Promoters for dispersing active phase metals in hydrotreating catalysts and methods for preparing the catalysts

Abstract

Disclosed is a composition comprising one or more catalytically active components and a promoter component comprising a mixture of one or more oxidized disulfide oil (ODSO) compounds, the ODSO compound comprising a water-soluble fraction. Also disclosed is a composition comprising an aqueous solution of one or more catalytically active components and a promoter component. In certain embodiments, the ODSO is obtained from the effluent of an enhanced MEROX process. The composition facilitates migration of the catalytically active components (or components that will be catalytically active in the finished solid catalyst material) onto the surface of the support material.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to active phase accelerator compositions and synthetic methods using the active phase accelerator compositions. [Background technology]

[0002] Solid catalysts are used in many applications in chemical and petrochemical processes. Catalyst selection and lifetime are often the dominant factors in determining appropriate reactor and operating conditions. Key variables of the catalyst itself include activity level, selectivity to desired reaction effluents, and structural stability.

[0003] Certain catalytic applications require specific active components. These active components can be added to a solid support material, for example, in elemental form or as oxides, carbides, or sulfides. Hydrotreating catalysts contain one or more active components of a metal or metal compound selected from IUPAC Groups 6-10 of the Periodic Table of the Elements (e.g., Co, Ni, Mo, and combinations thereof) on a support. Hydrocracking catalysts contain one or more active components of a metal or metal compound selected from IUPAC Groups 6-10 of the Periodic Table of the Elements (e.g., Co, Ni, W, Mo, and combinations thereof) on a support. Catalytic reforming catalysts generally contain one or more active components of a metal or metal compound selected from IUPAC Groups 8-10 of the Periodic Table of the Elements (e.g., Pt or Pd). Hydrogenation catalysts generally contain one or more active components of a metal or metal compound selected from IUPAC Groups 7-10 of the Periodic Table of the Elements (e.g., Pt or Pd). The oxidation catalyst generally contains one or more active components of a metal or metal compound selected from IUPAC Groups 4 to 10 of the Periodic Table of the Elements (eg, Mn, Co, Fe, Cr, and Mo).

[0004] Across many different types and purposes of catalysts, support materials can vary and are often made of two or more materials. Known support materials include amorphous or crystalline alumina, silica, silica-alumina, titania, and zeolites. The active component is incorporated onto the surface of the particle and / or within the pores of the particle. These are also known as impregnated catalysts, in which a preformed support is treated after shaping by various means to add the active metal component.

[0005] Within a typical refinery, there are by-product streams that must be treated or otherwise disposed of. The mercaptan oxidation process, commonly referred to as the MEROX process, has long been utilized to remove generally foul-smelling mercaptans found in many hydrocarbon streams and was introduced to the refining industry over 50 years ago. Due to regulatory requirements to reduce the sulfur content of fuels for environmental reasons, refineries have been and continue to be faced with the disposal of large amounts of sulfur-containing by-products. Disulfide oil (DSO) compounds are produced as a by-product of the MEROX process, which removes mercaptans from any of a variety of petroleum streams, including liquefied petroleum gas, naphtha, and other hydrocarbon fractions. The MEROX process is commonly referred to as a "sweetening process" because it removes rancid or rancid-smelling mercaptans present in crude oil. The term "DSO" is used for convenience in this specification and claims and is understood to include the mixture of disulfide oils produced as a by-product of the mercaptan oxidation process. Examples of DSO include dimethyl disulfide, diethyl disulfide, and methyl ethyl disulfide.

[0006] The by-product DSO compounds produced by the MEROX unit can be processed and / or disposed of during the operation of various other refinery units. For example, DSO can be added to a fuel oil pool, which increases the sulfur content of the resulting fuel oil pool. DSO can be processed in a hydrotreater / hydrocracker unit, but this comes at the expense of increased hydrogen consumption. DSO also has an unpleasant putrid or rancid odor, although its relatively low vapor pressure at room temperature somewhat counteracts this odor. However, handling this oil presents a challenge.

[0007] Commonly owned U.S. Patent No. 10,807,947, incorporated herein by reference in its entirety, discloses the controlled catalytic oxidation of DSO, a by-product of the MEROX process. The resulting oxidized material is called oxidized disulfide oil (ODSO). As disclosed in U.S. Patent No. 10,807,947, the by-product DSO compound from the mercaptan oxidation process can be oxidized in the presence of a catalyst. The oxidation reaction product is a rich source of ODSO compounds, sulfoxides, sulfonates, sulfinates, and sulfones.

[0008] The co-produced ODSO stream contains ODSO compounds disclosed in U.S. Patent Nos. 10,781,168 and 11,111,212 as compositions (e.g., solvents (generally)), U.S. Patent No. 10,793,782 as aromatic extraction solvents, and U.S. Patent No. 10,927,318 as lubricity additives, all of which are incorporated herein by reference in their entireties. If a refiner produces or has on hand quantities of DSO compounds in excess of their foreseeable needs for these or other uses, the refiner may wish to dispose of the DSO compounds to clear storage vessels and / or remove product from inventory for tax reasons. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] U.S. Patent No. 10,807,947 [Patent Document 2] U.S. Patent No. 10,781,168 [Patent Document 3] U.S. Patent No. 11,111,212 [Patent Document 4] U.S. Patent No. 10,793,782 [Patent Document 5] U.S. Patent No. 10,927,318 Summary of the Invention [Problem to be solved by the invention]

[0010] Therefore, there is a clear and long-standing need to provide an efficient and economical process for treating large quantities of DSO by-products and their derivatives, to realize and modify their properties to facilitate and simplify their environmentally acceptable disposal, and to utilize the modified products in an economical and environmentally friendly manner, thereby increasing the value of this type of by-product to refiners.

[0011] With the above background information in mind, the present disclosure is directed to providing a technical solution of an effective composition for promoting the dispersion of active ingredients during the manufacture of catalytic materials. [Means for solving the problem]

[0012] In certain embodiments, a composition is provided that includes a promoter component. The composition is used to promote active phase dispersion of catalytically active components on a porous support material having an exterior surface and interior pore surfaces. The composition may include one or more oxide disulfide oil (ODSO) compounds that are used to promote active phase dispersion of one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0013] In certain embodiments, a composition is provided comprising an aqueous solution of catalytically active components dispersed on a porous support material having an exterior surface and interior pore surfaces. The solution may include one or more catalytically active components and a promoter component comprising one or more oxide disulfide oil (ODSO) compounds used to promote active phase dispersion of the one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0014] In certain embodiments, the catalytically active component is selected from the periodic table IUPAC groups 4 to 14. In certain embodiments, the catalytically active component is one or more of Co, Ni, Mo, W, Pt, and Pd.

[0015] In certain embodiments, the accelerator component comprises an ODSO compound and water in a ratio (V%) of ODSO:HO ranging from 100:0 to 0.1:99.9. In certain embodiments, the accelerator component comprises ODSO and one or more other accelerator compounds. In certain embodiments, the other accelerator compounds comprise one or more of citric acid, ethylenediaminetetraacetic acid (EDTA), malic acid, oxalic acid, or formic acid. In certain embodiments, the one or more additional acidic accelerator components have a pKa in the range of about 1-10 or 1-6.

[0016] In certain embodiments, a method for producing a catalytic material is disclosed. The method includes providing a porous support material having an exterior surface and interior pore surfaces. The support material is contacted with an effective amount of a composition to produce a reinforced support material. The composition includes a promoter component comprising one or more oxide disulfide oil (ODSO) compounds. The reinforced support material is contacted with an aqueous solution of catalytically active components to promote active phase dispersion of the catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0017] In certain embodiments, a method for producing a catalytic material is disclosed. The method includes providing a porous support material having an exterior surface and an interior pore surface, and contacting the support material with an effective amount of a composition to promote active phase dispersion of catalytically active components on the exterior surface and the interior pore surface of the support material. The composition includes an aqueous solution of catalytically active components for dispersion on the porous support material having an exterior surface and an interior pore surface. The solution includes one or more catalytically active components and a promoter component including one or more oxide disulfide oil (ODSO) compounds used to promote active phase dispersion of the one or more catalytically active components on the exterior surface and the interior pore surface of the support material.

[0018] In certain embodiments, the support material is subjected to heating prior to contact with the composition. In certain embodiments, the composition is contacted with the supported solid catalyst particles and / or solid catalyst support particles in one or more steps. In certain embodiments, the supported solid catalyst particles and / or solid catalyst support particles are subjected to one or more heat treatments during one or more steps. In certain embodiments, the mass ratio of the ODSO compound to the support material is in the range of 0.001 to 1, and the mass ratio of the active component to the support material is in the range of 0.001 to 1. In certain embodiments, contacting the reinforced support material with the aqueous solution of the catalytically active component is by immersion, incipient wetness, or evaporative impregnation. In certain embodiments, the support comprises a zeolite component and a binder component. In certain embodiments, the binder comprises one or more amorphous inorganic oxide materials selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

[0019] In certain embodiments, the one or more ODSO compounds are water-soluble ODSO compounds having three or more oxygen atoms, and include one or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR), where X represents an ester and is (R-SO) or (R-SOO), and R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl. In certain embodiments, the one or more ODSO compounds are water-soluble ODSO compounds having three or more oxygen atoms and include a mixture of two or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR), where X represents an ester and is (R-SO) or (R-SOO), and R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl. In certain embodiments, the one or more ODSO compounds are water-soluble ODSO compounds having three or more oxygen atoms, including one or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), (wherein R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl). In certain embodiments, the one or more ODSO compounds are water-soluble ODSO compounds having three or more oxygen atoms and include a mixture of two or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), (wherein R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl).

[0020] In certain embodiments, the mixture of ODSO compounds corresponds to oxidized disulfide oil compounds present in a refinery hydrocarbon discharge stream recovered after catalytic oxidation of mercaptans present in the refinery hydrocarbon discharge stream. In certain embodiments, the one or more ODSO compounds are contained in a reaction product, or a fraction of a reaction product, resulting from the oxidation of the disulfide oil compounds in the presence of an oxidation catalyst, wherein all or a portion of the oxidation catalyst is contained in the reaction product or a fraction of the reaction product and is all or a portion of one or more catalytically active components in the active component-supported composition, and in certain embodiments, the oxidation catalyst is a metal or metal compound containing one or more transition metals.

[0021] Any combination of the various embodiments and examples disclosed herein may be used. These and other aspects and features will be understood from the following description of certain specific embodiments and the accompanying drawings and claims. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a simplified schematic diagram of a generalized version of the conventional mercaptan oxidation or MEROX process for liquid-liquid extraction of mercaptan-containing hydrocarbon streams. [Figure 2] FIG. 2 is a simplified schematic diagram of a generalized version of the enhanced mercaptan oxidation or E-MEROX process. [Figure 3A] FIG. 3A is an experimental 1H-NMR spectrum of the polar, water-soluble ODSO fraction used as the active ingredient carrier herein. [Figure 3B] FIG. 3B is an experimental 13C-DEPT-135-NMR spectrum of the polar, water-soluble ODSO fraction used as the active ingredient carrier herein. [Figure 4] FIG. 4 shows temperature programmed reduction data for catalysts with and without ODSO to promote active phase dispersion. DETAILED DESCRIPTION OF THE INVENTION

[0023] In some embodiments, a composition comprising a promoter component is disclosed. The composition is used to promote active phase dispersion of catalytically active components on a porous support material having an exterior surface and interior pore surfaces. The composition may also include one or more oxide disulfide oil (ODSO) compounds and is used to promote active phase dispersion of one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0024] In some embodiments, a composition is disclosed that includes an aqueous solution of catalytically active components. The composition is dispersed on a porous support material having an exterior surface and interior pore surfaces. The solution may include one or more catalytically active components and a promoter component. The promoter component may include one or more oxide disulfide oil (ODSO) compounds and is used to promote active phase dispersion of the one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0025] In one particular embodiment, ODS0 is obtained from the effluent of an enhanced MEROX process. The active phase promoter composition facilitates post-synthesis migration of catalytically active components (or components that will become catalytically active in the finished solid catalyst material) to the surface of the support material.

[0026] In certain embodiments, a method for producing a catalytic material is disclosed. The method includes providing a porous support material having an exterior surface and an interior pore surface, and contacting the support material with an effective amount of a composition for promoting active phase dispersion of catalytically active components on the exterior surface and the interior pore surface of the support material. The composition includes an aqueous solution of catalytically active components for dispersion on the porous support material having an exterior surface and an interior pore surface. The solution includes one or more catalytically active components and a promoter component including one or more oxide disulfide oil (ODSO) compounds used to promote active phase dispersion of the one or more catalytically active components on the exterior surface and the interior pore surface of the support material.

[0027] The one or more active ingredients are added after the support material having an exterior surface and interior pore surfaces has formed and become solid using an aqueous impregnation solution containing a promoter component with an effective amount of one or more ODSO compounds. Generally, adding the active ingredient to the support material, referred to herein as post-synthesis active ingredient incorporation, involves contacting the solid support material (e.g., in the form of a powder, particles, granules, and / or extrudates) with the impregnation solution for a suitable period of time, followed by drying. In certain applications, the solid material is activated, for example, by calcination, reduction, or other suitable treatment. In the processes herein, an effective amount of one or more ODSO compounds is included in the impregnation solution used for post-synthesis active ingredient incorporation.

[0028] Post-synthesis active ingredient incorporation, also referred to as active ingredient impregnation, involves known techniques for loading an active ingredient onto a given solid carrier material, typically by solid-state transfer or wet impregnation. Solid-state transfer involves physically mixing the active ingredient and the solid carrier material in solid form. Wet impregnation uses the active ingredient dissolved in a liquid solution, an impregnation solution, to transfer the active ingredient to the solid carrier material.

[0029] The impregnation solution is typically an aqueous solution containing one or more active ingredients and / or precursors of one or more active ingredients. Other conventional components include pH adjusters to control the solubility of the active ingredient and the strength of its adsorption onto the support surface, viscosity adjusters to slow or speed metal ion diffusion during evaporation to achieve the desired metal distribution, chelating agents (including citric acid, formic acid, and EDTA) that react with metal ions in solution to reduce interactions between the metal ions and the surface, and surface modifiers (including phosphoric acid) that react with the oxide support.

[0030] The one or more ODSO compounds in the accelerator component of the impregnation solution can act as a pH adjuster, a viscosity adjuster, a chelating agent, a surface modifier, or a combination thereof.

[0031] The active ingredient can be added to the carrier material using several methods, including, but not limited to, immersion, incipient wetness, and evaporation, or any other suitable method. Although certain techniques are described herein, it should be understood that other techniques may benefit from modifications.

[0032] In a specific embodiment of wet impregnation, the support material is immersed in an impregnation solution having a suitable concentration of active ingredient adjusted to achieve the target loading level. This solution fills the unblocked pores and is adsorbed onto the support surface, and excess solution is removed. For example, the support is placed on a screen and immersed in an excess amount of impregnation solution for a suitable time to completely impregnate the support. The solid material is then drained and dried. Such an operation can be carried out continuously, for example, using a suitable conveyor system that conveys screened buckets of support material through a tank containing the impregnation solution.

[0033] In certain embodiments of wet impregnation, an effective amount of impregnation solution is repeatedly applied to the support material in a technique known as dry impregnation or impregnation to incipient wetness. The support material is typically rotated and / or sprayed with an amount of impregnation solution having a suitable concentration of active ingredient adjusted to achieve a target loading level, equal to or slightly less than the pore volume of the support. The support material is contacted with an appropriate concentration of solution, for example, corresponding to a known total pore volume or slightly less. For example, the support material may be kept in motion by a rotating cylinder or drum while the impregnation solution is sprayed onto the support material.

[0034] In one particular embodiment of wet impregnation, known as evaporation impregnation, the support material is saturated with water or an acidic solution, and the saturated support material is immersed in an impregnation solution having a suitable concentration of the active ingredient adjusted to achieve a target loading level, after which the active ingredient diffuses through the aqueous phase into the pores of the support material.

[0035] In a further embodiment of post-synthesis active component incorporation, a wet support material is used. The wet support material contains water in all or a portion of the pore volume, e.g., in the range of about 1-100, 1-99, 1-90, 50-100, 50-99, or 50-90 V% of the total pore volume. This amount can be controlled by partial drying of the material to vary the degree of wetting. Whether provided by immersion, incipient wetness, or evaporative impregnation, the impregnation solution is completely or partially blocked from the saturated pores, resulting in reduced diffusion of the active component into the pores. Thus, the metal may be located primarily on the exterior surface of the support material, with only limited amounts contained within the pores. This embodiment can be used as a first step in post-synthesis active component incorporation or as a second step in post-synthesis active component incorporation, e.g., after a certain amount of active component (the same or a different active component added to the wet support) is already present within the support material pores, e.g., on a partially loaded support material.

[0036] In certain embodiments, a method for producing a catalytic material is disclosed. The method includes providing a porous support material having an exterior surface and interior pore surfaces. The support material is contacted with an effective amount of a composition to produce a reinforced support material. The composition includes a promoter component comprising one or more oxide disulfide oil (ODSO) compounds. The reinforced support material is contacted with an aqueous solution of catalytically active components to promote active phase dispersion of the catalytically active components on the exterior surface and interior pore surfaces of the support material.

[0037] In these embodiments, the process for producing the catalytic material is similar to the impregnation process described above. However, in these embodiments, the support material is formed and first solidified, and then the support material is contacted with an effective amount of a composition including a promoter component to produce a reinforced support material. In these embodiments, the reinforced support material can then undergo any of the impregnation techniques described above to add the active component to the reinforced support material.

[0038] In certain embodiments in which a reinforced support material is produced, contacting one or more ODSO compounds with the support material can be by one or more of soaking, incipient wetness, or evaporative impregnation. The reinforced support material can then undergo an additional soaking, incipient wetness, or evaporative impregnation process to add an active ingredient.

[0039] The support material to which the active component is added according to embodiments herein may comprise a catalytically active material or may be an inert material that functions as a binder and / or structural support. With respect to catalytically active materials, this activity may be due to the acidity of the solid material, which imparts catalytic functionality, including the ability to enhance hydrocarbon cracking reactions. Suitable solid acid catalysts are Lewis acids, Bronsted acids, or mixtures thereof. Suitable materials, which may encompass both catalytically active and inert support materials, may be amorphous and / or structured. Support materials include, but are not limited to: Alumina (amorphous or crystalline); Silica (amorphous (including mesoporous such as SBA-15) or crystalline); amorphous silica-alumina; Titania; Amorphous titanium dioxide Titania-silica; Zeolites (including, but not limited to, types of zeolites): faujasite (FAU) including zeolite X, zeolite Y, HY zeolite, USY zeolite; MFI framework zeolites including beta zeolite (BEA), mordenite (MOR), ZSM-5; MTW framework zeolites including ZSM-12; TON framework zeolites including ZSM-22; MEL framework zeolites including ZSM-11; MWW framework zeolites including MCM-22 or MCM-56; CON framework zeolites including SSZ-26 or SSZ-33; or another effective zeolite form; USY zeolite; ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ER I, ESV, ETL, ETR, ETV, EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFT, - IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JN T, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, M EL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, N PO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS, PSI, PTO, PTT, PTY, PUN, PWN,PWO, PWW, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SO D, SOF, SOR, SOS, SOV, SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, one or more synthesized zeolites including VNI, VSV, WEI, -WEN, YFI, YUG, ZON, *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS, *SFV, *-SSO, *STO, *-SVY, or *UOE, or a co-crystal product of two or more of the above-identified zeolites, or a zeolite comprising a crystalline silica material with an SAR approaching infinity, such as silicalites (e.g., silicalite-1); it is noted that the three-letter codes designated herein correspond to framework types established by the International Zeolite Association; Silicon-substituted aluminophosphates, silicoaluminophosphates (SAPO) (including but not limited to, including SAPO-18 (AEI), including SAPO-11 (AEL), including SAPO-5 (AFI), including SAPO-41 (AFO), including SAPO-40 (AFR), including SAPO-56 (AFX), including SAPO-39 (ATN), including SAPO-31 (ATO), including SAPO-34 and -47 (CHA), including SAPO-37 (FAU), including SAPO-43 (GIS), including SAPO-35 (LEV), and including SAPO-42 (LTA)); Crystalline microporous aluminophosphates (AlPOs) (including, but not limited to, AlPO-18 (AEI), AlPO-11 (AEL), AlPO-53 (AEN), AlPO-8 (AET), AlPO-5 (AFI), AlPO-14 (AFN), AlPO-41 (AFO), AlPO-40 (AFR), AlPO-52 (AFT), AlPO-24 (ANA), containing AlPO-16 (AST), containing AlPO-31 (ATO), containing AlPO-36 (ATS), containing AlPO-33 (ATT), containing AlPO-25 (ATV), containing AlPO-21 (AWO), containing AlPO-22 (AWW), containing AlPO-34 (CHA), containing AlPO-17 (ERI), containing AlPO-35 (LEV), containing AlPO-20 (SOD), containing AlPO-54 (VFI); and Metal aluminophosphates (MAPO) (including, but not limited to, MAPO-5 (AFI), MAPO-46 (AFS), MAPO-39 (ATN), MAPO-31 (ATO), MAPO-36 (ATS), and MAPO-43 (GIS)).

[0040] In certain embodiments, the support comprises a zeolite component and a binder component. The binder may comprise one or more amorphous inorganic oxide materials selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phospho-alumina, silica-alumina-boria, phospho-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

[0041] The support material can be subjected to treatments to alter support properties such as pore volume, surface area, and average pore size, for example, by mesostructuring treatments including one or more of desilication, steam treatment, acid leaching, and template recrystallization. Typically, these treatments are applied prior to active ingredient impregnation.

[0042] In embodiments in which zeolites or other crystalline materials are used, they are conventionally formed with one or more binder components such as alumina, silica, silica-alumina, clay, titania, and mixtures thereof.

[0043] In certain embodiments, particles formed from the supported support material have a pore volume (cc / gm) in the range of about 0.15-1.70, 0.15-1.50, 0.30-1.50, or 0.30-1.70, a specific surface area (m) in the range of about 100-900, 100-500, 100-450, 180-900, 180-500, 180-450, 200-900, 200-500, or 200-450. 2 / g), and an average pore size of at least about 10, 20, 30, 45, 50, 500, 1000, in certain embodiments in the range of about 10-20, 10-80, 30-80, 45-80, 50-80, 10-100, 30-100, 45-100, 50-100, 10-200, 30-200, 45-200, 50-200, 20-500, 50-500, 100-500, or 100-1000 Angstrom units.

[0044] In certain embodiments, the support material to be calcined is subjected to heating prior to contact with the composition. In certain embodiments, the support material is heated to a temperature of up to 150°C. In certain embodiments, the support material is heated to a temperature in the range of 100-150°C, 100-125°C, 120-150°C, 120-125°C, or 140-150°C. In certain embodiments, the composition is contacted with the supported solid catalyst particles and / or solid catalyst support particles in one or more steps. In certain embodiments, the supported solid catalyst particles and / or solid catalyst support particles are subjected to one or more heat treatments during one or more steps.

[0045] In the processes disclosed herein, an effective amount of a promoter component is used to facilitate incorporation of the active component into the catalyst material. In certain embodiments, the promoter component is used as a component during post-synthesis active component incorporation.

[0046] In certain embodiments, compositions comprising aqueous solutions include pure or diluted ODSO active phase promoter components mixed with one or more additional metal sources. The additional metal sources may be sources of one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, or Mg. The additional metal sources may be combined with the pure or diluted ODSO active phase promoter components to form the compositions herein.

[0047] The active ingredients are incorporated at effective concentrations. In certain embodiments, the active ingredients are added to the ODSO or mixtures containing ODSO components based on their solubility. In certain embodiments, the effective concentration of the active ingredient in the active phase accelerator composition is in the range of about 0.01 to 5, 0.05 to 5, 0.1 to 5, 0.01 to 3, 0.05 to 3, 0.1 to 3, 0.01 to 2, 0.05 to 2, or 0.1 to 2 weight percent of the active phase accelerator composition.

[0048] In certain embodiments, a promoter composition is provided that is undiluted from the controlled catalytic oxidation of DSO and comprises about 50-100, 75-100, 90-100 weight percent of one or more ODSO compounds or ODSO mixtures, with an active ingredient loading in the range of about 0.01-5, 0.05-5, 0.1-5, 0.01-3, 0.05-3, 0.1-3, 0.01-2, 0.05-2, or 0.1-2 weight percent (referred to herein for convenience as a "pure" ODSO active phase promoter composition).

[0049] In certain embodiments, the accelerator component comprises a pure ODSO active phase accelerator composition diluted with water, for example, where the pure ODSO active phase accelerator composition (containing the active ingredient) comprises a 0.1-99.9, 1-99.9, 5-99.9, 10-99.9, 25-99.9, 50-99.9, 0.1-90, 1-90, 5-90, 10-90, 25-90, 50-90, 0.1-75, 1-75, 5-75, 10-75, 25-75, or 50-75 weight percent solution.

[0050] In certain embodiments, the promoter component comprises pure or diluted ODSO mixed with one or more additional acidic promoter components, such as hydrochloric acid, sulfuric acid, nitric acid, aqua regia (a mixture of nitric and hydrochloric acids, optimally in a 1:3 molar ratio of nitric acid to hydrochloric acid), oxalic acid, citric acid, acetic acid, EDTA, malic acid, formic acid, or a combination comprising one or more of the foregoing acids. The additional acids can be provided in pure (100 weight percent acid) form or in an aqueous diluted form, for example, a 0.1 to 99.9 weight percent solution, and the pure or diluted acid is combined with the diluted ODSO to form the promoter component herein. In certain embodiments, the one or more additional acidic promoter components have a pKa in the range of about 1 to 10 or 1 to 6.

[0051] One or more catalytically active components are included in a mixture with one or more ODSO compounds for use as an active component support. The one or more active components can vary depending on the intended use of the catalyst being produced. The active components may be metallic or non-metallic, either in elemental form or as compounds such as oxides, carbides, and sulfides. For example, one or more active components for a hydrotreating catalyst may include one or more metals or metal compounds selected from IUPAC Groups 4-12 of the Periodic Table of the Elements. In certain embodiments, one or more active components selected for producing a hydrotreating catalyst may include one or more metals or metal compounds selected from IUPAC Groups 6-10 of the Periodic Table of the Elements (e.g., Co, Ni, Mo, and combinations thereof). In certain embodiments, one or more active components selected for producing a hydrocracking catalyst may include one or more metals or metal compounds selected from IUPAC Groups 6-10 of the Periodic Table of the Elements (e.g., Co, Ni, W, Mo, and combinations thereof). In certain embodiments, the one or more active components are selected for producing catalytic reforming catalysts and may include one or more metals or metal compounds selected from IUPAC Groups 8-10 of the Periodic Table of the Elements (e.g., Pt or Pd). In certain embodiments, the one or more active components are selected for producing hydrogenation catalysts and may include one or more metals or metal compounds selected from IUPAC Groups 7-10 of the Periodic Table of the Elements (e.g., Pt or Pd) and / or one or more non-metallic compounds such as P. In certain embodiments, the one or more active components are selected for producing oxidation catalysts and may include one or more metals or metal compounds selected from IUPAC Groups 4-10 of the Periodic Table of the Elements (e.g., Ti, V, Mn, Co, Fe, Cr, and Mo) or IUPAC Groups 4-12 of the Periodic Table of the Elements (e.g., Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W, Mo).

[0052] In certain embodiments, the active ingredient in the promoter component is carried over from a prior catalytic oxidation of MEROX process by-product DSO, with the concentration depending accordingly on the amount used therein. In certain embodiments, the catalytic oxidation of MEROX process by-product DSO may occur with an increased amount of oxidation catalyst compared to the oxidation catalyst normally used, with the excess being transferred with the ODSO fraction and used as the promoter component herein (with or without additional active ingredient).

[0053] In certain embodiments, the promoter component, containing one or more ODSO compounds and one or more catalytically active components, is derived from a disulfide oil refinery sulfur-containing waste stream. The promoter component is derived from a reaction product, or a fraction of the reaction product, resulting from the oxidation of the disulfide oil compounds in the presence of an oxidation catalyst. All or a portion of the oxidation catalyst is contained in the reaction product or a fraction of the reaction product. The retained oxidation catalyst is then beneficially reused as all or a portion of one or more catalytically active components in the active phase promoter composition, and the active phase promoter composition is transferred to the formed catalyst material. For example, controlled catalytic oxidation of the MEROX process by-product DSO can be carried out as described above and in commonly owned U.S. Pat. No. 10,807,947, the entire contents of which are incorporated herein by reference. The resulting oxidation effluent contains ODSO. As disclosed in U.S. Pat. No. 10,807,947, by-product DSO compounds from a mercaptan oxidation process can be oxidized, typically in the presence of a catalyst. The oxidizing agent may be a liquid peroxide selected from the group consisting of alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters, and hydrogen peroxide. The oxidizing agent may also be a gas, including air, oxygen, ozone, and oxides of nitrogen. In embodiments herein, a catalyst is used in the oxidation process. The oxidation catalyst may contain an active metal from IUPAC Groups 4-12 of the Periodic Table. In certain embodiments, the oxidation catalyst is a metal or metal compound containing one or more transition metals. In certain embodiments, the oxidation catalyst is a metal or metal compound containing one or more metals selected from the group consisting of Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W, Mo, and combinations thereof. In certain embodiments, the oxidation catalyst is a compound containing one or more metals or metal compounds selected from the group consisting of Mo(VI), W(VI), V(V), Ti(IV), and combinations thereof.In certain embodiments, suitable homogeneous catalysts include molybdenum acetylacetonate, bis(acetylacetonato)dioxomolybdenum, molybdenum naphthenate, molybdenum hexacarbonyl, tungsten hexacarbonyl, sodium tungstate, and vanadium pentoxide. In certain embodiments, a suitable catalyst is sodium tungstate, Na2WO4·2H2O.

[0054] In certain embodiments, the weight ratio of ODSO compound to carrier material may be in the range of 0.001 to 1, 0.01 to 1, 0.1 to 1, 0.001 to 0.5, 0.01 to 0.5, or 0.1 to 0.5. In certain embodiments, the weight ratio of active ingredient to carrier material may be in the range of 0.001 to 1, 0.01 to 1, 0.1 to 1, 0.001 to 0.5, 0.01 to 0.5, or 0.1 to 0.5.

[0055] The accelerator component comprises one or more ODSO compounds. The active ingredient accelerator may also be a mixture comprising two or more ODSO compounds. In the description herein, the terms "oxidized disulfide oil," "ODSO," "ODSO mixture," and "ODSO compound" may be used interchangeably for convenience. As used herein, the abbreviations for oxidized disulfide oil ("ODSO") and disulfide oil ("DSO") are understood to refer to the singular and plural forms, and may also be expressed as "DSO compound" and "ODSO compound," and each form may be used interchangeably. In certain cases, a singular ODSO compound may also be referenced.

[0056] In certain embodiments, the promoter component is obtained from the controlled catalytic oxidation of disulfide oil from a mercaptan oxidation process. The effluent from the controlled catalytic oxidation of disulfide oil from a mercaptan oxidation process contains ODSO compounds and, in certain embodiments, DSO compounds that were unconverted in the oxidation process. In certain embodiments, the effluent contains water-soluble and water-insoluble compounds. The effluent contains at least one ODSO compound, or a mixture of two or more ODSO compounds, selected from the group consisting of compounds having the general formulas (R-SO-S-R'), (R-SOO-S-R'), (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), (X-SO-OR), and (X-SOO-OR). In certain embodiments, in the above formula, R and R' can be the same or different C1-C10 alkyl or C6-C10 aryl. Further, X represents an ester, (R-SO) or (R-SOO), where R is as defined above. Because the source of DSO is a refinery feedstream, it is understood that the R and X substituents, e.g., methyl and ethyl subgroups, can vary and the number of sulfur atoms, S, in the as-received feedstream for oxidation can be expanded to three, e.g., trisulfide compounds.

[0057] In certain embodiments, the water-soluble and water-insoluble compounds are separated from one another, and the promoter component comprises all or a portion of the water-soluble compounds separated from the total effluent from the oxidation of disulfide oil from a mercaptan oxidation process. For example, the different phases can be separated by decantation or partitioning using a separatory funnel, a separatory drum, decantation, or any other known device or process for separating two immiscible phases from one another. In certain embodiments, the water-soluble and water-insoluble components can be separated by distillation due to their different boiling ranges. It is understood that crossover of water-soluble and water-insoluble components will exist in each fraction due to the solubility of the components, typically in the ppmw range (e.g., about 1-10,000, 1-1,000, 1-500, or 1-200 ppmw). In certain embodiments, impurities can be removed from each phase, for example, by stripping or adsorption.

[0058] In certain embodiments, the accelerator component comprises, consists of, or consists essentially of at least one water soluble ODSO compound having three or more oxygen atoms selected from the group consisting of compounds having the general formula (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR). In certain embodiments, the accelerator component comprises, consists of, or consists essentially of a mixture or two or more water soluble ODSO compounds having three or more oxygen atoms selected from the group consisting of compounds having the general formula (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR). In certain embodiments, the accelerator component comprises, consists of, or consists essentially of an ODSO compound selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), and mixtures thereof. In certain embodiments, in the above formula, R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl. Furthermore, X represents an ester and is (R-SO) or (R-SOO), where R is as defined above. In certain embodiments, R and R' are methyl and / or ethyl groups. In certain embodiments, the ODSO compound used as the accelerator component has 1 to 20 carbon atoms.

[0059] In certain embodiments, the accelerator component comprises, consists of, or consists essentially of an ODSO compound having an average density greater than about 1.0 g / cc. In certain embodiments, the accelerator component comprises, consists of, or consists essentially of an ODSO compound having an average boiling point greater than about 80° C. In certain embodiments, the accelerator component comprises, consists of, or consists essentially of an ODSO compound having a dielectric constant of 100 or less at 0° C.

[0060] Table 1 includes examples of polar, water-soluble ODSO compounds containing three or more oxygen atoms. In certain embodiments, the identified ODSO compounds are obtained from the water-soluble fraction of the effluent from the oxidation of DSO obtained from MEROX by-products. ODSO compounds containing three or more oxygen atoms have some tolerable tolerance for carryover components from the effluent stream, for example, and are water-soluble over substantially all concentrations, with the water-insoluble fraction having two oxygen atoms being less than about 1, 3, or 5 weight percent.

[0061] In certain embodiments, the ODSO compound used as the active phase accelerator comprises all or a portion of the water-soluble ODSO compound contained in the oxidation effluent stream obtained from the controlled catalytic oxidation of MEROX process by-products, which is a DSO compound, as disclosed in U.S. Pat. Nos. 10,807,947 and 10,781,168, and incorporated herein by reference above.

[0062] In some embodiments, the ODSO compound used as the active phase promoter is derived from oxidized DSO compounds present in a refinery effluent hydrocarbon stream that are recovered after catalytic oxidation of mercaptans present in the hydrocarbon stream. In some embodiments, the DSO compounds are oxidized in the presence of a catalyst.

[0063] As mentioned above, the name "MEROX" arose from the function of the process itself: the conversion of mercaptans by oxidation. In all its applications, the MEROX process is based on the ability of organometallic catalysts in a basic environment, such as caustic, to promote the oxidation of mercaptans to disulfides at about room temperature and atmospheric pressure. The overall reaction can be represented as follows: RSH + 1 / 4 O2→ 1 / 2 RSSR + 1 / 2 H2O (1) where R is a hydrocarbon chain that may be linear, branched, or cyclic, and the chain may be saturated or unsaturated. Since mixtures of mercaptans are present in most petroleum fractions, R can have 1, 2, 3, and up to 10 or more carbon atoms in the chain. This variable chain length is designated R and R' in the reaction. The reaction is then described below: 2 R'SH + 2 RSH+ O2→2 R'SSR+ 2 H2O (2)

[0064] This reaction occurs spontaneously whenever any rancid mercaptan-containing distillate is exposed to atmospheric oxygen, but it proceeds at a very slow rate. In addition, the catalytic reaction (1) above requires the presence of an alkaline caustic solution, such as aqueous sodium hydroxide. Mercaptan oxidation proceeds at economically practical rates at moderate downstream refinery temperatures.

[0065] The MEROX process can be carried out on both liquid and combined gas-liquid streams. In the case of liquid streams, mercaptans are converted directly to disulfides, which remain in the product, without reducing the total sulfur content of the effluent stream. The MEROX process typically utilizes a fixed-bed reactor system for liquid streams, typically with feedstocks having end points above 135°C to 150°C. Mercaptans are converted to disulfides in the fixed-bed reactor system over a catalyst, such as activated carbon impregnated with MEROX reagent and wetted with caustic solution. Air is injected into the hydrocarbon feed stream prior to the reactor, and as it passes through the catalyst-impregnated bed, the mercaptans in the feed are oxidized to disulfides. The disulfides are substantially insoluble in the caustic and remain in the hydrocarbon phase. Post-processing is required to remove undesirable by-products resulting from known side reactions, such as neutralization of HS, oxidation of phenolic compounds, and trapped caustic.

[0066] The vapor pressure of disulfides is relatively low compared to that of mercaptans, so their presence is not as problematic from an odor standpoint, but they are environmentally unacceptable because they contain sulfur, and their disposal can be problematic.

[0067] In the case of mixed gas and liquid streams, extraction is applied to both phases of the hydrocarbon stream. The degree of completeness of mercaptan extraction depends on the solubility of the mercaptans in the alkaline solution, which in turn depends on the molecular weight of the individual mercaptans, the degree of branching of the mercaptan molecules, the concentration of caustic soda, and the temperature of the system. The resulting DSO compounds are then separated and regenerated for reuse by oxidizing the caustic solution with air in the presence of a catalyst.

[0068] Referring to the accompanying drawings, Figure 1 is a simplified schematic diagram of a generalized version of a conventional MEROX process utilizing liquid-liquid extraction to remove sulfur compounds. A MEROX unit 1010 is provided for processing a mercaptan-containing hydrocarbon stream 1001. In some embodiments, the mercaptan-containing hydrocarbon stream 1001 is LPG, propane, butane, light naphtha, kerosene, jet fuel, or mixtures thereof. The process generally includes the following steps: introducing a hydrocarbon stream 1001 into an extraction vessel 1005 containing a caustic solution 1002 along with a homogeneous catalyst, which in some embodiments is a homogeneous cobalt-based catalyst; passing the hydrocarbon catalyst stream in a countercurrent manner through an extraction section of the extraction vessel 1005, which extraction section includes one or more liquid-liquid contact extraction decks or trays (not shown) for catalytic reaction with the circulating caustic solution to convert the mercaptans to water-soluble alkali metal alkanethiolate compounds; extracting from the extraction vessel 1005 a mercaptan-free or substantially free, e.g., about 1000, 100, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10 ... withdrawing a hydrocarbon product stream 1003 having 10 or 1 ppmw or less of mercaptans; recovering a combined spent caustic and alkali metal alkanethiolate stream 1004 from extraction vessel 1005; subjecting the spent caustic and alkali metal alkanethiolate stream 1004 to catalytic wet air oxidation in reactor 1020, into which catalyst 1005 and air 1006 are introduced, to provide regenerated spent caustic 1008 and convert the alkali metal alkanethiolate compounds to disulfide oil; and recovering a by-product stream 1007 of DSO compounds and small proportions of other sulfides, such as monosulfides and trisulfides. The effluent of the wet air oxidation step in the MEROX process may contain a minor proportion of sulfides and a major proportion of disulfide oil. As known to those skilled in the art, the composition of this effluent stream depends on the efficiency of the MEROX process, and it is assumed that the sulfides are carryover materials. Various catalysts have been developed for commercial viability of the process. The efficiency of the MEROX process is also a function of the amount of H2S present in the stream. It is common refinery practice to include a pre-wash step to remove H2S.

[0069] The enhanced MEROX process ("E-MEROX") is an improved MEROX process that adds a new step: oxidation of DSO compounds with an oxidizing agent in the presence of a catalyst to produce a mixture of ODSO compounds. In some embodiments, the by-product DSO compounds from the mercaptan oxidation process are oxidized in the presence of a catalyst to produce a rich source of ODSO compounds, which are sulfoxides, sulfonates, sulfinates, sulfones, and their corresponding disulfur mixtures. Disulfide oils having the general formula RSSR' (where R and R' can be the same or different and can have 1, 2, 3, or up to 10 or more carbon atoms) can be oxidized without a catalyst or in the presence of one or more catalysts to produce a mixture of ODSO compounds. The oxidizing agent can be a liquid peroxide selected from the group consisting of alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters, and hydrogen peroxide. The oxidizing agent can also be a gas, including air, oxygen, ozone, and oxides of nitrogen. When the catalyst is used to oxidize disulfide oils having the general formula RSSR' to produce ODSO compounds, the catalyst may be a heterogeneous or homogeneous oxidation catalyst. The oxidation catalyst may be selected from one or more heterogeneous or homogeneous catalysts containing metals from IUPAC Groups 4-12 of the periodic table, including Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W, and Mo. The catalyst may also be a homogeneous, water-soluble compound that is a transition metal containing an active species selected from the group consisting of Mo(VI), W(VI), V(V), Ti(IV), and combinations thereof. In certain embodiments, suitable homogeneous catalysts include molybdenum naphthenate, sodium tungstate, molybdenum hexacarbonyl, tungsten hexacarbonyl, sodium tungstate, and vanadium pentoxide. An exemplary catalyst for the controlled catalytic oxidation of the MEROX process by-product DSO is sodium tungstate, Na2WO4·2H2O.In certain embodiments, suitable heterogeneous catalysts include Ti, V, Mn, Co, Fe, Cr, W, Mo, and combinations thereof deposited on a support such as alumina, silica-alumina, silica, natural zeolites, synthetic zeolites, and combinations comprising one or more of the above supports.

[0070] DSO oxidation is typically carried out in an oxidation vessel selected from one or more of a fixed-bed reactor, a suspension bubble column reactor, a slurry-bed reactor, a moving-bed reactor, a continuous stirred-tank reactor, and a tubular reactor. The ODSO compounds produced in the E-MEROX process generally contain two phases, a water-soluble phase and a water-insoluble phase, and can be separated into an aqueous phase containing the water-soluble ODSO compounds and a non-aqueous phase containing the water-insoluble ODSO compounds. The E-MEROX process can be adjusted depending on the desired ratio of water-soluble compounds to water-insoluble compounds present in the product ODSO mixture. Partial oxidation of the DSO compounds increases the relative amount of water-insoluble ODSO compounds present in the ODSO product, while near or near complete oxidation of the DSO compounds increases the relative amount of water-soluble ODSO present in the ODSO product. Details of ODSO composition are discussed in U.S. Patent No. 10,781,168, incorporated herein by reference.

[0071] FIG. 2 is a simplified schematic diagram of the E-MEROX process, including an E-MEROX unit 1030. The MEROX unit 1010 operates similarly to FIG. 1, with like reference numerals representing like equipment / feeds. In FIG. 2, the effluent stream 1007 from the generalized MEROX unit of FIG. 1 is processed. It will be understood that the process for processing the mercaptan-containing hydrocarbon stream of FIG. 1 is merely exemplary, and that separate streams of products, as well as combined or separate streams of other mixed and longer chain products, can be subjected to a process for recovering and oxidizing DSO to produce ODSO compounds, i.e., the E-MEROX process. To implement the E-MEROX process, an additional unit is added for recovering by-product DSO compounds from the MEROX process. Additionally, a suitable reactor 1035 is added to introduce the DSO compounds in the presence of a catalyst 1032 and an oxidant 1034 and subject the DSO compounds to a catalytic oxidation step to produce a combined stream of water and ODSO compounds 1036. A separation vessel 1040 is provided for separating the by-products 1044 from the ODSO compound 1042 .

[0072] The oxidation to produce OSDO can be carried out in a suitable oxidation reactor operating at a pressure ranging from about 1 to 30, 1 to 10, or 1 to 3 bar. The oxidation to produce OSDO can be carried out at a temperature ranging from about 20 to 300, 20 to 150, 20 to 90, 45 to 300, 15 to 150, or 45 to 90°C. The molar feed ratio of oxidant to sulfur can be in the range of about 1:1 to 100:1, 1:1 to 30:1, or 1:1 to 4:1. The residence time in the reactor can be in the range of about 5 to 180 minutes, about 5 to 90 minutes, about 5 to 30 minutes, about 15 to 180 minutes, about 15 to 90 minutes, or about 5 to 30 minutes. In certain embodiments, the oxidation of DSO is carried out in an environment without the addition of water as a reagent. When hydrogen peroxide is used as the oxidant, the by-product stream 1044 typically comprises wastewater. Alternatively, when other organic peroxides are used as the oxidizing agent, by-product stream 1044 generally contains the alcohol of the peroxide used. For example, when butyl peroxide is used as the oxidizing agent, by-product alcohol 1044 is butanol.

[0073] In certain embodiments, the water-soluble ODSO compounds are sent to a fractionation zone (not shown) for recovery after separation from the wastewater fraction. The fractionation zone may include a distillation apparatus. In certain embodiments, the distillation apparatus is a flash distillation apparatus with no theoretical plates to obtain distillation cuts with high overlap, or in other embodiments, the distillation apparatus may be a flash distillation apparatus with at least 15 theoretical plates to provide effective separation between the cuts. In certain embodiments, the distillation apparatus can operate at atmospheric pressure and temperatures ranging from 100°C to 225°C. In other embodiments, fractionation can be performed continuously under vacuum conditions. In these embodiments, fractionation is performed at reduced pressure and at the respective boiling temperatures. For example, at 350 mbar and 10 mbar, the temperature ranges are 80°C to 194°C and 11°C to 98°C, respectively. After fractionation, the wastewater is sent to a wastewater pool (not shown) for conventional treatment before disposal. The wastewater by-product fraction may contain small amounts of water-insoluble ODSO compounds, for example, in the range of 1 ppmw to 10,000 ppmw. The wastewater by-product fraction may contain small amounts of water-soluble ODSO compounds, for example, in the range of 1 ppmw to 50,000 ppmw, or 100 ppmw to 50,000 ppmw. In embodiments where the alcohol is a by-product alcohol, the alcohol can be recovered and sold as a commodity product or added to a fuel such as gasoline. The alcohol by-product fraction may contain small amounts of water-insoluble ODSO compounds, for example, in the range of 1 ppmw to 10,000 ppmw. The alcohol by-product fraction may contain small amounts of water-soluble ODSO compounds, for example, in the range of 100 ppmw to 50,000 ppmw. [Example]

[0074] The following examples and data are illustrative, and it is understood that other ratios and types of aluminum source, silica source, base, and structure directing agent can be used in comparison to the examples.

[0075] Reference Example The ODSO mixture used in the following examples was produced as disclosed in U.S. Pat. No. 10,781,168, incorporated by reference above, specifically the fraction designated Composition 2 therein. Catalytic oxidation of a refinery hydrocarbon feedstock containing 98 mass percent C1 and C2 disulfide oils was conducted. The oxidation of DSO compounds was carried out in a batch mode under atmospheric pressure, i.e., reflux at approximately 1.01 bar. The hydrogen peroxide oxidant was added at room temperature, i.e., approximately 23°C, resulting in an exothermic reaction. The molar ratio of oxidant to DSO compounds (calculated based on the monosulfur content) was 2.90. After the addition of the oxidant was completed, the temperature of the reaction vessel was set to reflux at 80°C for approximately 1 hour. Water-soluble ODSO was then produced (referred to herein and in U.S. Pat. No. 10,781,168 as Composition 2) and isolated after removing water. The catalyst used in the oxidation of DSO compounds was sodium tungstate. Composition 2, referred to herein as the "selected water-soluble ODSO fraction," was used. FIG. 3A shows experimental results of a polar aqueous ODSO mixture, which is a selected aqueous ODSO fraction in the Examples herein. 1 Figure 3B is an experimental H-NMR spectrum of a polar aqueous ODSO mixture, which is the aqueous ODSO fraction selected in the Examples herein. 13 This is a C-DEPT-135 NMR spectrum. Selected water-soluble ODSO fractions were mixed with CD3OD solvent, and the spectrum was acquired at 25 °C. Methyl carbons have positive intensities, while methylene carbons have negative intensities. The peaks in the 48-50 ppm region are assigned to carbon signals from the CD3OD solvent.

[0076] Figure 3B Experimental results of selected water-soluble ODSO fractions 13When the C-DEPT-135-NMR spectrum was compared to a database of stored predicted spectra, the predicted combination of alkyl-sulfoxide sulfonate (R-SO-SOO-OH), alkyl-sulfone sulfonate (R-SOO-SOO-OH), alkyl-sulfoxide sulfinate (R-SO-SO-OH), and alkyl-sulfone sulfinate (R-SOO-SO-OH) was found to correspond most closely to the experimental spectrum. This suggests that alkyl-sulfoxide sulfonate (R-SO-SOO-OH), alkyl-sulfone sulfonate (R-SOO-SOO-OH), alkyl-sulfoxide sulfinate (R-SO-SO-OH), and alkyl-sulfone sulfinate (R-SOO-SO-OH) are the major compounds in the selected water-soluble ODSO fraction. It is clear from the NMR spectra shown in Figures 3A and 3B that the selected water-soluble ODSO fraction contains a mixture of ODSO compounds that form the ODSO acid of the present disclosure.

[0077] Comparative Example 1 In a comparative example, amorphous silica-alumina and alumina-supported catalysts were impregnated onto Ni-Mo. The metal precursors used in this comparative example were nickel nitrate hydrate and ammonium molybdate tetrahydrate, with target metal-based loadings of 3.9 wt% nickel and 13.3 wt% molybdenum. A metal solution was prepared with 5.8 g of nickel nitrate, 6.3 g of ammonium molybdate tetrahydrate, and 35 g of water. A volatile-free support weighing 22.5 g was placed in a rotary evaporator. The metal solution was then slowly added to the evaporator. After all the metal solution was added, the heating bath was heated to 95°C, and the metal solution was allowed to dry overnight. The dried catalyst was transferred to a muffle furnace and calcined in air using the following temperature program: 10°C / min to 120°C, held for 3 hours; 10°C / min to 535°C, held for 2 hours; and 10°C / min to 30°C.

[0078] Example 1 Amorphous silica-alumina and alumina-supported catalysts were synthesized as described above, including ODSO, the active phase promoter composition described in the reference example. 1.2 g of ODSO was added to the metal solution, which was then introduced into the evaporator.

[0079] Figure 4 shows the temperature programmed reduction data for the catalysts prepared according to Comparative Example 1 and Example 1. The data are presented as hydrogen consumption rate (in arbitrary units per gram of material) versus temperature (in degrees Celsius). During this analysis, each catalyst was dried in argon at 500°C for 30 minutes and then cooled to room temperature. The gas was then switched from argon to H2, and the temperature was increased at 10°C / min to 800°C. H2 consumption was monitored with a thermal conductivity detector (TCD). It is clear from Figure 4 that the catalyst prepared using ODSO has a higher hydrogen uptake capacity.

[0080] The headings used herein are for organizational purposes only and are not intended to be used to limit the scope of the specification or the claims. As used throughout this application, the words "may" and "can" are used in a permissive sense (i.e., having the possibility of) rather than a mandatory sense (i.e., meaning that something must be).

[0081] It should be understood that like numerals in the drawings represent like elements throughout the several views, and that not all components and / or steps described and illustrated with reference to the figures are required for all embodiments or configurations.

[0082] Furthermore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "including," "comprising," "having," "containing," and "involving," and variations thereof, when used herein, specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0083] It should be noted that the use of ordinal numbers such as "first," "second," "third," etc. in the claims to modify claim elements does not, in itself, imply a priority, precedence, or order of one claim element relative to another, or the chronological order in which acts of a method are performed, but is merely used as a label to distinguish one claim element having a certain name from another element having the same name (but using an ordinal number).

[0084] In particular, the above numerical values ​​and examples are not intended to limit the scope of the present disclosure to a single embodiment, because other embodiments are possible by replacing some or all of the elements described or illustrated. Furthermore, when specific elements of the present disclosure can be implemented partially or completely using known components, only those portions of such known components necessary for understanding the present disclosure are described, and detailed descriptions of other portions of such known components are omitted so as not to obscure the present disclosure. In this specification, an embodiment showing a singular component should not necessarily be limited to other embodiments including multiple identical components, unless expressly stated otherwise in this specification, and vice versa. Furthermore, the applicant does not intend any term in this specification or claims to be given a non-generic or special meaning unless expressly defined as such. Furthermore, the present disclosure encompasses currently and future known equivalents to known components referred to herein for illustrative purposes.

[0085] The foregoing description of specific embodiments sufficiently clarifies the general nature of the present disclosure so that others, by applying knowledge within the skill of those in the relevant art, can readily modify and / or adapt such specific embodiments for various applications without undue experimentation and without departing from the general concepts of the present disclosure. Accordingly, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It is to be understood that the terms and phrases herein are for purposes of description and not limitation, as they would be interpreted by one of ordinary skill in the art in light of the teaching and guidance presented herein, in combination with the knowledge of those skilled in the relevant art. It is to be understood that the dimensions discussed or shown are for illustration purposes only, and that other dimensions can be used without departing from the present disclosure.

[0086] The subject matter described above is provided by way of example only and should not be construed as limiting. Various modifications and changes can be made to the subject matter described herein without following the exemplary embodiments and applications shown and described, and without departing from the true spirit and scope of the invention encompassed by this disclosure, as defined by the set of claims below and by structures and functions or steps equivalent to those descriptions.

[0087] [Table 1] [Explanation of symbols]

[0088] 1001 Mercaptan-containing hydrocarbon streams 1002 Caustic solution 1003 Hydrocarbon Product Stream 1004 Combined Spent Caustic and Alkali Metal Alkanethiolate Stream 1005 Extraction vessel, catalyst 1006 Air 1007 By-Product Stream 1007 Emission Stream 1008 Regenerated spent caustic 1010 MEROX equipment 1020 Reactor 1030 E-MEROX equipment 1032 Catalyst 1034 Oxidizing Agent 1035 Suitable reactor 1036 Mixed Stream 1040 Separation container 1042 ODSO compound 1044 By-products, by-product streams, by-product alcohols

Claims

1. 1. A composition comprising a promoter component for use in promoting active phase dispersion of one or more catalytically active components on a porous support material having an exterior surface and interior pore surfaces, the composition comprising one or more oxide disulfide oil (ODSO) compounds for use in promoting active phase dispersion of one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

2. 1. A composition comprising an aqueous solution of catalytically active components for dispersion on a porous support material having an exterior surface and interior pore surfaces, the solution comprising one or more catalytically active components and a promoter component comprising one or more oxide disulfide oil (ODSO) compounds used to promote active phase dispersion of the one or more catalytically active components on the exterior surface and interior pore surfaces of the support material.

3. 3. The composition according to claim 1, wherein the catalytically active component is selected from IUPAC Groups 4 to 14 of the Periodic Table.

4. 3. The composition according to claim 1, wherein the catalytically active component is one or more of Co, Ni, Mo, W, Pt, and Pd.

5. The accelerator component is a mixture of ODSO:H in the range of 100:0 to 0.1:99.

9. 2 5. The composition according to claim 1, comprising an ODSO compound and water in a ratio (V%) of 0.

6. 6. The composition of claim 1, wherein the enhancer component comprises ODSO and one or more other enhancer compounds.

7. 7. The composition of claim 6, wherein the other enhancer compounds include one or more of citric acid, ethylenediaminetetraacetic acid (EDTA), malic acid, oxalic acid, or formic acid.

8. 7. The composition of claim 6, wherein the one or more additional acidic promoter components have a pKa in the range of about 1-10 or 1-6.

9. 1. A method for producing a catalytic material, comprising: providing a porous support material having an exterior surface and interior pore surfaces; contacting the carrier material with an effective amount of the composition of claim 1 or any one of claims 3 to 8 to produce a reinforced carrier material; and contacting the reinforced support material with an aqueous solution of catalytically active components to promote active phase dispersion of the catalytically active components on the exterior and interior pore surfaces of the support material; A method comprising:

10. 1. A method for producing a catalytic material, comprising: providing a porous support material having an exterior surface and interior pore surfaces; contacting the support material with an effective amount of the composition of any one of claims 2 to 8 to promote active phase dispersion of the catalytically active component on the outer surface and inner pore surfaces of the support material. A method comprising:

11. 11. The method of claim 9 or 10, further comprising subjecting the carrier material to heating before contacting it with the composition.

12. 12. The method according to any one of claims 9 to 11, wherein the composition is contacted in one or more steps with supported solid catalyst particles and / or solid catalyst support particles.

13. 13. The method of claim 12, wherein the supported solid catalyst particles and / or the solid catalyst support particles are subjected to one or more heat treatments during one or more steps.

14. 14. The method according to any one of claims 9 to 13, wherein the mass ratio of ODSO compound to the carrier material is in the range of 0.001 to 1 and the mass ratio of active ingredient to the carrier material is in the range of 0.001 to 1.

15. 15. The method of any one of claims 9 to 14, wherein the step of contacting the reinforcing support material with an aqueous solution of catalytically active components is by immersion, incipient wetness, or evaporative impregnation.

16. The supported solid catalyst particles and / or the solid catalyst support particles have a pore volume (cc / gm) in the range of about 0.15 to 1.70, 0.15 to 1.50, 0.30 to 1.50, or 0.30 to 1.70, a specific surface area (m) in the range of about 100 to 900, 100 to 500, 100 to 450, 180 to 900, 180 to 500, 180 to 450, 200 to 900, 200 to 500, or 200 to 450. 2 16. The method of any one of claims 9-15, wherein the pore size is at least about 10, 20, 30, 45, 50, 500, 1000, in certain embodiments in the range of about 10-20, 10-80, 30-80, 45-80, 50-80, 10-100, 30-100, 45-100, 50-100, 10-200, 30-200, 45-200, 50-200, 20-500, 50-500, 100-500, or 100-1000 Angstrom units.

17. 17. The method of any one of claims 9 to 16, wherein the support comprises a zeolite component and a binder component.

18. ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS T, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, A VE、AVL、AWO、AWW、BCT、BEC、BIK、BOF、BOG、BOZ、BPH、BRE、BSV、CAN、CAS、CDO 、CFI、CGF、CGS、CHA、-CHI、-CLO、CON、CSV、CZP、DAC、DDR、DFO、DFT、DOH、DON、 EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, EZT, FA R、FAU、FER、FRA、GIS、GIU、GME、GON、GOO、HEU、IFO、IFR、-IFT、-IFU、IFW、IFY 、IHW、IMF、IRN、IRR、-IRY、ISV、ITE、ITG、ITH、ITR、ITT、-ITV、ITW、IWR、IWS 、IWV、IWW、JBW、JNT、JOZ、JRY、JSN、JSR、JST、JSW、KFI、LAU、LEV、LIO、-LIT、L OS、LOV、LTA、LTF、LTJ、LTL、LTN、MAR、MAZ、MEI、MEL、MEP、MER、MFI、MFS、MON 、MOR、MOZ、MRT、MSE、MSO、MTF、MTN、MTT、MTW、MVY、MWF、MWW、NAB、NAT、NES、NO N、NPO、NPT、NSI、OBW、OFF、OKO、OSI、OSO、OWE、-PAR、PAU、PCR、PHI、PON、POR 、POS、PSI、PTO、PTT、PTY、PUN、PWN、PWO、PWW、RHO、-RON、RRO、RSN、RTE、RTH、R UT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG SFH、SFN、SFO、SFS、SFW、SGT、SIV、SOD、SOF、SOR、SOS、SOV、SSF、SSY、STF、ST I、STT、STW、-SVR、SVV、SWY、-SYT、SZR、TER、THO、TOL、TON、TSC、TUN、UEI、UF I、UOS、UOV、UOZ、USI、UTL、UWY、VET、VFI、VNI、VSV、WEI、-WEN、YFI、YUG、ZON、18. The method of claim 17, wherein the zeolite is one or more zeolites identified by the International Zeolite Association, including those having *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS, *SFV, *-SSO, *STO, *-SVY, or *UOE, or one or more synthesized zeolites including a co-crystal product of two or more zeolites identified above, or a zeolite comprising a crystalline silica material with an SAR approaching infinity, such as silicalites (e.g., silicalite-1).

19. 18. The method of claim 17, wherein the zeolite is a USY zeolite.

20. 20. The method of any one of claims 16 to 19, wherein the binder comprises one or more amorphous inorganic oxide materials selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

21. 21. The method of any one of claims 1 to 20, wherein the ODSO is derived from the oxidation of disulfide oil compounds present in a refinery discharge hydrocarbon stream recovered after catalytic oxidation of mercaptans present in the mercaptan-containing hydrocarbon stream.

22. 22. The method of any one of claims 1 to 21, wherein the one or more ODSO compounds comprises an ODSO compound having three or more oxygen atoms.

23. 23. The method of any one of claims 1 to 22, wherein the one or more ODSO compounds comprises an ODSO compound having from 1 to 20 carbon atoms.

24. 24. The method of any one of claims 1 to 23, wherein the one or more ODSO compounds are in a mixture having an average density greater than about 1.0 g / cc.

25. 25. The method of any one of claims 1 to 24, wherein the one or more ODSO compounds are in a mixture having an average boiling point greater than about 80°C.

26. 26. The method of any one of claims 1 to 25, wherein the ODSO compound has three or more oxygen atoms and comprises one or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR), where R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl, and X represents an ester and is (R-SO) or (R-SOO).

27. 26. The method of any one of claims 1 to 25, wherein the ODSO compound has three or more oxygen atoms and comprises two or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SOO-SO-OH), (X-SO-OR) and (X-SOO-OR), where R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl, and X represents an ester and is (R-SO) or (R-SOO).

28. 26. The method of any one of claims 1 to 25, wherein the ODSO compound has three or more oxygen atoms and comprises one or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), (R-SOO-SO-OH), where R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl.

29. 26. The method of any one of claims 1 to 25, wherein the ODSO compound has three or more oxygen atoms and comprises two or more compounds selected from the group consisting of (R-SOO-SO-R'), (R-SOO-SOO-R'), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), (R-SOO-SO-OH), where R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl.

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