Method for Preparing Catalytic Carbon Fiber

Abstract

A method for producing catalytic carbon fibers includes oxidizing virgin carbon fibers to produce oxidized carbon fibers; reacting the oxidized carbon fibers with a polyamine compound to produce amine-modified carbon fibers; and reacting the amine-modified carbon fibers with an organometallic macrocycle to produce catalytic carbon fibers.

Description

Background Art

[0001] Chemical processes often require multiple unit operations to produce a product stream. A particular unit operation can be a liquid-liquid contacting operation, whereby two liquids are brought into intimate contact to effect mass transfer between the liquids, reaction between components in the liquids, or both. Another unit operation can be a gas-liquid contacting operation, whereby a gas and a liquid are brought into contact to effect mass transfer between the liquids, reaction between components in the liquids, or both. Liquid-liquid contact can be beneficial in some types of chemical reactions where one reactant is miscible in a first liquid but not in a second liquid. An example of such a reaction can be one where a first reactant is present in a polar solvent such as water and a second reactant is present in a nonpolar solvent such as a hydrocarbon, and water and the hydrocarbon are immiscible. Liquid-liquid contact can have other applications such as liquid-liquid extraction, whereby a species present in a first liquid is extracted into a second liquid by mass transfer across a liquid-liquid interface. Gas-liquid contact can be useful in some types of chemical reactions where a component in the gas phase reacts with a component in the liquid phase and the gas component is absorbed into the liquid phase.

[0002] A particular challenge for liquid-liquid contactors and gas-liquid contactors, collectively also referred to as "mass transfer devices", can be to ensure an appropriate contact area between the phases such that mass transfer or reaction occurs in an appropriate amount and in an economically viable manner. Generally, liquid-liquid contacting operations can be carried out using immiscible liquids such as, for example, an aqueous liquid and an organic liquid. Using two immiscible liquids will allow the liquids to be easily separated after liquid-liquid contact is complete. However, when a liquid-liquid contacting operation is carried out using immiscible liquids, phase separation may occur before appropriate contact between the liquids is achieved.

[0003] Several mass transfer devices and techniques, including but not limited to fiber bundle contactors, have been developed to enhance the contact area between phases. A fiber bundle contactor generally includes one or more fiber bundles suspended within a shell and two or more inlets where phases, including gas - liquid or liquid - liquid, can be introduced into the shell. The fiber bundles facilitate contact between the phases by allowing the first phase to flow along the individual fibers of the fiber bundle and the second phase to flow between the individual fibers, thereby increasing the effective contact area between the phases. The two phases may flow from the inlet section of the shell to the outlet section of the shell, maintaining intimate contact such that reaction, mass transfer, or both are sustained between the two phases.

[0004] Fiber bundle contactors have been developed for treating mercaptan sulfur - containing hydrocarbon streams. In these contactors, a liquid catalyst or a solid catalyst bed can be utilized in conjunction with a caustic agent to convert mercaptan sulfur to disulfide oil. However, there are challenges in this process, including ensuring that the degree of reaction is sufficient such that the resulting product stream meets specifications. Some ways to ensure that the degree of reaction is sufficient to produce a product stream that meets specifications can be to construct a physically larger mass transfer device, design the mass transfer device to have a longer contact time, or design a mass transfer device with features that enhance the effect of mixing from the inlet. The physical characteristics of the mass transfer device can be optimized to a certain extent, but due to the limitations of oxidation catalysts, there are limitations to the degree to which the reaction can proceed regardless of the physical configuration of the mass transfer device. SUMMARY OF THE INVENTION

[0005] Disclosed herein is an example of a method that includes oxidizing virgin carbon fibers to produce oxidized carbon fibers; reacting the oxidized carbon fibers with a polyamine compound to produce amine-modified carbon fibers; and reacting the amine-modified carbon fibers with an organometallic macrocyclic molecule to produce catalytic carbon fibers.

[0006] Also disclosed herein is an example of a method that includes providing carbon fibers and an aminated macrocyclic molecule, mixing the carbon fibers and the aminated macrocyclic molecule with a solvent; and reacting the carbon fibers and the aminated macrocyclic molecule to form an amide bond between the carbon fibers and the aminated macrocyclic molecule, thereby forming catalytic carbon fibers.

[0007] Also disclosed herein is a fiber bundle contactor that includes a flow path defined by a conduit; a catalytic carbon fiber bundle disposed in the conduit, where the catalytic carbon fibers include an amine compound covalently bonded to the carbon fibers, and an organometallic macrocyclic molecule covalently bonded to the amine compound; and an inlet that enables a fluid to flow within the flow path.

[0008] Also disclosed herein is a method that includes introducing a hydrocarbon containing mercaptan sulfur, an aqueous caustic solution, and an oxidizing agent into a container; reacting at least a portion of the mercaptan sulfur and the aqueous caustic solution to produce a mercaptide; and reacting the mercaptide and the oxidizing agent in the presence of a catalytic carbon fiber bundle to produce a disulfide oil, where the catalytic carbon fiber bundle includes carbon fibers, an amine compound covalently bonded to the carbon fibers, and an organometallic macrocyclic molecule covalently bonded to the amine compound.

[0009] These and other features and characteristics of the disclosed processes and the systems of the present disclosure and their advantageous uses and / or applications will become apparent from the following detailed description.

[0010] These drawings illustrate certain aspects of some embodiments of the present disclosure and should not be used to limit or define the present disclosure. **Brief Description of the Drawings**

[0011]

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[0012] The present disclosure relates to liquid-liquid and gas-liquid mass transfer devices and, in some embodiments, to mass transfer devices containing catalytic carbon fibers. The catalytic carbon fibers may include organometallic catalysts chemically grafted onto the surface of the carbon fibers. The catalytic carbon fibers may be used as heterogeneous catalysts in liquid-liquid and gas-liquid mass transfer devices.

[0013] Disclosed herein is a method for preparing catalytic carbon fibers. In some embodiments, the method for preparing catalytic carbon fibers may include a process that oxidizes virgin carbon fibers to produce oxidized carbon fibers, and then aminates them to produce amine-modified carbon fibers. The amine-modified carbon fibers are further reacted with organometallic macrocyclic molecules to produce catalytic carbon fibers. In some embodiments, the method for preparing catalytic carbon fibers may include reacting an aminated macrocyclic molecule with carbon fibers in the presence of a solvent to produce catalytic carbon fibers.

[0014] Any type of carbon fiber, including but not limited to carbon fibers prepared using polyacrylonitrile (PAN), mesophase pitch, and rayon, may be utilized in the present disclosure. Suitable carbon fibers may have any structural order or any structural order between them, including those classified as turbostratic or graphite-like. The carbon fibers can be of any quality containing from about 50 wt% carbon to about 100 wt% carbon, and can be low modulus carbon fibers having a tensile modulus of less than 240000000 kPa, intermediate modulus carbon fibers having a tensile modulus of from about 240000000 kPa to 500000000 kPa, or high tensile modulus carbon fibers having a tensile modulus of from about 500000000 kPa to 1000000000 kPa, etc. The carbon fibers can have any diameter including from about 5 micrometers to about 20 micrometers, or any diameter therebetween. The carbon fibers can be in the form of a twisted yarn or bundle, whereby hundreds to thousands of individual carbon fibers can be spun together to form a carbon fiber twisted yarn or carbon fiber bundle.

[0015] In some embodiments, a method of preparing catalytic carbon fibers may include, in a first step, oxidizing virgin carbon fibers to produce oxidized carbon fibers. The oxidation is carried out in a liquid or gaseous environment to form oxygen-containing functional groups on the surface of the carbon fibers. The oxygen-containing functional groups may include carboxyl, carbonyl, lactone, and hydroxyl that are covalently bonded to at least a portion of the carbon atoms making up the carbon fibers. The oxidation step oxidizes the carbon fibers to any suitable degree. Without limitation, the carbon fibers may be oxidized to contain from about 0.1 wt.% to about 25 wt.% oxygen-containing functional groups. Alternatively, the carbon fibers may be oxidized to contain from about 0.1 wt.% to about 1 wt.% oxygen-containing functional groups, from about 1 wt.% to about 5 wt.% oxygen-containing functional groups, from about 5 wt.% to about 10 wt.% oxygen-containing functional groups, from about 10 wt.% to about 15 wt.% oxygen-containing functional groups, from about 15 wt.% to about 20 wt.% oxygen-containing functional groups, from about 20 wt.% to about 25 wt.% oxygen-containing functional groups, or any range therebetween. The degree of oxidation may be utilized to control the final concentration of organometallic macrocyclic molecules dispersed on the catalytic carbon fibers, which in turn may directly affect the overall catalytic activity of the catalytic carbon fibers as well.

[0016] The oxidation of carbon fibers may be achieved by immersing virgin carbon fibers in an acid and allowing the acid to react with the virgin carbon fibers. Suitable acids may include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, hydroiodic acid, fluoroantimonic acid, carborane acid, fluoroboric acid, fluorosulfuric acid, hydrogen fluoride, triflic acid, and perchloric acid, and organic acids such as acetic acid, formic acid, citric acid, oxalic acid, and tartaric acid. In addition to or instead of oxidation using an acid, the oxidation step may also be carried out using plasma treatment in an oxygen atmosphere, gamma ray irradiation treatment, electrochemical oxidation using an oxidant such as sodium hydroxide, ammonium bicarbonate, ammonium carbonate, sulfuric acid, or nitric acid, and oxidation with potassium persulfate using sodium hydroxide or silver nitrate. Acidic oxidation may be carried out at any temperature in the range of about 0 °C to 150 °C. Alternatively, the oxidation may be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, about 100 °C to about 125 °C, about 125 °C to about 150 °C, or any temperature range therebetween. The oxidation may be carried out for any period appropriate to achieve the desired concentration of oxygen-containing functional groups on the carbon fibers. The time required to achieve the specified concentration of oxygen-containing functional groups may depend on many factors including the identity and concentration of the acid and the temperature conditions selected. Generally, the oxidation is carried out for a period in the range of about 1 hour to about 24 hours. Alternatively, the oxidation may be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range of time therebetween. After oxidation by acid treatment, the oxidized carbon fibers may optionally be washed using water or another solvent to remove excess acid. The oxidized carbon fibers may be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0017] The second step of preparing the catalytic carbon fiber may include generating an amine-modified carbon fiber. After the oxidized carbon fiber is generated, the oxidized carbon fiber may be reacted with an amine-containing compound to generate an amine-modified carbon fiber. The amine-containing compound may be any polyamine compound containing at least two amine groups, including diamines, triamines, and higher-order amines. The amine-containing compound may include linear, branched, or cyclic primary or secondary amines having a carbon number in the range of C2 to C20. Some specific amine-containing compounds may include, but are not limited to, ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof. The oxidized carbon fiber may be reacted with the amine-containing compound under any suitable conditions, including temperatures in the range of about 0°C to 250°C. Alternatively, the oxidation may be carried out at 0°C to about 25°C, about 25°C to about 50°C, about 50°C to about 75°C, about 75°C to about 100°C, about 100°C to about 125°C, about 125°C to about 150°C, about 150°C to about 175°C, about 175°C to about 200°C, about 200°C to about 225°C, about 225°C to about 250°C, or any temperature range therebetween. The time required to react the oxidized carbon fiber and the amine-containing compound may depend on many factors, including the identity of the amine-containing compound and the selected temperature conditions. Generally, the oxidized carbon fiber may be reacted with the amine-containing compound for a period in the range of about 1 hour to about 24 hours. Alternatively, the oxidized carbon fiber may be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range therebetween. After the amine reaction, the amine-modified carbon fiber may optionally be washed using water or another solvent to remove excess amine. The amine-modified carbon fiber may be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0018] A third step of preparing the catalytic carbon fiber may include reacting the amine-modified carbon fiber with an organometallic macrocyclic molecule to produce the catalytic carbon fiber. The organometallic macrocyclic molecule may include unsubstituted metal phthalocyanine, substituted metal phthalocyanine, and combinations thereof. Suitable metal phthalocyanines may include substituents of halogen, hydroxyl, amine, alkyl, aryl, thiol, alkoxy, nitrosyl group, or combinations thereof at one or more peripheral hydrogen atoms on the metal phthalocyanine. The metal phthalocyanine may include any suitable metal including, but not limited to, vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof. The organometallic macrocyclic molecule may be dispersed in a solvent including, but not limited to, water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, or combinations thereof prior to reacting with the amine-modified carbon fiber.

[0019] The amine-modified carbon fibers may be reacted with an organometallic macrocyclic molecule under any suitable conditions, including temperatures in the range of about 0 °C to 150 °C. Alternatively, the oxidation may be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, about 100 °C to about 125 °C, about 125 °C to about 150 °C, or any temperature range therebetween. The time required to react the amine-modified carbon fibers and the amine-containing compound may depend on many factors, including the identity of the organometallic macrocyclic molecule and the temperature conditions selected. Generally, the amine-modified carbon fibers may be reacted with the organometallic macrocyclic molecule for a period in the range of about 1 hour to about 24 hours. Alternatively, the oxidation may be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range therebetween. After the reaction of the organometallic macrocyclic molecule, the catalytic carbon fibers may optionally be washed using water or another solvent to remove excess organometallic macrocyclic molecule. The catalytic carbon fibers may be dried at an elevated temperature after washing to remove the water or solvent used in the washing step.

[0020] In a further embodiment, a synthesis method for producing catalytic carbon fibers may include reacting an aminated macrocyclic molecule with carbon fibers in the presence of a solvent to produce catalytic carbon fibers. The aminated macrocyclic molecule may include an organometallic macrocyclic molecule and an amine group grafted to the organometallic macrocyclic molecule. The amine group may include an amino group, and an imino group, or a combination thereof. The amine group enables the aminated macrocyclic molecule to react with an oxygen-containing group such as a carboxyl group on the surface of the carbon fiber to form an amide bond between the aminated macrocyclic molecule and the carbon fiber. Carbon fiber production may include the above-described oxidative surface treatment step that leaves oxygen-containing groups such as carboxyl groups on the surface of the carbon fiber. The concentration of oxygen-containing groups such as carboxyl groups may determine the amount of aminated macrocyclic molecule that can react with the carbon fiber. Further oxidative surface treatment may be utilized to increase the concentration of reactive groups containing carboxyl groups so that the carbon fiber can react with a greater amount of aminated macrocyclic molecule.

[0021] The aminated macrocyclic molecule may include any suitable organometallic macrocyclic molecule including, but not limited to, unsubstituted metal phthalocyanines, substituted metal phthalocyanines, and combinations thereof. The substituted metal phthalocyanine may include substituents of halogen, hydroxyl, alkyl, aryl, thiol, alkoxy, nitrosyl group, or combinations thereof at one or more peripheral hydrogen atoms on the metal phthalocyanine. The metal phthalocyanine may include any suitable metal including, but not limited to, vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof. The aminated macrocyclic molecule may include one or more amine groups (-NH2 or -NH) grafted to the organometallic macrocyclic molecule. The aminated macrocyclic molecule may include an amine-containing compound grafted to the organic macrocyclic molecule. The amine-containing compound may include C2-C20, monoamine, diamine, triamine, and higher-order amines. The amine-containing compound may include linear, branched, or cyclic amines. Some specific amine-containing compounds may include, but are not limited to, ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof. Some suitable aminated macrocyclic molecules may include aminocobalt phthalocyanines such as monoaminocobalt phthalocyanine and polyaminocobalt phthalocyanine. Polyaminocobalt phthalocyanine may include diamino cobalt phthalocyanine, triamino cobalt phthalocyanine, tetraamino cobalt phthalocyanine, and higher-order polyaminocobalt phthalocyanine. Other specific suitable aminated macrocyclic molecules may include porphyrin, heme, polyaza compounds, and crown ethers.

[0022] The catalytic carbon fiber can be prepared by reacting an aminated macrocyclic molecule with a carbon fiber to form an amide bond between the aminated macrocyclic molecules. There are several synthetic methods for the formation of an amide bond between a carbon fiber and an aminated macrocyclic molecule, and only some of them can be disclosed herein. One synthetic method can include the direct formation of an amide bond by reacting a carbon fiber and an aminated macrocyclic molecule at a high temperature in a suitable solvent. Another synthetic method can include amide formation via the production of an acyl chloride from a carboxylic acid using a chlorinating agent such as thionyl chloride. Another synthetic method can include amide formation using a coupling agent such as carbodiimide or benzotriazole. Another synthetic method can include enzyme-catalyzed amide formation.

[0023] In direct amide bond synthesis, carbon fibers and an aminated macrocyclic molecule are combined and heated in a solvent, thereby forming an amide bond between the carbon fibers and the aminated macrocyclic molecule to produce catalytic carbon fibers. Some suitable solvents can include, but are not limited to, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof. The carbon fibers can react with the aminated macrocyclic molecule under any suitable conditions, including temperatures in the range of about 100 °C to 200 °C. Alternatively, the reaction can be carried out in the range of 100 °C to about 125 °C, about 125 °C to about 150 °C, about 150 °C to about 175 °C, about 175 °C to about 200 °C, or any temperature range in between. The time required to react the carbon fibers and the aminated macrocyclic molecule can depend on many factors, including the identity of the aminated macrocyclic molecule and the selected temperature conditions. Generally, the carbon fibers can be reacted with the aminated macrocyclic molecule for a period in the range of about 1 hour to about 24 hours or longer. Alternatively, the reaction can be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range of time in between. After the reaction of the aminated macrocyclic molecule, the catalytic carbon fibers may optionally be washed using water or another solvent to remove excess aminated macrocyclic molecule. The catalytic carbon fibers can be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0024] In acyl chloride synthesis, the carbon fiber can be combined with a chlorinating agent such as thionyl chloride, phosphorus trichloride, or terephthaloyl chloride and heated. The chlorinating agent can react with an oxygen-containing group such as a carboxyl group on the carbon fiber to produce an acyl chloride on the carbon fiber. The carbon fiber may be reacted with the chlorinating agent under any suitable conditions below the boiling point of the chlorinating agent, including temperatures in the range of about 0 °C to 150 °C. Alternatively, the reaction may be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, about 100 °C to about 125 °C, about 125 °C to about 150 °C, or any temperature range therebetween. Generally, the carbon fiber may be reacted with the chlorinating agent for a period in the range of about 1 hour to about 24 hours or longer. The carbon fiber modified with the chlorinating agent may be reacted with an aminated macrocyclic molecule to produce a catalytic carbon fiber. For example, the carbon fiber modified with the chlorinating agent and the aminated macrocyclic molecule may be combined and heated in a solvent, thereby forming an amide bond between the carbon fiber and the aminated macrocyclic molecule to produce a catalytic carbon fiber. Some suitable solvents may include, but are not limited to, water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof. The carbon fiber modified with the chlorinating agent may be reacted with the aminated macrocyclic molecule under any suitable conditions, including temperatures in the range of about 0 °C to 150 °C. Alternatively, the reaction may be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, about 100 °C to about 125 °C, about 125 °C to about 150 °C, or any temperature range therebetween. The time required to react the carbon fiber modified with the chlorinating agent and the aminated macrocyclic molecule may depend on many factors, including the identity of the aminated macrocyclic molecule and the selected temperature conditions. Generally, the carbon fiber modified with the chlorinating agent may be reacted with the aminated macrocyclic molecule for a period in the range of about 1 hour to about 24 hours or longer.Alternatively, the reaction may be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours or any range in between. After the reaction of the aminated macrocyclic molecule, the catalytic carbon fiber may optionally be washed using water or another solvent to remove excess aminated macrocyclic molecule. The catalytic carbon fiber may be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0025] Another synthetic method may involve amide formation using a coupling agent. In this method, the carbon fiber and the coupling agent can be combined and heated in a suitable solvent. The coupling agent can react with oxygen-containing functional groups on the carbon fiber or the carbon fiber to form a functionalized carbon fiber. Some suitable coupling agents can include, but are not limited to, carbodiimide, benzotriazole, and combinations thereof. The functionalized carbon fiber can be combined with an aminated macrocyclic molecule and a solvent that can react to form a catalytic carbon fiber. Some suitable solvents can include, but are not limited to, water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof. The functionalized carbon fiber can react with the aminated macrocyclic molecule under any suitable conditions, including temperatures in the range of about 0 °C to 150 °C. Alternatively, the reaction can be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, about 100 °C to about 125 °C, about 125 °C to about 150 °C, or any temperature range in between. The time required to react the functionalized carbon fiber and the aminated macrocyclic molecule can depend on many factors, including the identity of the aminated macrocyclic molecule and the selected temperature conditions. Generally, the functionalized carbon fiber can be reacted with the aminated macrocyclic molecule for a period in the range of about 1 hour to about 24 hours or longer. Alternatively, the reaction can be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range in between. After the reaction of the aminated macrocyclic molecule, the catalytic carbon fiber may optionally be washed using water or another solvent to remove excess aminated macrocyclic molecule. The catalytic carbon fiber can be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0026] Other synthetic methods may include amide formation using enzymes. Enzymatic catalysts may allow the amination reaction to occur at relatively low temperatures and may allow for a wider solvent compatibility. In this method, carbon fibers and the aminated macrocyclic molecules are combined with an enzyme in a suitable solvent. The enzyme may include any enzyme capable of catalyzing the formation of an amide bond between the carbon fiber and the aminated macrocyclic molecule. Some examples of suitable enzymes may include, but are not limited to, proteases, subtilisins, acylases, amidases, lipases, and combinations thereof. Some suitable solvents may include, but are not limited to, water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof. The carbon fibers may be reacted with the aminated macrocyclic molecule under any suitable conditions, including temperatures in the range of about 0 °C to 100 °C. Alternatively, the reaction may be carried out in the range of 0 °C to about 25 °C, about 25 °C to about 50 °C, about 50 °C to about 75 °C, about 75 °C to about 100 °C, or any temperature range in between. The time required to react the carbon fibers and the aminated macrocyclic molecule may depend on many factors, including the identity of the aminated macrocyclic molecule and the temperature conditions selected. Generally, the carbon fibers may be reacted with the aminated macrocyclic molecule for a period in the range of about 1 hour to about 24 hours or longer. Alternatively, the reaction may be carried out for a time in the range of about 1 hour to about 3 hours, about 3 hours to about 6 hours, about 6 hours to about 9 hours, about 9 hours to about 12 hours, about 12 hours to about 15 hours, about 15 hours to about 18 hours, about 18 hours to about 21 hours, about 21 hours to about 24 hours, or any range in between. After the reaction of the aminated macrocyclic molecule, the catalytic carbon fibers may optionally be washed using water or another solvent to remove excess aminated macrocyclic molecule. The catalytic carbon fibers may be dried at a high temperature after washing to remove the water or solvent used in the washing step.

[0027] When the catalytic carbon fiber is synthesized as described above, the catalytic carbon fiber may be further processed by shaping the catalytic carbon fiber. For example, the individual fibers of the catalytic carbon fiber may be drawn together and fixed to form a catalytic carbon fiber bundle. The catalytic carbon fiber bundle may be utilized in a reactor to form a reaction zone within the reactor. Additional processing of the carbon fiber may include reducing the size of the carbon fiber to produce a catalytic carbon fiber suitable for a fluidized bed, e.g., within a fluidized bed reactor, or being pelletized or adapted for use in a packed bed reactor.

[0028] Hydrocarbon streams in refineries and chemical plants often contain unwanted contaminants such as organically bound sulfur compounds, carboxylic acids, and hydrogen sulfide. Product specifications may require the reduction and / or removal of these contaminants during the refining process. Organically bound sulfur, such as mercaptan sulfur, may be present in some hydrocarbon streams within a refinery or chemical plant. It may be desirable to reduce the mercaptan sulfur content of a hydrocarbon stream to produce a product stream with a reduced mercaptan sulfur content. Generally, there are two options for treating mercaptan sulfur-containing streams. Mercaptan extraction may be utilized, whereby mercaptan sulfur is reacted with a caustic stream to produce an organic sulfur compound such as a mercaptide. Some of the mercaptide is dissolved in the aqueous portion of the caustic stream, thereby removing mercaptan sulfur from the hydrocarbon stream. Generally, the solubility of organic sulfur compounds is a function of the hydrocarbon chain length, whereby relatively low molecular weight mercaptans may produce more soluble products when reacted with a caustic stream, and relatively high molecular weight mercaptans may produce relatively insoluble products when reacted with a caustic stream. The organic sulfur compound may be further oxidized to a disulfide oil by reacting the organic sulfur compound with oxygen in the presence of a catalyst. For some hydrocarbon streams containing heavier mercaptan sulfur-containing compounds, a mercaptan sweetening agent may be utilized to directly convert mercaptan sulfur to a disulfide oil by reacting mercaptan sulfur with oxygen in the presence of a catalyst. Direct sweetening to a disulfide oil may be preferred in some hydrocarbon streams where the organic sulfur compound produced is relatively insoluble in the aqueous portion of the caustic stream. Some operations may include extraction and sweetening continuously, whereby a mixed hydrocarbon stream containing some relatively low molecular weight mercaptan sulfur and some relatively high molecular weight mercaptan sulfur is contacted with a caustic stream and then oxidized to produce a disulfide oil. Such operations may be performed in separate units or as an integrated process within a single vessel. An example of a single vessel extraction / oxidation is the Mericat™ II process available from Merichem Company.

[0029] There are hydrocarbon streams in various forms that contain contaminants that can be removed. Although this application may only disclose embodiments related to some specific hydrocarbon streams, the disclosure herein may be readily applicable to other hydrocarbon streams not specifically enumerated herein. The caustic treatment process would be suitable for the treatment of any hydrocarbon feed, including but not limited to hydrocarbons such as alkanes, alkenes, alkynes, and aromatics. The hydrocarbons may include, for example, hydrocarbons having a chain length of about C3 to about C 30 , or greater, and may include any amount of branching. Some representative hydrocarbon feeds can include, but are not limited to, crude oil, propane, LPG, butane, light naphtha, isomerate, heavy naphtha, reformate, jet fuel, kerosene, diesel oil, hydrotreated distillate, heavy vacuum gas oil, light vacuum gas oil, gas oil, coker gas oil, alkylate, fuel oil, light cycle oil, and combinations thereof. Some non-limiting examples of hydrocarbon streams can include light naphtha, heavy naphtha, jet fuel, and kerosene, fluid catalytic cracking or residue fluid catalytic cracking gasoline, or RCC, natural gasoline from NGL fractionation, and crude distillation unit streams such as gas condensate.

[0030] A method for extracting mercaptan sulfur can include contacting a caustic agent stream containing a hydroxide with a hydrocarbon stream and reacting at least a portion of the hydroxide in the caustic agent stream with the mercaptan sulfur content of the hydrocarbon stream. The hydroxide can be any hydroxide capable of reacting with mercaptan sulfur. Some representative hydroxides can include Group I and Group II hydroxides such as, for example, NaOH, KOH, RbOH, CsOH, Ca(OH)2, and Mg(OH)2. The hydroxide may be present in an aqueous solution at a concentration suitable for a particular application, generally from about 5 wt.% to saturation and including saturation.

[0031] The generalized reaction of hydroxide and mercaptan sulfur is shown in Reaction 1, where mercaptan sulfur (RSH) reacts with hydroxide (XOH) to form the corresponding mercaptide (RSX) and water, where X is a cation of Group I or Group II.

[0032]

Number

[0033] As discussed above, depending on the molecular weight of the mercaptan sulfur reacted with the hydroxide, a portion of the mercaptan sulfur produced may dissolve in the aqueous portion of the caustic stream. When mercaptan sulfur is reacted with the caustic stream, a "spent caustic" or "rich caustic" solution containing water, residual hydroxide, and soluble components can be produced. The spent caustic is regenerated to form a dilute caustic with a reduced mercaptide content for recycling back to Reaction 1. One process for regeneration can include mixing oxygen or air with the spent caustic and contacting the resulting mixture with a catalyst to regenerate the caustic stream. The generalized process for regeneration is shown in Reaction 2, where mercaptide (RSX) reacts with water and oxygen in the presence of a catalyst to produce disulfide (RSSR), also called disulfide oil (DSO), caustic, and water.

[0034]

Number

[0035] As discussed above, one of the problems in the treatment of mercaptan sulfur is that there are issues regarding the degree of reaction, whereby the mercaptan sulfur concentration is not reduced to the level required for the resulting product stream to meet specifications. In units that utilize an extractor section and an oxidation section, such as UOP Merox™, the catalyst may be distributed in the caustic stream that circulates through the extraction and oxidation sections of the unit. In a sweetening unit, the catalyst may be contained in a fixed bed within the reactor. The catalyst may be impregnated with carbon or activated carbon, where the catalyst bed may be wetted with a caustic solution. In either case, the catalyst may not have sufficient catalytic activity and / or the residence time within the reactor may be too short to effectively oxidize the mercaptide. One of the representative uses of the catalytic carbon fibers disclosed herein is to replace the conventional oxygenation catalysts currently utilized in the oxidation of mercaptides to produce disulfide oils. As discussed in detail below, the catalytic carbon fibers exhibit high reactivity towards the oxidation of mercaptides and have the desired physical properties suitable for use in a mercaptide oxidation reactor.

[0036] There can be a wide variety of process conditions suitable for the oxidation of mercaptides, and the exact conditions can vary depending on the hydrocarbon feed. For lighter hydrocarbons, the operating pressure can be controlled to be slightly above the bubble point to ensure liquid-phase operation. For relatively heavier hydrocarbons, the pressure may be set to maintain the air dissolved in the oxidation section. The operating temperature can also be selected based on the hydrocarbon feed under general conditions in a temperature range of about 20°C to about 100°C.

[0037] Figure 1 illustrates one embodiment of a hydrocarbon desulfurization process 100 that utilizes catalytic carbon fibers in mercaptide oxidation. In Figure 1, a hydrocarbon feed 102 containing a mercaptan sulfur compound can be processed in a countercurrent multiple-stage caustic treatment section. Dilute caustic 104 may be fed to the last stage 108, where the dilute caustic extracts mercaptan from the hydrocarbon entering the last stage 108 after being first treated in the first stage 106. The caustic is removed from the last stage 108 as stream 110 and can be fed to the first stage 106 and contacted with the hydrocarbon feed 102. The spent caustic stream 112 may be withdrawn from the first stage 106, and the treated hydrocarbon 114 may be withdrawn from the last stage 108. The specific design of the caustic treatment section is not critical to the functionality of the catalytic carbon fibers of the present disclosure, but one design may include a staged contactor operating in a countercurrent configuration as schematically illustrated in Figure 1, and another design may use a fiber film liquid-liquid contactor to assist in the mass transfer of mercaptan from the hydrocarbon feed 102 into the caustic treatment solution.

[0038] The spent caustic 112 withdrawn from the first stage 106 and the oxidant 118 may be fed to the oxidation section 116. The oxidant 118 may include any suitable oxidant, including air, oxygen, hydrogen peroxide, or any other oxygen-containing gas or compound that releases oxygen. The oxidation section 116 may include the catalytic carbon fibers disclosed herein that can oxidize the mercaptide present in the spent caustic 112 to form disulfide oil. The mercaptide, water, and oxygen in the spent caustic 112 react according to Reaction 2 in the presence of the catalytic carbon fibers to produce disulfide oil, regenerated caustic, and water. The regenerated caustic may be discharged as the regenerated caustic stream 118, and the disulfide oil may be discharged as the disulfide stream 124. Offgas steam 126 containing residual gaseous hydrocarbons, air, oxygen, or other gases may be withdrawn from the oxidation section 116 and sent to a downstream unit for further processing or to a flare if necessary.

[0039] The conditions within the oxidation section 116 can contribute to forming an explosive mixture having a combination of hydrocarbons and an oxidizing agent, so it may be desirable to operate the oxidation section 116 such that the gas present in the oxidation section 116 is below the lower explosive limit (LEL) or above the upper explosive limit (UEL). The gas stream 120 may in some cases be introduced into the oxidation section 116 such that the LEL / UEL condition is maintained. The gas stream 120 can include fuel gas, inert gas, or any other suitable gas for controlling the LEL / UEL. Another alternative may include a solvent stream 122 into the oxidation section 116. The solvent stream 122 can be from any source, but preferably contains little or no disulfide oil. The solvent stream 122 can be mixed with the spent caustic stream 112 before entering the oxidation section 116, or it can be injected as a separate stream at the bottom of the oxidation section 116. The solvent can be any light hydrocarbon or mixture of light hydrocarbons, such as naphtha and kerosene, that aids in the separation of disulfide oil from the caustic solution after the oxidation of mercaptans. Disulfide oil may have higher solubility in DSO compared to the aqueous portion of the spent caustic 112, and the difference in their solubilities provides the driving force for extraction in DSO. In embodiments where a solvent is utilized, the solvent may be withdrawn along with the disulfide oil of the disulfide stream 124.

[0040] In some embodiments, the regenerated caustic stream 118 may be further purified in a solvent wash section 128, whereby the solvent stream 130 contacts the regenerated caustic stream 118 to further remove DSO from the regenerated caustic stream 118. The spent caustic stream 132 is withdrawn from the solvent wash section 128, and additional fresh caustic from the fresh caustic stream 134 may be added to form the dilute caustic 104.

[0041] Figure 2 illustrates one embodiment of a hydrocarbon desulfurization vessel 200 that includes the catalytic carbon fibers described herein. As will be described, the hydrocarbon desulfurization vessel 200 includes a caustic treatment section 202 that includes a fiber bundle 204 and an oxidation section 206 that includes catalytic carbon fibers 208. The conduit 210 may include a caustic treatment section 202 that includes a fiber bundle 204 that physically separates the caustic treatment section 202 from the oxidation section 206 and provides a flow path for fluid to pass through. The oxidation section 206 that includes catalytic carbon fibers 208 may be disposed in an annular space formed between the conduit 210 and the wall of the vessel 200.

[0042] A hydrocarbon feed 212 that includes a mercaptan sulfur compound to be treated may be mixed with an oxidant 214 and introduced into the conduit 210. In some embodiments, a sparger 218 may be utilized to distribute the oxidant 214 into the hydrocarbon feed 21. The oxidant 214 may include any suitable oxidant, including air, oxygen, hydrogen peroxide, or any other oxygen-containing gas or compound that releases oxygen. Generally, the amount of oxidant 214 introduced should be sufficient to oxidize all of the mercaptan sulfur compounds present in the hydrocarbon feed 212. When the hydrocarbon / oxidant feed is introduced into the conduit 210, it flows through the conduit 210 and contacts the fiber bundle 204. A caustic stream 220 may be introduced into the conduit 210 such that the caustic stream 220 is mixed with the hydrocarbon / oxidant feed before the hydrocarbon / oxidant feed contacts the fiber bundle 204. In some embodiments, it may be desirable to disperse the caustic from the caustic stream 220 to enhance the contact between the hydrocarbon phase from the hydrocarbon feed 212 and the aqueous phase from the caustic stream 220. In such embodiments, the line 222 may be connected to a distributor 224 disposed over the fiber bundle 204, whereby the caustic stream 220 is connected to the distributor 224 via the line 222 and the hydrocarbon / oxidant feed may be mixed with the caustic from the caustic stream 220 over the fiber bundle 204.

[0043] In any embodiment, the hydrocarbon / oxidant feed and the caustic from caustic stream 220 may contact the fiber bundle 204 such that the aqueous caustic wets the individual fibers of the fiber bundle 204. The aqueous caustic solution forms a film on the fibers 204 which is dragged downstream through conduit 210 as the hydrocarbon passes through the same conduit. Both liquids may be discharged into the separation zone 226 of the vessel 200. The volume of the hydrocarbon will be greater since the aqueous caustic passes through the fiber bundle at a lower volumetric flow rate than the hydrocarbon. During the relative movement of the hydrocarbon with respect to the aqueous caustic film on the fibers, a new interface between the hydrocarbon and the aqueous caustic solution is continuously formed such that the new aqueous caustic solution comes into contact with this surface and is enabled to react with mercaptan sulfur or other impurities such as phenols, naphthenic acids and other organic acids in the hydrocarbon. Mercaptan sulfur present in the hydrocarbon feed may react with the caustic to form mercaptide as shown in Reaction 1.

[0044] In the separation zone 226, the aqueous caustic solution and the hydrocarbon may be collected in the lower portion of the vessel 200 and separated into a hydrocarbon phase 228 and a caustic phase 230. The interface 232 within the vessel 200 may be maintained at a level above the bottom of the downstream end of the fiber bundle 204 such that the aqueous caustic film can be collected directly at the bottom of the vessel 200 without being dispersed into the hydrocarbon phase 228. Most of the phenolate or naphthenic acid impurities that can cause clogging in the packed bed are thus removed from the hydrocarbon in the caustic phase. This not only increases the oxidation efficiency but also reduces the maintenance cost. However, some impurities may remain in the hydrocarbon which may need to be further treated with the caustic solution in the oxidation section 206. The caustic phase 230 may be withdrawn from the vessel 200 via pump 234 and returned to conduit 210 via caustic stream 220. The height of the interface 232 within the vessel 200 may be controlled by a level control system 236 including a level sensor, a level controller, and a purge valve and may be configured to maintain the interface 232 at a level above the downstream end of the fiber bundle 204.

[0045] From the separation zone 226, the hydrocarbon phase 228 may flow upward into the oxidation section 206, whereby the hydrocarbon phase 228 contacts the catalytic carbon fiber 208. Additional caustic may be introduced into the oxidation section 206 via line 238 if necessary. A distribution grid may be present in the oxidation section 206 to distribute the caustic from line 238 into the oxidation section 206. In the oxidation section 206, mercaptide, water, and oxygen may react according to reaction 2 in the presence of the catalytic carbon fiber to produce disulfide oil, regenerated caustic, and water, which may flow upward through the oxidation section 206. Additional caustic and hydrocarbon may contact and flow simultaneously through the oxidation section 206. At the upper end of the catalytic carbon fiber, additional caustic may be separated from the hydrocarbon by a liquid separation device such as a chimney type tray in the separation section 240. A chimney type tray is shown, but there are many alternative types of liquid separators that can be used, such as a weir overflow. Additional hydroxide may be collected in the separation section 240 and discharged as a stream 242 that is reintroduced into the oxidation section 206. Makeup caustic 244 may be added intermittently and a purge of caustic may be utilized as needed. Hydrocarbon product 246 may be withdrawn from the top of the separation section 240. The offgas increasing in the vessel 200 may be discharged through line 248 and processed in a downstream unit.

[0046] Figure 3 illustrates another embodiment of the hydrocarbon desulfurization vessel 300 including the catalytic carbon fibers described herein. Figure 3 illustrates a process that is carried out in a single vessel into which a hydrocarbon feed 302, an oxidant 304, a caustic stream 306, and optionally a solvent stream 308 are introduced into the oxidation section 310. The oxidant 304 may include any suitable oxidant including air, oxygen, hydrogen peroxide, or any other oxygen-containing gas or compound that releases oxygen. Each of the streams may be introduced into the vessel 300 through a distributor 312 that may distribute the feed into the oxidation section 310. The oxidation section 310 includes catalytic carbon fibers 314 that are arranged to receive the feed from the distributor 312.

[0047] In the oxidation section 310, the hydrocarbon from the hydrocarbon feed 302 and the caustic from the caustic stream 306 may contact the catalytic carbon fibers 314, which causes the aqueous caustic to wet the individual fibers of the catalytic carbon fibers 314. The aqueous caustic solution forms a film on the catalytic carbon fibers 314, which is drawn downstream through the oxidation zone 310 by the passage of the hydrocarbon through the vessel 300. During the relative movement of the hydrocarbon with respect to the aqueous caustic film on the fibers, a new interface between the hydrocarbon and the aqueous caustic solution is continuously formed, such that a new aqueous caustic solution comes into contact with this surface and is enabled to react with mercaptan sulfur or other impurities such as phenols, naphthenic acids, and other organic acids in the hydrocarbon. Mercaptan sulfur present in the hydrocarbon feed may be reacted with the caustic to produce mercaptide as shown in Reaction 1. The produced mercaptide may further react with the oxygen provided by the oxidant 304 as shown in Reaction 2 in the presence of the catalytic carbon fibers 314 to produce disulfide oil, regenerated caustic, and water.

[0048] The oxidation of the mercaptide to disulfide oil occurring within the acidification section 310 can result in a mixture composed of the caustic agent in the continuous phase, the organic (disulfide oil and, if present, solvent) droplets of the discontinuous phase dispersed in the caustic agent phase, and the gas (nitrogen and unreacted oxygen from air). The mixture of the product, unreacted reactants, and inert species exits the acidification section 310, contacts the fiber bundle 318, and can flow into the separation section 316. The fiber bundle can facilitate phase separation as previously described. In the separation section 316, the aqueous caustic agent and the hydrocarbon can be collected in the lower portion of the separation section 316 and separated into a hydrocarbon phase 320, a caustic agent phase 322, and a gas phase 324. The gas from the oxidizing agent 304 separates from the liquid stream at the outlet of the fiber bundle 318 and exits through the mist eliminator 326 as offgas 328. The two immiscible liquids flow downward along the fiber bundle 318 as a single stream, during which the organic hydrocarbon droplets coalesce to form the hydrocarbon phase 320, while the aqueous caustic agent adheres to the fibers and flows further downward to form the caustic agent phase 322.

[0049] The hydrocarbon phase 320 containing the hydrocarbon from the hydrocarbon feed 302 and, if present, the produced disulfide oil and solvent can be drawn off as stream 330. The caustic agent phase 322 contains residual disulfide oil, which may be further reduced before the caustic agent is recycled within the vessel 300. The caustic agent phase 322 may be drawn off as stream 332, which may be mixed with a new solvent stream 334 before contacting the fiber bundle 338 and flowing into the separation section 336. In the separation section 336, the aqueous caustic agent from the caustic agent phase 322 and the solvent from the solvent stream 334 can be collected in the lower portion of the separation section 336 and separated into a solvent phase 340 and a caustic agent phase 342. The solvent phase 340 may contain most of any residual disulfide oil present in the caustic agent phase 322 after flowing through the fiber bundle 338. The solvent phase 340 can be drawn off into the vessel 300 as the solvent stream 308 and recycled. The caustic agent phase 342 can be drawn off as stream 344 and recycled.

[0050] FIG. 4 illustrates a stand-alone caustic regenerator unit 400 that includes catalytic carbon fibers 402 disposed in an oxidation zone 404. A spent caustic stream 406 may be mixed with an oxidant 408 and introduced into the caustic regenerator unit 400 through a distributor 410. The spent caustic stream can be from any unit, including those already described herein, and it includes spent caustic and mercaptides. The oxidant 408 can include any suitable oxidant, including air, oxygen, hydrogen peroxide, or any other oxygen-containing gas or compound that releases oxygen. The mixture of the oxidant 408 and the spent caustic stream 406 may contact the catalytic carbon fibers, which causes the aqueous caustic to wet the individual fibers of the catalytic carbon fibers 402. The mercaptides present in the caustic stream 406 further react with the oxygen provided by the oxidant 408 as shown in Reaction 2 in the presence of the catalytic carbon fibers 402 to produce disulfide oil, regenerated caustic, and water, which flow upward along the catalytic carbon fibers 402. The resulting disulfide oil, regenerated caustic, or both may be withdrawn from the regenerator unit 400 as stream 412. Although illustrated as one stream in FIG. 4, stream 412 can be two or more streams, such as in previous drawings, where the aqueous and oily phases are withdrawn separately. Off-gas 414 may also be withdrawn from the caustic regenerator unit 400.

[0051] Figure 5a illustrates a stand-alone caustic regenerator unit 500 that includes catalyst fibers 502 disposed in an oxidation zone 504. A concentrated caustic stream 506, which contains mercaptides and / or sulfides, enters at the top of the vessel. An oxidizing agent 508 enters onto a distributor tray 510. The oxidizing agent 508 can include any suitable oxidizing agent, including air, oxygen, hydrogen peroxide, or any other oxygen-containing gas or compound that releases oxygen. One example of a distributor tray is shown in Figure 5b, although other variations may be similarly applicable. At the distributor tray 510, a solvent stream 520 may also be introduced onto the distributor tray 510. The distributor tray 510 distributes these phases to the catalyst fibers 502. In some embodiments, a riser tube 516 may be disposed above the distributor tray 510. At least a mixture of the oxidizing agent 508 and the concentrated caustic stream 506 may contact the catalytic carbon fibers 502, which causes the aqueous caustic to wet the individual fibers of the catalytic carbon fibers 502. Mercaptides present in the caustic stream 506 further react with the oxygen provided by the oxidizing agent 508 as shown in Reaction 2 in the presence of the catalytic carbon fibers 502 to produce disulfide oil, regenerated caustic, and water, which flow downward along the catalytic carbon fibers 502. The resulting disulfide oil, regenerated caustic, or both may be withdrawn from the regenerator unit 500 as stream 512. Although illustrated as one stream in Figure 5, stream 512 may be two or more streams, such as in previous drawings where the aqueous and oily phases are withdrawn separately. An off-gas 514 may also be withdrawn from the caustic regenerator unit 500. Figure 5b shows a top view of the distributor tray 510 having riser tubes 516 and holes 518 that allow fluid to flow through the distributor tray 510.

[0052] Accordingly, the present disclosure provides methods, systems, and apparatuses that may relate to fluid-fluid contact. The methods, systems, and apparatuses may include any of the various features disclosed herein, including one or more of the following statements.

[0053] Statement 1. Oxidizing virgin carbon fiber to produce oxidized carbon fiber; reacting the oxidized carbon fiber with a polyamine compound to produce amine-modified carbon fiber; and reacting the amine-modified carbon fiber with an organometallic macrocyclic molecule to produce catalytic carbon fiber, a method for producing catalytic carbon fiber comprising these steps.

[0054] Statement 2. The method of Statement 1, wherein the oxidation step comprises contacting the carbon fiber with an acid selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, hydroiodic acid, fluoroantimonic acid, carborane acid, fluoroboric acid, fluorosulfuric acid, hydrogen fluoride, triflic acid, perchloric acid, acetic acid, formic acid, citric acid, oxalic acid, tartaric acid, and combinations thereof.

[0055] Statement 3. The method of Statement 2, wherein the oxidation step is carried out at a temperature in the range of about 0°C to about 150°C.

[0056] Statement 4. The method according to any one of Statements 1 to 3, wherein the polyamine compound comprises a primary or secondary polyamine having a carbon chain length of C2 to C20.

[0057] Statement 5. The method according to any one of Statements 1 to 4, wherein the polyamine compound comprises at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

[0058] Statement 6. The method according to any one of Statements 1 to 5, wherein the step of reacting the oxidized carbon fiber with the polyamine compound is carried out at a temperature in the range of about 0°C to 250°C.

[0059] Statement 7. The method according to any one of Statements 1 to 6, wherein the step of reacting the amine-modified carbon fiber with the organometallic macrocyclic molecule is carried out at a temperature in the range of about 0 °C to 150 °C.

[0060] Statement 8. The method according to any one of Statements 1 to 7, wherein the organometallic macrocyclic molecule comprises an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof.

[0061] Statement 9. The method of Statement 8, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof.

[0062] Statement 10. The method of Statement 8, wherein the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine comprises a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0063] Statement 11. A method for producing a catalytic carbon fiber, comprising oxidizing virgin carbon fiber to produce oxidized carbon fiber; reacting an organometallic macrocyclic molecule with a polyamine compound to produce an amine-modified organometallic macrocyclic molecule; and reacting the oxidized carbon fiber with the amine-modified organometallic macrocyclic molecule to produce a catalytic carbon fiber.

[0064] Statement 12. The method of Statement 11, wherein the oxidation step comprises contacting carbon fiber with an acid selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, hydroiodic acid, fluoroantimonic acid, carborane acid, fluoroboric acid, fluorosulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid, perchloric acid, acetic acid, formic acid, citric acid, oxalic acid, tartaric acid, and combinations thereof.

[0065] Statement 13. The method according to any one of Statements 11 to 12, wherein the polyamine compound comprises at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

[0066] Statement 14. The method according to any one of Statements 11 to 13, wherein the organometallic macrocyclic molecule comprises unsubstituted metal phthalocyanine, substituted metal phthalocyanine, or combinations thereof.

[0067] Statement 15. The method of Statement 14, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or combinations thereof.

[0068] Statement 16. The method according to any one of Statements 14 to 15, wherein the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine comprises a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0069] Statement 17. A catalytic carbon fiber comprising a carbon fiber, an amine compound covalently bonded to the carbon fiber; and an organometallic macrocyclic molecule covalently bonded to the amine compound.

[0070] Statement 18. The catalytic carbon fiber of Statement 17, wherein the amine compound comprises at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

[0071] Statement 19. The catalytic carbon fiber according to any one of Statements 17 to 18, wherein the amine compound comprises ethylenediamine.

[0072] Statement 20. The catalytic carbon fiber of Statement 19, wherein the organometallic macrocyclic molecule comprises a metal phthalocyanine.

[0073] Statement 21. A fiber bundle contactor comprising a flow path defined by a conduit; a bundle of catalytic carbon fibers disposed in the conduit; and an inlet that enables fluid to flow through the flow path.

[0074] Statement 22. The fiber bundle contactor of Statement 21, wherein the bundle of catalytic carbon fibers comprises a carbon fiber, an amine compound covalently bonded to the carbon fiber, and an organometallic macrocyclic molecule covalently bonded to the amine compound.

[0075] Statement 23. The fiber bundle contactor according to any one of Claims 21 to 22, wherein the amine compound comprises a primary or secondary polyamine having a carbon chain length of C2 to C20.

[0076] Statement 24. The fiber bundle contactor of any one of Statements 21 to 23, wherein the amine compound contains at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

[0077] Statement 25. The fiber bundle contactor of any one of Statements 21 to 24, wherein the organometallic macrocyclic molecule contains unsubstituted phthalocyanine, substituted phthalocyanine, or a combination thereof.

[0078] Statement 26. The fiber bundle contactor of any one of Statements 21 to 25, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof.

[0079] Statement 27. The fiber bundle contactor of any one of Statements 21 to 26, wherein the unsubstituted phthalocyanine or the substituted phthalocyanine contains a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0080] Statement 28. The fiber bundle contactor of any one of Statements 21 to 27, wherein the catalytic carbon fiber bundle contains carbon fiber, ethylenediamine covalently bonded to the carbon fiber, and phthalocyanine.

[0081] Statement 29. The fiber bundle contactor of any one of Statements 21 to 28, wherein the catalytic carbon fiber has a secondary mercaptan oxidation rate constant of at least 5.45×10^-4 (1 / M×min) at 38°C.

[0082] Statement 30. A method comprising: introducing a hydrocarbon containing mercaptan sulfur, an aqueous caustic solution, and an oxidizing agent into a container; reacting at least a part of the mercaptan sulfur and the aqueous caustic solution to produce a mercaptide; and reacting the mercaptide and the oxidizing agent in the presence of a catalytic carbon fiber bundle to produce a disulfide oil.

[0083] Statement 31. The method of Statement 30, wherein the catalytic carbon fiber bundle comprises carbon fibers, an amine compound covalently bonded to the carbon fibers, and an organometallic macrocyclic molecule covalently bonded to the amine compound.

[0084] Statement 32. The method according to any one of Statements 30 to 31, wherein the amine compound comprises a primary or secondary polyamine having a carbon chain length of C2 to C20.

[0085] Statement 33. The method according to any one of Statements 30 to 32, wherein the amine compound comprises at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

[0086] Statement 34. The method according to any one of Statements 30 to 33, wherein the organometallic macrocyclic molecule comprises an unsubstituted phthalocyanine, a substituted phthalocyanine, or a combination thereof.

[0087] Statement 35. The method according to any one of Statements 30 to 34, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof.

[0088] Statement 36. The method of Statements 30-35, wherein the unsubstituted phthalocyanine or substituted phthalocyanine comprises a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0089] Statement 37. The method of Statements 30-36, further comprising contacting a hydrocarbon containing mercaptan sulfur and an aqueous caustic solution on a fiber bundle, wherein reacting a portion of the mercaptan sulfur and the aqueous caustic solution to produce a mercaptide occurs within the fiber bundle.

[0090] Statement 38. The method of Statements 30-37, wherein reacting a mercaptide and an oxidizing agent in the presence of a catalytic carbon fiber bundle further produces a regenerated caustic agent stream, and the regenerated caustic agent stream is recycled to a vessel.

[0091] Statement 39. A method comprising introducing an aqueous solution containing a mercaptide and an oxidizing agent into a vessel; and reacting the mercaptide and the oxidizing agent in the presence of a catalytic carbon fiber bundle to produce an aqueous caustic solution.

[0092] Statement 40. The method of Statement 40, wherein the catalytic carbon fiber bundle comprises carbon fibers, a primary or secondary polyamine having a C2-C20 carbon length covalently bonded to the carbon fibers, and an unsubstituted phthalocyanine or substituted phthalocyanine covalently bonded to the amine compound.

[0093] Statement 41. A method for producing a catalytic carbon fiber, comprising: providing a carbon fiber and an aminated macrocyclic molecule; mixing the carbon fiber and the aminated macrocyclic molecule with a solvent; and reacting the carbon fiber and the aminated macrocyclic molecule to form an amide bond between the carbon fiber and the aminated macrocyclic molecule, thereby forming a catalytic carbon fiber.

[0094] Statement 42. The method of Statement 41, wherein the aminated macrocyclic molecule comprises an organometallic macrocyclic molecule and an amine group grafted to the organometallic macrocyclic molecule.

[0095] Statement 43. The method of Statement 42, wherein the organometallic macrocyclic molecule comprises an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof.

[0096] Statement 44. The method of Statement 43, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, a sulfonic acid group, or a combination thereof.

[0097] Statement 45. The method of Statements 43-44, wherein the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine comprises a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0098] Statement 46. The method according to claim 42, wherein the amine group comprises an amine having a carbon chain length of C2-C20.

[0099] Statement 47. A method according to any of Statements 41 - 46, wherein the solvent comprises at least one solvent selected from the group consisting of water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof.

[0100] Statement 48. A method according to Statement 42, wherein the amine group comprises a reaction product of at least one amine compound selected from ethylenediamine, propane - 1,3 - diamine, butane - 1,4 - diamine, pentane - 1,5 - diamine, hexamethylenediamine, diethylenetriamine, benzene - 1,3,5 - triamine, and combinations thereof.

[0101] Statement 49. A method according to any of Statements 41 - 48, wherein the aminated macrocyclic molecule comprises at least one of monoaminocobalt phthalocyanine, diaminocobalt phthalocyanine, triaminocobalt phthalocyanine, tetraaminocobalt phthalocyanine, and combinations thereof.

[0102] Statement 50. A method according to any of Statements 41 - 49, wherein reacting is carried out at a temperature in the range of about 100 °C to about 200 °C.

[0103] Statement 51. A method for producing a catalytic carbon fiber, comprising: providing a carbon fiber; reacting the carbon fiber with a chlorinating agent to produce a carbon fiber containing an acyl chloride; and reacting the carbon fiber containing an acyl chloride with an aminated macrocyclic molecule to form an amide bond between the carbon fiber containing an acyl chloride and the aminated macrocyclic molecule, thereby forming a catalytic carbon fiber.

[0104] Statement 52. A method according to Statement 51, wherein the chlorinating agent comprises a chlorinating agent selected from the group consisting of thionyl chloride, phosphorus trichloride, terephthaloyl chloride, and combinations thereof.

[0105] Statement 53. The method according to any one of Statements 51 to 52, wherein the aminated macrocyclic molecule comprises an organometallic macrocyclic molecule and an amine group grafted to the organometallic macrocyclic molecule.

[0106] Statement 54. The method according to Statement 53, wherein the organometallic macrocyclic molecule comprises an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof.

[0107] Statement 55. The method according to any one of Statements 53 to 54, wherein the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, a sulfonic acid group, or a combination thereof.

[0108] Statement 56. The method according to any one of Statements 53 to 55, wherein the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine comprises a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof.

[0109] Statement 57. The method according to any one of Statements 51 to 56, further comprising removing thionyl chloride from the carbon fiber containing acyl chloride and dispersing the carbon fiber containing acyl chloride in a solvent before reacting the aminated macrocyclic molecule with the carbon fiber containing acyl chloride.

[0110] Statement 58. The method according to any one of Statements 51 to 57, wherein the step of reacting the aminated macrocyclic molecule with the carbon fiber containing acyl chloride comprises reacting in the presence of pyridine.

[0111] Statement 59. A method for producing a catalytic carbon fiber, comprising: providing a carbon fiber; reacting the carbon fiber with a coupling agent to produce a functionalized carbon fiber; and reacting the functionalized carbon fiber with an aminated macrocyclic molecule to form an amide bond between the carbon fiber and the aminated macrocyclic molecule, thereby forming a catalytic carbon fiber.

[0112] Statement 60. The method of Statement 59, wherein the coupling agent comprises a carbodiimide, benzotriazole, or a combination thereof.

[0113] Statement 61. A method for producing a catalytic carbon fiber, comprising: providing a carbon fiber; providing an enzyme capable of catalyzing amide bond formation; and reacting the carbon fiber with an aminated macrocyclic molecule in the presence of the enzyme to form a bond between the carbon fiber and the aminated macrocyclic molecule, thereby forming a catalytic carbon fiber.

[0114] Statement 62. The method of Statement 61, wherein the enzyme comprises an enzyme selected from the group consisting of protease, subtilisin, acylrase, amidase, lipase, and combinations thereof.

[0115] Examples To facilitate a better understanding of the present disclosure, some of the following illustrative examples of embodiments are provided. Such examples should in no way be read as limiting or defining the scope of the present disclosure.

[0116] Example 1 In this example, the mercaptan oxidation potential of virgin carbon fiber was evaluated. Kerosene containing 300 ppm of mercaptan sulfur was prepared. A 3-gram sample of virgin carbon fiber and 150 mL of mercaptan sulfur-containing kerosene were vigorously mixed at 300 RPM and 38 °C in a shaker bath. The kerosene samples were withdrawn over 30 minutes, and the mercaptan concentration in each sample was determined by titration. The secondary mercaptan oxidation rate constant was calculated to be 0.22×10 -4 (l / M×min). It was observed that virgin carbon fiber showed little catalytic activity for mercaptan oxidation.

[0117] Example 2 In this example, carbon fiber modified with cobalt phthalocyanine was prepared, and the mercaptan oxidation of the modified carbon fiber was evaluated. A dimethyl sulfoxide (DMSO) solution was prepared by mixing 4 g of 4-aminopyridine with 200 mL of DMSO. Then, 4 grams of virgin carbon fiber was weighed and added to the DMSO solution, and the mixture was maintained at 80 °C for 22 hours. The carbon fiber was washed with isopropyl alcohol, followed by washing with distilled water, and dried in air at 60 °C. After drying, the carbon fiber was mixed at room temperature for 15 hours in an aqueous solution containing 1% cobalt phthalocyanine dibromide. Then, the carbon fiber modified with cobalt phthalocyanine was washed with distilled water and dried at 60 °C.

[0118] Kerosene containing 300 ppm of mercaptan sulfur was prepared. A 3-gram sample of the carbon fiber modified with cobalt phthalocyanine from this example and 150 mL of mercaptan sulfur-containing kerosene were vigorously mixed at 300 RPM and 38 °C in a shaker bath. The kerosene samples were withdrawn over 30 minutes, and the mercaptan concentration in each sample was determined by titration. The secondary mercaptan oxidation rate constant was calculated to be 3.5×10 -4 (l / M×min).

[0119] Example 3 In this example, carbon fibers modified with cobalt phthalocyanine were prepared by the method described above, and the mercaptan oxidation of the modified carbon fibers was evaluated. 10 g of virgin carbon fibers were weighed and added to 175 mL of 70% nitric acid at 80 °C for 5 hours. After the nitric acid treatment, the carbon fibers were washed with distilled water and then mixed with ethylenediamine at 105 °C for 3 hours to obtain amine-modified carbon fibers. Then, the amine-modified carbon fibers were added to a pyridine solution containing 1.3 wt.% of cobalt phthalocyanine dibromide at room temperature for 22 hours.

[0120] Kerosene containing 300 ppm of mercaptan sulfur was prepared. 3 grams of a sample of the carbon fibers modified with cobalt phthalocyanine from this example and 150 mL of the mercaptan sulfur-containing kerosene were vigorously mixed in a shaker bath at 300 RPM and 38 °C. The kerosene samples were withdrawn over 30 minutes, and the mercaptan concentration in each sample was determined by titration. The secondary mercaptan oxidation rate constant was calculated to be 5.45×10 -4 (l / M×min). It was observed that the mercaptan oxidation activity increased by 56% using the amine method for preparing carbon fibers modified with cobalt phthalocyanine.

[0121] Accordingly, the present disclosure is well-suited to attain the stated objects and advantages and all that is essential thereto. Since the present disclosure may be modified and embodied in different but equivalent manners which will be apparent to those skilled in the art having the benefit of the teachings herein, the specific embodiments disclosed above are merely illustrative. While individual embodiments are considered, the present disclosure covers all combinations of all such embodiments. Further, no limitation is intended with respect to the details of the structure or design shown herein other than as described in the claims below. Also, the terms of the claims have their plain ordinary meaning unless explicitly and clearly defined by the patentee. Therefore, it is evident that the specific illustrative embodiments disclosed above may be changed or modified and that all such variations are to be considered within the scope or spirit of the present disclosure. In case of any dispute in the use of words or terms in this specification and one or more patents or other documents incorporated herein by reference, the definitions consistent with this specification should be adopted.

Claims

1. oxidizing virgin carbon fibers to produce oxidized carbon fibers; reacting the oxidized carbon fibers with a polyamine compound to produce amine-modified carbon fibers and forming a covalent bond between the oxidized carbon fibers and the polyamine compound; and reacting the amine-modified carbon fibers with a metal phthalocyanine to produce catalytic carbon fibers and forming a covalent bond between the amine-modified carbon fibers and the metal phthalocyanine A method for producing catalytic carbon fibers, comprising:

2. The method according to claim 1, wherein the oxidation step comprises contacting the virgin carbon fibers with an acid selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, hydroiodic acid, fluoroantimonic acid, carborane acid, fluoroboric acid, fluorosulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid, perchloric acid, acetic acid, formic acid, citric acid, oxalic acid, tartaric acid, and combinations thereof.

3. The method according to claim 1, wherein the polyamine compound comprises a primary or secondary polyamine having a carbon chain length of C2-C20.

4. The method according to claim 1, wherein the polyamine compound comprises at least one polyamine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof.

5. The metal phthalocyanine includes an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof, the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof, and the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine includes a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof. The method according to claim 1.

6. Providing carbon fibers and an unsubstituted metal phthalocyanine and / or a substituted metal phthalocyanine, wherein an amine having a carbon chain length of C2-C20 is covalently bonded to the unsubstituted metal phthalocyanine and the substituted metal phthalocyanine, the substituted metal phthalocyanine is substituted with at least one of a halogen group, a hydroxyl group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, a sulfonic acid group, or a combination thereof, and the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine includes a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof. Mixing the carbon fibers with the unsubstituted metal phthalocyanine and / or the substituted metal phthalocyanine in a solvent; and Reacting the carbon fibers with the unsubstituted metal phthalocyanine and / or the substituted metal phthalocyanine to form a covalent bond therebetween, thereby forming catalytic carbon fibers. A method for producing catalytic carbon fibers, comprising **Claim 7** The method according to claim 6, wherein the solvent comprises at least one solvent selected from the group consisting of water, pyridine, DMSO, DMF, THF, ethanol, acetonitrile, chloroform, ethylene glycol, methanol, benzene, and combinations thereof. **Claim 8** The method according to claim 6, wherein the amine comprises at least one amine compound selected from ethylenediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, diethylenetriamine, benzene-1,3,5-triamine, and combinations thereof, and the unsubstituted metal phthalocyanine and / or the substituted metal phthalocyanine comprises at least one of monoaminocobalt phthalocyanine, diaminocobalt phthalocyanine, triaminocobalt phthalocyanine, tetraaminocobalt phthalocyanine, and combinations thereof. **Claim 9** A flow path defined by a conduit; A catalytic carbon fiber bundle disposed in the conduit, wherein the catalytic carbon fibers comprise carbon fibers, an amine compound covalently bonded to the carbon fibers, and an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof covalently bonded to the amine compound, the substituted metal phthalocyanine being substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof, and the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine comprising a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof; and An inlet allowing the flow of fluid into the flow path A fiber bundle contactor comprising **Claim 10** The fiber bundle contactor according to claim 9, wherein the amine compound comprises a primary or secondary polyamine having a carbon chain length of C2 - C20. **Claim 11** The fiber bundle contactor according to claim 9, wherein the amine compound comprises at least one polyamine compound selected from ethylenediamine, propane - 1,3 - diamine, butane - 1,4 - diamine, pentane - 1,5 - diamine, hexamethylenediamine, diethylenetriamine, benzene - 1,3,5 - triamine, and combinations thereof. **Claim 12** The fiber bundle contactor according to claim 9, wherein the catalytic carbon fiber bundle comprises carbon fibers and ethylenediamine and phthalocyanine covalently bonded to the carbon fibers. **Claim 13** Introducing a hydrocarbon containing mercaptan sulfur, an aqueous caustic solution, and an oxidizing agent into a container; Reacting at least a portion of the mercaptan sulfur and the aqueous caustic solution to produce a mercaptide; and Reacting the mercaptide and the oxidizing agent in the presence of a catalytic carbon fiber bundle to produce a disulfide oil, wherein the catalytic carbon fiber bundle comprises carbon fibers, an amine compound covalently bonded to the carbon fibers, and an unsubstituted metal phthalocyanine, a substituted metal phthalocyanine, or a combination thereof covalently bonded to the amine compound, the substituted metal phthalocyanine being substituted with at least one of a halogen group, a hydroxyl group, an amine group, an alkyl group, an aryl group, a thiol group, an alkoxy group, a nitrosyl group, or a combination thereof, and the unsubstituted metal phthalocyanine or the substituted metal phthalocyanine containing a metal selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and combinations thereof, the reacting A method comprising.

14. The method according to claim 13, wherein the amine compound comprises a primary or secondary polyamine having a carbon chain length of C2 - C20.

15. The method according to claim 13, wherein the amine compound comprises at least one polyamine compound selected from ethylenediamine, propane - 1,3 - diamine, butane - 1,4 - diamine, pentane - 1,5 - diamine, hexamethylenediamine, diethylenetriamine, benzene - 1,3,5 - triamine, and combinations thereof.

16. The method according to claim 13, further comprising contacting the hydrocarbon containing mercaptan sulfur and the aqueous caustic solution on the fiber bundle, wherein the reaction of the portion of the mercaptan sulfur and the aqueous caustic solution to produce a mercaptide occurs within the fiber bundle.

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