Trinuclear basic iron (III) acetate solid absorbent compositions and methods for removing mercaptan sulfur compounds or desulfurizing from hydrocarbon streams

Abstract

Solid absorbent compositions and methods for removing mercaptan sulfur compounds from hydrocarbon streams are provided. These compositions can include porous granular activated carbon particles having an internal pore surface containing a bound trinuclear basic iron(III) acetate complex containing a [Fe3(μ 3 -O)] core structure.

Description

Technical Field

[0001] This application broadly relates to compositions and methods for removing thiols and sulfur compounds from hydrocarbon streams. Specifically, this application relates to porous granular activated carbon particles having an internal pore surface containing a bonded trinuclear basic ferric acetate (III) complex containing a [Fe3(µ3-O)] core structure. Background Technology

[0002] Sulfur-containing compounds, such as thiols, are common components of hydrocarbons. However, polar thiols are undesirable and dangerous due to their characteristic toxicity and corrosiveness. Therefore, it is desirable to remove them from hydrocarbon streams or to react thiols to form other compounds that are less toxic and corrosive.

[0003] The U.S. Environmental Protection Agency (EPA), along with other federal, state, and local agencies, has a history of developing policies and enforcement standards to reduce air and water pollutants from various processes. Its authority stems from the Clean Air Act, the Clean Water Act, and subsequent legislation. Examples of such policy development include the National Ambient Air Quality Standards (NAAQS), which define permissible air quality limits for compounds such as volatile organic compounds, nitrogen oxides, sulfur oxides, and others.

[0004] Another example of this is the EPA's vehicle emissions and fuel standards, or simply Stage II and Stage III standards, which lower the permissible sulfur content in fuels such as diesel and gasoline. As a result of these regulations, the removal / limitation of sulfur compounds from sulfur-generating fuels and from water sources has become a growing issue in the United States and other developed and developing countries.

[0005] Many conventional systems and methods are capable of controlling the concentration of hydrogen sulfide and other sulfur compounds in a variety of matrices. For example, one conventional method for removing thiols utilizes a patented process commercially known as the Merox treatment, in which a catalyst is used in combination with a caustic base to oxidize the thiol to a disulfide. Such conventional systems require multiple processing steps, are capital-intensive, have higher operating costs, and are not suitable for short-term or mobile applications. Other conventional methods, such as caustic extraction, are capable of processing certain highly reactive small sulfur compounds, such as hydrogen sulfide and methylthiols (thiols), but are not very efficient at removing larger thiols such as butyl or propylthiols (thiols).

[0006] Therefore, there is a need for a system and method that overcomes one or more of the aforementioned deficiencies of conventional systems and methods for larger thiols, and has one or more advantageous features, such as flexible operating requirements, always economical operation, and operability to extract or desulfurize R-SH (especially thiols, ethyl mercaptan, propyl mercaptan, and butyl mercaptan, as well as their branched isomers and higher carbon number thiols, when present) from natural gasoline, propane, butane, mixtures of propane and butane, light naphtha, heavy naphtha, kerosene / turbine fuels, and other hydrocarbon fluids, thereby improving the toxicity and corrosivity of the product, quality issues, resulting basic structure issues, marketability, and / or availability. Brief description of the attached diagram

[0008] To describe the ways in which the advantages and features of this application can be obtained, reference is made to embodiments thereof shown in the accompanying drawings. It should be understood that these drawings depict only exemplary embodiments of this application and are therefore not intended to be considered as limiting its scope. The principles herein are described and explained with additional specificity and detail using the drawings, in which:

[0009] Figure 1 This is a flowchart depicting a method for synthesizing bonded complexes according to an exemplary embodiment of this application;

[0010] Figure 2 The 3-D chemical structure of an iron(III) acetate coordination complex chemically bound to sites on the surface of a solid absorbent according to an exemplary embodiment of this application is depicted.

[0011] Figure 3 A simplified method according to an exemplary embodiment of this application is described, by which the alkaline ferric acetate (III) solid absorbent disclosed in this invention can be used to treat thiols in hydrocarbon fluids;

[0012] Figure 4 A system for processing hydrocarbon fluids containing thiols is described according to an exemplary embodiment of this application;

[0013] Figure 5 A method for regenerating a complexed solid absorbent according to an exemplary embodiment of this application is described; and

[0014] Figure 6 Exemplary embodiments according to this application are depicted. Figure 5 Another aspect of the method described therein.

[0015] Overview

[0016] This application provides compositions and methods for treating hydrocarbon streams by removing thiol sulfur compounds. In particular, the compositions and methods disclosed herein can be used in the field of extracting and desulfurizing thiol sulfur compounds from hydrocarbon streams, aqueous liquids, and gases. The compositions may include porous solid substrates or solid absorbents, such as porous granular activated carbon particles, wherein a basic ferric acetate (III) complex is bonded to the inner surface of the porous solid substrate. Specifically, the novel [Fe3(µ3-O)] core structure of the basic ferric acetate (III) complex is chemically bonded to the surface of the porous solid substrate and, once bonded, retains its structure and the chemical reactions associated with thiol sulfur compounds present in many hydrocarbon streams.

[0017] This application also provides methods and systems for treating mercaptan sulfur (R-SH) compounds, such as, but not limited to, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, and higher carbon number mercaptan, from natural gas, propane, butane, mixtures of propane and butane, natural gasoline, light naphtha and heavy naphtha, kerosene / turbine fuel, and other hydrocarbon fluids, by extraction or desulfurization.

[0018] According to another aspect of this application, a method is provided for preparing compositions for treating hydrocarbon streams and other streams containing thiols and sulfur compounds. This method may include preparing a specific transition metal compound, a basic ferric acetate (III) anionic complex [Fe3(µ3-O)(OAc)6(H2O)3], from ferric nitrate (III) and glacial acetic acid in an aqueous solution. + This nucleocomplex is known to oxidize compounds such as sulfur without decomposing them. Therefore, one of the three Fe atoms is reduced to +2, and the complex, while now neutral, remains stable, and the reduced Fe... +2 It can be re-oxidized to +3 with a suitable oxidant; for example, any of the Fe atoms in the (µ3-O) stable cluster can undergo a redox cycle and remain intact, so that the solution uniformly fills and wets the pore surface and quantitatively distributes the complex within the medium, such as acid-washed activated carbon.

[0019] This application provides a novel method for solvent removal, in which an iron complex is chemically bonded to the pore surface of activated carbon, and nitrate anions from the Fe(NO3)3 starting material are also removed from the complex-coated activated carbon product. Solvent-dried and complex-bonded activated carbon can retain (extract) thiol sulfur compounds such as butyl mercaptan, or can convert (desulfurize) thiol sulfur to non-reactive disulfide hydrocarbon soluble sulfur substances (a process commonly referred to as desulfurization in refining operations). A unique feature of solvent-dried and complex-bonded activated carbon is that it can directly extract and / or desulfurize thiol sulfur from a continuous hydrocarbon phase in contact with or through the pores of the complex-bonded activated carbon; for example, extraction and desulfurization can be carried out without a caustic aqueous phase. The bonded complex retains its redox properties.

[0020] It should be understood that trimetallic triatoms with shared (µ3-O) atoms can also be synthesized starting with ferric chloride (III) and can form complexes using carboxylic acids other than acetic acid. It should also be understood that Fe2 / Co (µ3-O) mixed metal complexes can be synthesized and incorporated into activated carbon by the methods described above. These variations are also included within the scope of this application, but preferred products are those formulated using ferric nitrate (III), glacial acetic acid, and acid-washed lignite-based activated carbon as described above.

[0021] Detailed Explanation

[0022] It should be understood that the concept of the invention, in its application, is not limited to the embodiments of construction details and components set forth in the following description or shown in the accompanying drawings. The drawings and written description are provided to teach any person skilled in the art how to prepare and use this patent-seeking invention. The concept of the invention is capable of having other embodiments and can be implemented and carried out in various ways. Those skilled in the art will understand that the development of practical commercial implementations including aspects of the concept of the invention will require many specific implementations—determined by the developer to achieve the ultimate goals of the commercial implementation. While these efforts may be complex and time-consuming, they will be routine tasks for those skilled in the art who benefit from this application.

[0023] It should be understood that many specific details have been set forth in order to provide a thorough understanding of the embodiments described herein. However, those skilled in the art will understand that the embodiments described herein can be implemented without these specific details. In other instances, methods, procedures, and components have not been described in detail to avoid obscuring the relevant features described. Furthermore, the description should not be construed as limiting the scope of the embodiments described herein.

[0024] This application provides a method for preparing a specific aqueous / alcoholic solution of a trinuclear ferric acetate (µ3-O) complex, which can be distributed onto the internal pore surface of a porous solid medium substrate, followed by solvent removal (along with starting material impurities) and chemical bonding of the complete complex to the surface. The resulting product formulation and the method using such material allow for the direct treatment of thiols and sulfur compounds from hydrocarbon streams. The trinuclear ferric acetate (µ3-O) complex bound to the substrate is a known basic ferric acetate (CAS # 1834-30-6) and is derived from the formula [Fe3(µ3-O)(OAc)6(L)3][A] -1 This indicates that, when the complex is in solution, L is a trans-neutral ligand and [anion] - [ ] is a counter ion. When in solution used in this method, depending on the relative solution concentration, the trans-neutral ligand L will be one of the oxygen compounds present; water, alcohol (such as ethanol), or acetic acid, but which compound is in the "L" position is not critical to the product chemistry. When in solution, the charge-balanced counter ion [anion] - It can be the acetate anion (OAc) - ) or nitrate (NO3) - When the [Fe3(µ3-O)(OAc)6(L)3] complex is bound to the activated carbon surface, the solution anions no longer play a role in the process chemistry, and one of the "L" positions is used to generate pore surface bonds that hold the complex in place and connect the Fe3(µ3-O) triangle to the electron-rich activated carbon surface.

[0025] Basic ferric acetate (III) in aqueous / alcohol complex solutions is composed of the cation [Fe3(µ3-O)(OAc)6(H2O)3]. + and acetate anion (OAc) - or CH3CO2 - ) or anions from iron(III) starting materials (NO3) - or Cl - A soluble salt composed of [Fe3(µ3-O)(OAc)]. The only function of the anion is to stabilize the charge of the solution. Therefore, the key chemical formula for basic ferric acetate is [Fe3(µ3-O)(OAc)]. - )6(L)3] +The soluble cation is represented by the trans-neutral "L", which is H₂O or OAcH. In most aqueous solution formulations, the trans-neutral ligand is assumed to be water, but in our surface deposition and bonding, the actual solution "L" is not critical for the oxygen content occupying the "L" positions on the two non-surface-bonded Fe atoms in the [Fe₃(µ₃-O)] core structure. The trinuclear basic iron(III) acetate (µ₃-O) complex is associated with polarity (S) due to its relatively unique [Fe₃(µ₃-O)] core structure. -2 Sulfur is reactive, in which iron forms a triangular nucleus complex with an equally shared oxygen molecule at its center. Acetate molecules chelate with Fe atoms to form a 4-coordinate planar substrate for each Fe atom in the triangular structure. The central shared oxygen atom is the substrate of the out-of-plane ligands, and another (trans) out-of-plane position is occupied by an orbital with two unpaired Fe electrons. This allows each Fe atom to accept and exchange ligands without covalent bonds. The characteristic of the shared oxygen-stabilized Fe cluster is that it can have at least one Fe atom through a +2 / +3 redox cycle without destabilizing the [Fe3(µ3-O)] core structure of the molecule. This allows for the potential to regenerate iron complexes bonded to the pore surface of granular activated carbon particles using desulfurization-type reactions.

[0026] The aqueous solution of ferric acetate (III) complex disclosed in this invention can be introduced into the pores of a medium (GAC) using an alcohol co-solvent mixed with the aqueous solution of ferric acetate (III) complex, to produce a mixture that provides a uniform pore distribution of the solution and promotes wetting of the pore surfaces. The alcohol co-solvent solution mixture is provided to the porous solid medium by immersing the GAC particles in an excess of the co-solvent solution for a sufficient time (e.g., 6-12+ hours), allowing the excess mixed solvent to displace air from the pores and ensuring uniform dispersion within the internal pores of the porous solid medium. Excess mixed solvent not retained in the medium pores is discharged, recovered, and reused. The solvent mixture containing / dissolving the complex is removed in two evaporation drying steps with specific temperatures and purge gas (air) rates. The first step selectively removes most (90+%) of the alcohol while removing minimal water. The second step removes most of the aqueous phase under specific temperature and gas (air) purge rates, leaving the basic ferric acetate (III) complex [Fe3(µ3-O)(CH3CO2] - )6(ligand)3] + It is uniformly deposited and distributed on the pore surface. Additionally, the starting material anions (NO3) - GAC is deposited on the hydrogen-deficient carbon surface with internal pores. Two key chemistry steps are achieved using additional thermal steps; 1) thermally driven redox reaction (NO3) on the carbon surface. -To generate gaseous NO2, remove potential anionic impurities from the final product, and secondly chemically bond one of the three Fe3(µ3-O) atoms to the inner surface of the porous activated carbon solid medium through its trans "L" bonding site.

[0027] It has been unexpectedly discovered that, when the compositions disclosed in this application are prepared according to the methods and techniques disclosed herein, the iron(III)(µ3-O) trinucleoacetate complex can be bonded to the surface of the granular activated carbon particles, thereby maintaining its [Fe3(µ3-O)] core structure and reactivity with thiols. Furthermore, the compositions disclosed herein are unexpectedly characterized by a stable bond between the granular activated carbon particles and the iron(III)(µ3-O) trinucleoacetate complex solution, preventing the bonded iron complex from being removed by hydrocarbons or aqueous solvents. Moreover, the stable iron(III)(µ3-O) trinucleoacetate complex solution can be regenerated by oxidizing the reduced Fe atoms after chemical removal of any remaining thiols through conventional desulfurization processes (conversion to non-iron-bonded hydrocarbon-soluble disulfides).

[0028] Figure 1 This is a flowchart describing method 100 for producing the composition disclosed in this invention, used to treat hydrocarbon streams and other streams containing thiols, including the synthesis of bonded complexes. At 110, an aqueous / acidic complex solution is synthesized. At 115, the aqueous / acidic complex solution is subjected to controlled dilution with an alcohol to obtain a desired complex pore wetting and distribution solution mixture at 120. The target complex solution mixture typically has an alcohol concentration in the range of about 40% to 60%. At 125, the selected porous medium is exposed to sufficient complex solution from 120 to completely liquid-fill the pore volume of the medium by immersion and soaking for 6-12 hours. In at least some cases, the preferred medium is acid-washed lignite activated carbon. At 130, the interparticle (excess) complex solution is drained from the medium and recovered, wherein the complex solution remains within the pores of the medium relative to the pore volume. Typically, 40%-50% of the soaking solution remains in the pores of the medium. At 135°C, a first-stage evaporative drying is performed, in which the alcohol content of the complex solution retained in the pores is reduced by >90%, while water removal is controlled to <10%. A second-stage evaporative drying occurs at 140°C, in which >90% of the remaining aqueous phase and excess acetic acid are removed. A third-stage solidification occurs at 145°C, which results in surface bonding of the complex and the conversion of nitrates to nitrogen dioxide. After completion of synthesis and product cooling, the composition is operable to retain thiol sulfur and desulfurized hydrocarbon streams, as well as other waste streams containing thiol sulfur substances.

[0029] Figure 2 The iron(III) acetate coordination complex [Fe3O(OAc)6(H2O)3] was described.+ (OAc) - It is CH3CO2 - The 3-D chemical structure of is commonly referred to as "basic ferric acetate". Figure 2 It also shows the use of Figure 1 The iron(III) acetate coordination complexes synthesized by methods described herein and elsewhere in this application are chemically bonded to the inner surface of a selected solid medium. In particular, Figure 2 Examples of stable bonded complexes on the surface of a selected medium are described, wherein they can be chemically bonded to the inner surface of the medium pores, any or any of the mesopores, macropores, or micropores, or any combination of any surface of the medium. In at least some cases, the selected porous solid medium is acid-washed lignite activated carbon from lignite mines in Texas.

[0030] In at least one aspect of this application, the basic iron(III) acetate complex [Fe3(µ3-O)(CH3CO2] - )6(ligand)3] + [Anion] - Salts selected from hydrated ferric nitrate (III) salts (Fe(NO3)) can be used. 3- The synthesis uses an iron salt of one of the following (nH2O), preferably 9H2O, as the starting material. In one such embodiment, the basic iron(III) acetate complex [Fe3(µ3-O)(CH3CO2] is used. - )6(ligand)3] + [Anion] - The synthesis can be carried out using other hydrated iron salts such as ferric(III) hexahydrate. Further, the use of iron salts other than nitrates is envisioned, but this requires more complex preparation methods. A basic ferric(III) acetate complex reagent solution can be prepared using the molar ratio of the iron and acetic acid complex formulation in an aqueous solution to the desired concentration for preparing an alcohol co-solvent complex solution.

[0031] According to at least one aspect of this application, the solid media substrate may consist of acid-washed granular activated carbon (GAC) having the pore size, distribution, and internal surface area desired for the target application. Preferred granular activated carbon (GAC) is acid-washed lignite-based granular activated carbon manufactured by NORIT / CABOT and having a sieve size of approximately 8×30. The selective sieve size is determined based on common techniques used for the target application. Surface acid washing conforming to the NORIT / CABOT Petrodarco 8×30 specification is a critical requirement / necessity. In at least some cases, the solid media substrate may be acid-washed granular activated carbon (GAC) produced from lignite, and particularly from the Darco mine in Texas.

[0032] The selected media substrate particles used in liquid phases (hydrocarbon or aqueous solutions) may have a particle size of about 8 mesh (2.36 mm) to about 30 mesh (0.60 mm), or about 0.50 mm to about 2.50 mm, or about 0.75 mm to about 2.00 mm, or about 0.75 mm to about 1.50 mm, or about 0.85 mm to about 1.25 mm, or about 1.00 mm to about 2.00 mm, or about 0.60 mm to about 1.25 mm.

[0033] The selected substrate particles can also have a particle size of approximately 250 m. 2 / g to approximately 1000 m 2 / g, or approximately 550 m 2 / g to approximately 750 m 2 / g, or approximately 600 m 2 / g to approximately 700 m 2 / g, or approximately 500 m 2 / g to approximately 800 m 2 / g, or approximately 625 m 2 / g to approximately 675m 2 The particles may also have a surface area of ​​about 0.75 to about 1.15 ml / g, or about 0.90 to about 1.0 ml / g, or about 0.85 to about 1.05 ml / g.

[0034] Those skilled in the art will further understand that other embodiments for forming stable basic ferric acetate (III) complexes can be developed using other solid media having similar surface characteristics to the selected GAC, and such solid media are within the scope of this application. Those skilled in the art will further understand that other embodiments may include the formation of stable basic ferric acetate (III) complexes bonded to other media with different surface chemistry properties, selected based on the specific requirements of the application. Those skilled in the art will further understand that other embodiments for forming ferric acetate (III) complexes can be developed using other solid media, which may not form stable bonds with the surface of the media, but will still function as a single-use product.

[0035] Furthermore, it should be understood that the concentration of the stable ferric trinucleotide (III) (µ3-O) complex can be increased, wherein the bonding of the stable ferric trinucleotide (III) (µ3-O) complex is performed by completing multiple or more bonding, aqueous / alcoholic solution removal, and curing steps consistent with the teachings of this patent. It should further be understood that the initial and subsequent molar ratios of the aqueous / alcoholic solutions can be equal or different to achieve the desired concentration of the stable ferric trinucleotide (III) (µ3-O) complex.

[0036] The porous solid substrates with bonded iron complexes disclosed in this invention can be used for the quantitative removal of polar sulfur compounds, such as thiols, from hydrocarbon streams. For example, the compositions and methods disclosed in this invention can effectively retain and remove butyl mercaptan (C4SH) and thiols with higher carbon numbers, which are difficult to extract from liquid hydrocarbon streams using conventional catalyst / caustic alkali treatment. The compositions disclosed in this invention can also be used to remove C1-5SH (and higher carbon number) thiols, with butyl mercaptan (C4SH) as a prime example.

[0037] In one such embodiment, the porous solid substrate with bound iron complexes disclosed in this invention can be used to quantitatively convert reactive thiols (R-SH) sulfur compounds into non-reactive hydrocarbon soluble sulfur compounds (R-SS-R) via oxidation, without requiring a caustic aqueous phase. For example, the compositions and methods disclosed in this invention can efficiently convert butyl mercaptan (C4H9SH) directly into butyl disulfide (C8H9SH). 18 S2). The compositions disclosed in this invention can also be used to convert small C1-2SH thiols such as methyl thiols (CH3SH) into methyl disulfides (C2H6S2) and to convert a wider range of C1-2SH thiols into methyl disulfides (C2H6S2). 6-8 SH thiols, such as hexylthiols, are converted into their disulfides.

[0038] Figure 3 A basic simplified method 300 is described, in which the compositions disclosed in this invention comprise a porous solid substrate having bound iron complexes to treat hydrocarbon fluids containing thiol sulfur. At 310, the source hydrocarbon stream containing thiol sulfur is fed into the treatment method 300. Method 300 may optionally include a pre-filtration / treatment step 315, which may consist of particulate filtration and / or caustic alkali pretreatment for the primary purpose of removing solids and hydrogen sulfide. In some cases, the pretreatment step 315 may also include bulk separation of any mixed hydrocarbon / aqueous solution. Pretreatment can be performed to ensure that the complexes disclosed in this invention are not artificially sacrificed due to the washing of other contaminants in the source hydrocarbon stream 310.

[0039] At 320, the hydrocarbon stream can be fed into the treatment contactor. When the hydrocarbon fluid is introduced into the treatment contactor, it interacts with activated carbon having a bonded complex at 325, and at least one thiol sulfur molecule is retained by the complex at 330. The treated hydrocarbon fluid is then discharged from the contactor at 340, wherein the at least one thiol sulfur molecule is removed from the hydrocarbon fluid. At 335, the at least one thiol sulfur molecule retained by the complex can undergo a conversion to a hydrocarbon-soluble disulfide oil, wherein once the conversion occurs, the disulfide oil is removed from the complex by the hydrocarbon fluid and leaves the contactor as a component of the hydrocarbon fluid. Those skilled in the art will understand that the treatment contactor can have many configurations and forms. According to one aspect of this application, a solid absorbent composition having a bonded complex, as described herein, can be introduced into the hydrocarbon fluid in particulate form and filtered to remove the complex having the bonded thiol sulfur.

[0040] Figure 4 A processing system according to at least one aspect of this application is described. For example... Figure 4 As shown, a hydrocarbon fluid containing at least one thiol molecule is fed into a processing contactor. In at least some cases, the processing contactor may be a container constructed of carbon steel. The processing contactor includes orifices for guiding the flow of the hydrocarbon fluid into the processing contactor. Within the processing contactor, a certain amount of solid medium having bonded surface complexes is positioned to contact at least some of the hydrocarbon fluid having at least one thiol molecule as part of its composition, such that at least one thiol molecule is retained by the solid medium having bonded surface complexes, allowing at least some of the treated hydrocarbon fluid to leave the processing system with reduced or no thiol molecule as part of its composition. Additionally, it can be observed that the retained thiol molecule can undergo further chemical reaction to form an oil-soluble disulfide oil, such that the treated hydrocarbon fluid leaving the processing system may contain disulfide oil as part of its composition.

[0041] Figure 5 A method 500 for regenerating a complexed solid medium according to an embodiment of this application is described. In method 500, regeneration is achieved by offline R-SH removal via R-SS-R formation. Figure 5The general concept of method 500 is described; however, those skilled in the art will recognize that many additional steps can be taken to complete the regeneration process. At 510, the processing vessel used to remove R-SH and which has been at least partially saturated with bound complexes within the pores of the medium is taken offline, meaning the hydrocarbon flow is stopped and it can be directed to a second processing vessel for the ongoing treatment. Once “offline,” the processing vessel is isolated from the hydrocarbon connection. Once the flow is stopped and the vessel is isolated, at 510, a hot liquid pentane / butane saturated with air is directed to the top of the processing vessel, where a C4 / C5 liquid mixture is filled and thus comes into contact with the R-SH containing the bound complexes within the pore surface of the medium. When the R-SH is contacted with an oxygenated liquid mixture, the formation of R-SS-R is observed.

[0042] At 515, the liquid C4 / C5 mixture is discharged from an orifice located at the bottom of the vessel. The liquid C4 / C5 mixture contains relatively high-boiling-point R-SS-R until R-SH is sufficiently removed from the surface of the medium orifice. The discharged mixture is directed to a flash tank at 530, where the liquid C4 / C5 mixture can be separated from the disulfide oil by flash evaporation / boiling (conversion to vapor) of the C4 / C5 mixture, leaving the disulfide oil as a residue (530).

[0043] At 520, the flashed C4 / C5 mixture vapor is condensed and directed back to the top of processing vessel 525, where processes 515, 520, and 525 are repeated continuously until the C4 / C5 mixture in 515 is free of disulfide oil. In at least some cases, it may be necessary to reheat the C4 / C5 mixture in 515 to 520.

[0044] Figure 6 The embodiments of the present application are described for use in accordance with... Figure 5 The method 500 shown in the diagram regenerates the complexed solid medium in a system 600. For example... Figure 6As shown, system 600 includes contactor 610. During operation of system 600, air-saturated C4 / C5 vapor / condensate is directed to the top of contactor 610, which contains a medium having bound complexes within the surface of the medium pores. The effluent from the lower part of the processing contactor 610 is directed to heat exchanger 615 and flash tank 620, where sufficient heat is added to flash the C4 / C5 mixture. During the flashing of the light C4 / C5 mixture in flash tank 620, disulfide oils separate and are collected in the boot of the flash tank, and the C4 / C5 vapor mixture from the flash tank is condensed via heat exchanger 625 and directed back to the top of processing contactor 610. Method 500 of system 600 can be continuously repeated until all R-SH retained on the pores of the medium by the bound complexes is sufficiently converted to R-SS-R and removed from the medium. System 600 can be used to remove all or a portion of the R-SH from the bound complex, allowing for the additional extraction and retention of R-SH from the hydrocarbon source onto the bound complex. Those skilled in the art will recognize that many additional steps are necessary to complete the regeneration process, and that this regeneration can be carried out through various processes.

[0045] Importantly, the compositions disclosed in this invention effectively remove thiols and sulfur compounds from hydrocarbons without the use of alkali or caustic alkali solutions. Specifically, the compositions disclosed in this invention are capable of retaining and removing sulfur compounds from hydrocarbons without exposing or saturating the disclosed compositions to caustic alkali solutions or aqueous phases to drive nuclear chemistry. Instead, the sulfur compounds present in the hydrocarbons interact directly with the Fe reaction sites of iron complexes bonded to the surface of granular activated carbon (GAC). In particular, the compositions disclosed in this invention effectively retain thiols, especially C2-5SH and larger thiols.

[0046] Furthermore, the compositions disclosed in this invention efficiently perform direct redox desulfurization of sulfur compounds from hydrocarbons without the use of alkaline or caustic solutions, external catalysts such as cobalt complexes, or oxygen injection. Specifically, the compositions disclosed in this invention are capable of donating electrons from the iron(III) trinuclear acetate (µ3-O) complex to R-SH compounds to directly form R-SS-R compounds, without exposing or saturating the disclosed compositions to caustic solutions or aqueous phases to drive nucleochemistry. Instead, sulfur compounds present in hydrocarbons or aqueous solutions interact directly with the Fe reaction sites of the iron complexes bound to the surface of granular activated carbon. In particular, the compositions disclosed in this invention efficiently desulfurize thiols, especially C1-5SH or higher carbon thiols.

[0047] Furthermore, the compositions disclosed in this invention provide surface-fixed, complexed iron active sites for the removal or desulfurization of thiol sulfur compounds from hydrocarbon streams, rather than reacting soluble chelated (organically complexed) iron with sulfur compounds. Therefore, the compositions disclosed in this invention can be used in a fixed-bed configuration to treat hydrocarbon phases containing thiol sulfur compounds.

[0048] Statement regarding publicly disclosed information:

[0049] Statement 1: A composition for removing one or more thiol sulfur compounds from a hydrocarbon fluid stream and / or reacting them, the composition comprising: a porous solid medium containing a bound stable basic iron(III) acetate complex bonded to the surface of a porous solid medium, wherein the bound stable basic iron(III) acetate complex contains a [Fe3(µ3-O)] core structure.

[0050] Statement 2: The composition according to Statement 1, wherein the combined stable basic iron(III) acetate complex comprises [Fe +3 3(µ3-O)(OAc - )6] Triangular complexes and / or reduced [Fe +3 2Fe +2 (µ3-O)(OAc - )6] Triangular complexes, wherein the triangular complexes and / or the reduced triangular complexes remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

[0051] Statement 3: The composition according to Statement 1 or Statement 2, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron(III) acetate complex is bonded to the one or more internal pore surfaces.

[0052] Statement 4: The composition according to any one of Statements 1-3 above, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

[0053] Statement 5: The composition according to any one of Statements 1-4 above, wherein the porous solid medium is acid-washed lignite-based activated carbon.

[0054] Statement 6: The composition according to any one of Statements 1-5 above, wherein the porous solid medium comprises particles having a particle size of about 0.50 mm to about 2.50 mm.

[0055] Statement 7: The composition according to any one of statements 1-6 above, wherein the porous solid medium comprises having a density of about 250 μm 2 / g to approximately 1000 m2 / g of surface area of ​​particles.

[0056] Statement 8: The composition according to any one of Statements 1-7 above, wherein the porous solid medium comprises particles having a total pore volume of about 0.75 to about 1.15 ml / g.

[0057] Statement 9: The composition according to any one of Statements 1-8 above, wherein the combined stable basic iron(III) acetate complex is formed as a soluble cation in solution, delivered to the selected pore surface of the medium with a mixed alcohol / acidic aqueous solution and bonded within the pore surface of the porous solid medium by staged solvent removal and thermal curing.

[0058] Statement 10: According to the composition of Statement 9, the combined stable basic iron(III) acetate complex is formed from iron(III) nitrate hydrate (Fe3(NO3)3-9H2O) starting material, and the nitrate anions present in the starting material are decomposed into nitrogen dioxide (NO2) gas and removed during the thermosetting.

[0059] Statement 11: The composition according to Statement 9, wherein the combined stable basic ferric acetate (III) complex is in ferric nitrate (III) hydrate [Fe(NO3)2] - It is formed in an aqueous solution of [3–9H2O] and glacial acetic acid (CH3COOH) at a ratio consistent with the complex composition.

[0060] Statement 12: The composition according to Statement 9, wherein the combined stable basic ferric acetate (III) complex is formed in a solution containing a mixture of water and alcohol to achieve high dispersion of the mixture within the pores of the porous solid medium.

[0061] Statement 13: According to the composition of Statement 9, the combined stable basic iron(III) acetate complex is formed in a solution containing a mixture of water and alcohol to achieve high porosity surface wetting and promote uniform distribution of the complex on the surface of the selected porous solid medium.

[0062] Statement 14: The composition according to Statement 12, wherein the aqueous / alcoholic solution is removed in stages, resulting in the complete complex being dispersed and chemically bonded to the surface of the porous solid medium.

[0063] Statement 15: The composition according to Statement 14, wherein once the aqueous / alcoholic solution is removed, a final heating / curing step is performed to chemically bond the complex to the pore surface of the porous solid medium.

[0064] Statement 16: According to the composition of Statement 15, the stable basic ferric acetate (III) complex is formed by providing more than one mixed solution, an associated aqueous / alcoholic solution removal stage and a final heating / curing stage to achieve an increased concentration of basic ferric acetate (III) complex formation.

[0065] Statement 17: The composition according to any one of statements 1-16, wherein the composition is utilized in a fixed bed or fluidized bed absorber.

[0066] Statement 18: The composition according to any one of statements 2-17, wherein, when bonded to the porous solid medium in the absence of a caustic alkali phase, the previously characterized [Fe] +3 3(µ3-O)] triangular Fe +2 / +3 In a redox cycle, the composition was observed to undergo a conversion of thiols to disulfides in the presence of thiols.

[0067] Statement 19: The composition according to any one of statements 2-17, wherein the [Fe +3 The triangular chemical activity of 3(µ3-O)] can be regenerated and the nucleocomplex chemistry is retained by oxidizing any retained thiols to hydrocarbon-phase soluble disulfides.

[0068] Statement 20: The composition according to Statement 19, wherein the regeneration can be carried out using soluble oxygen and recyclable light (low boiling point) hydrocarbon solvents.

[0069] Statement 21: A method for treating a hydrocarbon fluid stream comprising one or more thiols, the method comprising: contacting the hydrocarbon fluid stream comprising thiols sulfide R-SH with a composition comprising: a porous solid medium comprising a bound stable basic iron(III) acetate complex bonded to the surface of the porous solid medium, wherein the bound stable basic iron(III) acetate complex comprises a [Fe3(µ3-O)] core structure; and retaining at least a portion of the thiols sulfide R-SH at iron (Fe) sites of the core structure.

[0070] Statement 22: According to the method of Statement 21, the hydrocarbon fluid stream comprises one or more components selected from the group consisting of: propane, butane, mixtures of propane and butane, hydrocarbon condensate, light and heavy naphtha, kerosene, jet fuel, natural gasoline, and any combination thereof.

[0071] Statement 23: The method according to Statement 21 or Statement 22, wherein the combined stable basic iron(III) acetate complex comprises [Fe +3 3(µ3-O)(OAc -)6] Triangular complexes and / or reduced [Fe +3 2Fe +2 (µ3-O)(OAc - )6] Triangular complex, wherein the triangular complex and / or the reduced triangular complex remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

[0072] Statement 24: The method according to any one of the preceding statements 21-23, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron acetate (III) complex is bonded to the one or more internal pore surfaces.

[0073] Statement 25: The method according to any one of the preceding statements 21-24, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

[0074] Statement 26: The method according to any one of the preceding statements 21-25, wherein the porous solid medium is acid-washed lignite-based activated carbon.

[0075] Statement 27: The method according to any one of the preceding statements 21-26, wherein the porous solid medium comprises particles having a particle size from about 0.50 mm to about 2.50 mm.

[0076] Statement 28: According to any one of the preceding statements 21-27, the porous solid medium comprises having a density of about 250 μm. 2 / g to approximately 1000 m 2 / g of surface area of ​​particles.

[0077] Statement 29: The method according to any one of the preceding statements 21-28, wherein the porous solid medium comprises particles having a total pore volume of about 0.75 to about 1.15 ml / g.

[0078] Statement 30: The method according to any one of statements 21-29 above, wherein contacting the hydrocarbon fluid flow comprises allowing the hydrocarbon fluid flow to flow into the pores and channels of the porous solid medium substrate, thereby allowing the thiol sulfur compound to react with the [Fe] +3 3(µ3-O)] triangular non-surface bonded Fe +3 Site interaction, wherein the R-SH is initially retained on the Fe sites on the pore surface within the porous solid medium.

[0079] Statement 31: According to the method of Statement 30, it is observed that [Fe] passes through the pore surface of the porous solid medium. +3The retention of R-SH in the triangular complex of 3(µ3-O) is quantitative, with no disulfide formation, up to an iron:sulfur molar ratio of 1:1, and an increased rate of R-SS-R formation compared to R-SH retention or a molar ratio close to 1:2.

[0080] Statement 32: According to the method of Statement 30, the oxidative conversion of R-SH to R-SS-R initially occurs at an iron:sulfur molar ratio of at least 1:1, and becomes quantitative on a continuous basis when the molar load reaches 1:2.

[0081] Statement 33: According to the method of Statement 32, wherein the R-SS-R is an oil-soluble disulfide oil, the method further includes removing the R-SS-R as a soluble non-reactive component in the hydrocarbon fluid stream.

[0082] Statement 34: In the method according to any one of the preceding statements 21-33, the thiol thiols R-SH may be straight-chain or branched thiols having a target carbon chain in the C1-C8 range for retention and desulfurization, and a higher carbon number (kerosene range) thiol for quantitative desulfurization.

[0083] Statement 35: The method according to any one of statements 21-34 above, wherein the hydrocarbon fluid stream comprises at least one selected from the group consisting of: pressurized propane, pressurized butane, pressurized isobutane (ambient boiling point range of -42°C to 12°C), unstabilized / pressurized γ-condensate (ambient boiling point range of -42°C to 150°C), stabilized natural gasoline (ambient boiling point range of 30°C to 250°C), light gas oil / kerosene / turbine fuel (ambient boiling point range of 150°C to 300°C), and any combination or mixture thereof.

[0084] Statement 36: The method according to any one of the preceding statements 21-35 further comprises: pretreating the hydrocarbon fluid stream with a caustic alkaline aqueous solution to extract hydrogen sulfide and methyl mercaptan.

[0085] Statement 37: According to the method of statement 36, the caustic alkaline aqueous solution comprises an aqueous solution of sodium hydroxide.

[0086] Statement 38: The method according to any one of the preceding statements 21-37 further comprises: pretreating the hydrocarbon fluid stream using a particulate filter.

[0087] Statement 39: The method according to any one of statements 21-38 above further comprises: performing a recycling step, which includes: passing light oxidized hydrocarbons (pentane / butane) through an R-SH saturated treatment vessel to convert the retained R-SH into soluble R-SS-R; heating the eluted washing solvent / R-SS-R mixture such that the solvent flashes and the R-SS-R is condensed; condensing the flashed solvent at the top of the treatment vessel, allowing the "hot" solvent to continue removing the retained R-SH; and repeating the recycling step until the eluted solvent is free of R-SS-R.

[0088] Statement 40: The method according to statement 39, wherein the recycling step includes the use of heat or steam.

[0089] Statement 41: The method according to any one of the preceding statements 21-40 further comprises pretreating the hydrocarbon fluid flow with heat or steam to reduce the viscosity of the hydrocarbon fluid flow before contacting the hydrocarbon fluid flow with the composition.

[0090] Statement 42: A system for processing a hydrocarbon fluid stream comprising one or more thiols, the system comprising: a processing contactor comprising a porous solid medium composition comprising a bound stable basic ferric acetate (III) complex bonded to the surface of the porous solid medium, wherein the bound stable basic ferric acetate (III) complex comprises a [Fe3(µ3-O)] core structure; wherein the processing contactor is operable to receive a hydrocarbon fluid stream to be processed and to contact the hydrocarbon fluid stream with the composition.

[0091] Statement 43: The system according to Statement 42 further includes a flash tank in fluid communication with the processing contactor, the flash tank being operable to receive effluent from the lower part of the processing contactor and to sufficiently heat the effluent to flash the effluent, or a portion thereof, to produce a flashed effluent portion, and thereby causing the disulfide oil to be separated and collected at the sleeve of the flash tank.

[0092] Statement 44: The system according to Statement 43 further includes a first heat exchanger in fluid communication with the flash tank and the processing contactor, wherein the first heat exchanger is operable to receive a portion of the flashed effluent from the flash tank and remove heat from the portion of the flashed effluent to condense the portion of the flashed effluent to form a condensed effluent.

[0093] Statement 45: According to the system described in Statement 44, the processing contactor is further operable to receive the condensate effluent from the heat exchanger.

[0094] Statement 46: The system according to Statement 45 further includes a second heat exchanger for sufficiently heating the effluent in order to flash the effluent or a portion thereof in the flash tank.

[0095] Statement 47: The system according to any one of the preceding statements 42-46, wherein the processing contactor comprises a fixed bed or fluidized bed absorber, the fixed bed or fluidized bed absorber comprising the porous solid media composition.

[0096] Statement 48: The system according to any one of the preceding statements 42-47, wherein the processing contactor comprises a packed bed containing the porous solid media composition.

[0097] Statement 49: The system according to any one of the preceding statements 42-48, wherein the processing contactor comprises a fluidized bed containing the porous solid media composition.

[0098] Statement 50: The system according to Statement 46 includes a plurality of processing contactors, thereby allowing continuous processing of the hydrocarbon fluid flow.

[0099] Statement 51: According to the system of Statement 50, wherein the system is operable to perform parallel regeneration steps, whereby the flow of the hydrocarbon fluid is stopped at a first processing contactor, the retention of R-SH that has occurred at the first processing contactor is separated, and is redirected to a second processing contactor having a new or recycled porous solid media composition.

[0100] Statement 52: The system according to any one of the preceding statements 42-51, wherein the combined stable basic iron(III) acetate complex comprises [Fe +3 3(µ3-O)(OAc - )6] Triangular complexes and / or reduced [Fe +3 2Fe +2 (µ3-O)(OAc - )6] Triangular complexes, wherein the triangular complexes and / or the reduced triangular complexes remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

[0101] Statement 53: The system according to any one of the preceding statements 42-52, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron(III) acetate complex is bonded to the one or more internal pore surfaces.

[0102] Statement 54: The system according to any one of the preceding statements 42-53, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

[0103] Statement 55: The system according to any one of the preceding statements 42-54, wherein the porous solid medium is acid-washed lignite-based activated carbon.

[0104] Statement 56: The system according to any one of the preceding statements 42-55, wherein the porous solid medium comprises particles having a particle size of about 0.50 mm to about 2.50 mm.

[0105] Statement 57: The system according to any one of statements 42-56 above, wherein the porous solid medium comprises having a density of about 250 μm 2 / g to approximately 1000 m 2 / g of surface area of ​​particles.

[0106] Statement 58: The system according to any one of the preceding statements 42-57, wherein the porous solid medium comprises particles having a total pore volume of about 0.75 to about 1.15 ml / g.

[0107] Statement 59: According to the system described in Statement 52, the processing contactor further includes a distribution / diffusion mechanism to allow the hydrocarbon fluid flow to flow into the pores and channels of the porous solid medium, whereby the thiol sulfur compound reacts with the [Fe] +3 3(µ3-O)] triangular non-surface bonded Fe +3 Site interaction, wherein the R-SH is initially retained on the Fe sites on the pore surface within the porous solid medium.

Claims

1. A composition for removing one or more thiol sulfur compounds from a hydrocarbon fluid stream and / or reacting them, said composition comprising: A porous solid medium comprising a stable basic ferric acetate (III) complex bonded to the surface of the porous solid medium. The combined stable basic iron(III) acetate complex contains a [Fe3(μ3-O)] core structure.

2. The composition according to claim 1, wherein the bound stable basic iron(III) acetate complex comprises [Fe 3+ 3(μ3-O)(OAc - )6] Triangular complexes, wherein the triangular complexes remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

3. The composition of claim 1, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron(III) acetate complex is bonded to the one or more internal pore surfaces.

4. The composition according to claim 1, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

5. The composition according to claim 1, wherein the porous solid medium is acid-washed lignite-based activated carbon.

6. The composition of claim 1, wherein the porous solid medium comprises particles having a particle size of 0.50 mm to 2.50 mm.

7. The composition according to claim 1, wherein the porous solid medium comprises having a density of 250 μm 2 / g to 1000m 2 / g of surface area of ​​particles.

8. The composition of claim 1, wherein the porous solid medium comprises particles having a total pore volume of 0.75 to 1.15 ml / g.

9. The composition according to claim 1, wherein the combined stable basic iron(III) acetate complex is formed as a soluble cation in solution, delivered to the selected pore surface of the medium by a mixed alcohol / acidic aqueous solution and bonded within the pore surface of the porous solid medium by staged solvent removal and thermal curing.

10. The composition according to claim 9, wherein the combined stable basic ferric acetate (III) complex is formed from ferric nitrate (III) hydrate starting material, and wherein the nitrate anions present in the starting material are decomposed into nitrogen dioxide gas and removed during the thermosetting process.

11. The composition according to claim 9, wherein the combined stable basic ferric acetate (III) complex is formed in an aqueous solution of ferric nitrate (III) hydrate and glacial acetic acid.

12. The composition according to claim 9, wherein the combined stable basic iron(III) acetate complex is formed in a solution containing a mixture of water and alcohol to achieve high dispersion of the mixture within the pores of the porous solid medium.

13. The composition of claim 12, wherein once the aqueous / alcoholic solution is removed, a final heating / curing step is performed to chemically bond the complex to the pore surface of the porous solid medium.

14. The composition of claim 13, wherein the stable basic ferric acetate (III) complex is formed by providing more than one mixed solution, an associated aqueous / alcoholic solution removal stage, and a final heating / curing stage to achieve an increased concentration of basic ferric acetate (III) complex formation.

15. The composition according to claim 2, wherein [Fe 3+ The chemical activity of the 3(μ3-O)] triangle can be regenerated and the nucleocomplex is retained by oxidizing any retained thiols to hydrocarbon-phase soluble disulfides.

16. A method for processing a hydrocarbon fluid stream containing one or more thiols, the method comprising: A hydrocarbon fluid stream containing thiols (R-SH) is contacted with the composition, said composition comprising: A porous solid medium comprising a stable basic iron(III) acetate complex bonded to the surface of the porous solid medium. The combined stable basic iron(III) acetate complex comprises a [Fe3(μ3-O)] core structure; and At least a portion of the thiol sulfur R-SH is retained at the iron (Fe) sites of the core structure.

17. The method of claim 16, wherein the hydrocarbon fluid stream comprises one or more components selected from the group consisting of: propane, butane, mixtures of propane and butane, hydrocarbon condensate, light and heavy naphtha, kerosene, jet fuel, natural gasoline, and any combination thereof.

18. The method of claim 17, wherein the combined stable basic iron(III) acetate complex comprises [Fe 3+ 3(μ3-O)(OAc - )6] Triangular complexes, wherein the triangular complexes remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

19. The method of claim 16, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron(III) acetate complex is bonded to the one or more internal pore surfaces.

20. The method of claim 16, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

21. The method of claim 16, wherein the porous solid medium is acid-washed lignite-based activated carbon.

22. The method of claim 16, wherein the porous solid medium comprises particles having a particle size of 0.50 mm to 2.50 mm.

23. The method of claim 16, wherein the porous solid medium comprises having a density of 250 μm 2 / g to 1000m 2 / g of surface area of ​​particles.

24. The method of claim 16, wherein the porous solid medium comprises particles having a total pore volume of 0.75 to 1.15 ml / g.

25. The method of claim 18, wherein contacting the hydrocarbon fluid flow comprises allowing the hydrocarbon fluid flow to flow into the pores and channels of the porous solid medium substrate, thereby allowing the thiol sulfur compound to react with the [Fe] 3+ 3(μ3-O)] triangular non-surface bonded Fe 3+ Site interaction, wherein the R-SH is initially retained on the Fe sites on the pore surface within the porous solid medium.

26. The method of claim 25, wherein R-SS-R is an oil-soluble disulfide oil, the method further comprising removing the R-SS-R as a soluble non-reactive component in the hydrocarbon fluid stream.

27. The method of claim 16, wherein the thiol thio (R-SH) comprises a straight-chain or branched thiol having a target carbon chain in the C1-C8 range.

28. The method of claim 16, wherein the hydrocarbon fluid stream comprises at least one selected from the group consisting of: pressurized propane, pressurized butane, pressurized isobutane, stabilized natural gasoline, light gas oil / kerosene / turbine fuel, and any combination or mixture thereof.

29. The method of claim 16, further comprising: The hydrocarbon stream was pretreated with a caustic alkaline aqueous solution to extract hydrogen sulfide and methyl mercaptan.

30. The method of claim 29, wherein the caustic alkaline aqueous solution comprises an aqueous solution of sodium hydroxide.

31. The method of claim 16, further comprising: The hydrocarbon fluid stream is pretreated using particulate filtration.

32. The method of claim 16, further comprising: The recycling step includes: Light oxidized hydrocarbons are passed through an R-SH saturation treatment vessel, thereby converting the retained R-SH into soluble R-SS-R; The washing solvent / R-SS-R mixture is heated and eluted, causing the solvent to flash and the R-SS-R to condense. The flashed solvent is condensed at the top of the processing vessel, allowing the solvent to continue removing the retained R-SH; and Repeat the recirculation steps until the eluted solvent is free of R-SS-R.

33. The method of claim 32, wherein the recycling step comprises using heat or steam.

34. The method of claim 16, further comprising pretreating the hydrocarbon fluid flow with heat or steam to reduce the viscosity of the hydrocarbon fluid flow before contacting the hydrocarbon fluid flow with the composition.

35. A system for processing a hydrocarbon fluid stream containing one or more thiols, the system comprising: A processing contactor comprising a porous solid medium composition comprising a bound stable basic iron(III) acetate complex bonded to the surface of the porous solid medium, wherein the bound stable basic iron(III) acetate complex comprises a [Fe3(μ3-O)] core structure; The processing contactor is operable to receive a hydrocarbon fluid flow to be processed and to contact the hydrocarbon fluid flow with the composition.

36. The system of claim 35, further comprising a flash tank in fluid communication with the processing contactor, the flash tank being operable to receive effluent from the lower part of the processing contactor and to sufficiently heat the effluent to flash the effluent, or a portion thereof, to produce a flashed effluent portion, thereby causing the disulfide oil to be separated and collected at the sleeve of the flash tank.

37. The system of claim 36, further comprising a first heat exchanger in fluid communication with the flash tank and the processing contactor, wherein the first heat exchanger is operable to receive a portion of the flashed effluent from the flash tank and remove heat from the portion of the flashed effluent to condense the portion of the flashed effluent to form a condensed effluent.

38. The system of claim 37, wherein the processing contactor is further operable to receive the condensate effluent from the heat exchanger.

39. The system of claim 38, further comprising a second heat exchanger for sufficiently heating the effluent to flash the effluent or a portion thereof in the flash tank.

40. The system of claim 35, wherein the processing contactor comprises a fixed bed or fluidized bed absorber, the fixed bed or fluidized bed absorber comprising the porous solid media composition.

41. The system of claim 35, wherein the processing contactor comprises a packed bed containing the porous solid media composition.

42. The system of claim 35, wherein the processing contactor comprises a fluidized bed, the fluidized bed comprising the porous solid media composition.

43. The system of claim 39, comprising a plurality of processing contactors, thereby allowing continuous processing of the hydrocarbon fluid flow.

44. The system of claim 35, wherein the combined stable basic iron(III) acetate complex comprises [Fe 3+ 3(μ3-O)(OAc - )6] Triangular complexes, wherein the triangular complexes remain intact and retain their chemical structure and associated chemical activity during the reaction with thiols and are not deactivated by other sulfur or oxygen compounds.

45. The system of claim 35, wherein the porous solid medium comprises one or more internal pore surfaces, and wherein the combined stable basic iron(III) acetate complex is bonded to the one or more internal pore surfaces.

46. ​​The system of claim 35, wherein the porous solid medium comprises one or more porous granular activated carbon (GAC) particles.

47. The system of claim 35, wherein the porous solid medium is acid-washed lignite-based activated carbon.

48. The system of claim 35, wherein the porous solid medium comprises particles having a particle size of 0.50 mm to 2.50 mm.

49. The system of claim 35, wherein the porous solid medium comprises having a density of 250 μm 2 / g to 1000m 2 / g of surface area of ​​particles.

50. The system of claim 35, wherein the porous solid medium comprises particles having a total pore volume of 0.75 to 1.15 ml / g.

51. The system of claim 44, wherein the processing contactor further comprises a distribution / diffusion mechanism to allow the hydrocarbon fluid flow to flow into the pores and channels of the porous solid medium, thereby allowing the thiol sulfur compound to react with the [Fe] 3 + 3(μ3-O)] triangular non-surface bonded Fe 3+ Site interactions, wherein R-SH is initially retained on the Fe sites on the pore surface within the porous solid medium.

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