6. The aqueous solution may be modified based on the alkalinity of the FOG - lower pH for low alkalinity and higher pH for high alkalinity - while the 200-6000 mg / kg FOG alkalinity range is maintained in the pH range of about 4 to 9.

[0105] Refer to Figure 1, the volume ratio of FOG feed 101 to aqueous solution 102 can be 10:1 to 100:1, depending on the dilution level of the chelating agent and the concentration of phosphorus and metals in the FOG feed 101. In a preferred embodiment, the volume ratio of FOG feed 101 to aqueous solution 102 is 20:1 to 80:1.

[0106] The temperature of the FOG feed 101 when contacting the aqueous solution 102 may be between 140°F and 300°F, preferably between 180°F and 260°F. Figure 1 The mixer 10 is a continuous high shear mixer. Such mixers are known to those skilled in the art and are characterized by a rotor (rotating part) and a stator (stationary part), wherein the rotor is connected to the motor by a shaft and the stator is provided with holes or slots. Thus, the aqueous solution 102 is sheared into fine droplets within the FOG, producing a two-phase mixture 103 comprising a dispersed phase and a continuous phase. The droplet size of the two-phase mixture 103 may be in the range of 1-1000 microns, of which at least 80% are in the range of 10-100 microns in size. One of ordinary skill in the art will appreciate that the purpose of the mixer 10 may be achieved by other devices, including static mixers, orifice plates / valves, ejectors or stirred tanks.

[0107] The two-phase mixture 103 is directed to a retention tank 20 to provide a mixture 104. The purpose of the retention tank 20 is to provide the residence time required for metal chelation, conversion of non-hydratable phospholipids (NHPs) to hydratable phospholipids, migration of hydratable phospholipids to the droplet oil / water interface, and agglomeration of fine droplets into larger droplets (thereby facilitating subsequent oil / water separation). The residence time in the retention tank 20 is 5 minutes to 100 minutes, preferably 10 minutes to 60 minutes. The retention tank 20 may be equipped with a mixing device to provide tank circulation while avoiding vigorous agitation. Additional water may be added to the retention tank 20.

[0108] The mixture 104 is directed to a first centrifuge 30, wherein a first heavy phase 105 comprising water and chelated metals is separated from a first light phase (i.e., comprising treated FOG). The heavy phase 105 may optionally be further treated according to water treatment methods known to those of ordinary skill in the art (e.g., as described previously herein) to remove metals or other chemical contaminants in the water.

[0109] The first centrifuge 30 is a disc centrifuge. Disc centrifuges can be used for separation tasks involving low solid concentrations and small particles and droplet sizes, which are encountered in the types of liquid-liquid and liquid-solid compositions that constitute the chelated product compositions used in the disclosed method. Disc centrifuges usually use very high centrifugal forces to separate solids and one or two liquid phases from each other in a single continuous process. The denser phase (e.g., the heavy phase containing water, chelated metals dissolved therein and the phospholipids concentrated in the oil / water interface) is subject to such a large force that they are forced to outwardly abut against the rotating drum wall (bowlwall), while the less dense liquid (the light phase containing the treated FOG) forms a concentric inner layer. The centrifuge can be adjusted to allow accurate division of the oil / water interface to optimize separation. The "disc" part of the centrifuge includes a plate that provides additional surface area, and the components of the feed being centrifuged can be settled on this surface area according to density. It is the special configuration, shape and design of these plates that enable the centrifuge to continuously separate a wide range of solids from a liquid mixture. Concentrated solids (such as sludge) can be removed continuously, intermittently or manually according to the needs of the operator. Disk centrifuges suitable for use in methods according to the present technology are available from, for example, Alfa Laval (Sweden) and GEA Westfalia Separator Group (Germany). It will be appreciated by those skilled in the art that the purpose of centrifuge 30 can be achieved by other equipment, including horizontal centrifuges, three-phase centrifuges or solid bowl centrifuges.

[0110] Depending on the metal and phosphorus contaminant content of the FOG feed 101, the first light phase 106 may have a total concentration of polyvalent metals iron, calcium, magnesium, and copper of less than 3 wppm (e.g., less than 2.5 wppm, less than 2 wppm, less than 1.5 wppm, less than 1.0 wppm, or less than 0.5 wppm), and a total concentration of polyvalent metals Fe, Ca, Mg, and Cu of 0.1 wppm to 2.0 wppm or 0.2 wppm to 1.5 wppm. The first light phase 106 may contain monovalent metals Na and K of less than 3 wppm (e.g., less than 2.5 wppm, less than 2 wppm, or less than 1.5 wppm). The first light phase 106 may have a phosphorus content of less than 4 wppm (e.g., less than 3.5 wppm, less than 3.0 wppm, less than 2.5 wppm, less than 2.0 wppm, or less than 1.5 wppm).

[0111] The first light phase 106 can show at least an 80% reduction in metals and phosphorus compared to the FOG feed 101 (i.e., the amount of total metals and phosphorus is 20% of the FOG feed 101). The reduction in Ca, Cu, Fe, Mg, Na, K, Li, and P can be at least 85%, and can be at least 90%. The reduction in phosphorus can be at least 90% (e.g., at least 94%), and the reduction in iron can be at least 95% (e.g., at least 96%). Thus, the first light phase 106 can be suitable for conversion into renewable diesel, renewable gasoline, or other biofuels, for example, in an HDO reactor.

[0112] The first light phase 106 can optionally be contacted with a pH adjustment solution 107 in the contactor 40 to provide a pH-adjusted first light phase 108. This option can be performed to lower the pH using an acid when the aqueous chelating agent pH is above 7; and to increase the pH using a base when the aqueous chelating agent pH is below 7. The aqueous solution 102 can have a pH of 4 to 6, and the pH adjustment solution 107 can be a 10 wt.% to 30 wt.% caustic solution (e.g., a 10 wt.-%-30% aqueous sodium hydroxide solution). When the pH of the aqueous solution 102 is 8 to 9, the pH adjustment solution 107 can be a 20% to 50% citric acid solution (i.e., a 20 wt.%-50 wt.% citric acid aqueous solution). The pH adjustment solution 107 can also be a 20% to 80% phosphoric acid solution.

[0113] Contactor 40 is a device for intimately contacting the first light phase (oil) and the pH adjustment solution (aqueous).Contactor 40 may be a static mixer, or may be a high shear mixer similar to the high shear mixer described previously herein.

[0114] like Figure 1 As shown, the light phase 108 of pH adjustment is processed by the second centrifuge 50, so that the second heavy phase 109 is separated from the second light phase 110. Centrifuge 50 can be identical with the centrifuge 30 described above in function. The pH of the second heavy phase 109 can be used for controlling the relative amount of pH adjustment solution 107. In addition, extra water can be introduced into the first and / or second centrifuge. Preferably, the water used is deionized water, softened water or steam condensate.

[0115] The second light phase 110 has the same or less total metals and phosphorus as the first light phase 106. As described above, the second light phase 110 can be contacted with additional water and can be subjected to additional separation steps (not shown) in the form of a centrifuge or a decantation tank to produce the third light phase. The second light phase 110 can have a phosphorus content less than about 3wppm, a total Ca, Cu, Fe, Mg, Na and K metal content less than about 3wppm, and can be directed to at least one HDO reactor. Optionally, the first, second and / or third light phase can be treated with an adsorbent medium (not shown) to provide an adsorbent-treated raw material for HDO conversion. The adsorbent-treated raw material has phosphorus and total Ca, Cu, Fe, Mg, Na and K metal content lower than the second light phase 110.

[0116] As discussed previously in this disclosure, various adsorbent media are known to those skilled in the art. Such media are typically in powder form and are contacted with the light phase 106 or 110 in a slurry tank prior to separation in a pressurized leaf filter. It is possible that at least one HDO reactor includes a high porosity inert media as the final filtration layer of the treated FOG (e.g., first light phase, second light phase, first light phase, and / or adsorbent-treated feedstock) described herein prior to contacting it with the HDO catalyst.

[0117] The present technology, thus generally described, will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present technology. Example

[0118] Comparative Example 1: Citric acid alone and Na4EDTA alone

[0119] According to the prior art, such as U.S. Patent No. 6,407,271 and U.S. Patent Publication No. 2010 / 0056833, two different grades of tetrasodium EDTA are used. B and BX (available from BASF) treats a mixture of fats, oils and greases (crude FOG) comprising used cooking oil from a commercial source with a fatty acid content of greater than 5 wt.% (potentiometric titration indicated FFA of about 9.5 wt.%). These are labeled "Na4EDTA-1" and "Na4EDTA-2", respectively. The process involves mixing about 100 grams of crude FOG with about 0.68 grams of a 50 wt.% aqueous solution of Na4EDTA in a beaker equipped with a high shear mixer at a temperature of about 65°C. The high shear mixer is a Silverson model LM5-A, operating at a setting of 2000 rpm. After 60 seconds, the shear mixer is stopped and about 2.1 grams of deionized water is added to the beaker and sheared again at 2000 rpm for about 2 seconds to incorporate the water. The beaker is then placed on a stir plate and mixed at 82°C for about 20 minutes using a PTFE stir bar. After 20 minutes, about 0.1 grams of 50% sodium hydroxide solution and 2.1 grams of deionized water were added to the beaker. The contents were allowed to continue mixing on a stirring plate at 82°C for about another 5 minutes. Finally, the contents of the beaker were divided into two equal parts, distributed into 100mL glass centrifuge tubes, and centrifuged at 1800rpm for about 10 minutes at about 82°C using a laboratory centrifuge. The light phase was then pipetted into a beaker and mixed with about 3.9 grams of water at 82°C for 10 seconds using a high shear mixer. The contents were centrifuged again under the same conditions as the first centrifugation to obtain a treated FOG sample. The treatment was repeated with citric acid at the same molar addition rate as the EDTA run. The elemental contaminants of the crude FOG and treated FOG samples were analyzed using a SpectroArcos inductively coupled plasma optical emission spectrophotometer. The results of these experiments are summarized in Table I.

[0120] Table I highlights the inadequacy of the prior art in improving the treatment of FOG containing relatively high free fatty acid content using more effective chelating agents. Although Na4EDTA significantly improves the removal of phosphorus and some polyvalent metals, this improvement is offset by the greatly increased amount of sodium due to the reaction of sodium with FFA in the FOG to form sodium fatty acids (as evidenced by the increase in basicity shown in Table II). Therefore, the net effect is an increase in the contaminant content of the treated FOG.

[0121] Table 1. Distribution of contaminating elements (wppm) of crude FOG of Example 1 treated with different chelating agents

[0122]

[0123] Table II. Basicity distribution of crude FOG of Example 1 treated with different chelating agents (wppm, sodium oleate)

[0124] Pollutants Citric Acid <![CDATA[Na4EDTA-1]]> <![CDATA[Na4EDTA-2]]> Alkalinity 40 2200 2200

[0125] Comparative Example 2. Adsorption treatment of treated FOG from Comparative Example 1

[0126] In order to see whether the prior art teachings on fatty acid salt removal address the deficiencies of the EDTA prior art, samples of FOG treated in the experiment from Comparative Example 1 were subjected to adsorption treatment. See, e.g., U.S. Pat. No. 5,298,639, U.S. Pat. No. 5,231,201. For this set of experiments, about 100 grams of each FOG product treated in Comparative Example 1 was mixed with about 0.4 grams of 300 silica hydrogel (product of Grace Materials Technologies) and 0.4 grams of Celatom FW40 diatomaceous earth (DE) purchased from EPMinerals were contacted. This was carried out in a glass conical flask at 87°C with stirring at 500 rpm. After 35 minutes, the slurry was vacuum filtered through Whatman 5 filter paper and analyzed by ICP-AES as described above. The results are summarized in Table III.

[0127] As observed in Table III, the adsorption media was unable to remove the high levels of sodium introduced by the Na4EDTA in Comparative Example 1. In other words, combining prior art chelation with prior art adsorption does not correct the deficiencies associated with applying prior art chelation to FOG feedstocks having relatively high free fatty acid contents.

[0128] Table III. Distribution of contaminant elements (wppm) of FOG treated in Comparative Example 2 (corresponding to the chelating agent of Comparative Example 1)

[0129]

[0130] Example 3. Examples of methods of the present technology

[0131] The crude FOG of Example 1 was treated in two steps with (1) a chelating agent and (2) an adsorption medium according to Examples 1 and 2, respectively, except that Na4EDTA was replaced by chelating agents of the present technology: a combination of Na4EDTA and citric acid, (NH4)2H2EDTA, and (NH4)4EDTA. Citric acid as the sole chelating agent was rerun as a control (prior art) chelating agent. The results are summarized in Table IV.

[0132] As observed in Table IV, the high sodium problem associated with the use of sodium EDTA salt for FOG feedstocks with relatively high free fatty acid content is solved by the process of the present technology, while also retaining the phosphorus reduction advantage of EDTA compared to the citric acid control. The reduction in sodium provided by the combination of Na4EDTA and citric acid is much greater than that indicated by comparing the results of Comparative Examples 1 and 2 using citric acid alone and Na4EDTA alone, indicating the synergistic advantage of the combination of citric acid and Na4EDTA.

[0133] Surprisingly, and in contrast to the use of Na4EDTA alone which significantly increased the sodium level, neither (NH4)2H2EDTA nor (NH4)4EDTA individually increased the nitrogen content in the crude FOG. The nitrogen in all treated FOG samples of Example 3 was in the range of 46 to 54 ppm, and well below the 63.1 ppm nitrogen content of the crude FOG, indicating that the net removal of nitrogen compounds (without being limited by theory) may include ammonium soaps that may have been formed.

[0134] Table IV. Distribution of contaminating elements (wppm) of crude FOG treated with different chelating agents in Example 3

[0135]

[0136] Although certain embodiments have been shown and described, it will be appreciated that changes and modifications may be made thereto according to ordinary skill in the art without departing from the broader aspects of the technology as defined in the following claims. Each of the aspects and embodiments described above may also include or be combined with such changes or aspects as disclosed with respect to any or all other aspects and embodiments.

[0137] With respect to the specific aspects and / or embodiments described herein that are intended to be a single illustration of various aspects and / or embodiments of the present technology, the present technology is not limited thereto. Many modifications and variations can be made without departing from its spirit and scope, which will be apparent to those skilled in the art. In addition to those listed herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art based on the above description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the terms of the appended claims and the full scope of equivalents to which these claims are entitled. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which can of course all vary. It should also be understood that the terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limiting.

[0138] The embodiments illustratively described herein may be appropriately implemented in the absence of any one or more elements, one or more limitations not specifically disclosed herein. Thus, for example, the terms "comprising", "including", "containing", etc. should be understood expansively without limitation. In addition, the terms and expressions used herein have been used as terms of description rather than limitation, and when using these terms and expressions, it is not intended to exclude any equivalents of the features shown and described, or portions thereof, but it should be recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "essentially consisting of..." will be understood to include those elements specifically enumerated and those additional elements that do not substantially affect the basic and novel features of the claimed technology.

[0139] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0140] As will be appreciated by those skilled in the art, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also include any and all possible subranges and combinations of subranges thereof. Any listed range can be easily considered to be fully described, and the same range can be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be easily decomposed into a lower third, a middle third, and an upper third, etc. As will be appreciated by those skilled in the art, all language, such as "at most," "at least," "greater than," "less than," etc., includes the numbers listed, and refers to a range that can be subsequently decomposed into subranges as described above. Finally, it will be appreciated by those skilled in the art that a range includes each individual member.

[0141] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference, as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0142] The present technology may include, but is not limited to, the features and combinations of features described in the following lettered paragraphs, with the understanding that the following paragraphs shall not be interpreted as limiting the scope of the appended claims or mandating that all such features must be included in these claims:

[0143] A. A method comprising

[0144] The composition is contacted with an aqueous solution to produce a mixture, wherein

[0145] The composition comprises

[0146] One or more of animal fats, animal oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases and used cooking oils,

[0147] about 5 wt.-% or more of free fatty acids,

[0148] About 10wppm or more total metals,

[0149] About 8wppm or more phosphorus,

[0150] About 20 wppm or more nitrogen, and

[0151] The aqueous solution comprises ((NH4)2H2EDTA, (NH4)4EDTA, the monoammonium salt of diethylenetriaminepentaacetic acid, the diammonium salt of diethylenetriaminepentaacetic acid, the triammonium salt of diethylenetriaminepentaacetic acid, the tetraammonium salt of diethylenetriaminepentaacetic acid, (NH4)5DTPA, a combination of citric acid and Na4EDTA, a combination of citric acid and Na2H2EDTA, a combination of citric acid and the monosodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the disodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the trisodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the tetrasodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and Na5DTPA, or a combination of any two or more thereof; and

[0152] The mixture is centrifuged to produce a first treated composition, wherein the first treated composition has less total metals and less phosphorus than the composition.

[0153] B. The method of paragraph A, wherein, prior to centrifugation, a caustic solution is added to the mixture

[0154] C. The method of paragraph B, wherein the caustic solution comprises an aqueous ammonium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, or a combination of any two or more thereof.

[0155] D. The method of any of paragraphs A to C, wherein water is added to the mixture prior to centrifugation.

[0156] E. The method of any of paragraphs A to D, wherein the method further comprises

[0157] combining the first treated composition with an adsorption medium to form a slurry comprising the resulting adsorption medium and a second treated composition; and

[0158] separating the second treated composition from the slurry;

[0159] wherein the total amount of metals and phosphorus in the second treated composition is about 20% or less of the total amount of metals and phosphorus in the composition.

[0160] F. The method of paragraph E, wherein the adsorption medium comprises one or both of silica and diatomaceous earth.

[0161] G. The method of paragraph F, wherein the adsorption medium comprises both silica and diatomaceous earth, and the adsorption medium has a weight ratio of diatomaceous earth to silica of about 0.1:1 to about 1.5:1.

[0162] H. The method of any of paragraphs A to G, wherein during contacting, the weight ratio of (NH4)2H2EDTA in the composition and the aqueous solution is from about 50:1 to about 500:1.

[0163] I. The method of any of paragraphs A to H, wherein during contacting, the weight ratio of the composition to (NH4)4EDTA is from about 50:1 to about 500:1.

[0164] J. The method of any of paragraphs A to I, wherein during contacting, the weight ratio of the composition to the Na4EDTA in the aqueous solution is from about 50:1 to about 500:1.

[0165] K. The method of any of paragraphs A to J, wherein the combination of citric acid and Na4EDTA comprises a molar ratio of citric acid to Na4EDTA of about 1:3 to about 3:1.

[0166] L. The method of any of paragraphs A to K, wherein the combination of citric acid and Na2H2EDTA comprises a molar ratio of citric acid to Na2H2EDTA of about 1:3 to about 3:1.

[0167] M. The method of any of paragraphs A to L, wherein the aqueous solution comprises citric acid in combination with (NH4)2H2EDTA.

[0168] N. The method of paragraph M, wherein the combination of citric acid and (NH4)2H2EDTA comprises a molar ratio of about 1:3 to about 3:1 citric acid to (NH4)2H2EDTA.

[0169] O. The method of any of paragraphs A to N, wherein the aqueous solution comprises a combination of citric acid and (NH4)4EDTA.

[0170] P. The method of paragraph O, wherein the combination of citric acid and (NH4)4EDTA comprises a molar ratio of citric acid to (NH4)4EDTA of about 1:3 to about 3:1.

[0171] Q. The method of any of paragraphs A to P, wherein during contacting, the weight ratio of (NH4)5DTPA in the composition and the aqueous solution is from about 50:1 to about 500:1.

[0172] R. The method of any of paragraphs A to Q, wherein the aqueous solution comprises a combination of citric acid and (NH4)5EDTA.

[0173] S. The method of paragraph R, wherein the combination of citric acid and (NH4)5EDTA comprises a molar ratio of citric acid to (NH4)5EDTA of about 1:3 to about 3:1.

[0174] T. The method of any of paragraphs A to S, wherein during the contacting, the weight ratio of Na5DTPA in the composition and the aqueous solution is from about 50:1 to about 500:1.

[0175] U. The method of any of paragraphs A to T, wherein the combination of citric acid and Na5DTPA comprises a molar ratio of citric acid to Na5DTPA of about 1:3 to about 3:1.

[0176] V. The method of any of paragraphs A to U, wherein the composition comprises about 5 wt.% to about 15 wt.% free fatty acids.

[0177] W. The method of any of paragraphs A to V, wherein the contacting comprises high shear mixing of the composition and the aqueous solution.

[0178] X. The method of any of paragraphs A to W, wherein the centrifuging comprises a disk centrifuge.

[0179] Y. The method of any of paragraphs A to X, wherein the composition has a basicity value of about 200 mg / kg to about 6,000 mg / kg as measured by AOCS Test Method Cc 17-95.

[0180] Z. The method of any of paragraphs A to Y, wherein the pH of the aqueous solution is from about 4 to about 6.

[0181] AA. The method of any of paragraphs A to Z, wherein the first treated composition comprises about 1 wppm or less of sodium fatty acid.

[0182] AB. The method of any of paragraphs A to AA, wherein the second treated composition comprises about 1 wppm or less of sodium fatty acid.

[0183] AC. The method of any of paragraphs A to AB, wherein the method further comprises hydroprocessing the first treated composition.

[0184] AD. The method of any of paragraphs E to AC, wherein the method further comprises hydroprocessing the second treated composition.

[0185] AE. The method of any of paragraphs A to AD, wherein the method does not comprise contacting the composition with a bleaching clay.

[0186] AF. The method of any of paragraphs A to AE, wherein the method comprises centrifuging the mixture to produce the first treated composition and water-soluble waste.

[0187] AG. The method of paragraphs AF, wherein the water-soluble waste is treated to reduce the metal content of the water-soluble waste, reduce the biological oxygen demand of the water-soluble waste, and / or reduce the chemical oxygen demand of the water-soluble waste.

[0188] AH. A method for pretreating a feedstock for producing a biofuel, the method comprising

[0189] (a) providing a fat, oil and grease (FOG) feed comprising mono-, di- and triglycerides with a free fatty acid content of greater than 5 wt.-%;

[0190] (b) providing an aqueous chelating agent comprising ethylenediaminetetraacetic acid (EDTA);

[0191] (b) contacting the aqueous chelating agent with the FOG feed to provide a two-phase mixture, and

[0192] (c) separating the two-phase mixture into a light phase and a heavy phase in a centrifuge,

[0193] in

[0194] The FOG feed has a total multivalent metal concentration of 10 to 50 wppm, a total monovalent metal sodium, potassium and lithium concentration in the same range, a phosphorus content greater than 10 wppm, and the light phase metals and phosphorus show at least 80% reduction compared to the FOG feed.

[0195] AI. The method of paragraphs AH, wherein the aqueous chelating agent comprises an ammonium salt of EDTA.

[0196] AJ. The method of paragraph AH or paragraph AI, wherein the aqueous chelating agent and the FOG feed are contacted in a high shear mixer.

[0197] AK. The method of any of paragraphs AH to AJ, wherein the centrifuge is a disk centrifuge.

[0198] AL. The process of any of paragraphs AH to AK, wherein the light phase is further processed in a second centrifuge.

[0199] AM. The method of any of paragraphs AH to AJ, wherein the light phase is treated with an adsorbent.

[0200] AN. The process of any of paragraphs AH to AM, wherein the light phase is directed to a hydrodeoxygenation reactor.

[0201] AO. The process of any of paragraphs AH to AN, wherein the FOG feed has a basicity value of 200 to 6,000 mg / kg.

[0202] AP. The method of any of paragraphs AH to AO, wherein the aqueous chelating agent has a pH of 4 to 6.

[0203] AQ. The method of any of paragraphs AH to AP, wherein formation of sodium fatty acids in the light phase is less than 1 wppm as sodium.

[0204] Other embodiments are set forth in the following claims.

Claims

1. A method comprising: The composition is contacted with an aqueous solution to produce a mixture, wherein The composition comprises oil, 5 wt.-% or more of free fatty acids, 10wppm or more total metals, 8wppm or more phosphorus, 20wppm or more nitrogen, and The aqueous solution comprises ((NH4)2H2EDTA, (NH4)4EDTA, the monoammonium salt of diethylenetriaminepentaacetic acid, the diammonium salt of diethylenetriaminepentaacetic acid, the triammonium salt of diethylenetriaminepentaacetic acid, the tetraammonium salt of diethylenetriaminepentaacetic acid, (NH4)5DTPA, a combination of citric acid and Na4EDTA, a combination of citric acid and Na2H2EDTA, a combination of citric acid and the monosodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the disodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the trisodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and the tetrasodium salt of diethylenetriaminepentaacetic acid, a combination of citric acid and Na5DTPA, or a combination of any two or more thereof; and The mixture is centrifuged to produce a first treated composition, wherein the first treated composition has less total metals and less phosphorus than the composition.

2. The method of claim 1, wherein the composition comprises one or more of an animal oil and a vegetable oil.

3. The method of claim 1, wherein the composition comprises one or more of animal fat and vegetable fat.

4. The method of claim 1, wherein the composition comprises vegetable oil.

5. The method of claim 1, wherein the composition comprises vegetable fat.

6. The method of claim 1, wherein the composition comprises used edible oil.

7. The method of any one of claims 1-6, wherein a caustic solution is added to the mixture prior to centrifugation.

8. The method of claim 7, wherein the caustic solution comprises an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, or a combination of any two or more thereof.

9. The method of any one of claims 1 to 6, wherein an aqueous ammonium hydroxide solution is added to the mixture prior to centrifugation.

10. The method according to any one of claims 1 to 6 and 8, wherein water is added to the mixture before centrifugation.

11. The method according to any one of claims 1 to 6 and 8, wherein the method further comprises combining the first treated composition with an adsorption medium to form a slurry comprising the resulting adsorption medium and the second treated composition; and separating the second treated composition from the slurry; wherein the total amount of metals and phosphorus in the second treated composition is 20% or less of the total amount of metals and phosphorus in the composition.

12. The method of claim 11, wherein the adsorption medium comprises one or both of silica and diatomaceous earth.

13. The method of claim 12, wherein the adsorption medium comprises both silica and diatomaceous earth, and the adsorption medium has a weight ratio of diatomaceous earth to silica of 0.1:1 to 1.5:

1.

14. The method of any one of claims 1 to 6, 8 and 12-13, wherein during contacting, the weight ratio of the composition to the (NH4)2H2EDTA in the aqueous solution is 50:1 to 500:

1.

15. The method of any one of claims 1 to 6, 8 and 12-13, wherein during contacting, the weight ratio of the composition to (NH4)4EDTA is from 50:1 to 500:

1.

16. The method of any one of claims 1 to 6, 8 and 12-13, wherein during contacting, the weight ratio of Na4EDTA in the composition and the aqueous solution is 50:1 to 500:

1.

17. The method of any one of claims 1 to 6, 8 and 12-13, wherein the combination of citric acid and Na4EDTA comprises a molar ratio of citric acid to Na4EDTA of 1:3 to 3:

1.

18. The method of any one of claims 1 to 6, 8, and 12-13, wherein the combination of citric acid and Na2H2EDTA comprises a molar ratio of citric acid to Na2H2EDTA of 1:3 to 3:

1.

19. The method of any one of claims 1 to 6, 8 and 12-13, wherein the aqueous solution comprises citric acid in combination with (NH4)2H2EDTA.

20. The method of claim 19, wherein the combination of citric acid and (NH4)2H2EDTA comprises a molar ratio of citric acid to (NH4)2H2EDTA of 1:3 to 3:

1.

21. The method of any one of claims 1 to 6, 8, 12-13 and 20, wherein the aqueous solution comprises a combination of citric acid and (NH4)4EDTA.

22. The method of claim 21, wherein the combination of citric acid and (NH4)4EDTA comprises a molar ratio of citric acid to (NH4)4EDTA of 1:3 to 3:

1.

23. The method of any one of claims 1 to 6, 8, 12-13, 20 and 22, wherein during contacting, the weight ratio of (NH4)5DTPA in the composition and the aqueous solution is from 50:1 to 500:

1.

24. The method of any one of claims 1 to 6, 8, 12-13, 20 and 22, wherein the aqueous solution comprises a combination of citric acid and (NH4)5DTPA.

25. The method of claim 24, wherein the combination of citric acid and (NH4)5DTPA comprises a molar ratio of citric acid to (NH4)5DTPA of 1:3 to 3:

1.

26. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein during contacting, the weight ratio of Na5DTPA in the composition and the aqueous solution is from 50:1 to 500:

1.

27. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein the combination of citric acid and Na5DTPA comprises a molar ratio of citric acid to Na5DTPA of 1:3 to 3:

1.

28. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein the composition comprises 5 to 15 wt.% free fatty acids.

29. The method of any one of claims 1 to 6, 8, 12-13, 20, 22, and 25, wherein contacting comprises high shear mixing of the composition and the aqueous solution.

30. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein centrifuging comprises a disk centrifuge.

31. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein the composition has a basicity value of 200 mg / kg to 6,000 mg / kg as measured by AOCS Test Method Cc 17-95.

32. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein the pH of the aqueous solution is 4 to 6.

33. The method of any one of claims 1 to 6, 8, 12-13, 20, 22, and 25, wherein the first treated composition comprises 1 wppm or less of sodium fatty acid.

34. The method of claim 11, wherein the second treated composition comprises 1 wppm or less of sodium fatty acids.

35. The method of any one of claims 1 to 6, 8, 12-13, 20, 22, and 25, wherein the method further comprises hydroprocessing the first treated composition.

36. The method of claim 11, further comprising hydroprocessing the second treated composition.

37. The method of any one of claims 1 to 6, 8, 12-13, 20, 22 and 25, wherein the method does not comprise contacting the composition with a bleaching clay.

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