EP3867336A1 - Use of peroxyacids/hydrogen peroxide for removal of metal components from petroleum and hydrocarbon streams for downstream applications - Google Patents
Use of peroxyacids/hydrogen peroxide for removal of metal components from petroleum and hydrocarbon streams for downstream applicationsInfo
- Publication number
- EP3867336A1 EP3867336A1 EP19824170.5A EP19824170A EP3867336A1 EP 3867336 A1 EP3867336 A1 EP 3867336A1 EP 19824170 A EP19824170 A EP 19824170A EP 3867336 A1 EP3867336 A1 EP 3867336A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- peroxyacid
- oil
- emulsion
- particulates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Definitions
- TITLE USE OF PEROXYACIDS/HYDROGEN PEROXIDE FOR
- the disclosure relates to the use of peroxyacid formulations, including but not limited to peracetic acid and performic acid, for enhancement of downstream processes through removal of soluble and particulate metal complexes from petroleum oils and refinery feedstocks and/or streams. This serves to minimize fouling, decrease the propensity for a solid stabilized emulsion and in turn, improve waste water quality.
- the methods and compositions are particularly useful for mitigation of heavy metals in petroleum oil and for offsetting potential solid loading resulting from use of a metal based H2S scavenger or other commonly applied metal-based additives.
- the methods and compositions are also useful for enhancing coke quality via decreased metal concentrations, reducing bacteria in slop oil and crude tanks, as well as reducing downstream catalyst poisoning.
- an enhanced solids removal agent or demulsifier that can promote partitioning of inorganic particulate, such as iron sulfide, from an emulsion phase to a water phase. This is essential to increase the lifetime of process equipment downstream of the desalter in a refinery, to ensure compliance with environmental regulations in streams processed by refinery waste water treatment plants and to enhance profitability.
- U.S. Pat. Nos. 4,778,589 and 4,789,463 disclose the use of hydroxycarboxylic acids as chemical aids for metals removal in refinery desalting processes.
- U.S. Pat. No. 4,833,109 to Reynolds discloses the use of dibasic carboxylic acids, particularly oxalic acid, for the removal of divalent metals, including calcium and iron. Wash water addition of hydroxyacids for removing metals during desalting processes is taught in U.S. Pat. Nos. 7,497,943, 4,778,589 and 4,789,463.
- U.S. Pat. Nos. 5,114,566 and 4,992,210 teach the removal of corrosive contaminants from crude oil by adding a composition including certain organic amines having a pKb from 2 to 6 and potassium hydroxide to the desalter wash water. The composition is stated to effectively remove chlorides from the crude oil at the desalter.
- U.S. Pat. No. 5,078,858 suggests the addition of an oxalic or citric acid chelant to the desalter wash water.
- U.S. Pat. No. 5,256,304 is directed to the addition of a polymeric tannin material to oily waste water to demulsify oil and flocculate metal ions.
- U.S. Pat. No. 5,080,779 teaches the use of a chelant in a two stage desalter process for the removal of iron. Other methods involve the use of increased concentrations of emulsion breakers (aka demulsifiers).
- Peroxyacids particularly peracetic acid
- US. Pat. No 9,242,879 discloses their use for treatment of drilling fluids, frac fluids, flowback water and disposal water.
- Application of peroxyacids in the area of commercial well drilling operations have been limited to use as biocides in aqueous systems.
- use of peracetic acid has a small environmental footprint, due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, carbon dioxide and water).
- a further objective of the invention is to develop methods for solids stabilized emulsion control.
- a disclosure on a mechanism to prevent this phenomenon Minimizing the concentration of particulate content in crude oil should ultimately facilitate better salt removal and dehydrating efficiency during emulsion resolution processes. Therefore, the peroxyacid formulations can also be considered emulsion breakers in their own right.
- a further objective of the invention is to develop methods for removal of organometallic complexes such as porphyrinic iron, nickel or vanadium or calcium naphthenates. These organometallic compounds are not readily removed by normal desalting practices and can cause coker furnace fouling, finished products outside of specification and deactivation of hydroprocessing catalysts.
- the present disclosure is related to the use of peroxyacids compositions and methods of employing peroxyacids for removal of metals and particulate contained in petroleum oil, crude oil, slop oil, and other hydrocarbon streams in various refinery applications.
- the use of peroxyacid compositions and methods of employing them in various petroleum oil and refinery streams overcomes a significant need in the art for improved methods for removing particulate iron sulfide and zinc sulfide, along with other contaminants.
- a method for removing particulates in petroleum oil and/or hydrocarbon feedstocks includes the steps of: mixing petroleum oil and/or hydrocarbon feedstock with water to form an emulsion comprising a hydrocarbon phase and a water phase; adding a peroxyacid composition to the emulsion, wherein the peroxyacid causes the
- the peroxyacid oxidizes and chelates the particulates in the emulsion, and wherein the particulates are soluble and particulate metal complexes.
- the peroxyacid composition comprises a C1-C22 peroxyacid, a C1-C22 carboxylic acid, and hydrogen peroxide.
- the peroxyacid is at least one of peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxy ascorbic, peroxyhydroxyacetic, peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxy adipic, peroxypimelic and peroxy subric acid.
- At least 100 ppm of the peroxyacid is added to the emulsion, or up to about 10,000 ppm of the peroxyacid is added to the emulsion.
- at least one additional agent that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents is added to the emulsion with the peroxyacid composition.
- the mixture of petroleum oil and/or hydrocarbon feedstock in water is resolved in an electrostatic desalting unit.
- the methods further include adding an effective amount of an emulsion breaker or demulsifier to aid in the separation of the oil from the water phase containing the particulates.
- the methods further include settling the petroleum oil and/or hydrocarbon feedstock in a tank to enable the water, peroxyacid composition and particulates to settle on the bottom thereof from the petroleum oil and/or hydrocarbon feedstock.
- the petroleum oil and/or hydrocarbon feedstock is a produced crude oil and is obtained from a pipeline that directs a flow of produced crude oil.
- the petroleum oil and/or hydrocarbon feedstock once separated from the water phase does not contain any peroxyacid composition.
- the petroleum oil and/or hydrocarbon feedstock comprise petroleum oil, crude oil, slop oil, and other hydrocarbon streams from a refinery application.
- the method can exclude the use of phosphoric or phosphorus acids.
- a crude oil emulsion treatment consists of: crude oil; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water.
- the treated crude oil emulsion further comprises at least one additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- an emulsion treatment consists of: petroleum oil, crude oil, slop oil, or another hydrocarbon stream in a refinery application; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water.
- the treated emulsion further comprises at least one
- additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- FIG. 1 shows a general diagram of a desalting process.
- FIG. 2 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 3 shows a graph of nickel removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 4 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 5 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 6 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 7 is a graph showing iron removal in a resolved water phase by various peroxy carboxylic and carboxylic acids.
- FIG. 8 is a graph showing nickel and zinc removal in a resolved water phase by various chemistries.
- FIG. 9 is a graph showing the amount (ppm) of filterable solids that remained on the top oil fraction after emulsion resolution using various chemistries.
- FIG. 10 is a color photograph of four samples after centrifugation showing the resulting resolved emulsions of EC2111A and EC6779A samples at 1000 ppm and 5000 ppm.
- the present invention relates to the methods and application of peroxyacid compositions for particulate and metal removal for improving or enhancing downstream processes for petroleum oil and refinery hydrocarbon feedstocks and streams.
- the methods of using peroxyacid compositions have many advantages over conventional demetallization technologies. For example, the methods can take place before, after or simultaneous with a desalting step. The effective removal of metals and particulates before a desalting process can significantly minimize the effects of these contaminants on the crude unit and further downstream operations. Having metals and particulates removed before a desalting step then promotes more efficient desalting as well. Benefits can include reduced crude unit corrosion, crude system fouling, energy costs and desalting process demarks, and finished product contamination.
- a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 1 1 ⁇ 2, and 4 3 ⁇ 4 This applies regardless of the breadth of the range. So that the present invention may be more readily understood, certain terms are first defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain.
- the term“about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, distance, wave length, frequency, voltage, current, and electromagnetic field. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like.
- the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. The term“about” also encompasses these variations. Whether or not modified by the term“about,” the claims include equivalents to the quantities.
- compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein.
- consisting essentially of means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.
- actives or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the concentration of those ingredients involved expressed as a percentage minus inert ingredients such as water or salts.
- the terms "preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.
- waters includes water in industrial and/or energy service applications.
- Waters in industrial and/or energy service applications include for example: aquifer water, river water, sea water, produced water, fresh water, water for injection, secondary flooding water, hot water or feedwater, ethanol/bio-fuels process waters, pretreatment and utility waters, membrane system liquids, ion-exchange bed liquids, water used in the process/manufacture of paper, ceiling tiles, fiber board, microelectronics, E-coat liquids, electrodeposition liquids, process cleaning liquids, oil exploration services liquids, oil well completion fluids, oil well workover fluids, drilling additive fluids, oil fracturing fluids, oil and gas wells, flowline water systems, natural gas water systems, or the like.
- weight percent refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100
- peroxyacids and peroxyacid compositions are able to increase the hydrophilicity of particulate materials (including soluble and particulate metal complexes) in petroleum oil and refinery streams to enhance their removal from the oil/water emulsions.
- the approximate amount of peroxyacid required to achieve the desired amount of metal or particulate removal from an oil stream can be determined by one skilled in the art by taking into account characteristics of the stream being treated.
- the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can range from 1 ppm to 10,000 ppm, between about 1,000 ppm and about 5,000 ppm, or ranges there between.
- the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can be at least about 100 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- Suitable peroxyacids include both organic and inorganic peroxyacids as set forth herein.
- Organic peroxyacids include for example peroxycarboxylic acids that generally have the formula RCO3H, where, for example, R is defined as an alkyl, alkenyl, alkyne, acyclic, alicyclic group, aryl, arylalkyl, cycloalkyl, aromatic, heteroaryl, heterocyclic group, or hydrogen.
- R-group can be saturated or unsaturated as well as substituted or unsubstituted.
- Peroxyacids can be made, for example, by the direct action of an oxidizing agent on a carboxylic acid, by auto-oxidation of aldehydes, or from acid chlorides, and hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide.
- any suitable C1-C26 peroxyacid such as a peroxycarboxylic acid can be used.
- the C1-C26 percarboxylic acid is a Ci, C2, C3, Cy C5, Ce, C7, Cs, C9, C10, C 11, C12, Ci3, Ci4, Ci5, Ci6, Ci7, Ci8, Ci9, C20, C21, C22, C23, C24, C25, and/or C26 percarboxylic acid.
- a C1-C22 peroxyacid is preferred, or combinations thereof.
- Peroxyacids may include short chain and/or medium chain peroxyacids.
- a“short chain peracid” refers to a peroxyacid having a carbon chain between 1 and 4 carbons. Short chain peracids have the benefit of often being highly miscible in water at 25 °C. Examples of short chain carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid.
- Peroxyacetic (or peracetic) acid is a peroxyacid having the formula: CH3COOOH.
- peroxyacetic acid is a liquid having an acrid odor at higher concentrations and is freely soluble in water, alcohol, ether, and sulfuric acid.
- Peroxyacetic acid can be prepared through any number of methods known to those of skill in the art including preparation from acetaldehyde and oxygen in the presence of cobalt acetate.
- a solution of peroxyacetic acid can be obtained by combining acetic acid with hydrogen peroxide.
- the compositions of the invention employ a Cl to C4 peroxyacid.
- the phrase “medium chain peracid” refers to a peroxyacid having a carbon chain between 5 and 22 carbons in length.
- the phrase “medium chain carboxylic acid” can refer to a carboxylic acid that has a critical micellization concentration greater than 1 mM in aqueous buffers at neutral pH. It is also common for medium chain carboxylic acids to have an unpleasant odor.
- Medium chain carboxylic acids exclude carboxylic acids that are infinitely soluble or miscible with water at 20°C.
- Medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 180 to 300° C.
- medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 200 to 300° C. In an embodiment, 20 medium chain carboxylic acids include those with solubility in water of less than 1 g/L at 25° C. Examples of medium chain carboxylic acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
- Peroxyacids useful in the methods described herein include meta- chloroperoxybenzoic, peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic, peroxyoxalic, meta-chloroperoxybenzoic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid and mixtures thereof.
- Inorganic peroxyacids such as peroxymonosulfuric acid (Caro's acid) are not excluded from the peroxyacid and/or peroxyacid compositions
- the composition includes one or more Cl to C4 peroxyacids and one or more C5 to C22 peroxyacids.
- the ratio of short chain peroxyacid to medium chain peroxyacid can be about 1 : 1 to about 10: 1.
- a peroxyacid composition also includes an organic acid (i.e. corresponding carboxylic acid) and an oxidizing agent.
- the peroxyacid composition can be formed by an organic acid and an oxidizing agent.
- the compositions can be pre-formed.
- peroxyacid compositions may be generated in situ. Additional description of exemplary in situ methods for peroxyacids is provided for example in U.S. Patent Nos. 9,845,290, 9,518,013, 8,846,107 and 8,877,254, which are herein incorporated by reference in its entirety.
- the peroxyacid compositions may also include an oxidizing agent.
- the oxidizing agent is hydrogen peroxide.
- Hydrogen peroxide, H2O2 provides the advantages of having a high ratio of active oxygen because of its low molecular weight (34.014 g/mole) and by being compatible with numerous substances that can be treated by methods of the invention because it is a weakly acidic, clear, and colorless liquid.
- Another advantage of hydrogen peroxide is that it decomposes into innocuous water and oxygen.
- the peroxyacid compositions can include any desired ratio of hydrogen peroxide.
- the hydrogen peroxide in the percarboxylic acid composition has a concentration from about 0.5 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 10wt-%. In other embodiments, the hydrogen peroxide has a concentration from about 1 wt-% to about 2 wt-%.
- the hydrogen peroxide has a concentration at about 0.5 wt-%, 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-%, 7 wt- %, 8 wt-%, 9 wt-%, or 10 wt-%.
- the hydrogen peroxide has a concentration at about 1 wt-%, 1.1 wt-%, 1.2 wt-%, 1.3 wt-%, 1.4 wt-%, 1.5 wt-%, 1.6 wt-%, 1.7 wt-%, 1.8 wt-%, 1.9 wt-%, 2 wt-%, 2.1 wt-%, 2.2 wt-%, 2.3 wt-%, 2.4 wt-%, 2.5 wt-%, 2.6 wt-%, 2.7 wt-%, 2.8 wt-%, 2.9 wt-%, 3 wt-%, 3.1 wt-%, 3.2 wt-%, 3.3 wt- %, 3.4 wt-%, 3.5 wt-%, 3.6 wt-%, 3.7 wt-%, 3.8 wt-%, 3.9 wt-%, or 4
- Additional oxidizing agents include for example, the following types of compounds or sources of these compounds, or alkali metal salts including these types of compounds, or forming an adduct therewith: hydrogen peroxide, urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1 (IA) oxidizing agents, for example lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, for example magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizing agents, for example zinc peroxide; group 13 (IIIA) oxidizing agents, for example boron compounds, such as perborates, for example sodium perborate hexahydrate of the formula Na2[B2(02)2(0H)4] 6H2O (also called sodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of the formula Na2B2(02)2[(0H)4] 4H20 (also called sodium per
- peroxyacids or peroxyacid compositions
- the feedstocks include any hydrocarbon feedstock including for example crude oil, slop oil, heavy residua, atmospheric or vacuum residua, deasphalted oils derived from the crude oil or residua, shale oil, liquified coal and tar sand effluent, and the like and blends thereof.
- removing the metals and/or particulates from the petroleum oil and feedstocks (namely the hydrocarbon phase) is meant to include any and all partitioning, sequestering, separating, transferring, eliminating, dividing, removing, of one or more metal and/or particulate from the hydrocarbon phase to any extent.
- particulates can include inorganic fines that are naturally occurring in crude oil such as silt, clays, silicates and metal oxides. These inorganic materials may not reactive with the peroxyacids but can be removed indirectly during an emulsion resolution process treated with the additive (vide infra). Particulates can also include alkali metal salts, including but not limited to, calcium carbonate (CaCCb), calcium sulfate (CaSCri), iron oxides (Fe203 and FesCri), and barium sulfate (BaSCri).
- CaCCb calcium carbonate
- CaSCri calcium sulfate
- Fe203 and FesCri iron oxides
- BaSCri barium sulfate
- other heavy metals can include, but are not limited to, metal sulfides, metal chlorides, organo-porphyrins or other organometallic complexes that may react with the peroxyacid.
- Metals suitable for removal using the process of this invention include, but are not limited to those of Groups 1, 2, 4, 5, 8, and 10 of the Periodic Table.
- Exemplary metals include iron, zinc, nickel, vanadium, aluminum, magnesium, titanium, sodium, potassium, calcium, and silicon.
- the particulates can also include chloride salts, sulfur, oxides and sulfides.
- Particulates can also include inorganic molecules such as iron sulfide (FeS), zinc sulfide (ZnS) and aluminum chloride (AlCb) that are naturally occurring or arise from other chemical additives or corrosion processes.
- refinery applications include, but are not limited to raw crude processing, desalting, tankage treatment and dehydration, slop oil resolution and mitigation, FCC desalter performance enhancement, and waste water contaminate removal and processing.
- the methods of employing peroxyacids to remove fine particulates and metals from petroleum oils and refinery feedstocks includes applying or adding a peroxyacid to a wash water source, a petroleum oil and/or hydrocarbon feedstock. As referred to herein, this includes, but is not limited to, crude oil, slop oil, and water in oil or oil in water emulsions.
- the oil or feedstock to be treated should preferably be in a liquid state at the selected process conditions in order to facilitate contact between the oil and the aqueous extractant (i.e. the peroxyacid and/or water). As one skilled in the art appreciates this may be accomplished by heating the oil or by the addition of a suitable solvent, e.g. a lower boiling hydrocarbon oil, as needed.
- a suitable solvent e.g. a lower boiling hydrocarbon oil, as needed.
- the petroleum oil or feedstock to be treated is delivered to a pipeline with a heat exchanger.
- a water supply line connects to the flow of heated oil and is delivered with the oil.
- the methods may comprise, consist of and/or consist essentially of one or more of the following steps: add water and peroxyacid to a petroleum oil or hydrocarbon feedstock; add a peroxyacid to an emulsion of oil (hydrocarbon phase) and water (aqueous / water phase); water-wet particulates; oxidize metals; chelate a metal; separate the water phase containing residual peroxyacid, water soluble metal complexes, and particulates from the hydrocarbon phase.
- the peroxyacid can be added to an emulsion formed of a hydrocarbon phase and a water phase without further addition of water.
- the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a desalting step.
- a refinery’s desalting unit is designed to remove entrained water, water-soluble contaminants and oil-insoluble particulates from crude oil.
- Crude oil is defined here as any hydrocarbon stream entering a refinery that will be processed through the desalter. This crucial step of the refining process is necessary to extend the lifetime of process equipment downstream of the unit, render the crude oil less corrosive, protect downstream refinery equipment from fouling, and to maximize throughput.
- the desalter achieves this by (1) providing crude oil; (II) adding wash water to the crude oil and mixing the two phases together to form an emulsion; (III) subsequently breaking the emulsion that is formed to provide an aqueous phase and a hydrocarbon phase containing a lower concentration of salt, particulate and metals.
- the resolved hydrocarbon phase is commonly drawn off the top of the unit and sent to a fractionator tower.
- the water phase containing water-soluble metal salt compounds and sediment is discharged out the bottom of the unit and sent to a waste water treatment plant for processing.
- a general schematic of this process is given in FIG. 1.
- Desalting is traditionally enhanced by application of a high voltage electric field, heat, and by the addition of chemical additives such as emulsion breakers, solids-removal agents, and coagulants.
- Water soluble salts in crude oil are typically chloride, sulfate or carbonate salts of sodium, magnesium, or calcium. If the salts are not effectively removed to the water phase, scale may result. This will reduce throughput and potentially increase operating costs.
- the salts will hydrolyze to form their acid analog, which will accelerate corrosion rates in the process vessels downstream of the unit and compromise their structural integrity.
- Sediment is largely composed of naturally occurring materials, such as silicas, clays, asphaltenes, and metal oxides, resulting from the geologic formation from which the crude oil was extracted or from corrosion. This material may gravity settle in the desalter if the particle size of the sediment and conditions within the unit (emulsion viscosity, crude oil retention times etc.) are favorable. Effective removal of this water-insoluble material will increase throughput by diminishing fouling rates and will increase profitability for the refiner by decreasing the frequency at which heat exchangers must be cleaned.
- naturally occurring materials such as silicas, clays, asphaltenes, and metal oxides
- Fine particulate also known as suspended solids, are hydrocarbon and water insoluble inorganics that are too small to gravity settle in the desalter. These inorganics are largely introduced into crude oil from the geological formation (sand, silt, alkali metal salts, etc), from corrosion processes (FeS) or from upstream additives (metal based FES scavengers, aluminum-based coagulants, etc).
- FES corrosion processes
- upstream additives metal based FES scavengers, aluminum-based coagulants, etc.
- FCC fluid catalytic cracking
- fine particulate can act as an emulsifier and exacerbate emulsion stability at the desalter, which may lead to a decrease in desalting efficiency and/or an increase in the volume of slop oil generated.
- the crude oil aforementioned and desalter emulsions may have high concentrations of metals, including iron sulfide, and the methods disclosed herein beneficially removes those metals and particulates more efficiently than in a typical desalting operation.
- the peroxyacid formulation may enhance overall desalter performance by promoting increased removal of salt, sediment and fine particulate from the hydrocarbon phase.
- the peroxyacid is provided or introduced ( e.g . injected) into a pipe and/or tank upstream of the desalter to contact the hydrocarbon.
- the peroxyacid is preferably injected upstream of a location where the treated feed will have adequate settling time to allow the water and hydrocarbon phases to resolve and the particulates to migrate to the water phase.
- the methods of adding a peroxyacid to the petroleum oil or feedback may be before, simultaneous, or after the addition of wash water to the crude oil.
- the method of adding a peroxyacid may also be directly into a water phase.
- the methods may also include the step of adding an effective amount of at least one additional agent or component that is water or a solvent, a corrosion inhibitor, a demulsifier (such as an oxyalkylate), a scale inhibitor, metal chelants, wetting agents and mixtures thereof.
- the methods may also include the step of adding an effective amount of an emulsion breaker (i.e. demulsifier) to aid in the separation of the oil from the water phase containing the particulates.
- the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a tankage dehydration step. This may relate to dehydration of a hydrocarbon or petroleum oil stream entering a refinery tank farm or static settling of an emulsion downstream of the desalter.
- the contact time for the peroxyacid will vary depending upon the process and wash water, petroleum oil and/or hydrocarbon feedstock to be treated.
- the peroxyacid is simply added and mixed with the oil, and then is removed along with the water phase and particulates.
- the amount of peroxyacid added to the petroleum oil or feedstock will depend upon the oil or feedstock to be treated.
- the amount of metals (e.g. iron) or particulates in the oil or feedstock can vary significantly.
- slop oil may have a higher concentration of metals and particulates than crude oil.
- the concentration of peroxyacid provided is between about 1 ppm and about 50,000 ppm, between about 1,000 ppm and about 30,000 ppm, between about 1,000 ppm and about 20,000 ppm, or ranges there between. In an aspect, the concentration of peroxyacid is at least about 1 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- one or more demulsifiers are added to the crude oil or wash water.
- the peroxyacid may also act as a demulsifier.
- the methods beneficially reduce the metals and particulate content in the petroleum oil or refinery stream by at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, or complete removal.
- the percentage of reduction of metals and particulates will be determined by the concentration of the materials in the oil and/or hydrocarbon feedstock to be treated, along with the concentration of peroxyacid employed.
- the reduction of the metals and particulate content is achieved without any residual peroxyacid in the petroleum oil or feedstock.
- the methods beneficially remove the metals and particulates from the hydrocarbon phase of the emulsion with little or no additional hydrocarbon entrainment into the aqueous phase.
- the methods of using peroxyacids and peroxyacid compositions to remove fine particulates from petroleum oils and refinery feedstocks and/or streams are also useful in various additional applications.
- the methods of mitigation of other metals using the peroxyacids are also useful for minimizing fouling, resolving emulsions and improving waste water quality associated with petroleum oil and refinery feedstocks.
- the peroxyacids can be added to the oil and feedstocks to remove metals and particulates and are effective to improve the waste water from the system due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, CC and H2O).
- the biocidal efficacy of the peroxyacids can also improve the waste water.
- the methods are also useful for enhancing coke quality via contaminate removal.
- Highly crystalline needle coke that can be used for anodes in the aluminum and steel industry is more valuable than fuel grade coke.
- the crystal structure does not form in the presence of metal contaminants. Removing metals with peroxyacids promotes a higher grade of coke.
- the methods are also useful for mitigating fine particulates resulting from use of metal based H2S scavengers in aqueous and hydrocarbon streams.
- the methods are also useful for mitigating fine particulates resulting from Aluminum and Zinc based chemical additives.
- the peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially remove various types of particulates from these streams, including solids imparted by the various chemical additives used in the processing of the oil.
- the methods are useful for mitigation of downstream catalyst poisoning and fouling, resulting in elongation of catalyst lifetimes.
- the peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially removes these poisons from the oil and feedstock, taking them out of the downstream product which minimizes downstream catalyst poisoning and fouling.
- various metals and contaminants can poison or deactivate catalysts, it is beneficial to remove the various metals and particulates with the peroxyacids.
- the methods are useful for reducing bacteria in slop oil and crude tanks.
- the combination of removing bacteria, contaminants, and particulates from slop oil and crude tanks is beneficial, as these sources are known to have greater amounts of iron and would therefore benefit from treatment with the peroxyacid.
- the portable electric desalter (PED) screening uses an Interav Model EPPT-228 apparatus. The following test method was used:
- Steps 7 - 10 for each of the remaining samples, placing Sample #2 in the second position, etc. Use a clean blender container for each sample.
- the emulsions are poured into glass tubes (100 ml centrifuge tubes), which are then placed into the heating block of a PED heater unit, the emulsions are resolved with the assistance of constant heating and intermittent application of an electric field.
- the water coalescence was performed as follows:
- Electric field applications are generally ten-minutes in duration and the applied voltage is adjustable between 0 - 4000 V.
- the first electric field application is normally 3000 V, but the value may vary depending on observations from previous tests.
- the steps permit the resolution of the emulsion to be observed as the volume of free water resolved at fixed intervals during the testing.
- the resulting water phase was collected and submitted for analysis by Inductively Coupled Plasma (ICP).
- ICP Inductively Coupled Plasma
- Bottle testing was performed to identify chemistries most effective at migrating metal content to the water phase following emulsion resolution.
- a known amount of a representative sample of the crude oil and 10-20 mL of distilled water were placed in a series of standard bottles. One of these samples remained untreated and was used as a reference blank while the others were treated with the evaluated chemistries.
- the bottles were agitated simultaneously and replaced in the water bath. At specific times the amount of separated water was observed and recorded. The times of dehydration is according to the retention time in the separations vessels of the plant. Finally, this separated water was removed and submitted for analysis by ICP.
- EC2472A emulsion breaker
- EC6779A peracetic acid
- R-3461 sodium gluconate in water
- the additives were added to either the water or hydrocarbon phase at a concentration of 0, 1000, or 5000 ppm based on the total volume as specified in Table 2.
- the peracetic acid sample used was off-spec and reported at 16% actives.
- the solutions were then heated to 90°C for 30 minutes and then emulsified using 50% shear power.
- Percent iron removal to the water phase following addition of 0-1000 ppm of a metals removal agent, is shown in FIG. 2.
- the brown (hydrocarbon addition) versus blue (water addition) designations are used to define which phase the metal removal agent was charged into prior to emulsification.
- the blank sample which contained no metals removal agent, had considerably less iron in the water at the conclusion of the test than the emulsions treated with EC6779A.
- R-3461 sodium gluconate
- Example #1 A second test was conducted to verify reproducibility of the observed trends in Example #1.
- a sample of light crude oil was used and total metals analysis by ICP is given in Table 3.
- the concentration of iron in the sample was abnormally high. This was likely a result of corrosion of the metal container the sample was stored in.
- Example 1 The only modifications to the Example 1 method were as follows.
- the additives were added to either the water or hydrocarbon phase at a concentration of 500 ppm based on the total volume as specified in Table 4.
- the solutions were then heated to 90 °C for 30 minutes and then emulsified using 80% shear power.
- the concentration of Fe, Al, Ni, and Zn found in the water is tabulated in Table 4.
- Example 2 EC6779A, EC6818A, EC2111A and EC2483A. Test methodology of Example 1 was followed using 25 ppm of EC2472A and a sample of light crude oil from the United States. EC6818A, EC6779A, EC2111 A and EC2483A were tested at 1000 ppm each and compared to a blank. The emulsions were formed with 10% deionized water at 80% Variac power. Total metals analysis by ICP is given in shown in Table 5 and the results shown in Table 6.
- Example 3 testing was repeated under the same conditions to analyze increased dosages of the chemistries and the effect of R-3461 on EC6818A and EC6779A performance.
- the experimental design and concentration of metals found in the resolved water is shown in Table 7.
- the percent metals removal is substantially higher than expected based on the ICP analysis of the crude oil.
- the blanks show considerably different values for Zn and Ni suggesting the homogeneity of the crude oil sample may be of concern.
- R- 3461A did not boost the peroxyacid formulations’ performances demonstrating that the use of sodium gluconate is not required in combination with the peroxyacid compositions.
- the two peroxyacid formulations outperformed the carboxylic acids EC2111 A (acetic acid) and EC2483A (malic acid) as shown in FIG. 8.
- Bottle Testing methodology was used to assess efficacy of various metal removal agents. Characterization of the emulsion band formed while processing this slate found 9300 ppm Fe, suggesting the Fe may play a role in emulsion stabilization.
- the crude oil (treated at the refinery with emulsion breaker) was homogenized and then 90 mL aliquots were transferred into five medicine bottles containing 10 mL of distilled water each. Three of the bottles were charged with one of the following metal removal agents at 1000 ppm: EC2111 A, EC6779A or CORR11540 A. The samples were emulsified using 100% shear and transferred to a heating block set to 120 °C. The emulsions were then shocked with 4000 V for 20 minutes to facilitate complete emulsion resolution.
- the ability of peroxyacetic acid to remove metals from slop oil was further analyzed.
- the emulsion does not resolve after prolonged periods of quiescent settling in the absence of chemical treatment.
- the sample received was homogenized and sampled into 100 mL aliquots. One aliquot each was treated with 1000 or 5000 ppm of EC2111A (acetic acid) or EC6779A (peracetic acid).
- the treated emulsions were stored for 24 hours.
- the two samples treated with EC6779A contained 1% resolved water.
- the samples were then centrifuged at 140 °C for 30 minutes. Pictures of the resulting resolved emulsion are provided in FIG. 10.
- the EC6779A samples contained yellow water and significantly more oil free solids were observed at the bottom of the tubes. ICP analysis on the top oil fraction and the resolved water phase are given in Table 10.
- a gallon of a light crude oil from the Gulf Coast was collected for ICP analysis. An aliquot of this crude oil found 25 ppm Fe, 4 ppm Ni, and 1 ppm Zn. The crude oil was homogenized and then 90 mL aliquots were transferred into eight medicine bottles containing 10 mL of distilled water each. The bottles were all charged with 25 ppm EC2472A and the metal removal agents as outlined in Table 11.
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Abstract
Description
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US201862774625P | 2018-12-03 | 2018-12-03 | |
PCT/US2019/064105 WO2020117724A1 (en) | 2018-12-03 | 2019-12-03 | Use of peroxyacids/hydrogen peroxide for removal of metal components from petroleum and hydrocarbon streams for downstream applications |
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US (1) | US20200172817A1 (en) |
EP (1) | EP3867336A1 (en) |
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CN115943195A (en) * | 2020-06-17 | 2023-04-07 | 埃克森美孚化学专利公司 | Hydrocarbon pyrolysis with advantageous feeds |
EP4237515A1 (en) | 2020-10-29 | 2023-09-06 | Marathon Petroleum Company L.P. | Systems and methods for separating water and removing solids from pre-treated and unfiltered feedstock |
US11613715B1 (en) | 2021-10-12 | 2023-03-28 | Marathon Petroleum Company Lp | Systems and methods of converting renewable feedstocks into intermediate hydrocarbon blend stocks and transportation fuels |
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- 2019-12-03 SG SG11202105464XA patent/SG11202105464XA/en unknown
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US20200172817A1 (en) | 2020-06-04 |
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