Accelerator for active phase metal dispersion in hydrotreating catalyst and method for preparing said catalyst

Abstract

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

Description

Technical Field

[0001] The present disclosure generally relates to active phase accelerator compositions and synthetic methods using the same. Background Art

[0002] Solid catalysts are used in a variety of applications within chemical and petrochemical processes. Catalyst selection and life are often the controlling factors in determining appropriate reactor and operating conditions. Important variables in the catalyst itself include activity level, selectivity to the desired reaction effluent, and structural stability.

[0003] Some catalytic applications require specific active components. These active components can be, for example, used as a single substance, or added to a solid support material as an oxide, carbide or sulfide. Hydrotreating catalysts include one or more active components (such as Co, Ni, Mo, and combinations thereof) of metals or metal compounds selected from the 6th to 10th families of the periodic table IUPAC on a carrier. Hydrocracking catalysts include one or more active components (such as Co, Ni, W, Mo, and combinations thereof) of metals or metal compounds selected from the 6th to 10th families of the periodic table IUPAC on a carrier. Catalytic reforming catalysts generally contain one or more active components (such as Pt or Pd) of metals or metal compounds selected from the 8th to 10th families of the periodic table IUPAC. Hydrogenation catalysts generally contain one or more active components (such as Pt or Pd) of metals or metal compounds selected from the 7th to 10th families of the periodic table IUPAC. Oxidation catalysts generally contain one or more active components (such as Mn, Co, Fe, Cr and Mo) of metals or metal compounds selected from the 4th to 10th families of the periodic table IUPAC.

[0004] Across many different types and purposes of catalyst, the support material can vary, and is usually formed from two or more materials. Known support materials are amorphous or crystalline alumina, silica, silica alumina, titania or zeolites. The active component(s) are incorporated on the surface of the particles, and / or within the pores of the particles. These are also known as impregnated catalysts, where the preformed support is treated by various means after its formation to add the active metal component.

[0005] In a typical oil refinery, there are byproduct streams that must be treated or disposed of. The mercaptan oxidation process, conventionally referred to as the MEROX process, has long been used to remove malodorous mercaptans generally found in many hydrocarbon streams and was introduced into the oil refining industry more than fifty years ago. Because of regulatory requirements for reducing the sulfur content of fuels due to environmental reasons, oil refineries have been and continue to face the disposal of a large number of sulfur-containing byproducts. Disulfide oil (DSO) compounds are produced as a byproduct of the MEROX process, wherein mercaptans are removed from any of the various petroleum streams including liquefied petroleum gas, naphtha, and other hydrocarbon fractions. It is conventionally referred to as a "sweetening process" because it removes mercaptans of acidic (sour, sulfur-containing) or malodorous odors present in crude oil. For convenience, the term "DSO" used in this specification and in the claims will be understood to include a mixture of disulfide oils produced as a byproduct of the mercaptan oxidation process. Examples of DSO include dimethyl disulfide, diethyl disulfide, and methyl ethyl disulfide.

[0006] The byproduct DSO compound 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 the fuel oil pool at the expense of a higher sulfur content of the pool. DSO can be processed in a hydrotreating / hydrocracking unit at the expense of higher hydrogen consumption. DSO also has an unpleasant malodor or sour smell that is somewhat less common due to its relatively lower vapor pressure at ambient temperature; however, there are problems in the processing of such oils.

[0007] Co-owned U.S. Patent No. 10,807,947 discloses controlled catalytic oxidation of DSO, a byproduct of the MEROX process, which is incorporated herein by reference in its entirety. The resulting oxidized material is referred to as oxidized disulfide oil (ODSO). As disclosed in 10,807,947, the byproduct DSO compound from the mercaptan oxidation process can be oxidized in the presence of a catalyst. The oxidation reaction product constitutes a rich source of ODSO compounds, sulfoxides, sulfonic acids (salts / esters), sulfinic acids (salts / esters), and sulfones.

[0008] The co-produced ODSO stream contains ODSO compounds as disclosed in U.S. Pat. Nos. 10,781,168 and 11,111,212 as compositions (such as solvents, generally), in U.S. Pat. No. 10,793,782 as an aromatic extraction solvent, and in U.S. Pat. No. 10,927,318 as a lubricant additive, all of which are incorporated by reference in their entireties. In the event that a refiner has produced or has on hand an amount of DSO compounds in excess of foreseeable demand for these or other uses, the refiner may wish to dispose of the DSO compounds to purge storage vessels and / or to eliminate the product from inventory for tax reasons.

[0009] Therefore, there exists a need to provide efficient and economical processes for the treatment of large quantities of DSO by-products and their derivatives in order to influence and modify their properties, to facilitate and simplify their environmentally acceptable treatment, and to utilize the modified products in an economical and environmentally friendly manner, and thereby enhance the value of this class of by-products to refiners.

[0010] With regard to the above background information, the present disclosure aims to provide technical solutions to effective compositions for promoting the dispersion of active components during the manufacture of catalyst materials. Summary of the invention

[0011] In certain embodiments, a composition comprising a promoter component is provided. The composition is used to promote the active phase dispersion of catalytically active components on a porous support material having an outer surface and an inner surface of the pores. The composition may include one or more oxidized disulfide oil (ODSO) compounds, which are used to promote the active phase dispersion of one or more catalytically active components on the outer surface and inner surface of the pores of the support material.

[0012] In certain embodiments, a composition comprising an aqueous solution of catalytically active components is provided. The catalytically active components are dispersed on a porous support material having an outer surface and an inner surface of the pores. The solution may comprise one or more catalytically active components and a promoter component comprising one or more oxidized disulfide oil (ODSO) compounds, which is used to promote the active phase dispersion of the one or more catalytically active components on the outer surface of the support material and the inner surface of the pores.

[0013] In certain embodiments, the catalytically active component is selected from IUPAC Groups 4 to 14 of the Periodic Table of Elements. In certain embodiments, the catalytically active component is one or more of Co, Ni, Mo, W, Pt, Pd.

[0014] In certain embodiments, the promoter component comprises an ODSO compound and water in a ratio (V%) of ODSO:HO in the range of from 100:0 to 0.1:99.9. In certain embodiments, the promoter component comprises ODSO and one or more other promoter compounds. In certain embodiments, the other promoter compounds include one or more of citric acid, ethylenediaminotetraacetic acid (EDTA), malic acid, oxalic acid, or formic acid. In certain embodiments, the one or more additional acidic promoter components have a pKa in the range of from about 1-10 or 1-6.

[0015] In certain embodiments, a method for making a catalyst material is disclosed. The method includes providing a porous support material having an outer surface and an inner pore surface. The support material is contacted with an effective amount of a composition to produce an enhanced support material. The composition includes a promoter component including one or more oxidized disulfide oil (ODSO) compounds. The enhanced support material is contacted with an aqueous solution of a catalytically active component to promote the active phase dispersion of the catalytically active component on the outer surface of the support material and the inner pore surface.

[0016] In certain embodiments, a method for making a catalyst material is disclosed. The method includes providing a porous support material having an outer surface and an inner surface of a hole, and contacting the support material with an effective amount of a composition to promote the active phase dispersion of catalytically active components on the outer surface and the inner surface of the hole of the support material. The composition comprises an aqueous solution of catalytically active components dispersed on a porous support material having an outer surface and an inner surface of the hole. The solution comprises one or more catalytically active components and a promoter component comprising one or more oxidized disulfide oil (ODSO) compounds, which is used to promote the active phase dispersion of one or more catalytically active components on the outer surface and the inner surface of the hole of the support material.

[0017] In some embodiments, the support material is subjected to heating before contacting with the composition. In some embodiments, the composition is contacted with the solid catalyst particles and / or solid catalyst support particles of the load in one or more steps. In some embodiments, the solid catalyst particles and / or solid catalyst support particles of the load are subjected to one or more heat treatments between one or more steps. In some embodiments, the mass ratio of ODSO compound to support material is in the range of 0.001-1, and the mass ratio of active component to support material is in the range of 0.001-1. In some embodiments, the contact of the enhanced support material with the aqueous solution of catalytically active components is carried out by immersion, initial wetting or evaporative impregnation. In some embodiments, the carrier 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.

[0018] In certain embodiments, the one or more ODSO compounds are water-soluble ODSO compounds having 3 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), wherein X represents an ester and is (R-SO) or (R-SOO), and 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 3 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), wherein X represents an ester and is (R-SO) or (R-SOO), and 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 3 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-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 3 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.

[0019] In certain embodiments, the mixture of ODSO compounds corresponds to the oxidized disulfide oil present in the refinery effluent hydrocarbon stream recovered after catalytic oxidation of the mercaptans present in the refinery effluent hydrocarbon stream. In certain embodiments, the one or more ODSO compounds are contained in a reaction product or a fraction of a reaction product derived from oxidation of a disulfide oil compound 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-support composition; in certain embodiments, the oxidation catalyst is a metal or metal compound containing one or more transition metals.

[0020] Any combination of the various embodiments and implementations disclosed herein may be used.These and other aspects and features may be understood from the following description of certain embodiments and the accompanying drawings and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 1 is a simplified schematic diagram of a generalized version of a conventional mercaptan oxidation or MEROX process for liquid-liquid extraction of mercaptan-containing hydrocarbon streams.

[0023] FIG. 2 is a simplified schematic diagram of a generalized version of the Enhanced Mercaptan Oxidation or E-MEROX process.

[0024] Figure 3A The polar water-soluble ODSO fraction used as the active ingredient carrier in this article is experimental 1 H-NMR spectrum.

[0025] Figure 3B The polar water-soluble ODSO fraction used as the active ingredient carrier in this article is experimental 13 C-DEPT-135-NMR spectrum.

[0026] Figure 4 Temperature programmed reduction data are shown for a catalyst using ODSO to promote active phase dispersion and a catalyst not using ODSO to promote active phase dispersion. DETAILED DESCRIPTION

[0027] In some embodiments, a composition comprising a promoter component is disclosed. The composition is used to promote the active phase dispersion of catalytically active components on a porous support material having an outer surface and an inner surface of the pores. The composition may include one or more oxidized disulfide oil (ODSO) compounds and is used to promote the active phase dispersion of one or more catalytically active components on the outer surface and the inner surface of the pores of the support material.

[0028] In some embodiments, a composition comprising an aqueous solution of a catalytically active component is disclosed. The composition is dispersed on a porous support material having an outer surface and an inner surface of a hole. The solution may include one or more catalytically active components and a promoter component. The promoter component may include one or more oxidized disulfide oil (ODSO) compounds and is used to promote the active phase dispersion of one or more catalytically active components on the outer surface of the support material and the inner surface of the hole.

[0029] In certain embodiments, the ODSO is obtained from the effluent of an enhanced MEROX process.The active phase promoter composition facilitates post-synthesis transfer of catalytically active components (or components that will be catalytically active in the final solid catalyst material) to the surface of the support material.

[0030] In certain embodiments, a method for making a catalyst material is disclosed. The method includes providing a porous support material having an outer surface and an inner surface of a hole, and contacting the support material with an effective amount of a composition to promote the active phase dispersion of catalytically active components on the outer surface and inner surface of the hole of the support material. The composition comprises an aqueous solution of catalytically active components dispersed on a porous support material having an outer surface and inner surface of the hole. The solution comprises one or more catalytically active components and a promoter component comprising one or more oxidized disulfide oil (ODSO) compounds, which is used to promote the active phase dispersion of one or more catalytically active components on the outer surface and inner surface of the hole of the support material.

[0031] The one or more active components are added after the support material with the outer surface and the inner surface of the hole is formed and in its solid state, using an aqueous impregnation solution containing a promoter component, which has an effective amount of one or more ODSO compounds. Generally, the active component is added to the support material, which is referred to as the post-synthesis active component incorporation herein, and involves contacting the solid support material (e.g., in the form of a powder, microparticle, granular material, and / or extrudate) with the impregnation solution for a suitable period of time, and then drying. For some applications, the solid material is activated, for example, by calcining, reduction or other appropriate treatments. In the process herein, an effective amount of one or more ODSO compounds is included in the impregnation solution for the post-synthesis active component incorporation.

[0032] Post-synthesis active component incorporation, also referred to as active component impregnation, includes known techniques for loading a provided solid support material with active components, generally by solid state transfer or wet impregnation. Solid state transfer involves physical mixing of (one or more) active components and a solid support material in a solid state. Wet impregnation uses (one or more) active components dissolved in a liquid solution (impregnation solution) to transfer the active component to a solid support material.

[0033] The impregnation solution is typically an aqueous solution containing one or more active components and / or one or more active component precursors. Other conventional ingredients include: pH adjusters to adjust the solubility of the active components and the adsorption strength of the active components on the support surface; viscosity modifiers to slow down or accelerate the diffusion of metal ions during evaporation to achieve the desired metal distribution; chelating agents (including citric acid, formic acid and EDTA), which will react with the metal ions in the solution to reduce the interaction between the metal ions and the surface; and surface modifiers (including phosphoric acid) to react with the oxide support.

[0034] The one or more ODSO compounds in the accelerator component of the impregnation solution may act as a pH modifier, a viscosity modifier, a chelating agent, a surface modifier, or a combination thereof.

[0035] Several methods may be used to add the active component(s) to the support material, including but not limited to immersion, incipient wetness, and evaporation or any other suitable method.While descriptions of certain techniques are provided herein, it is understood that other techniques may benefit from improved techniques.

[0036] In some embodiments of wet impregnation, the carrier material is immersed in an impregnation solution with an active component of a suitable concentration customized to achieve a target loading level. The solution fills the hole, which is not blocked and is also adsorbed on the carrier surface, and excess solution is removed. For example, the carrier material is placed on a screen and immersed in an excessive amount of impregnation solution for a suitable time to carry out all impregnations. The solid is then discharged and dried. Such operation can be carried out continuously with a suitable conveyor system, such as a bucket carrying the screened carrier material through a basin containing an impregnation solution.

[0037] In certain embodiments of wet impregnation, an effective amount of an 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 tumbled and / or sprayed with a volume of an impregnation solution having a suitable concentration of active component, tailored to achieve a target loading level, equal to or slightly less than the pore volume of the support. The support material is contacted with a solution of the appropriate concentration, e.g., in an amount corresponding to the total known pore volume or slightly less. For example, the support material can be held in motion by a rotating cylinder or barrel where the impregnation is sprayed onto the support material.

[0038] In certain embodiments of wet impregnation, known as evaporative impregnation, the support material is saturated with water or with an acidic solution, and the saturated support material is immersed in an impregnation solution having an appropriate concentration of active component tailored to achieve the target loading level. The active component then diffuses into the pores of the support material through the aqueous phase.

[0039] In a further embodiment of post-synthesis active component incorporation, a wet carrier material is used. The wet carrier material contains water in all or part of the pore volume, for example in the range of about 1-100, 1-99, 1-90, 50-100, 50-99 or 50-90 V%, relative to the total pore volume. The volume can be controlled by changing the degree of wetting by partial drying of the material. The impregnation solution, whether provided by immersion, initial wetness or evaporative impregnation, is completely or partially blocked by the saturated pores, and therefore there are fewer active components diffusing into the pores. Therefore, the metal can be mainly located at the outer surface of the carrier material with a limited amount in the pores. This embodiment can be used as a primary step for post-synthesis active component incorporation, or as a secondary step for post-synthesis active component incorporation, for example after a certain amount of active component (the same or different active component added to the wet carrier) is already in the pores of the carrier material (e.g., partially loaded carrier material).

[0040] In certain embodiments, a method for making a catalyst material is disclosed. The method includes providing a porous support material having an outer surface and an inner pore surface. The support material is contacted with an effective amount of a composition to produce an enhanced support material. The composition includes a promoter component including one or more oxidized disulfide oil (ODSO) compounds. The enhanced support material is contacted with an aqueous solution of a catalytically active component to promote the active phase dispersion of the catalytically active component on the outer surface of the support material and the inner pore surface.

[0041] In these embodiments, the process for making the catalyst material is similar to the impregnation process described above. However, in these embodiments, the support material is formed and first in a solid state, and then the support material is contacted with an effective amount of a composition comprising a promoter component to produce an enhanced support material. In these embodiments, the enhanced support material can then be subjected to any of the impregnation techniques described above to add the active component(s) to the enhanced support material.

[0042] In certain embodiments of producing an enhanced support material, contacting the one or more ODSO compounds with the support material can be accomplished by one or more of immersion, incipient wetness, or evaporative impregnation. The enhanced support material can then be subjected to additional immersion, incipient wetness, or evaporative impregnation processes to add (one or more) active components.

[0043] According to embodiments herein, the support material to which the active components are added includes 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, the activity may be due to the acidity of the solid material, which imparts a catalytic function including the ability to enhance cracking reactions of hydrocarbons. Suitable solid acid catalysts are Lewis acids, Bronsted acids, or mixtures thereof. Suitable materials that may encompass both catalytically active support materials and inert support materials may be amorphous and / or structured. Support materials include, but are not limited to:

[0044] Aluminium oxide (amorphous or crystalline);

[0045] Silica (amorphous (including mesoporous such as SBA-15) or crystalline);

[0046] Amorphous silica-alumina;

[0047] Titanium dioxide;

[0048] Amorphous Titanium Dioxide

[0049] Titanium dioxide-silicon dioxide;

[0050] Zeolite (including but not limited to zeolite types): faujasite (FAU), including zeolite X, zeolite Y, HY zeolite, USY zeolite; beta zeolite (*BEA), mordenite (MOR), MFI framework zeolite, including ZSM-5; MTW framework zeolite, including ZSM-12; TON framework zeolite, including ZSM-22; MEL framework zeolite, including ZSM-11; MWW framework zeolite, including MCM-22 or MCM-56; CON framework zeolite, 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, C AN, 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, 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, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, 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, NON, 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, RUT, 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, STI, STT, STW, -SVR, SVV, SWY, - SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YFI, YUG, Z ON, *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS, *SFV, *-SSO, *STO, *-SVY, or *UOE, or one or more synthetic zeolites comprising the co-crystallized product of two or more types of zeolites defined above, or a zeolite comprising siliceous crystalline material in which the SAR approaches infinity, such as silicalites (e.g., Silicalite-1); note that the three letter codes designated herein correspond to the framework types established by the International Zeolite Association;,

[0051] Silicon-substituted aluminophosphates, silicoaluminophosphates (SAPO) (including but not limited to (AEI) including SAPO-18, (AEL) including SAPO-11, (AFI) including SAPO-5, (AFO) including SAPO-41, (AFR) including SAPO-40, (AFX) including SAPO-56, (ATN) including SAPO-39, (ATO) including SAPO-31, (CHA) including SAPO-34 and -47, (FAU) including SAPO-37, (GIS) including SAPO-43, (LEV) including SAPO-35 and (LTA) including SAPO-42);

[0052] Crystalline microporous aluminum phosphate (AlPO) (including but not limited to (AEI) including AlPO-18, (AEL) including AlPO-11, (AEN) including AlPO-53, (AET) including AlPO-8, (AFI) including AlPO-5, (AFN) including AlPO-14, (AFO) including AlPO-41, (AFR) including AlPO-40, (AFT) including AlPO-52, (ANA) including AlPO-24, (AST) including AlPO-16, (ATO) includes AlPO-31, (ATS) includes AlPO-36, (ATT) includes AlPO-33, (ATV) includes AlPO-25, (AWO) includes AlPO-21, (AWW) includes AlPO-22, (CHA) includes AlPO-34, (ERI) includes AlPO-17, (LEV) includes AlPO-35, (SOD) includes AlPO-20, and (VFI) includes AlPO-54); and

[0053] Metal aluminophosphates (MAPO) (including but not limited to (AFI) including MAPO-5, (AFS) including MAPO-46, (ATN) including MAPO-39, (ATO) including MAPO-31, (ATS) including MAPO-36, and (GIS) including MAPO-43).

[0054] In certain embodiments, the support comprises a support comprising 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-boron, phosphorus-alumina, silica-alumina-boron, phosphorus-alumina-boron, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

[0055] The support material may be subjected to treatments to alter support properties such as pore volume, surface area, and average pore size, such as by mesostructuring treatments including one or more of desiliconization, steaming, acid leaching, and templated recrystallization. Typically, these treatments are applied prior to impregnation of the active component.

[0056] In embodiments where a zeolite or other crystalline material is used, it is conventionally formed with one or more binder components such as alumina, silica, silica-alumina, clay, titania, and mixtures thereof.

[0057] In certain embodiments, particles formed from the loaded support material have a pore volume in the range of about (cc / gm) 0.15-1.70, 0.15-1.50, 0.30-1.50, or 0.30-1.70; about (m 2 / g) in the range of 100-900, 100-500, 100-450, 180-900, 180-500, 180-450, 200-900, 200-500 or 200-450; and an average pore size of at least about 10, 20, 30, 45, 50, 500, 1000, and in certain embodiments, 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.

[0058] In certain embodiments, the calcined support material is subjected to heating before contacting 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 solid catalyst particles and / or solid catalyst support particles of the load in one or more steps. In certain embodiments, the solid catalyst particles and / or solid catalyst support particles of the load are subjected to one or more heat treatments between one or more steps.

[0059] In the methods disclosed herein, an effective amount of a promoter component is used to promote the incorporation of the active component into the catalyst material. In certain embodiments, a promoter component is employed as a component during post-synthesis active component incorporation.

[0060] In certain embodiments, the composition comprising an aqueous solution comprises a clean or diluted ODSO active phase promoter component mixed with one or more additional metal sources. The additional metal source can be one or more sources of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd or Mg. The additional metal source can be combined with the clean or diluted ODSO active phase promoter component to form the composition herein.

[0061] (One or more) active components are incorporated with effective concentrations. In certain embodiments, (one or more) active components are added to ODSO or a mixture comprising ODSO components based on their solubility. In certain embodiments, the effective concentration of (one or more) active components in the active phase accelerator composition is 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 mass percent of the active phase accelerator composition.

[0062] In certain embodiments, a promoter component is provided which is undiluted from the controlled catalytic oxidation of DSO and comprises about 50-100, 75-100, 90-100 mass percent of one or more ODSO compounds or ODSO mixtures; and wherein carries (one or more) active components 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 mass percent (referred to herein as a "clean" ODSO active phase promoter composition for convenience).

[0063] In certain embodiments, the accelerator component comprises a clean ODSO active phase accelerator composition diluted with water, for example, wherein the clean ODSO active phase accelerator composition (which contains (one or more) active components) comprises 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 mass percent of the solution.

[0064] In certain embodiments, the accelerator component comprises clean or diluted ODSO mixed with one or more additional acidic accelerator components, such as hydrochloric acid, sulfuric acid, nitric acid, aqua regia (a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of nitric acid: hydrochloric acid of 1:3), oxalic acid, citric acid, acetic acid, EDTA, malic acid, formic acid, or a combination comprising one or more of the foregoing acids. The additional acid can be provided pure (100 mass percent acid) or in the form of a diluted aqueous solution, such as a solution of from 0.1-99.9 mass percent; the pure or diluted acid is combined with the diluted ODSO to form the accelerator component herein. In certain embodiments, the one or more additional acidic accelerator components have a pKa in the range of from about 1-10 or 1-6.

[0065] One or more catalytically active components are included in a mixture with one or more ODSO compounds used as active component carriers. The one or more active components may vary according to the application of the catalyst manufactured. The active component may be a metal or a non-metal, in a simple form or as a compound such as an oxide, a carbide or a sulfide. For example, one or more active components for hydroprocessing catalysts may include one or more metals or metal compounds selected from the periodic table IUPAC 4-12 families. In certain embodiments, one or more active components are selected to produce hydroprocessing catalysts and may include one or more metals or metal compounds (such as Co, Ni, Mo, and combinations thereof) selected from the periodic table IUPAC 6-10 families. In certain embodiments, one or more active components are selected to produce hydrocracking catalysts and may include one or more metals or metal compounds (such as Co, Ni, W, Mo, and combinations thereof) selected from the periodic table IUPAC 6-10 families. In certain embodiments, one or more active components are selected to produce catalytic reforming catalysts and may include one or more metals or metal compounds (such as Pt or Pd) selected from the periodic table IUPAC 8-10 families. In certain embodiments, the one or more active components are selected to produce a hydrogenation catalyst and may include one or more metals or metal compounds selected from IUPAC Groups 7-10 of the Periodic Table (e.g., Pt or Pd), and / or one or more non-metal compounds such as P. In certain embodiments, the one or more active components are selected to produce an oxidation catalyst and may include one or more metals or metal compounds selected from IUPAC Groups 4-10 of the Periodic Table (e.g., Ti, V, Mn, Co, Fe, Cr, and Mo) or selected from IUPAC Groups 4-12 of the Periodic Table (e.g., Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W, Mo).

[0066] In certain embodiments, the active component(s) in the promoter component are carried over from a previous catalytic oxidation of a MEROX process byproduct DSO, and accordingly the concentration depends on the amount used therein. In certain embodiments, the catalytic oxidation of a MEROX process byproduct DSO may occur with an increased amount of oxidation catalyst compared to the catalytic oxidation typically used, wherein the excess oxidation catalyst is passed through the ODSO fraction and used herein as a promoter component (with or without additional active component(s)).

[0067] In certain embodiments, the promoter component containing the one or more ODSO compounds and the one or more catalytically active components are derived from a sulfur-containing refinery waste stream of disulfide oil. The promoter component is derived from a reaction product or a fraction of a reaction product, which is obtained from the oxidation of a disulfide oil compound 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 reused in a beneficial manner as all or a portion of the one or more catalytically active components in the active phase promoter composition, which is transferred to the formed catalyst material. For example, as described above and in co-owned U.S. Patent No. 10,807,947, a controlled catalytic oxidation of the MEROX process byproduct DSO can be performed, and the patent is incorporated herein by reference in its entirety. The resulting oxidation effluent contains ODSO. As disclosed in 10,807,947, the byproduct DSO compound from the mercaptan oxidation process can be oxidized, typically in the presence of a catalyst. The oxidant may be a liquid peroxide selected from the following: alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters and hydrogen peroxide. The oxidant may also be a gas, including air, oxygen, ozone and nitrogen oxides. In the embodiments herein, the catalyst is used in the oxidation process. The oxidation catalyst may contain an active metal from the 4th to 12th group of the IUPAC elements 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 following: 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 following: Mo (VI), W (VI), V (V), Ti (IV), and combinations thereof. In certain embodiments, suitable homogeneous catalysts include acetylacetonate molybdenum, bis (acetylacetonate) dioxy molybdenum, cyclopentane acid molybdenum, hexacarbonyl molybdenum, hexacarbonyl tungsten, sodium tungstate and vanadium pentoxide. In certain embodiments, a suitable catalyst is sodium tungstate, Na2WO4·2H2O.

[0068] In certain embodiments, the mass ratio of the ODSO compound to the carrier material may be in the range of 0.001-1, 0.01-1, 0.1-1, 0.001-0.5, 0.01-0.5, or 0.1-0.5. In certain embodiments, the mass ratio of the active component to the carrier material may be in the range of 0.001-1, 0.01-1, 0.1-1, 0.001-0.5, 0.01-0.5, or 0.1-0.5.

[0069] The promoter component comprises one or more ODSO compounds. The active component promoter can be a mixture comprising two or more ODSO compounds. In the description herein, for convenience, the terms "oxidized disulfide oil", "ODSO", "ODSO mixture" and "(one or more) ODSO compounds" are used interchangeably. As used herein, the abbreviations of oxidized disulfide oil ("ODSO") and disulfide oil ("DSO") will be understood to refer to singular and plural forms, which can also occur as "DSO compounds" and "ODSO compounds", and each form can be used interchangeably. In some cases, a single ODSO compound may also be mentioned.

[0070] In certain embodiments, the promoter component is obtained from the controlled catalytic oxidation of disulfide oil from the mercaptan oxidation process. The effluent from the controlled catalytic oxidation of disulfide oil from the mercaptan oxidation process includes ODSO compounds, and in certain embodiments includes unconverted DSO compounds in the oxidation process. In certain embodiments, the effluent contains water-soluble compounds and water-insoluble compounds. The effluent contains at least one ODSO compound or a mixture of two or more ODSO compounds, which is selected from compounds with the following general formula: (R-SO-SR′), (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' may be the same or different C1-C10 alkyl or C6-C10 aryl. Further, X represents an ester and is (R-SO) or (R-SOO), wherein R is defined above. It will be appreciated that since the source of DSO is a refinery feed stream, the R and X substituents vary, such as methyl and ethyl subgroups, and the number of sulfur atoms S in the received feed stream to oxidation may extend to 3, for example, trisulfide compounds.

[0071] In certain embodiments, water-soluble compounds and water-insoluble compounds are separated from each other, and the promoter component comprises all or part of the water-soluble compounds separated from the total effluent from the oxidation of the disulfide oil from the mercaptan oxidation process. For example, the different phases can be separated by decantation or with a separation funnel, a separation cartridge, by decantation or any other known device or process for separating two immiscible phases from each other. In certain embodiments, the water-soluble and water-insoluble components can be separated by distillation because they have different boiling point ranges. It is understood that there will be a crossover of water-soluble and water-insoluble components in each fraction because the solubility of the components is typically within the range of ppmw (e.g., about 1-10,000, 1-1,000, 1-500 or 1-200 ppmw). In certain embodiments, pollutants from each phase can be removed, for example, by stripping or adsorption.

[0072] In certain embodiments, the promoter component comprises, consists of, or consists essentially of at least one water-soluble ODSO compound having 3 or more oxygen atoms selected from 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 promoter component comprises, consists of, or consists essentially of a mixture of two or more water-soluble ODSO compounds having 3 or more oxygen atoms selected from 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 promoter 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. Further, X represents an ester and is (R-SO) or (R-SOO), wherein R is as defined above. In certain embodiments, R and R' are methyl and / or ethyl groups. In certain embodiments, the ODSO compound(s) used as the promoter component have 1 to 20 carbon atoms.

[0073] In certain embodiments, the promoter 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 promoter 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 promoter component comprises, consists of, or consists essentially of an ODSO compound having a dielectric constant less than or equal to 100 at 0° C.

[0074] Table 1 includes examples of polar water-soluble ODSO compounds containing 3 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 the MEROX byproduct. The ODSO compounds containing 3 or more oxygen atoms are water-soluble in all concentrations that are effective, for example, with some small acceptable tolerances for carryover components from the effluent stream and in the water-insoluble fraction having no more than about 1, 3 or 5 mass percent of 2 oxygen atoms.

[0075] In certain embodiments, the ODSO compound used as an active phase promoter comprises all or a portion of a water-soluble ODSO compound contained in an oxidation effluent stream derived from the controlled catalytic oxidation of a MEROX process byproduct DSO compound, as disclosed in U.S. Pat. Nos. 10,807,947 and 10,781,168, which are incorporated herein by reference.

[0076] In some embodiments, the ODSO compound used as an active phase promoter is derived from an oxidized DSO compound present in an effluent refinery hydrocarbon stream recovered after catalytic oxidation of mercaptans present in the hydrocarbon stream. In some embodiments, the DSO compound is oxidized in the presence of a catalyst.

[0077] As mentioned above, the designation "MEROX" is derived from the function of the process itself, namely the conversion of mercaptans by oxidation. The MEROX process in all its applications is based on the ability of an organometallic catalyst in a basic environment (such as caustic) to accelerate the oxidation of mercaptans to disulfides at near ambient temperature and pressure. The overall reaction can be represented as follows:

[0078] RSH+1 / 4O2→1 / 2RSSR+1 / 2H2O (1)

[0079] Where R can be a straight, branched or cyclic hydrocarbon chain, and the chain can be saturated or unsaturated. In most petroleum fractions, there will be a mixture of mercaptans so that R can have 1, 2, 3 and up to 10 or more carbon atoms in the chain. This variable chain length is represented by R and R' in the reaction. The reaction is then written as:

[0080] 2 R'SH+2 RSH+O2→2 R'SSR+2 H2O (2)

[0081] This reaction occurs spontaneously any time any mercaptan-bearing acidic distillate is exposed to atmospheric oxygen, but at a very slow rate. Furthermore, the catalytic reaction (1) set forth 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.

[0082] The MEROX process can be carried out both on a liquid stream and on a combined gas and liquid stream. In the case of a liquid stream, mercaptans are directly converted to disulfides which remain in the product so that there is no reduction in the total sulfur content of the effluent stream. The MEROX process typically utilizes a fixed bed reactor system for liquid streams and is usually employed with feedstocks having endpoints above 135°C-150°C. Mercaptans are converted to disulfides in a fixed bed reactor system by a catalyst (e.g., activated carbon impregnated with a MEROX reagent and wetted with a caustic solution). Air is injected into the hydrocarbon feed stream before the reactor and in the bed impregnated with the catalyst, and mercaptans in the feed are oxidized to disulfides. Disulfides are substantially insoluble in caustic and remain in the hydrocarbon phase. Post-treatment is required to remove undesirable byproducts from known side reactions, such as neutralization of H2S, oxidation of phenolic compounds, entrained alkali, and others.

[0083] The vapor pressure of disulfides is relatively low compared to that of mercaptans, so their presence is much less objectionable from an odor standpoint; however, they are not environmentally acceptable because of their sulfur content and their handling can be problematic.

[0084] In the case of mixed gas and liquid streams, the extraction is applied to both phases of the hydrocarbon stream. The extent to which the mercaptan extraction is complete depends on the solubility of the mercaptans in the alkaline solution, which is a function of 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. Thereafter, the resulting DSO compounds are separated and the alkaline solution is oxidized by air in the presence of a catalyst and reused.

[0085] Referring to the drawings, FIG1 is a simplified schematic diagram of a generalized version of a conventional MEROX process using liquid-liquid extraction to remove sulfur compounds. A MEROX unit 1010 is provided for treating a hydrocarbon stream 1001 containing mercaptans. In some embodiments, the hydrocarbon stream 1001 containing mercaptans is LPG, propane, butane, light naphtha, kerosene, jet fuel, or a mixture thereof. The process generally includes the following steps: introducing a hydrocarbon stream 1001 having a homogeneous catalyst into an extraction vessel 1005 containing an alkaline solution 1002, in some embodiments, the catalyst is a homogeneous cobalt-based catalyst; allowing the hydrocarbon catalyst stream to flow in countercurrent through an extraction portion of the extraction 1005 vessel, wherein the extraction portion includes one or more liquid-liquid contact extraction tables or trays (not shown) to perform a catalytic reaction with a circulating alkaline solution to convert mercaptans into water-soluble alkali metal alkanethiolate compounds; a hydrocarbon product stream 1003 (e.g., having no more than about 1000, 100 , 10 or 1 ppmw of mercaptans) are removed from an extraction vessel 1005; a combined used alkali and alkali metal alkanethiolate stream 1004 is collected from the extraction vessel 1005; the used alkali and alkali metal alkanethiolate stream 1004 is subjected to catalytic wet air oxidation in a reactor 1020, a catalyst 1005 and air 1006 are introduced into the reactor 1020 to provide regenerated used alkali 1008 and convert the alkali metal alkanethiolate compound into a disulfide oil; and a byproduct stream 1007 of DSO compounds and a small portion of other sulfides such as monosulfides and trisulfides are collected. The effluent of the wet air oxidation step in the MEROX process may contain a small portion of sulfides and a large portion of disulfide oil. As known to those skilled in the art, the composition of the effluent stream depends on the effectiveness of the MEROX process, and it is assumed that the sulfides are carryover materials. A variety of catalysts have been developed for commercial practice of the process. The effectiveness of the MEROX process is also a function of the amount of H2S present in the stream. It is customary refinery practice to provide a pre-wash step to remove H2S.

[0086] Enhanced MEROX process ("E-MEROX") is an improved MEROX process with an additional step added, wherein the DSO compound is oxidized with an oxidant in the presence of a catalyst to produce a mixture of ODSO compounds. In some embodiments, in the presence of a catalyst, the byproduct DSO compound from the mercaptan oxidation process is oxidized and constitutes a rich source of ODSO compounds, which are sulfoxides, sulfonic acids (salts / esters), sulfinic acids (salts / esters), sulfones, and disulfide mixtures corresponding thereto. Disulfide oils with the general formula RSSR' (wherein R and R' may be the same or different and may have 1, 2, 3 and up to 10 or more carbon atoms) may be oxidized in the absence of a catalyst or in the presence of one or more catalysts to produce a mixture of ODSO compounds. The oxidant may be a liquid peroxide selected from the following: alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters and hydrogen peroxide. The oxidant may also be a gas, including air, oxygen, ozone, and nitrogen oxides. If a catalyst is used in the oxidation of a disulfide oil having the general formula RSSR' to produce an ODSO compound, it may be a heterogeneous or homogeneous oxidation catalyst. The oxidation catalyst may be selected from one or more heterogeneous or homogeneous catalysts comprising 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 be a homogeneous water-soluble compound that is a transition metal containing an active species selected from 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 byproduct 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 supports such as alumina, silica-alumina, silica, natural zeolites, synthetic zeolites, and combinations comprising one or more of the foregoing supports.

[0087] The oxidation of DSO is typically carried out in one or more oxidation containers selected from the group consisting of a fixed bed reactor, an ebullating bed reactor, a slurry bed reactor, a moving bed reactor, a continuous stirred tank reactor, and a tubular reactor. The ODSO compound produced in the E-MEROX process generally comprises two phases: a water-soluble phase and a water-insoluble phase, and can be separated into an aqueous phase containing a water-soluble ODSO compound and a non-aqueous phase containing a water-insoluble ODSO compound. The E-MEROX process can be adjusted according to the desired ratio of water-soluble and water-insoluble compounds present in the product ODSO mixture. The partial oxidation of the DSO compound results in a relatively high amount of water-insoluble ODSO compounds present in the ODSO product, and the near or almost complete oxidation of the DSO compound results in a relatively high amount of water-soluble ODSO present in the ODSO product. The details of the ODSO composition are discussed in USP 10,781,168, which is incorporated herein by reference above.

[0088] Fig. 2 is a simplified schematic diagram of the E-MEROX process including E-MEROX unit 1030. MEROX unit 1010 units operate similarly to Fig. 1, wherein similar reference numbers (references numbers) represent similar units / feeds. In Fig. 2, the effluent stream 1007 of the generalized MEROX unit from Fig. 1 is processed. It will be understood that the processing of the hydrocarbon stream containing mercaptan of Fig. 1 is only illustrative and the independent stream of product and other mixed and long-chain product combinations or independent streams can be the subject of the process for collecting and oxidizing DSO to produce ODSO compounds, i.e., E-MEROX process. In order to practice E-MEROX process, the equipment for collecting byproduct DSO compounds from MEROX process is added. In addition, suitable reactor 1035 is added, DSO compounds are introduced therein in the presence of catalyst 1032 and oxidant 1034, and DSO compounds are subjected to catalytic oxidation steps to produce the mixed stream 1036 of water and ODSO compounds. A separation vessel 1040 is provided to separate the byproduct 1044 from the ODSO compound 1042 .

[0089] The oxidation to produce OSDO may be carried out in a suitable oxidation reaction vessel operating at a pressure in the range of from about 1-30, 1-10, or 1-3 bar. The oxidation to produce OSDO may be carried out at a temperature in the range of from about 20-30, 20-150, 20-90, 45-300, 15-150, or 45-90° C. The molar feed ratio of oxidant to monosulfur may be in the range of from about 1:1 to 100:1, 1:1 to 30:1, or 1:1 to 4:1. The residence time in the reaction vessel may be in the range of from about 5-180, 5-90, 5-30, 15-180, 15-90, or 5-30 minutes. In certain embodiments, the oxidation of DSO is carried out in an environment without the addition of water as a reagent. The byproduct stream 1044 generally comprises waste water when hydrogen peroxide is used as the oxidant. Alternatively, when other organic peroxides are used as oxidants, byproduct stream 1044 generally contains the alcohol of the peroxide used. For example, if butyl peroxide is used as the oxidant, byproduct alcohol 1044 is butanol.

[0090] In certain embodiments, the water-soluble ODSO compound is sent to a classification zone (not shown) for collection after it is separated from the waste water fraction. The classification zone may include a distillation unit. In certain embodiments, the distillation unit may be a flash unit without a theoretical plate to obtain distillation fractions with a large overlap with each other, or alternatively, in other embodiments, the distillation unit may be a flash unit with at least 15 theoretical plates to have effective separation between fractions. In certain embodiments, the distillation unit may be operated at atmospheric pressure and at a temperature in the range of 100°C to 225°C. In other embodiments, fractionation may be performed continuously under vacuum conditions. In those embodiments, classification occurs under reduced pressure and at their respective boiling temperatures. For example, at 350 mbar and 10 mbar, the temperature ranges are from 80°C to 194°C and 11°C to 98°C, respectively. After classification, the waste water is sent to a waste water pool (not shown) for conventional treatment before its disposal. The waste water by-product fraction may contain a small amount of water-insoluble ODSO compounds, for example, in the range of from 1ppmw to 10,000ppmw. The waste water by-product fraction may contain a small amount of water-soluble ODSO compounds, for example, in the range of from 1ppmw to 50,000ppmw, or 100ppmw to 50,000ppmw. In an embodiment where alcohol is a by-product alcohol, alcohol may be collected and sold as a commodity product or added to a fuel such as gasoline. The alcohol by-product fraction may contain a small amount of water-insoluble ODSO compounds, for example, in the range of from 1ppmw to 10,000ppmw. The alcohol by-product fraction may contain a small amount of water-soluble ODSO compounds, for example, in the range of from 100ppmw to 50,000ppmw.

[0091] Example

[0092] The following examples and data are exemplary. It is understood that other ratios and types of aluminum source, silica source, base, and structure directing agent may be used in comparison to the examples.

[0093] Reference Example: The ODSO mixture used in the following examples is produced according to the disclosure in U.S. Pat. No. 10,781,168, and in particular the fraction referred to as Composition 2, which is incorporated herein by reference. A hydrocarbon refinery feedstock having 98 mass percent of C1 and C2 disulfide oils was subjected to catalytic oxidation. The oxidation of the DSO compound was carried out in batch mode under reflux at atmospheric pressure, i.e., about 1.01 bar. The hydrogen peroxide oxidizing agent was added at room temperature, i.e., about 23°C, and an exothermic reaction was produced. The molar ratio of the oxidant to the DSO compound (calculated based on the monosulfur content) was 2.90. After the addition of the oxidant was completed, the reaction vessel temperature was set to reflux at 80°C for about 1 hour. Thereafter, water-soluble ODSO (referred to as Composition 2 herein and in U.S. Pat. No. 10,781,168) was produced and separated after removing water. The catalyst used in the oxidation of the DSO compound was sodium tungstate. Composition 2, referred to as "selected water-soluble ODSO fraction" herein, was used. Figure 3A Experimental study of polar water-soluble ODSO mixture 1 H-NMR spectrum, the mixture is the water-soluble ODSO fraction selected in the Examples herein. Figure 3B Experimental study of polar water-soluble ODSO mixture 13 C-DEPT-135-NMR spectrum, described mixture is the water-soluble ODSO fraction selected in the embodiment herein.The water-soluble ODSO fraction selected is mixed with CD3OD solvent and collects spectrum at 25 ℃.Methyl carbon has positive intensity, and methylene carbon shows negative intensity.The peak in 48-50ppm region belongs to the carbon signal of CD3OD solvent.

[0094] When the water-soluble ODSO fraction is selected Figure 3B Experiment 13 When the C-DEPT-135-NMR spectrum was compared with a stored database of predicted spectra, the predicted alkyl sulfoxide sulfonic acid (R-SO-SOO-OH), alkyl sulfone sulfonic acid (R-SOO-SOO-OH), alkyl sulfoxide sulfinic acid (R-SO-SO-OH) and alkyl sulfone sulfinic acid (R-SOO-SO-OH) were found to correspond most closely to the experimental spectrum. This suggests that alkyl sulfoxide sulfonic acid (R-SO-SOO-OH), alkyl sulfone sulfonic acid (R-SOO-SOO-OH), alkyl sulfoxide sulfinic acid (R-SO-SO-OH) and alkyl sulfone sulfinic acid (R-SOO-SO-OH) are the major compounds in the selected water-soluble ODSO fraction. Figure 3Aand Figure 3B It is clear from the NMR spectrum shown in that the selected water-soluble ODSO fraction contains a mixture of ODSO compounds that form the ODSO acids of the present disclosure.

[0095] Comparative Example 1: In the comparative example, an amorphous silica alumina and alumina supported catalyst was impregnated with Ni-Mo. The metal precursors used for this comparative example were nickel nitrate hydrate and ammonium molybdate tetrahydrate, with the target metal-based loading being 3.9 wt % for Ni and 13.3 wt % for Mo. 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 weight of 22.5 g of the support, which contained no volatiles, was charged into a rotary evaporator. The metal solution was then slowly added to the evaporator. After all the metal solution was added, the heating bath was raised to 95°C and the metal solution was dried overnight. The dried catalyst was transferred to a muffle furnace and calcined in air with the following temperature program: maintaining 10°C / min to 120°C for 3 hours; maintaining 10°C / min to 535°C for 2 hours; 10°C / min to 30°C.

[0096] Example 1: Synthesis of amorphous silica alumina and alumina supported catalyst as described above, including an active phase promoter composition, ODSO as described in the reference example. 1.2 g of ODSO was added to the metal solution before introduction into the evaporator.

[0097] Figure 4 Programmed temperature reduction data are shown for 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) vs. temperature (in degrees Celsius). During this analysis, each catalyst was dried at 500°C in argon for 30 minutes before cooling to room temperature. The gas was then switched from argon to H2 and the temperature was increased to 800°C at 10°C / min. H2 consumption was monitored by a thermal conductivity detector (TCD). From Figure 4 It is clear that the catalyst prepared with ODSO has more hydrogen uptake capacity.

[0098] The headings used herein are for organizational purposes only and are not meant to limit the scope of the specification or claims. As used throughout this application, the words "may" and "may" are used in a permissive sense (i.e., meaning having the potential to), rather than in a mandatory sense (i.e., meaning must).

[0099] It is understood that like numbers in the drawings represent like elements through the several drawings, and not all components and / or steps described and illustrated with reference to the drawings are required for all embodiments or arrangements.

[0100] Further, the terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. As used herein, the singular forms "one (a kind of)" and "a (one)" are intended to also include plural forms, unless the context clearly indicates otherwise. It will be further understood that the terms "include", "comprise" or "have", "contain", "involve", and variations thereof in this article, when used in this specification, specifically describe the existence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the existence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof.

[0101] It should be noted that the use of ordinal terms such as "first", "second", "third", etc., used in the claims to modify claim elements does not, by itself, indicate any priority, precedence or order of one claim element relative to another claim element, nor does it indicate a temporal order in which the actions of the method are performed, but rather serves merely as labels to distinguish one claim element having a certain name from another element having the same name (but for the use of ordinal terms) to distinguish the claim elements.

[0102] In particular, the accompanying drawings and the above examples (embodiments) do not mean that the scope of the present disclosure is limited to a single implementation, because other implementations are also possible by the interchange of some or all described or shown elements. In addition, the situation that some elements of the present disclosure can be implemented partially or completely using known components (assemblies), only those parts of such known components (assemblies) required for understanding the present disclosure are described, and the detailed description of other parts of such known components (assemblies) is omitted, so as not to blur the present disclosure. In this specification, the implementation of a single component (assembly) is shown not to be necessarily limited to other implementations including a plurality of identical components (assemblies), and vice versa, unless otherwise clearly stated herein. In addition, the applicant does not intend to give any term in this specification or claim an uncommon or special meaning, unless so clearly stated. Further, the present disclosure covers the present and future known equivalents referred to as known components herein by way of example.

[0103] The foregoing description of specific implementations will fully reveal the general nature of the present disclosure, so that others can easily modify and / or adapt such specific implementations for various applications by applying the knowledge within the technology of (one or more) related fields, without excessive experimentation, and without departing from the general concept of the present disclosure. Therefore, such adaptations and modifications are intended to be within the meaning and scope of equivalents of the disclosed implementations based on the teachings and guidance presented herein. It is understood that the words or terms in this article are for descriptive purposes rather than for limiting purposes, so that the terms or words of this specification are interpreted by those skilled in the art based on the teachings and guidance presented herein and the knowledge of the technicians in (one or more) related fields. It is understood that the dimensions discussed or shown are according to the drawings of an example, and other dimensions can be used without departing from the present disclosure.

[0104] The subject matter described above is provided by way of illustration only and should not be construed as limiting. Various modifications and changes may be made to the subject matter described herein without following the illustrated and described example implementations and applications, and without departing from the true spirit and scope of the invention encompassed by the present disclosure, which is defined by the set of recitations in the following claims and by structures and functions or steps equivalent to those recitations.

[0105]

Claims

1. A composition comprising a promoter component for promoting active phase dispersion of catalytically active components on a porous support material having an outer surface and an inner surface of pores, the composition comprising one or more oxidized disulfide oil (ODSO) compounds for promoting active phase dispersion of one or more catalytically active components on the outer surface and the inner surface of pores of the support material.

2. A composition comprising an aqueous solution of catalytically active components for dispersion on a porous support material having an outer surface and an inner surface of pores, the solution comprising one or more catalytically active components and a promoter component comprising one or more oxidized disulfide oil (ODSO) compounds, which is used to promote active phase dispersion of the one or more catalytically active components on the outer surface and the inner surface of pores of the support material.

3. A composition as claimed in claim 1 or 2, wherein the catalytically active component is selected from IUPAC Groups 4 to 14 of the Periodic Table.

4. The composition of claim 1 or 2, wherein the catalytically active component is one or more of Co, Ni, Mo, W, Pt, Pd.

5. A composition as claimed in any one of the preceding claims, wherein the accelerator component comprises an ODSO compound and water in a ratio (V %) of ODSO:H2O in the range of from 100:0 to 0.1:99.

9.

6. A composition as claimed in any preceding claim, wherein the accelerator component comprises ODSO and one or more other accelerator compounds.

7. The composition of claim 6, wherein the other accelerator compound comprises one or more of citric acid, ethylenediaminotetraacetic acid (EDTA), malic acid, oxalic acid or formic acid.

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

9. A method for producing a catalyst material, comprising: providing a porous support material having an outer surface and a pore inner surface; contacting the support material with an effective amount of a composition as described in claims 1 or 3-8 to produce a reinforced support material; and The enhanced support material is contacted with an aqueous solution of catalytically active components to promote active phase dispersion of the catalytically active components on the external surface and internal pore surfaces of the support material.

10. A method for producing a catalyst material, comprising: providing a porous support material having an outer surface and a pore inner surface; The support material is contacted with an effective amount of a composition as claimed in any one of claims 2 to 8 for promoting active phase dispersion of catalytically active components on the outer surface and inner pore surfaces of the support material.

11. The method of claim 9 or 10, further wherein the support material is subjected to heating prior to contacting with the composition.

12. The process as claimed in 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. A method as claimed in claim 12, wherein the supported solid catalyst particles and / or solid catalyst support particles are subjected to one or more heat treatments between said one or more steps.

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

15. A method as claimed in any one of claims 9 to 14, wherein the contacting of the reinforced support material with the aqueous solution of the catalytically active components is carried out by immersion, incipient wetness or evaporative impregnation.

16. The method of any one of claims 9-15, wherein the supported solid catalyst particles and / or solid catalyst support particles have a pore volume in the range of about (cc / gm) 0.15-1.70, 0.15-1.50, 0.30-1.50, or 0.30-1.70; 2 / g) in the range of 100-900, 100-500, 100-450, 180-900, 180-500, 180-450, 200-900, 200-500 or 200-450; 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.

17. A method as claimed in any preceding claim, wherein the support comprises a zeolite component and a binder component.

18. The method of claim 17, wherein the zeolite is one or more zeolites defined by the International Zeolite Association, including those having the following designations: 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, ERI, ESV, ETL, ETR, ETV, EUO, EVO, 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、JNT、JOZ、 JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, 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, NON, 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, RUT, 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, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL,UWY, VET, VFI, VNI, VSV, WEI, -WEN, YFI, YUG, ZON, *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS, *SFV, *-SSO, *STO, *-SVY or *UOE, or a synthetic zeolite comprising the co-crystallized product of two or more types of zeolites identified above, or a zeolite comprising a siliceous crystalline material having a SAR approaching infinity, such as silicalite (e.g., Silicalite-1).

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

20. The method of any one of claims 16-19, 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-boron, phosphorus-alumina, silica-alumina-boron, phosphorus-alumina-boron, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.

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

22. The method of any one of claims 1-21, wherein the one or more ODSO compounds comprise an ODSO compound having 3 or more oxygen atoms.

23. The method of any one of claims 1-22, wherein the one or more ODSO compounds comprise ODSO compounds having 1 to 20 carbon atoms.

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

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

26. The method of any one of claims 1-25, wherein the ODSO compound has 3 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), wherein 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. The method of any one of claims 1-25, wherein the ODSO compound has 3 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), and wherein 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. The method of any one of claims 1-25, wherein the ODSO compound has 3 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), wherein R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl.

29. The method of any one of claims 1-25, wherein the ODSO compound has 3 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), wherein R and R' may be the same or different C1-C10 alkyl or C6-C10 aryl.

Images