CA2807839A1

CA2807839A1 - Process, method, and system for removing heavy metals from fluids

Info

Publication number: CA2807839A1
Application number: CA2807839A
Authority: CA
Inventors: Darrell Lynn Gallup; Sujin Yean
Original assignee: Chevron USA Inc
Current assignee: Chevron USA Inc
Priority date: 2010-09-16
Filing date: 2011-09-09
Publication date: 2012-03-22
Also published as: AU2011302353A1; CN103097495A; SG188484A1; AU2011302353B2; EP2616526A4; WO2012036986A2; EP2616526A2; WO2012036986A3

Abstract

Trace element levels of heavy metals such as mercury in crude oil are reduced by contacting the crude oil with an iodine source, generating a water soluble heavy metal complex for subsequent removal from the crude oil. In one embodiment, the iodine source is generated in-situ in an oxidation-reduction reaction, by adding the crude oil to an iodine species having a charge and a reductant or an oxidant depending on the charge of the iodine species. In one embodiment with an iodine species having a positive charge and a reducing reagent, a complexing agent is also added to the crude oil to extract the heavy metal complex into the water phase to form water soluble heavy metal complexes which can be separated from the crude oil, for a treated crude oil having reduced levels of heavy metals.

Description

Process, Method, and System for Removing Heavy Metals from Fluids CROSS-REFERENCE TO RELATED APPLICATIONS
[001] This application claims benefit under 35 USC 119 of US Patent Application Serial Nos. 12/883,578; 12/883,971; and 12/883,995, all with a filing date of September 16, 2010. This application claims priority to and benefits from the foregoing, the disclosures of which are incorporated herein by reference.

TECHNICAL FIELD

[002] The invention relates generally to a process, method, and system for removing heavy metals such as mercury and the like from hydrocarbon fluids such as crude oil.

BACKGROUND

[003] Heavy metals such as lead, zinc, mercury, arsenic, silver and the like can be present in trace amounts in all types of fuels such as crude oils. It is desirable to remove the trace elements of these metals from crude oils.

[004] Various methods for removing trace metal contaminants in liquid hydrocarbon feed prior to fractional distillation have been developed. One of the metal contaminants in crude oil is mercury, which can be present as elemental dissolved Hg(0) and particulate Hg (liquid droplets or liquid Hg adhering to sand particles). To remove existing Hg particulates or fine HgS and/or Hg0 crystals precipitated upon treatment of the liquid hydrocarbon, hydrocyclones and / or filters are typically used. Filtering crude oil to remove HgS and / or Hg0 and other Hg-containing solids is expensive and cumbersome.

[005] In the prior art, iodide impregnated granular activated carbons have been used to remove mercury from water. US Patent No. 5,336,835 discloses the removal of mercury from liquid hydrocarbon using an adsorbent comprising an activated carbon impregnated with a reactant metal halide, with the halide being selected from the group consisting of I, Br and Cl. US Patent No. 5,202,301 discloses removing mercury from liquid hydrocarbon with an activated carbon adsorbent impregnated with a composition containing metal halide or other reducing halide. US Patent Publication No. 2010/0051553 discloses the removal of mercury from liquid streams such as non-aqueous liquid hydrocarbonaceous streams upon contact with a Hg-complexing agent for mercury to form insoluble complexes for subsequent removal.

6 PCT/US2011/051033 [006] There is still a need for improved methods for trace elements, e.g., mercury, extraction from hydrocarbons such as crude oil, wherein the heavy metals form water soluble metal complexes for subsequent removal from the crude oil by phase separation.

SUMMARY OF THE INVENTION

[007] In one aspect, a method to reduce mercury in a crude oil is provided.
The method comprises converting at least a portion of mercury in the crude oil to mercuric iodide in an oil-water emulsion upon contact with a molecular iodine source; and separating the water containing the soluble mercuric iodide from the crude oil for a treated crude oil having a reduced concentration of mercury.

[008] In another aspect, the invention relates to a method to reduce or remove trace elements of heavy metals such as mercury from a crude oil. The method comprises converting at least a portion of mercury in the crude oil to mercuric iodide in an oil-water emulsion upon contact with an iodine source, wherein molecular iodine is generated in-situ in an oxidation-reduction reaction between an iodine species having a negative charge and an oxidizing reagent; and separating the water containing the soluble mercuric iodide from the crude oil for a treated crude oil having a reduced concentration of mercury.

[009] In yet another aspect, the molecular iodine is generated in-situ in an oxidation-reduction reaction between an iodine species having a positive charge and a reducing reagent.
In this method, a complexing agent is further added to the crude oil to form a water-soluble heavy metal compound, for the water containing the soluble heavy metal compound to be subsequently separated from the crude oil, resulting in a treated crude oil having a reduced concentration of heavy metal.

DETAILED DESCRIPTION

[010] The following terms will be used throughout the specification and will have the following meanings unless otherwise indicated.

[011] "Crude oil" refers to natural and synthetic liquid hydrocarbon products including but not limited to petroleum products; intermediate petroleum streams such as residue, naphtha, cracked stock; refined petroleum products including gasoline, other fuels, and solvents. The liquid hydrocarbon products can be directly from oil wells or after the products have been further processed or derived. The term "petroleum products"
refer to crude oil, solid, and semi-solid hydrocarbon products including but not limited to tar sand, bitumen, etc. The term "petroleum products" also refer to petroleum products derived from coal.

[012] "Heavy metals" refer to gold, silver, mercury, platinum, palladium, iridium, rhodium, osmium, ruthenium, arsenic, and uranium.

[013] "Trace element" refers to the amount of heavy metals to be removed from the crude oil, or for the concentration to be significantly reduced. The amount of trace element varies depending on the crude oil source and the type of heavy metal, for example, ranging from a few ppb to up to 30,000 ppb for mercury.

[014] Mercury sulfide may be used interchangeably with HgS, referring to mercurous sulfide, mercuric sulfide, or mixtures thereof Normally, mercury sulfide is present as mercuric sulfide with a stoichiometric equivalent of one mole of sulfide ion per mole of mercury ion.

[015] "Mercury salt" or "mercury complex" meaning a chemical compound formed by replacing all or part of hydrogen ions of an acid with one or more mercury ions.

[016] "Oil-water" as used herein means any mixture containing a crude oil with water, inclusive of both oil-in-water emulsions and water-in-oil emulsions. In one embodiment, the emulsion particles are of droplet sizes. In another embodiment, the emulsion particles are of micron or nano particle sizes. In one embodiment, oil is present as fine droplets contained in water in the form of an emulsion, i.e., emulsified hydrocarbons, or in the form of undissolved, yet non-emulsified hydrocarbons.

[017] "Interphase" or "interphase layer" or "interface layer" or "emulsion layer"
may be used interchangeably, referring to the layer in between the oil and water phases, having characteristics and properties different from the oil and water phases.
In one embodiment, the interface layer is a cloudy layer in between the water and oil phases. In another embodiment, the interface layer comprises a plurality of aggregates of coalescence (or droplets), with the aggregates being randomly dispersed in either the water phase or the oil phase.

[018] "Complexing agent" or "chelating agent" refers to a compound that is capable of reacting with another chemical group, e.g., mercury compounds, to form a covalent bond, i.e. is covalently reactive under suitable reaction conditions.

[019] Crudes and crude blends are used interchangeably and each is intended to include both a single crude and blends of crudes. Crudes may contain small amounts of heavy metals such as mercury, which may be present as elemental mercury Hg , ionic Hg, inorganic mercury compounds, and / or organic mercury compounds. Examples include but are not limited to: mercuric halides (e.g., HgXY, X and Y could be halides, oxygen, or halogen-oxides), mercurous halides (e.g., Hg2XY, X and Y could be halides, oxygen, or halogen-oxides), mercuric oxides (e.g., Hg0), mercuric sulfide (e.g., HgS, meta-cinnabar and/or cinnabar), mercuric sulfate (HgSO4), mercurous sulfate (Hg2SO4), mercury selenide (e.g., HgSe2, HgSeg, HgSe), mercury hydroxides, and organo-mercury compounds (e.g., alkyl mercury compounds) and mixtures of thereof. Mercury can be present in various forms, e.g., in dissolved form, as particles, and / or adsorbed onto the surfaces such as clay minerals, inorganic mineral scale, sand, and asphaltenes.

[020] The invention effectively decreases the levels of heavy metals such as mercury, lead, zinc, etc. from crude oil. In one embodiment, the mercury in crude oil is converted into a water soluble form that would partition into the aqueous phase for subsequent separation and convenient disposal by methods including but not limited to re-injection, or disposed back into the reservoir. In one embodiment, the mercury is converted into soluble by-products upon reaction with molecular iodine (12), metallic mercury (Hg ) being converted into mercury ions (Hg2'), subsequently forming aqueous soluble Hg2' complexes.

[021] Trace Element Removal with Iodine: In one embodiment, the crude oil is first brought into contact with iodine, or a compound containing iodine such as alkali metal salts of iodine, e.g., halides or iodide of a cation. In one embodiment, the iodide is selected from ammonium iodide, alkali metal iodide, an alkaline earth metal iodide, and etheylenediamine dihydroiodide.

[022] In one embodiment, the amount of the iodine is chosen to result in an atomic ratio of iodine to mercury of at least 1:1. In a second embodiment, a ratio ranging from 1.5:1 to 6:1. In a third embodiment, a ratio of 2:1 to 4:1. In one embodiment, the crude oil is brought into contact with solid iodine. In another embodiment, an iodine solution in petroleum distillate is injected into the liquid hydrocarbon, e.g., gas condensate or crude oil.
Upon contact with the crude oil, molecular iodine (12) reacts with elemental Hg droplets, elemental Hg adsorbed on formation minerals, elemental Hg dissolved in the crude oil, as well as mercury compounds including but not limited to HgS, HgSe, and Hg0. In the reactions, Hg is oxidized to Hg2', and 12 is reduced to 2I-. In one embodiment, a slight excess of iodine is employed to prevent the formation of water insoluble Hg2I2. Mercuric iodide is highly soluble in water and not very soluble in hydrocarbons.

[023] Hg (solution) + 12 (solution) = HgI2 (solution) Hg2 (aq) + 2I-(aq)

[024] HgI2 (solution) + Hg (liquid) = Hg2I2 (solid)

[025] Hg2I2 (solid) + 12 (solution) = 2HgI2 (solution) 2Hg2 ' (aq) + 4I-(aq).

[026] With respect to solids such as HgS, the solids are dissolved by 12, wherein 12 oxidizes the solids to form Hg2 ' and elemental S or S042-. The reactions proceed very fast at room temperature (e.g., 25 C), and even faster at elevated temperatures.

[027] Trace Element Removal with In-situ Iodine Formation: Elemental iodine is a rather expensive reagent. Elemental iodine is in the form of crystals, which sublime readily to generate a violet colored vapor. Other chemicals are often used to combine in some form with elemental iodine to provide stable preparations. In one embodiment, instead of using molecular iodine 12, a reagent is used which reacts with at least an iodide salt to covert iodine anion (E) to molecular iodine (12) in an oxidation-reduction reaction, allowing for the economical in-situ generation of 12.

[028] In the oxidation-reduction reaction, the crude oil is brought into contact with an oxidizing agent and a negatively charged iodine, or the crude oil can be brought into contact with a reducing agent plus a positively charged iodine.

[029] In one embodiment, molecular iodine is formed by reducing an iodine species with a positive oxidation state (a positively charged iodine) or oxidizing a negatively charged iodine (iodide O. Reagents with lower oxidation potentials can be used to reduce the iodine species to molecular iodine. Reagents with a higher oxidation potential than iodide can oxidize iodide into molecular iodine.

[030] Iodine species exist in different oxidation states. The positive oxidation states are usually found in inorganic species such as acids, salts, oxides, or halides. The negative oxidation states appear in iodine species that are in the form of iodide salts or organic iodo-compounds. Examples of iodide salts include but are not limited to iodides selected from the group of ammonium, alkali metal, and alkaline earth metal.

[031] Examples of iodine species with a positive oxidation state that can be used to generate molecular iodine in-situ include but are not limited to: periodic acid (H5I06), potassium periodate (1(104), sodium periodate (NaI04) all with oxidation state of +7; iodic acid (HI03), potassium iodate (1(103), potassium hydrogen iodate (KHI206), sodium iodate (NaI03), iodine oxide (1205), all with oxidation state of +5; iodine trichloride (IC13) with oxidation state of +3; iodine monobromide (IBr), iodine monochloride (IC1) all with oxidation state of +1.

[032] Iodine compounds with negative oxidation state (-1) include but are not limited to hydriodic acid (HI), sodium iodide (NaI), potassium iodide (1(1), ammonium iodide (NH4I), aluminum iodide (A1I3), boron triodide (BI3), calcium iodide (CaI2), magnesium5 iodide (MgI2), iodoform (CHI3), tetraiodoethylene (C214), iodoethanol, iodoacetic anhydride, iododecane, and iodobenzene.

[033] In one embodiment, a reagent that is an iodine reductant is used to react with an iodine species having a positive oxidation state to generate molecular iodine in-situ.
Examples of reagents that function as iodine reductants include but are not limited to thioureas, thiols, ascorbates, imidazoles, and thiosulfates such as sodium thiosulfate.

[034] In one embodiment, a reagent that is an iodine oxidant is employed to react with a source of iodine anion to generate molecular iodine in-situ. The excess negatively charged iodides function as complexing agents, moving mercury compounds from the oil phase and / or the interphase to the water phase for subsequent removal.
Examples of oxidizing reagents that can be used to generate iodine in-situ include but are not limited to sources of peroxide (including hydrogen peroxide, urea peroxide, peroxy acids, alkylperoxides, etc.), bromine (Br2), ozone (03), cumene hydroperoxide, t-butyl hydroperoxide, Na0C1, iodate (such as potassium iodate I(103 and sodium iodate NaI03), monopersulfate, percarbonate, perchlorate, permanganate, perphosphate, and peroxidases that are capable of oxidizing iodide. The reaction can be at atmospheric pressure and ambient temperature.

[035] H202 + 2H + 21- 12 (solution) + 2H20;

[036] 03(g) + 2H' + 21- 02(g) +12 (solution) + H20;

[037] Oa + H20 + 2I- 12 (solution) + Cl- + 20H-.

[038] In one embodiment, once in-situ molecular iodine is produced, the molecular iodine will convert Hg into mercury ions Hg2 ', with excess I- from the iodide salt forming water soluble Hg-I complexes. The ratio of molecular iodine generated in-situ with starting iodine materials ranges between 0.5 ¨ 1 in one embodiment. In a second embodiment, the ratio ranges from 0.65 to 1. In a third embodiment, from 0.8 to 1. In a fifth embodiment, from 0.95 to 1. In one embodiment, the higher the ratio of molecular iodine to total iodine, the higher the removal of trace elements from the crude oil.

[039] In one embodiment, the rate of iodine generation is quite rapid with at least 50% of the equilibrium concentration of the molecular iodine being generated within the first 10 minutes of contact between the starting reagents.

[040] With respect to the amount of required iodine (whether generated in-situ or elemental iodine), in one embodiment, the molar ratio of iodine to heavy metals such as mercury ranges from at least 1:1 to 30,000:1 in one embodiment; from 2:1 to 1,000:1 in a second embodiment; from 5:1 to 100:1 in a third embodiment; greater than 3:1 in a fourth embodiment, and less than 10,000:1 in a fifth embodiment. In a sixth embodiment, the amount is sufficient to form water soluble Hg2 complexes in the system.

[041] Addition of a Complexing Agent to Reduction Agent: In one embodiment wherein iodine is generated in-situ with positively charged iodine containing species such as K10, IC13, etc., a complexing agent is also added to the crude oil to extract the mercury cations from the oil phase and / or the interphase to the water phase. In one embodiment, the complexing agent essentially forms a soluble mercury compound, e.g., mercury complexes, when contacting the mercury cations.

[042] In one embodiment, a complexing agent having a large equilibrium binding constant for non-complexed mercury ions is selected. Examples include thiol groups, dithiocarbamic acid, thiocarbamic acid, thiocarbazone, cryptate, thiophene groups, thioether groups, thiazole groups, thalocyanine groups, thiourenium groups, amino groups, polyethylene imine groups, hydrazido groups, N-thiocarbamoyl-polyalkylene polyamino groups, derivatives thereof, and mixtures thereof. Other examples of complexing agents include but are not limited to hydrazines, sodium metabisulfite (Na2S205), sodium thiosulfate (Na2S203), thiourea, the group of sulfides, ammonium thiosulfate, alkali metal thiosulfates, alkaline earth metal thiosulfates, iron thiosulfates, alkali metal dithionites, alkaline earth metal dithionites, and mixtures thereof Examples of sulfides include but are not limited to potassium sulfide, alkaline earth metal sulfides, sulfides of transition elements number 25-30, aluminum sulfides, cadmium sulfides, antimony sulfides, Group IV sulfides, and mixtures thereof

[043] In one embodiment, the inorganic sulfur complexing agents are oxygen-containing compounds such as thiosulfates and dithionites. Examples include alkali metal thiosulfates, alkaline earth metal thiosulfates, iron thiosulfates, alkali metal dithionites, and alkaline earth metal dithionites and mixtures thereof. Suitable alkali metal thiosulfates include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, and lithium thiosulfate. Examples of alkaline earth metal thiosulfates include calcium thiosulfate and magnesium thiosulfate. Ferric thiosulfate exemplifies an iron thiosulfate which may be employed. Alkali metal dithionites include sodium dithionite and potassium dithionite.
Calcium dithionite is suitable as an alkaline earth metal dithionite complexing agent.

[044] In one embodiment, the complexing agent is a polyamine for forming stable cationic complexes with the ions of heavy metals. Exemplary polyamines include ethylenediamine (EDA), propylenediamine, triaminotriethylamine, diethylenetriamine, triethylenetetramine (TRIEN), tetraethylenepentamine and tetra-2-aminoethylethlenediamine.7 In one embodiment, the polyamine may include carboxyl groups, hydroxyl groups and / other substituents, as long as they do not weaken the complex formed with polyamine.
In one embodiment, the complexing agent is tetraethylenepentamine (TETREN), which forms a stable complex with mercury at a pH around 4.

[045] In one embodiment, the complexing agent is selected from the group of DEDCA (diethyl dithiocarbamic acid) in a concentration of 0.1 to 0.5M, DMPS
(sodium 2,3-dimercaptopropane-1-sulfonate), DMSA (meso-2,3-dimercaptosucccinic acid), EDTA

(ethylene-diamine-tetra-acetic acid), DMSA (Dimercaptosuccinic acid), BAL (2,3-dimercapto-propanol), CDTA (1,2-cyclohexylene-dinitrilo-tetraacetic acid), DTPA
(diethylene triamine pentaacetic acid), NAC (N-acetyl L-cystiene), sodium 4,5-dihydroxybenzene-1,3-disulfonate, polyaspartates; hydroxyaminocarboxylic acid (HACA);
hydroxyethyliminodiacetic (HEIDA); iminodisuccinic acid (IDS);
nitrilotriacetic acid (NTA), sodium gluconate, and other carboxylic acids and their salt forms, phosphonates, acrylates, and acrylamides, and mixtures thereof

[046] The complexing agents are employed in a sufficient amount to effectively stabilize (forming complexes with) the soluble heavy metals in the oil-water mixture. In one embodiment, the molar ratio of complexing agent to soluble mercury in the mixture ranges from 1:1 to about 5,000:1. In a second embodiment from 2:1 to about 3,000:1.
In a third embodiment from 5:1 to about 1,000:1. In a fourth embodiment, from 20:1 to 500:1. In a fifth embodiment, the amount is sufficient to form water soluble Hg2 complexes in the system.

[047] Method for Removing / Decreasing Levels of Heavy Metals in Crude Oil: As iodine is soluble in crude oil, in one embodiment, iodine is introduced into the crude oil as a solid, with the crude oil being routed through a column or bed containing solid iodine provided as tablets, in granular form, or as finely divided iodine. In another embodiment, iodine is added to the crude oil as a solution in solvents such as methanol, naphtha, diesel, gasoline, mercury-free crude oil, solvents, and the like. In a third embodiment, iodine may be introduced into the crude oil as a gas with the iodine-containing gas stream being sparged into a pipeline or vessel containing crude oil at various intervals, using means known in the art. The iodine-containing gas stream may be formed by providing a solid iodine source and contacting the solid iodine with an inert gas stream, e.g., helium, nitrogen, argon, and air.
The solid iodine source may be finely divided iodine. The gas stream is provided at a pre-determined temperature selected to vaporize the solid iodine at a pre-selected rate.

[048] In one embodiment wherein 12 is generated in-situ, an oxidizing agent is first prepared or obtained. The oxidizing agent can be prepared in an aqueous form.
In yet another embodiment, an organic oxidizing agent is used. The oxidant is brought in contact with the crude oil containing heavy metals, e.g., trace elements of mercury and the like, by means known in the art and in a sufficient (or effective amount) for to convert at least a portion of, e.g., at least 50%, of the heavy metals into cations. In one embodiment, a sufficient amount is added for at least 80% conversion. In another embodiment, at least 95%
conversion.

[049] In the next step, a reagent containing iodine species is prepared /
provided for the generation of iodine in-situ, and subsequently, for the reaction of iodine and mercury to form water soluble complexes. In yet another embodiment with the use of a reductant containing iodine species, a complexing agent is further added to extract cationic mercury from the oil phase / interphase into the water phase.

[050] In yet other embodiments wherein 12 is generated in-situ, an iodine column is first prepared by adsorbing the iodine species, e.g., KI3, to a strong anion exchanger, e.g., containing tertiary amine groups. In the next step, iodine is released from the column, i.e., being reduced to iodide, upon contact with a solid adsorbent containing the reagent that would function as the reductant / oxidant. In one embodiment, a thiol-containing adsorbent is used for the reducing step, releasing free iodine (as generated in-situ).

[051] The feeding of the iodine containing compound and / or reductant and /
or oxidant and / or complexing agents can be separate, or together as one composition. In one embodiment for in-situ iodine generation, the oxidant and complexing agent containing iodine species are first combined, then brought into contact with the crude oil. In another embodiment, the iodine containing species is first brought into contact with the crude oil, followed by the addition of the oxidant. In yet another embodiment, the oxidant is first mixed with the crude oil, then followed by the addition of a complexing agent containing iodine species. In a fourth embodiment, crude oil is first brought into contact with an oxidizing agent and a negatively charged iodine reagent, followed by the addition of a complexing agent to extract the cationic mercury into the water phase. In a fifth embodiment, crude oil is first brought into contact with a reducing agent and a positively charged iodine reagent, followed by the addition of a complexing agent to extract the cationic mercury into the water phase.

[052] The amount of reagents, i.e., oxidant, reductant, or iodine containing species should be sufficient to convert the heavy metals in the crude oil into heavy metal cations, and subsequently, into water soluble heavy metal complexes. In one embodiment, the added reagents make up from 0.5 to 50 volume percent of the total mixture (of crude oil and reagents). In a second embodiment, the added reagents make up less than 40 vol. % of the mixture. In a third embodiment, less than 30 vol. %. In a fourth embodiment, less than 10 vol. % percent. In a fifth embodiment, less than 5 vol. %.

[053] In one embodiment, mercury removal can be enhanced at a low pH
concentration with the addition of an acid, e.g., acidic potassium iodide solution with a mixture of KI and HC1, for a pH of 5 or less in one embodiment, and 2 or less in another embodiment. In yet another, the reagent is an acidic thiourea, with an acid concentration of up to 5M and thioureas concentration from 0.3 to 1.5M.

[054] In one embodiment, liquid reagents is introduced by utilizing high mechanical shearing such as those produced by forcing the liquid, under pressure, through fine hole nozzles or by utilizing dual fluid nozzles where the iodine generating reagent is atomized by a compressed fluid (e.g., air, steam or other gas). When the components selected in making the iodine in-situ is available as solids, they can be ground separately or in combination, if suitable, to a fine powder and injected/blown into a gas stream at appropriate temperatures for introduction into the crude oil. Liquid reagent component(s) can also be mixed with powder reagent components for introduction into the crude oil.

[055] The rate of in-situ iodine generation is rapid with at least 75% of the equilibrium concentration of molecular iodine being generated within the first 10 minute of contact between the specific iodine generating chemical agents and the crude oil. In a second embodiment, the at least 75% rate is achieved within the first 5 minutes. In a third embodiment, at least 90% rate is achieved within the first 10 minutes.

[056] The composition(s) can be introduced or fed continuously or intermittently, i.e., batch-wise, into operating gas or fluid pipelines, for example. Some of the reagents can be fed continuously, while other compositions can be fed intermittently.
Alternatively, batch introduction is effective for offline pipelines.

[057] The contact can be at any temperature that is sufficiently high enough for the crude oil to be completely liquid. In one embodiment, the contact is at room temperature. In another embodiment, the contact is at a sufficiently elevated temperature, e.g., at least 50 C.
In one embodiment, the contact time is at least a minute. In another embodiment, the contact time is at least 5 minutes. In a third embodiment, at least 1 hr. In a fourth embodiment, the contact is continuous for at least 2 hrs.

[058] In one embodiment, the iodine is introduced into the crude oil for a final concentration of 25 ¨ 100 ppm. In yet another embodiment, iodine is added to the crude oil as a mixture with a complexing agent reagent such as potassium iodide KI in concentrations of 5 wt. % KI, 10 wt. % KI, 20 wt. % KI, or 40 wt. % KI (mixtures also known as Lugol's Solution). Concentration of 12 added can be controlled by means known in the art, including mass or volume flow controllers, online analyzers, ORP (redox potential) and iodine ion specific detection instruments. Potassium iodide combines with mercuric iodide to form a water soluble compound K2HgI4. Besides potassium iodide, other water soluble halide having the formula RX or RX2 can also be used as complexing agents, with R
being selected from the group consisting of potassium, lithium, sodium, calcium, magnesium, and ammonium and X is iodide, bromide or chloride. In one embodiment, an aqueous solution containing sodium iodide and sodium iodate is employed to essentially convert 100% of the iodide to molecular iodine.

[059] Once water soluble heavy metal complexes are formed (and extracted from the emulsion), the water phase containing the heavy metal complexes can be separated from the crude oil in a phase separation device known in the art, e.g., a cyclone device, electrostatic coalescent device, gravitational oil-water separator, centrifugal separator, etc., resulting in a treated crude oil with a significantly reduced level of heavy metals. The heavy metal complexes can be isolated / extracted out of the effluent and subsequently disposed. In one embodiment, mercury is electrochemically removed from the aqueous extractant to regenerate a mercury-free aqueous extractant composition.

[060] The mercury removal in one embodiment is done in the field, i.e., close to or at the upstream wellhead, for better quality crude to sell to the refinery.
After crude oil is removed from a well, the crude can be treated in a facility at the wellhead or on an off-shore platform, or right in the pipeline used to transport the crude to ports or refineries. The mixing of crude oil with the iodine source, and other materials such as oxidizing agents, in one embodiment is achieved with motion by pump stations along the pipeline. In another embodiment, the mercury removal is a process integrated with the refinery and downstream from the wellhead.

[061] Depending on the source, the crude oil feed has an initial mercury level of at least 50 ppb. In one embodiment, the initial level is at least 5,000 ppb. Some crude oil feed may contain from about 2,000 to about 100,000 ppb mercury. In one embodiment with mercury as the heavy metal for trace element removal or reduction, the mercury level in the crude oil after iodine treatment is reduced to 100 ppb or less. In another embodiment, the level is brought down to 50 ppb or less. In a third embodiment, the level is 20 ppb or less. In a fourth embodiment, the level is 10 ppb or less. In a fifth embodiment, the level is 5 ppb or less. In yet another embodiment, the removal or reduction is at least 50% from the original level of heavy metals such as mercury or arsenic. In a fifth embodiment, at least 75% of a heavy metal such as mercury is removed. In a seventh embodiment, the removal or the reduction is at least 90%.

[062] Mercury level can be measured by conventional techniques known in the art, including but not limited to cold vapor atomic absorption spectroscopy (CV-AAS), cold vapor atomic fluorescence spectroscopy (CV-AFS), gas chromatography combined with inductively coupled plasma mass spectrometry (or GC-ICP-MS with 0.1 ppb detection limit), and combustion amalgamation, etc.

[063] It should be further noted that the embodiments described herein can also be used for the removal of and reduction of other heavy metals from crude oil, including but not limited to lead, zinc, mercury, silver, arsenic and the like. It should be further noted that 12 is corrosive, thus its use requires precaution with appropriate materials.
Equipment for use in containing and / or handling 12 such as storage containers, pumps, injection quills in one embodiment is made of, or coated with materials such as Teflon, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), high nickel alloys, and the like. As 12 is introduced or mixed into the crude oil at a fairly low concentration, e.g., 25-200 ppm for example, normal carbon steel typically used for equipment containing crude oil is sufficient and not affected by the corrosivity inherent with 12. Additionally, as 12 oxidation of heavy metals occurs and 12 is reduced to I. Corrosion due to iodide is also less of an issue, particularly when complexing agents such as thiosulfate and the like are further added to the crude oil mixture.

[064] EXAMPLES: The following examples are given to illustrate the present invention. It should be understood, however, that the invention is not to be limited to the specific conditions or details described in these examples. In examples calling for mercury vapor feed, a sufficient amount of mercury (e.g., one or two drops of elemental mercury in a bottle) was sparged by using nitrogen (N2) gas into another bottle containing white mineral oil overnight.

[065] Example 1: 50 mL of mercury vapor feed preparation containing approximately 1,100 ppb Hg was added to a number of 100 mL glass tubes, then mercury level was measured using LUMEX mercury analyzer equipped with PYRO-915+. 50 mL
of distilled water was placed in the tubes, and the mercury level was measured using LUMEX
mercury analyzer equipped with PYRO-915+. A pre-determined volume of 3 different12 oxidants (hydrogen peroxide (H202), t-butyl hydroperoxide, and cumene hydroperoxide) was added to each reactor for a final oxidant concentration of 50 ppm. The oil-water mixture was stirred up for 1 minute. In the next step, different complexing reagents (potassium iodide (KI), sodium thiosulfate (Na2S203), TETREN, and Na4EDTA) were added to each reactor to make a final concentration of: 50, 500 and 5,000 ppm KI; 470 and 4,700 ppm Na2S203; 570 and 5,700 ppm TETREN; 1,200 and 12,000 ppm Na4EDTA. The tubes were shaken vigorously for 1 minute. Aliquots of both oil and water from each were analyzed for mercury. Results are presented in Table 1 showing the % of mercury removal for each combination of oxidants and reagents.

[066] Table 1.

KI (in ppm) Na2S203 TETREN
EDTA
O xid ant 5,000 500 50 4,700 470 5,700 570 1,200 12,000 50 ppm H202 99% 88% 30% -24% 17% 19% _ 2%

5Oppm tBHP* 40% 11% - 10% - 16% 14% 15% 12%

5Oppm CHP** 35% - - 16%
- - - - -* tBHP: t-butyl hydroperoxide ** CHP: cumene hydroperoxide

[067] Example 2: 50 mL of distilled water was placed in each of a number of mL glass tubes, and the mercury level was measured using LUMEX mercury analyzer equipped with PYRO-915+. 50 mL of mercury vapor feed preparation containing approximately 400 ppb Hg was added to each of the glass tubes, then mercury level was measured using LUMEX mercury analyzer equipped with PYRO-915+. A pre-determined volume of hydrogen peroxide (0.3% H202) stock solution was added to each of the tubes at molar ratio of H202 to Hg of 246:1. The mixture was stirred up for 1 minute at 600 rpm. In the next step, different complexing reagents (potassium iodide (KI), sodium thiosulfate (Na2S203), TETREN, and Na4EDTA) were added to each tube at a molar ratio of complexing agent to mercury as 5,000:1. The tubes were agitated at 600 rpm. Aliquots of both oil and water from each tube at 2, 5, 10, 15, and 30 minute intervals and analyzed for mercury.

Claims

1. A method for treating a crude oil to reduce its mercury level, comprising:
a) converting at least a portion of mercury in the crude oil to water soluble mercuric iodide in an oil-water emulsion upon contact with a molecular iodine source; and b) separating the water containing the soluble mercuric iodide from the crude oil for a treated crude oil having a reduced concentration of mercury.
2. The method of claim 1, wherein the crude oil is brought into contact with the molecular iodine source by routing the crude oil through a bed containing solid iodine.
3. The method of claim 1, wherein the crude oil is brought into contact with the molecular iodine source by mixing the crude oil with a solution containing iodine in a solvent selected from methanol, naphtha, diesel, gasoline, mercury-free crude oil, and mixtures thereof.
4. The method of claim 1, wherein the contact is carried out in a pipeline for transporting crude oil, and wherein the molecular iodine source is continuously or intermittently fed into the crude oil pipeline.
5. The method of claim 1, wherein the contact is carried out in a vessel containing crude oil.

6. The method of claim 1, wherein the crude oil is brought into contact with the molecular iodine source by sparging an iodine-containing gas into the crude oil.

7. The method of claim 6, wherein the iodine-containing gas stream is formed by contacting a solid iodine source with a gas stream.

8. The method of claim 1, wherein the molecular iodine source is generated in-situ in an oxidation-reduction reaction between an iodine species having a charge and a reagent which functions as a reductant or an oxidant depending on the charge of the iodine species.
9. The method of any of claims 1 - 8, wherein the molar ratio of iodine to mercury in the crude oil ranges from 1:1 to 30,000:1.14 14.

10. The method of any of claims 1 - 8, wherein the molar ratio of iodine to mercury in the crude oil ranges from 2:1 to 10,000:1.

11. A method for treating a crude oil to reduce its mercury level, comprising:
a) providing a reagent and an iodine species having a charge;
b) mixing the reagent and the iodine species with the crude oil containing mercury, wherein molecular iodine is generated in-situ in the crude oil in an oxidation-reduction reaction between the iodine species having a charge and the reagent to convert at least a portion of the mercury to water soluble mercuric iodide in an oil-water emulsion; and c) separating the water containing the water soluble mercuric iodide from the crude oil for a treated crude oil having a reduced concentration of mercury.

12. The method of claim 11, wherein at least 50% of the molecular iodine is generated in-situ within 10 minutes from mixing the iodine species having a charge and the reagent.

13. The method of any of claims 11 - 12, wherein the iodine species having a charge is positively charged, and the reagent functions as a reducing agent.

The method of any of claims 11 - 12, wherein the iodine species having a charge is negatively charged, and the reagent functions as an oxidizing agent.

15. The method of claim 13, wherein the positively charged iodine species is selected from the group of periodic acid (H5IO6), potassium periodate (KIO4), sodium periodate (NaIO4), iodic acid (HIO3), potassium iodate (KIO3), potassium hydrogen iodate (KHI2O6), sodium iodate (NaIO3), iodine oxide (I2O5), iodine trichloride (ICl3), iodine monobromide (IBr), and iodine monochloride (ICl).

16. The method of claim 13, wherein the reagent functioning as a reducing agent is selected from the group of thioureas, thiols, thiosulfates, ascorbates, imidazoles, and mixtures thereof.

17. The method of claim 14, wherein the negatively charged iodine species is selected from the group of hydriodic acid (HI), sodium iodide (NaI), potassium iodide (KI), ammonium iodide (NH4I), aluminum iodide (AlI3), boron triodide (BI3), calcium iodide (CaI2), magnesium iodide (MgI2), iodoform (CHI3), tetraiodoethylene (C2I4), iodoethanol, iodoacetic anhydride ((ICH2CO)2O), iododecane (CH3(CH2)3I), and iodobenzene.
18. A method for treating a crude oil to reduce its mercury level, comprising:
a) adding an effective amount of a reagent that functions as an oxidizing agent to the crude oil;b) adding a negatively charged iodine species in an excess amount at a molar ratio of iodine to heavy metals of at least 2:1 to generate molecular iodine in-situ in the crude oil in an oxidation-reduction reaction between the negatively charged iodine species and the reagent, wherein the in-situ iodine converts mercury to cationic mercury in a water-oil emulsion and forms water soluble mercury complexes; and c) separating the water containing the soluble mercury complexes from the crude oil for a treated crude oil having a reduced concentration of mercury.

19. The method of any of claims 14 and 18 wherein the reagent that functions as an oxidizing agent is selected from the group of peroxides, ozone (O3), NaOCl, iodates, bromine, alkali metal salts of peroxide, alkaline earth metal salts of peroxide, monopersulfates, perborate, percarbonate, perchlorate, permanganate, perphosphate, peroxidases, and mixtures thereof.

20. The method of claim 18, wherein the reagent that functions as an oxidizing agent is hydrogen peroxide.

21. The method of any of claims 1 - 8, 11, and 18, wherein the treated crude oil contains less than 100 ppb mercury.

22. The method of any of claims 1 - 8, 11, and 18, wherein the treated crude oil contains less than 50 ppb mercury.

23. The method of any of claims 1 - 8, 11, and 18, wherein the treated crude oil contains less than 10 ppb mercury.

24. The method of any of claims 11 and 18, wherein the ratio of molecular iodine generated in-situ to starting iodine in the iodine species ranges from 0.5 to 1.

25. The method of any of claims 11 and 18, wherein the ratio of molecular iodine generated in-situ to starting iodine in the iodine species ranges from 0.8 to 1.

26. The method of claim 18, wherein the iodine species is selected from the group of RX and RX2, wherein X is iodide and R is selected from potassium, lithium, sodium, calcium, magnesium, and ammonium.

27. A method for treating a crude oil to reduce its mercury level, comprising:
a) passing a stream of crude oil through a bed comprising molecular iodine to convert at least a portion of mercury in the crude oil to water soluble mercuric iodide in an oil-water emulsion phase; and b) separating the water containing the mercuric iodide from the crude oil in a phase separation device for a treated crude oil having a reduced concentration of mercury.

28. The method of claim 27, wherein the treated crude oil has less than 50 ppb mercury.

29. A method for treating a crude oil to reduce its mercury level, comprising:
a) converting at least a portion of mercury in the crude oil to soluble mercuric iodide in a water phase upon contact with iodine in a solvent; and b) separating the water containing the soluble mercuric iodide from the crude oil in a phase separation device for a treated crude oil having less than 50 ppb mercury.

30. The method of claim 29, wherein the solvent is selected from the group of methanol, diesel, naphtha, gasoline, mercury-free crude oil, and mixtures thereof.

31. A method for treating a crude oil to reduce its heavy metal level, comprising:
a) providing a reducing reagent and an iodine source containing an iodine species having a positive charge;

b) mixing the reducing reagent and the iodine source with the crude oil containing mercury, wherein molecular iodine is generated in-situ in the crude oil in an oxidation-reduction reaction between the iodine species having a positive charge and a reducing reagent, wherein the in-situ molecular iodine converts heavy metal to heavy metal cations;
b) contacting the heavy metal cations with a complexing agent to form a water soluble heavy metal compound in an oil-water emulsion; and c) separating the water containing the soluble heavy metal compound from the crude oil for a treated crude oil having a reduced concentration of heavy metal.

32. The method of claim 31, wherein the heavy metal is mercury.

33. The method of any of claims 31 - 32, wherein at least 50% of the molecular iodine is generated in-situ within 10 minutes from contact between the iodine species having a positive charge and the reducing reagent.

34. The method of any of claims 31 - 32, wherein at least 75% of the molecular iodine is generated in-situ within 10 minutes from contact between the iodine species having a positive charge and the reducing reagent.

35. The method of any of claims 31 - 32, wherein the positively charged iodine species is selected from the group of periodic acid (H5IO6), potassium periodate (KIO4), sodium periodate (NaIO4), iodic acid (HIO3), potassium iodate (KIO3), potassium hydrogen iodate (KHI2O6), sodium iodate (NaIO3), iodine oxide (I2O5), iodine trichloride (ICl3), iodine monobromide (IBr), and iodine monochloride (ICl).

36. The method of any of claims 31 - 32, wherein the reducing reagent is selected from the group of thioureas, thiols, thiosulfates, ascorbates, imidazoles, and mixtures thereof.

37. The method of any of claims 31 - 32, wherein the reducing reagent is selected from the group of sulfides, ammonium thiosulfate, alkali metal thiosulfates, alkaline earth metal thiosulfates, iron thiosulfates, alkali metal dithionites, alkaline earth metal dithionites, and mixtures thereof.18 38. The method of any of claims 31 - 32, wherein the complexing agent is a polyamine.

39. The method of any of claims 31 - 32, wherein the complexing agent is selected from the group of ethylenediamine, propylenediamine, triaminotriethylamine, diethylenetriamine, triethylenetetramine (TRIEN), tetra-2-aminoethylethlenediamine, tetraethylenepentamine (TETREN), ethylene-diamine-tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA), and mixtures thereof.

40. The method of any of claims 31 - 32, wherein the ratio of molecular iodine generated in-situ to starting iodine in the iodine species ranges from 0.5 to 1.

41. A method for reducing a trace element of mercury in a crude oil, comprising:
a) adding an effective amount of an iodine containing species and a reducing agent to the crude oil to generate iodine in-situ, converting mercury to cationic mercury in a water-oil emulsion;
b) adding an effective amount of a complexing agent to the water-oil emulsion mixture to form soluble mercury complexes in a water phase; and c) separating the water containing the soluble mercury complexes from the crude oil for a treated crude oil having a reduced concentration of mercury.