Process for modifying hydrogenation catalysts

Abstract

An embodiment of the present disclosure relates to a process for reforming a catalyst, the process including the steps of introducing a precursor reactant and hydrogen gas into a conversion reactor, contacting the precursor reactant with a conversion catalyst in the conversion reactor, thereby producing an active reactant, introducing the active reactant into a production reactor, and contacting the active reactant with a hydrogenation catalyst in the production reactor, thereby producing a reformed hydrogenation catalyst.

Description

Description of Related Applications

[0001] This application claims priority to U.S. Patent Application No. 17 / 147,682, filed January 13, 2021, the entire contents of which are incorporated herein by reference. [Technical Field]

[0002] FIELD OF THE DISCLOSURE This disclosure relates to catalyst modification, and more particularly to the pretreatment of hydrogenation catalysts. [Background technology]

[0003] Hydrotreating involves contacting a hydrocarbon feed with a hydrogenation catalyst in the presence of hydrogen. Hydrogenation catalysts typically contain active metals supported on alumina. These active metals are deposited in oxide form and must be converted to sulfides before they can catalyze hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrocracking (HCR), and hydrodemetalization (HDM) reactions.

[0004] Traditionally, catalyst sulfiding is performed in situ (within the reactor) by injecting a liquid sulfide precursor into the production catalyst bed along with hydrogen and the hydrocarbon feed. The sulfur in the liquid sulfide precursor and hydrocarbon feed is converted in situ to HS gas, which can then convert the oxide form of the active metal to the sulfide form. Pure HS gas can be used if it is readily available in the refinery, but pure HS gas is often not available in the required purity and concentration. Therefore, dimethyl disulfide (DMDS) is the most commonly used option in refineries.

[0005] Liquid sulfide precursors can contain contaminants such as sodium and potassium. Additionally, some sulfide precursors are inexpensive, and it would be desirable to use them if they did not contain relatively high levels of contaminants. For example, disulfide oil (DSO) is an inexpensive sulfide precursor that is not frequently used due to its relatively high levels of contaminants, including sodium, potassium, carbon, nitrogen, water, iron, mercury, phosphorus, and vanadium. When the sulfide precursor is converted to gaseous sulfide, contaminants initially present in the liquid can remain as residue on the surface of the hydrogenation catalyst, poisoning the catalyst.

[0006] Some hydrogenation catalysts, such as those containing zeolites, can become too active after the sulfiding step. This excess activity can cause temperature excursions after the introduction of the hydrocarbon feed. This excess activity is usually controlled by a process known as nitrogen or ammonia passivation. In the passivation process, ammonia compounds are injected into the reactor. The ammonia adsorbs onto the acidic sites of the catalyst, poisoning these sites. Once the cracking bed has been properly treated with ammonia, the hydrocarbon feed can be introduced into the unit without risk of temperature excursions. Ammonia passivation can also alter the selectivity of the catalyst.

[0007] However, liquid ammonia precursors are generally preferred over pure ammonia because handling ammonia can be expensive. Leaks and spills can pose serious health and safety hazards. Ammonia can damage pumps and valves. Therefore, injection of nitrogen-containing organic agents is generally preferred over ammonia. These organic compounds react with hydrogen on the hydrogenation catalyst to form the ammonia necessary to passivate the catalyst. Ammonia precursors, like sulfurized precursors, can also contain contaminants that can be left on the surface of the catalyst when ammonia is formed. These contaminants can cause problems with catalyst activity.

[0008] Conventional processes for modifying hydrogenation catalysts, such as sulfidation and ammonia deactivation, require direct contact between a liquid precursor of the sulfiding / ammonia agent and the hydrogenation catalyst, which can cause contaminants present in the liquid precursor to deposit on the surface of the hydrogenation catalyst, resulting in premature deactivation. Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, new processes for producing modified hydrogenation catalysts are desirable. [Means for solving the problem]

[0010] A process that does not require direct contact of a liquid precursor reactant with a hydrogenation catalyst. Embodiments of the present disclosure fill this need by providing a process and apparatus for converting a hydrogenation catalyst to a modified hydrogenation catalyst using a gaseous reactant. Specifically, the embodiments fill this need by converting a liquid precursor reactant to a gaseous active reactant in a conversion reactor and then contacting the hydrogenation catalyst with the gaseous active reactant.

[0011] In accordance with the subject matter of the present disclosure, a process for modifying a catalyst may include introducing a precursor reactant into a conversion reactor, contacting the precursor reactant with a conversion catalyst in the conversion reactor, thereby producing an active reactant, introducing the active reactant into a production reactor, and contacting the active reactant with a hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst.

[0012] Although the concepts of the present disclosure are described herein primarily with respect to sulfiding of hydrogenation catalysts, it is believed that the concepts will enjoy applicability to any reforming of hydrogenation catalysts.

[0013] Abbreviation m 3 = cubic meters kg = kilograms kg / m 3= kilogram per cubic metre DMDS = dimethyl disulfide mass% = mass percent MoO3 = molybdenum trioxide CoO = cobalt oxide H2S = Hydrogen Sulfide Mol. = mole ℃=degree Celsius temperature °C / hr = degrees Celsius per hour Min. = minutes Sec.=second Hr.=hour ppm=mass parts per million bpsd = barrels per working day DETAILED DESCRIPTION OF THE INVENTION

[0014] Traditionally, reforming of hydrogenation catalysts has been plagued by contamination from residues of liquid precursor reagents. Therefore, relatively expensive liquid precursor reagents with minimal levels of contaminants are required. Therefore, a process that allows the use of less pure (and therefore less expensive) liquid reforming precursors is desirable.

[0015] In accordance with the presently disclosed subject matter, a process for modifying a hydrogenation catalyst may include introducing a precursor reactant to a conversion reactor, contacting the precursor reactant with a conversion catalyst in the conversion reactor, thereby producing an active reactant, introducing the active reactant to a production reactor, and contacting the active reactant with a hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst.

[0016] As used herein, a "conversion reactor" may be any reactor configured to convert a precursor agent into an active agent. The conversion reactor may be located upstream of a production reactor. The conversion reactor may be part of a system structurally configured to transport the active agent from the conversion reactor to the production reactor. The conversion reactor may not be the same reactor as the production reactor.

[0017] The conversion reactor may be any reactor designed to convert precursor reactants into active reactants. For example, the conversion reactor may be a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, or a fluidized bed reactor. A fixed bed reactor may refer to a reactor in which the catalyst does not move during the catalytic reaction. A moving bed reactor may refer to a reactor in which the catalyst, along with the reactants, constantly flows through the reactor. A ebullated bed reactor may refer to a reactor in which the catalyst is suspended in liquid reactants. A fluidized bed reactor may refer to a reactor in which the catalyst is suspended in the reactant gas.

[0018] According to some embodiments, the conversion reactor may be decoupled from the production reactor so as to be independently controllable. For example, the conversion reactor may be completely decoupled from the production reactor except for a pipe or series of pipes connecting them.

[0019] The tubing connecting the conversion reactor with the production reactor may include a device for removing contaminants from the active agent. For example, the device for removing contaminants from the active agent may include one or more of a filter, scrubber, absorber, zeolite, magnet, liquid / gas separator, or flow pattern designed to remove solids. According to an alternative embodiment, the tubing connecting the conversion reactor with the production reactor may not have a device for removing contaminants. Without being limited by theory, it is believed that any contaminants will be deposited on the conversion catalyst and therefore will not be present in the active agent.

[0020] A precursor reactant may be introduced into the conversion reactor. The precursor reactant may be introduced into the conversion reactor through a pipe, inlet, valve, or other controllable inlet. The precursor reactant may be introduced into the conversion reactor using a pump.

[0021] The precursor agent may be introduced into the conversion reactor as a liquid. Alternatively, the precursor agent may be introduced into the conversion reactor as a vapor. Without being limited by theory, it is believed that using a liquid precursor agent is preferable to using a gaseous (precursor or active) agent because liquids tend to be easier to store and transport. Liquids are easier to store and transport due to their increased density and the fact that they often do not require a pressure vessel.

[0022] Hydrogen gas may be introduced into the conversion reactor. The hydrogen gas may be introduced into the conversion reactor along with the precursor agent at a hydrogen:precursor agent molar ratio of 1:1 to 10:1. For example, the hydrogen:precursor agent molar ratio may be 1:1 to 8:1, 1:1 to 6:1, 1:1 to 4:1, 1:1 to 2:1, 2:1 to 10:1, 2:1 to 8:1, 2:1 to 6:1, 2:1 to 4:1, 4:1 to 10:1, or any subrange thereof.

[0023] Without being limited by theory, it is believed that hydrogen gas may be necessary to convert certain precursor agents to their respective active agents. For example, when a carbon-sulfur bond is broken, one hydrogen atom is added to the hydrocarbon and one hydrogen atom is added to the sulfur. Therefore, two additional hydrogen atoms are required per carbon-sulfur bond.

[0024] The precursor reactant may contact a conversion catalyst in the conversion reactor, thereby producing an active reactant. The choice of conversion catalyst will depend on the precursor reactant required. The active reactant produced may be in gas form.

[0025] The precursor reactant may be contacted with the conversion catalyst at a conversion temperature sufficient to convert the precursor reactant to the active reactant by a given conversion catalyst. For example, the precursor reactant may be contacted with the conversion catalyst at a conversion temperature of 150° C. to 300° C., 200° C. to 300° C., 150° C. to 250° C., 200° C. to 250° C., 210° C. to 240° C., 220° C. to 230° C., or any subrange thereof.

[0026] The precursor agent may be contacted with the conversion catalyst at a pressure of 1 bar (100 kPa) to 100 bar (10 MPa). For example, the precursor agent may be contacted with a pressure of 1 bar (100 kPa) to 80 bar (8 MPa), 1 bar (100 kPa) to 60 bar (6 MPa), 1 bar (100 kPa) to 50 bar (5 MPa), 1 bar (100 kPa) to 40 bar (4 MPa), 10 bar (1 MPa) to 100 bar (10 MPa), 10 bar (1 MPa) to 80 bar (8 MPa), 10 bar (1 MPa) to 100 bar (10 ... The conversion catalyst may be contacted at a pressure from 10 bar (1 MPa) to 60 bar (6 MPa), 10 bar (1 MPa) to 40 bar (4 MPa), 20 bar (2 MPa) to 100 bar (10 MPa), 20 bar (2 MPa) to 80 bar (8 MPa), 20 bar (2 MPa) to 60 bar (6 MPa), 20 bar (2 MPa) to 40 bar (4 MPa), or any sub-range thereof.

[0027] The precursor reactant may be contacted with the conversion catalyst for a contact time sufficient to completely convert the precursor reactant to the active reactant. For example, the precursor reactant may have a residence time in the conversion reactor of 1 second to 1 hour, 15 seconds to 1 hour, 30 seconds to 1 hour, 1 minute to 1 hour, 10 minutes to 1 hour, 20 minutes to 1 hour, 30 minutes to 1 hour, 1 second to 30 minutes, 1 second to 10 minutes, 1 second to 1 minute, 30 seconds to 1 hour, 1 minute to 30 minutes, or any subrange thereof.

[0028] The precursor reactant may continue to be introduced into the conversion reactor after breakthrough is reached in the conversion reactor. As used herein, "breakthrough" may refer to the point at which the concentration of active reactant in the gas exiting the reactor reaches 5,000 ppm. Without being limited by theory, it is believed that prior to breakthrough, very little active reactant is found in the gas exiting the production reactor because the hydrogenation catalyst has consumed nearly all of the active reactant prior to breakthrough. Breakthrough is understood to signal that substantially all of the catalyst has been converted from its original form to a modified form. After breakthrough, continued exposure to the active reactant is believed to cause minimal further changes in the catalyst bed. Therefore, it is believed that the concentration of active reactant flowing from the conversion reactor to the production reactor will increase significantly once breakthrough is achieved in the conversion reactor.

[0029] The active agent may be passed from the conversion reactor to the production reactor. For example, the active agent may be passed from the conversion reactor to the production reactor through a pipe or duct.

[0030] The active agent may be introduced into the production reactor. The active agent may be introduced from the conversion reactor to the production reactor by piping. The active agent may be introduced into the production reactor using a valve or other metering device.

[0031] The production reactor may include any reactor adapted to carry out hydrotreating reactions. The production reactor may include a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, or a fluidized bed reactor.

[0032] Introducing the active agent into the production reactor may further include one or more of pumping, compressing, heating, or cooling the active agent. For example, introducing the active agent into the production reactor may include pumping the active agent. In an alternative embodiment, the active agent may flow from the conversion reactor to the production reactor due to a pressure gradient between the conversion reactor and the production reactor.

[0033] The active agent may be introduced into the production reactor as a gas. Without being limited by theory, it is believed that the most significant contaminants present in the precursor agent will be left behind as residue during decomposition of the precursor agent. Therefore, introducing the active agent into the production reactor will help prevent contaminants in the precursor agent from entering the production reactor and contaminating the hydrogenation catalyst.

[0034] The precursor agent may have a higher level of contaminants than would be desirable if directly exposed to a hydrogenation catalyst. Thus, the total mass of all contaminants in the precursor agent may be at least 1 ppm. For example, the total mass of all contaminants may be at least 10 ppm, at least 100 ppm, at least 1000 ppm, at least 10,000 ppm, or even at least 100,000 ppm. The contaminants may include one or more of sodium, potassium, carbon, nitrogen, water, iron, mercury, phosphorus, and vanadium.

[0035] The active agent may contact the hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst. According to some embodiments, such as those in which the hydrogenation catalyst is converted to a sulfided form, the modified hydrogenation catalyst may be more active than the unsulfided hydrogenation catalyst. According to alternative embodiments, such as those in which the hydrogenation catalyst is converted to an ammonia form, the modified hydrogenation catalyst may be less reactive than the hydrogenation catalyst.

[0036] The activating agent may be contacted with the hydrogenation catalyst at a reforming temperature sufficient to convert the hydrogenation catalyst to a modified hydrogenation catalyst. For example, the reforming temperature may be 150°C to 300°C, 175°C to 300°C, 200°C to 300°C, 225°C to 300°C, 150°C to 275°C, 150°C to 250°C, 150°C to 225°C, 175°C to 275°C, 175°C to 250°C, 175°C to 225°C, 200°C to 275°C, 200°C to 250°C, 200°C to 225°C, or any subrange thereof.

[0037] The activating agent may be contacted with the hydrogenation catalyst at a reforming pressure sufficient to convert the hydrogenation catalyst to a modified hydrogenation catalyst. For example, the reforming pressure may be from 50 bar (5 MPa) to 100 bar (10 MPa), from 50 bar (5 MPa) to 90 bar (9 MPa), from 60 bar (6 MPa) to 100 bar (10 MPa), from 60 bar (6 MPa) to 90 bar (9 MPa), from 70 bar (7 MPa) to 80 bar (8 MPa), or any subrange thereof.

[0038] The active agent may be contacted with the hydrogenation catalyst at an active agent partial pressure of from 50 bar (5 MPa) to 1000 bar (10 MPa), from 50 bar (5 MPa) to 90 bar (9 MPa), from 60 bar (6 MPa) to 100 bar (10 MPa), from 60 bar (6 MPa) to 90 bar (9 MPa), from 70 bar (7 MPa) to 80 bar (8 MPa), or any subrange thereof.

[0039] The active agent may be contacted with the hydrogenation catalyst until breakthrough is achieved for the production reactor. This may be done by introducing the precursor agent into the conversion reactor until breakthrough is achieved in the production reactor. It should be understood that the conversion reactor and the production reactor may reach breakthrough at different times.

[0040] Generally, it is necessary to change the activity of a hydrogenation catalyst by contacting it with an activating agent to form a modified hydrogenation catalyst. The activity of a hydrogenation catalyst can be increased by contacting it with sulfide molecules in a process known as "sulfiding." Some hydrogenation catalysts, particularly those containing zeolites, have high activity or can become highly active after sulfiding. In such cases, the activity of the hydrogenation catalyst can be decreased by contacting it with ammonia compounds in a process known as "ammonia passivation."

[0041] According to embodiments in which the active agent comprises a sulfide, the active agent may be introduced into the production reactor such that the molar ratio of active agent:active metal is greater than 1: 1. For example, the molar ratio of active agent:active metal may be from 1:1 to 4:1, from 2:1 to 4:1, from 3:1 to 4:1, from 1:1 to 3:1, from 1:1 to 2:1, or any subrange thereof.

[0042] According to some embodiments, the active agent may include a sulfide, such as hydrogen sulfide. The active agent may include at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 99% by weight, or even at least 99.9% by weight of hydrogen sulfide.

[0043] The precursor agent may include a sulfide precursor. The sulfide precursor may include any chemical that contains sulfur atoms and can be converted to a sulfur-containing gas. Without being limited by theory, it may be preferable to use a liquid sulfide precursor rather than a gaseous sulfide because a liquid sulfide precursor may have improved handling characteristics compared to a gaseous sulfide.

[0044] The sulfide precursor may include one or more organic monosulfides or polysulfides or oxides thereof. For example, the organic polysulfide may include one or more dialkyl-polysulfides having the formula R-Sn-R', where R and R' are carbon chains having 1 to 20 carbon atoms. For example, the sulfide precursor may include one or more tertiary butyl polysulfides (BPS, dimethyl disulfide (DMDS)). The sulfide precursor may include one or more thiophenes, mercaptans, dialkyl disulfides, and diaryl disulfides. The sulfide precursor may include one or more of carbon disulfide, DMDS, disulfide oil (DSO), dimethyl sulfide, diethyl sulfide, dimethyl sulfoxide, n-butyl mercaptan, di-tert-butyl polysulfide, or di-tert-nonyl polysulfide. According to some embodiments, the sulfide precursor may include dimethyl sulfoxide (DMSO).

[0045] The precursor agent can be any sulfur-containing hydrocarbon fraction. For example, the hydrocarbon fraction can be kerosene. Kerosene can refer to a hydrocarbon fraction boiling in the range of 150° C. to 275° C. Kerosene can refer to a hydrocarbon fraction having between 10 and 16 carbon atoms per molecule.

[0046] The sulfide precursor may be disulfide oil (DSO) or an oxide of disulfide oil. DSO would be a suitable sulfide precursor due to its extremely low cost and availability in many refinery environments. Without being limited by theory, it is believed that DSO would be a relatively inefficient sulfiding agent by conventional methods due to its relatively high concentration of contaminants. However, according to the method of the present invention, the conventional disadvantages of DSO would be less relevant because the disadvantages of DSO only affect the conversion reactor and not the production reactor.

[0047] DSO may be produced in refineries by the mercaptan oxidation (MEROX) process. In the MEROX process, light hydrocarbon fractions (such as liquid petroleum gas (LPG), C3-C4, light naphtha, heavy naphtha, and kerosene) are treated to convert mercaptans to metal thiolates, which are then converted to disulfide oils. A thorough description of the MEROX process can be found in U.S. Patent Application Publication No. 2020 / 0181073 A1.

[0048] The sulfide precursor may contain less than 100 ppm nitrogen. For example, the sulfide precursor may contain less than 80 ppm, less than 60 ppm, less than 40 ppm, less than 20 ppm, or even less than 10 ppm nitrogen.

[0049] The precursor conversion catalyst may include a sulfide conversion catalyst. The sulfide conversion catalyst may include any catalyst suitable for converting a sulfide precursor to a gaseous sulfide, such as HS. For example, the precursor conversion catalyst may include one or more of Co, Mo, Ni, W, and alumina. The alumina may be in the form of amorphous alumina, zeolite, or silica-alumina. The precursor conversion catalyst may have the same composition as the hydrogenation catalyst. Alternatively, the precursor conversion catalyst may have a different composition than the hydrogenation catalyst. According to some particular embodiments, the sulfide conversion catalyst may include Co-Mo.

[0050] According to some embodiments, the active agent may include a nitrogen compound. For example, the active agent may include ammonia. The active agent may include at least 1000 ppm ammonia. For example, the active agent may comprise 1000 ppm to 100,000 ppm, 1000 ppm to 75,000 ppm, 1000 ppm to 50,000 ppm, 1000 ppm to 10,000 ppm, 1000 ppm to 5000 ppm, 5000 ppm to 100,000 ppm, 5000 ppm to 75,000 ppm, 5000 ppm to 50,000 ppm, 5000 ppm to 10,000 ppm, 10,000 ppm to 100,000 ppm, 10,000 ppm to 75,000 ppm, 10,000 ppm to 50,000 ppm, 50,000 ppm to 100,000 ppm, or any sub-range thereof, of ammonia.

[0051] The precursor agent may include an ammonia precursor. The ammonia precursor may include any chemical that contains nitrogen atoms and can be converted to a gas that contains ammonia. The use of an ammonia precursor may be preferred over ammonia because the use of gaseous ammonia would require dedicated hardware and equipment.

[0052] According to some embodiments, the conversion catalyst may be sulfided prior to ammonia passivation. According to alternative embodiments, the conversion catalyst may not be sulfided prior to exposure to the ammonia passivation process.

[0053] The precursor agent may include an ammonia precursor. For example, the ammonia precursor may include a nitrogen-containing organic molecule. The organic molecule may be one or both of an amine and an aniline. For example, the ammonia precursor may include one or more of a primary amine, a secondary amine, a tertiary amine, a diamine, a polyamine, an alkylamine, an arylamine, an arylalkylamine, an aniline, a methylaniline, a dimethylaniline, a diphenylamine, and a triphenylamine. According to some embodiments, the ammonia precursor may include one or both of an alkylamine and an ethanolamine. The ethanolamine may include one or more of N-methyldiethanolamine (DMEA), N-methylethanolamine (MAE), triethanolamine (TEA), 3-diethylamino-propylamine (DEAPA), N,N-dimethyldipropylenetriamine (DMAPAPA), tri-n-butylamine (TNBA), hexadecylamine (HDA), and oleylamine (OL, octa-9-decenylamine).

[0054] The precursor conversion catalyst may include an ammonia conversion catalyst. The ammonia conversion catalyst may include any catalyst suitable for converting an ammonia precursor to ammonia gas. For example, the precursor conversion catalyst may include one or more of Co, Mo, Ni, W, and alumina. The alumina may be in the form of amorphous alumina, zeolite, or silica-alumina. The ammonia conversion catalyst may have the same composition as the hydrogenation catalyst. Alternatively, the ammonia conversion catalyst may have a different composition than the hydrogenation catalyst. According to some embodiments, the precursor conversion catalyst may include Ni and Mo, or Ni and W.

[0055] Hydrogen gas may be introduced into the production reactor. The hydrogen gas may be introduced into the production reactor with the active agent at a hydrogen:active agent ratio of greater than 1:1. For example, the hydrogen:active agent ratio may be from 1:1 to 5:1, from 1:1 to 3:1, from 1:1 to 2:1, from 2:1 to 5:1, or any subrange thereof.

[0056] Without being limited by theory, it is believed that hydrogen gas may be required to convert some of the hydrogenation catalysts of the present disclosure to their respective modified forms. The additional hydrogen may increase the conversion rate and alter the equilibrium constant for the conversion of the hydrogenation catalyst to the modified hydrogenation catalyst.

[0057] As shown in Reactions (I)-(IV) below, not all common hydrogenation catalysts and active agents contain enough hydrogen to carry out the reaction that converts the hydrogenation catalyst to its modified form. Therefore, additional hydrogen may be required to completely convert all hydrogenation catalyst molecules to modified hydrogenation catalyst molecules. The additional hydrogen may increase the conversion rate and may also change the equilibrium constant for the conversion of the hydrogenation catalyst to its modified form. TIFF0007807176000001.tif49114

[0058] According to some embodiments, the hydrogenation catalyst may be a hydrocracking catalyst. According to other embodiments, the hydrogenation catalyst may be a hydrotreating catalyst or a residue hydrogenation catalyst. The hydrogenation catalyst may be any catalyst suitable for catalyzing hydrodesulfurization (HDS), hydrocracking, hydrodemetallization, or hydrodenitrogenation (HDN) reactions.

[0059] The hydrogenation catalyst may comprise alumina, silica-alumina, zeolite, or a combination thereof. The alumina may comprise amorphous alumina. The silica-alumina may comprise amorphous silica-alumina. The alumina, silica-alumina, zeolite, or a combination thereof may comprise a support for the active metal.

[0060] The hydrogenation catalyst may comprise one or more active metals selected from the group of Mo, W, Co, and Ni. The active metals may be in their oxide or sulfide form.

[0061] According to embodiments in which the modification of the hydrogenation catalyst is sulfidation, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or even at least 99% by weight of the active metals of the hydrogenation catalyst may be in oxide form prior to exposure to sulfide gas. For example, the oxide form of Mo may be MoO, the oxide form of Co may be CoO, the oxide form of Ni may be NiO, and the oxide form of W may be WO.

[0062] According to embodiments in which the modification of the hydrogenation catalyst is sulfiding, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 99%, or even at least 99.9% by weight of the active metals of the modified hydrogenation catalyst may be in sulfide form. For example, the sulfide form of Mo may be MoS2, the sulfide form of Co may be Co9S8, the sulfide form of Ni may be Ni3S2, and the sulfide form of W may be WS2.

[0063] According to embodiments in which the modification of the hydrogenation catalyst is ammonia passivation, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 99%, or even at least 99.9% by weight of the active metals of the hydrogenation catalyst may be in sulfide form prior to exposure to ammonia gas. For example, the sulfide form of Mo may be MoS, the sulfide form of Co may be CoS, the sulfide form of Ni may be NiS, and the sulfide form of W may be WS.

[0064] According to some embodiments, both sulfiding and ammonia passivation may be required. Ammonia passivation may occur after sulfiding. Thus, the precursor agent may include a sulfide precursor. The process may further include introducing an ammonia precursor to a conversion reactor, introducing hydrogen gas to the conversion reactor, and contacting the ammonia precursor with a conversion catalyst in the conversion reactor, thereby producing ammonia gas. The ammonia gas may then be introduced to a production reactor and contacted with the modified hydrogenation catalyst in the production reactor, thereby producing a sulfided and passivated hydrogenation catalyst. The ammonia precursor may be introduced to the conversion reactor as a liquid, and the ammonia gas may be introduced to the production reactor as a gas.

[0065] The sulfided, passivated hydrogenation catalyst may comprise an active metal and sulfur atoms in a molar ratio. According to some embodiments, the active metal may be molybdenum or tungsten, or both, and the sulfur:active metal molar ratio may be 1.9:1 to 2.1:1. According to other embodiments, the active metal may be nickel, and the sulfur:nickel molar ratio may be 1.9:3 to 2.1:3. According to yet other embodiments, the active metal may be cobalt, and the sulfur:cobalt molar ratio may be 7.5:9 to 8.5:9.

[0066] One or both of the hydrogenation catalyst and the conversion catalyst may be dried before being heated. Without being limited by theory, it is believed that if the catalyst is not dried before being heated to the conversion and reforming temperatures, respectively, the catalyst may explode due to vapor buildup within the catalyst pores. Additionally, it is believed that the catalyst should be dry for optimal accessibility to the metal sites.

[0067] The hydrogenation catalyst may be dried before exposing the hydrogenation catalyst to an activating agent. For example, the hydrogenation catalyst may be dried before exposing the hydrogenation catalyst to a hydrocarbon feedstock. Drying the hydrogenation catalyst may include heating the hydrogenation catalyst to a drying temperature for a drying time. The drying temperature may be 80°C to 150°C, 90°C to 150°C, 100°C to 150°C, 80°C to 140°C, 90°C to 140°C, 100°C to 140°C, or any subrange thereof. The drying time may be at least 1 hour, at least 2 hours, at least 4 hours, at least 8 hours, or any subrange thereof.

[0068] The conversion catalyst may be dried before exposing the conversion catalyst to a precursor agent. For example, the conversion catalyst may be dried before exposing the conversion catalyst to a hydrocarbon feedstock. Drying the conversion catalyst may include heating the conversion catalyst to a drying temperature for a drying time. The drying temperature may be 80°C to 150°C, 90°C to 150°C, 100°C to 150°C, 80°C to 140°C, 90°C to 140°C, 100°C to 140°C, or any subrange thereof. The drying time may be at least 1 hour, at least 2 hours, at least 4 hours, at least 8 hours, or any subrange thereof.

[0069] The hydrocarbon feedstock may be introduced into a conversion reactor, a production reactor, or both. In the conversion reactor, the hydrocarbon feedstock may contact a conversion catalyst. In the production reactor, the hydrocarbon feedstock may contact a hydrogenation catalyst. Contacting the catalyst with the hydrocarbon feedstock prior to the introduction of the active agent may be known as pre-wetting. Pre-wetting may be used in a sulfiding or ammonia passivation process. According to some embodiments, the sulfiding or ammonia passivation process may be performed without pre-wetting. According to yet other embodiments, the sulfiding or ammonia passivation may be performed after pre-wetting the conversion catalyst but before pre-wetting the hydrogenation catalyst. Without being limited by theory, it is believed that pre-wetting may wet the pores of the catalyst with the hydrocarbon feedstock, resulting in a uniform distribution of the active agent during the reforming process.

[0070] The hydrocarbon feedstock may comprise any liquid hydrocarbon. Preferably, the hydrocarbon feedstock will be a "straight-run" feedstock. As used herein, "straight-run" feedstock may refer to a feedstock that has not undergone a cracking process. Without being limited by theory, it is believed that cracked feedstocks will contain highly reactive olefinic compounds. It is believed that the olefinic compounds may be converted to coke and may damage the catalyst if used during the prewetting process.

[0071] The production reactor outlet stream may be separated into a liquid effluent and a gaseous effluent. The liquid effluent may be a liquid, and the gaseous effluent may be a gas at a temperature of 200°C and pressure within the production reactor. The gaseous effluent may include one or more of hydrocarbons, hydrogen gas, and active agents. The liquid effluent may include one or more of hydrocarbons and water.

[0072] At least a portion of the gaseous effluent may be recycled back to the production reactor. At least a portion of the gaseous effluent may be withdrawn or separated for other uses. 0% to 40% by weight of the gaseous effluent may be recycled back to the production reactor. For example, 0% to 30%, 0% to 20%, 0% to 10%, 1% to 40%, 1% to 30%, 1% to 10%, 10% to 40%, 30% to 40%, or any subrange thereof, of the gaseous effluent may be recycled back to the production reactor.

[0073] At least a portion of the liquid effluent may be recycled back to the production reactor. At least a portion of the liquid effluent may be withdrawn or separated for other uses. 10% to 50% by weight of the liquid effluent may be recycled back to the production reactor. For example, 0% to 40%, 10% to 30%, 10% to 20%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 50%, 30% to 40%, 40% to 50%, or any subrange thereof, of the liquid effluent may be recycled back to the production reactor. According to an alternative embodiment, the liquid effluent is not recycled back to the production reactor.

[0074] The conversion catalyst may be removed from the conversion reactor without removing the modified hydrogenation catalyst from the production reactor. Without being limited by theory, it may be preferable to remove only the conversion catalyst because the conversion catalyst may become deactivated by contaminants before the need to replace the modified hydrogenation catalyst arises.

[0075] The mass ratio of conversion catalyst to hydrogenation catalyst can be from 1:1000 to 100:1000. For example, the mass ratio of conversion catalyst to hydrogenation catalyst can be from 1:1000 to 80:1000, from 1:1000 to 60:1000, from 1:1000 to 20:1000, from 10:1000 to 100:1000, from 10:1000 to 80:1000, from 10:1000 to 60:1000, from 20:1000 to 100:1000, from 20:1000 to 80:1000, from 30:1000 to 100:1000, from 40:1000 to 100:1000, or any subrange thereof.

[0076] The total mass of all contaminants in the modified hydrogenation catalyst may be less than 1 wt.% of the total mass of the modified hydrogenation catalyst. For example, the total mass of contaminants may be less than 0.5 wt.%, less than 0.1 wt.%, less than 0.01 wt.%, less than 0.001 wt.%, less than 0.0001 wt.%, or even less than 0.00001 wt.% of the total mass of the modified hydrogenation catalyst. The contaminants may include one or more of sodium, potassium, carbon, nitrogen, water, iron, mercury, phosphorus, and vanadium.

[0077] The process may further include contacting the modified hydrogenation catalyst with a hydrotreating material in a hydrotreating process. The hydrotreating material may be referred to as naphtha, kerosene, diesel, or vacuum gas oil. As used herein, naphtha refers to a crude oil distillate having a boiling point between 20°C and 180°C. As used herein, "kerosene" refers to a petroleum fraction having a boiling point between 180°C and 240°C. As used herein, "diesel" refers to a petroleum fraction having a boiling point between 240°C and 370°C. As used herein, "vacuum gas oil" refers to a petroleum fraction having a boiling point between 370°C and 565°C.

[0078] The hydrotreating process may include hydrocracking or hydrotreating. Hydrocracking may involve contacting the modified hydrotreating catalyst with a hydrotreater and hydrogen at a pressure of 65 bar (6.5 MPa) to 200 bar (20 MPa) and a temperature of 400°C to 500°C. Hydrotreating may involve contacting the modified hydrotreating catalyst with a hydrotreater and hydrogen at a pressure of 30 bar (3 MPa) to 130 bar (13 MPa) and a temperature of 300°C to 450°C.

[0079] According to some embodiments, the hydrotreatable material does not contact the conversion catalyst. For example, the conversion catalyst may be removed from the conversion reactor after sufficient reforming of the hydrotreatable material has occurred. Alternatively, the flow of the hydrotreatable material to the production reactor may be routed, such as by using a valve, to bypass the conversion reactor after sufficient reforming of the hydrotreatable material has occurred. Sufficient reforming may be defined as reaching breakthrough or adsorbing a predetermined amount of ammonia.

[0080] According to one embodiment, either alone or in combination with any other embodiment, a process for modifying a hydrogenation catalyst includes introducing a precursor reactant to a conversion reactor, introducing hydrogen gas into the conversion reactor, contacting the precursor reactant with the conversion catalyst in the conversion reactor, thereby producing an active reactant, introducing the active reactant to a production reactor, and contacting the active reactant with the hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst, wherein the precursor reactant is introduced to the conversion reactor as a liquid and the active reactant is introduced to the production reactor as a gas.

[0081] According to a second aspect, either alone or in combination with any other aspect, the precursor agent comprises a sulfide precursor and the precursor conversion catalyst comprises a sulfide conversion catalyst.

[0082] According to a third aspect, either alone or in combination with any other aspect, the sulfide conversion catalyst comprises one or more of Co, Mo, W, Ni, and alumina.

[0083] According to the fourth aspect, either alone or in combination with any other aspect, the sulfide precursor comprises one or more organic monosulfides or polysulfides.

[0084] According to a fifth aspect, either alone or in combination with any other aspect, the precursor agent is disulfide oil (DSO).

[0085] According to a sixth aspect, either alone or in combination with any other aspect, the precursor agent comprises an ammonia precursor and the precursor conversion catalyst comprises an ammonia conversion catalyst.

[0086] According to a seventh aspect, either alone or in combination with any other aspect, the ammonia conversion catalyst comprises one or more of Co, Mo, W, Ni, and alumina.

[0087] According to an eighth aspect, either alone or in combination with any other aspect, the ammonia precursor comprises one or more organic compounds containing nitrogen.

[0088] According to a ninth aspect, either alone or in combination with any other aspect, the conversion catalyst is not sulfided.

[0089] According to a tenth aspect, either alone or in combination with any other aspect, the precursor agent comprises a sulfide precursor, and the process further comprises the steps of introducing an ammonia precursor to a conversion reactor, introducing hydrogen gas to the conversion reactor, contacting the ammonia precursor with a conversion catalyst in the conversion reactor, thereby producing ammonia gas, introducing the ammonia gas to a production reactor, and contacting the ammonia gas with a modified hydrogenation catalyst in the production reactor, thereby producing a sulfided and passivated hydrogenation catalyst, wherein the ammonia precursor is introduced to the conversion reactor as a liquid and the ammonia gas is introduced to the production reactor as a gas.

[0090] According to an eleventh aspect, either alone or in combination with any other aspect, the process further comprises introducing hydrogen gas into the production reactor.

[0091] According to a twelfth aspect, either alone or in combination with any other aspect, the process further comprises introducing a hydrocarbon feedstock into a conversion reactor.

[0092] According to a thirteenth aspect, either alone or in combination with any other aspect, the process further comprises separating the production reactor outlet stream into a liquid effluent and a gaseous effluent.

[0093] According to a fourteenth aspect, either alone or in combination with any other aspect, the process further comprises recycling at least a portion of the gaseous effluent back to the production reactor.

[0094] According to a fifteenth aspect, either alone or in combination with any other aspect, the process further comprises recycling at least a portion of the liquid effluent back to the production reactor.

[0095] According to a sixteenth aspect, either alone or in combination with any other aspect, the hydrogenation catalyst comprises alumina, silica-alumina, zeolite, or a combination thereof.

[0096] According to a seventeenth aspect, either alone or in combination with any other aspect, the hydrogenation catalyst comprises one or more of Mo, W, Co, or Ni.

[0097] According to an eighteenth aspect, either alone or in combination with any other aspect, the process further comprises continuing to introduce precursor agent into the conversion reactor after breakthrough is achieved in the conversion reactor.

[0098] According to a nineteenth aspect, either alone or in combination with any other aspect, the combined mass of all contaminants in the modified hydrogenation catalyst is less than 1 mass % of the total mass of the modified hydrogenation catalyst.

[0099] According to a twentieth aspect, either alone or in combination with any other aspect, the process further comprises contacting the modified hydrogenation catalyst with a hydrotreating material in a hydrotreating process, wherein the hydrotreating material does not contact a conversion catalyst. [Example]

[0100] Comparative Example 1: Sulfurization with Dimethyl Disulfide (DMDS) in a Production Reactor 370 metric tons of pretreatment and hydrogenation catalyst was loaded into the first stage of the hydrocracker. 56 volume percent of the catalyst was pretreatment catalyst and 44 volume percent of the catalyst was cracking catalyst. The pretreatment catalyst was in a separate reactor upstream from and in series with the cracking catalyst.

[0101] Catalyst drying: Hydrogen gas was flushed into the atmosphere within the hydrocracker, and the pressure was increased to 30 bar (3 MPa). The reactor inlet temperature was then increased from room temperature to 105°C at a rate of 17 degrees Celsius per hour (°C / hr). Upon reaching 105°C, the heating rate was reduced to 6°C / hr, and heating continued until the peak temperature of the hydrogenation catalyst reached 135°C. The system pressure was then increased to 150 bar (15 MPa) by the addition of hydrogen gas. Water accumulation was observed in both the cold and hot high-pressure separators, indicating that the catalyst had been dried. Drying continued for 4 hours at 150 bar (15 MPa) and 135°C.

[0102] After the catalyst prewetting: catalyst drying process, the catalyst bed temperature was reduced from 135°C to 100-110°C. The catalyst bed temperature in the reactor was stabilized at 100°C. The system pressure was then reduced to 105 bar (10.5 MPa). The start-up oil was straight-run diesel containing 200 parts per million (ppm) nitrogen and 1% sulfur by weight, with a 95% mass point of 375°C. The start-up oil was blended with enough DMDS to achieve a total sulfur concentration of 2% by weight, and the mixture was introduced into the reactor at a rate of 25,000 barrels per working day (BPSD).

[0103] Catalyst sulfidation: The reactor inlet temperature was then increased to 238° C. at a rate of 17° C. / h. Breakthrough was reached when 45,000 kg of DMDS was injected.

[0104] Example 1 of the Invention: Sulfurization with H2S produced in a DMDS conversion reactor 370 metric tons of pretreatment and hydrogenation catalyst were loaded into the hydrocracker. 56% by volume of the catalyst was pretreatment catalyst and 44% by volume of the catalyst was cracking catalyst. The pretreatment catalyst was Ni-Mo on alumina and the cracking catalyst was Ni-Mo on silica-alumina containing 5% by weight of USY zeolite. An additional 1.5 m 3 of Co-Mo / alumina conversion catalyst was loaded into the conversion reactor.

[0105] Catalyst drying: Hydrogen gas was flushed into the atmosphere within the hydrocracker, and the pressure was increased to 30 bar (3 MPa). The reactor inlet temperature was then increased from room temperature to 105°C at a rate of 17 degrees Celsius per hour (°C / hr). Upon reaching 105°C, the heating rate was reduced to 6°C / hr, and heating continued until the peak temperature of the hydrogenation catalyst reached 135°C. The system pressure was then increased to 150 bar (15 MPa). Water accumulation was observed in both the cold and hot high-pressure separators, indicating that the catalyst had dried. Drying continued for 4 hours at 150 bar (15 MPa) and 135°C.

[0106] After the catalyst prewetting: catalyst drying process, the catalyst bed temperature was reduced from 135°C to 100-110°C. The catalyst bed temperature in the reactor was stabilized at 100°C. The system pressure was then reduced to 105 bar (10.5 MPa). The start-up oil was straight-run diesel containing 200 parts per million (ppm) nitrogen and 1% sulfur by weight, with a 95% mass point of 375°C. The start-up oil was combined with sufficient DMDS to achieve a total sulfur concentration of 2% by weight, and the mixture was introduced into the reactor at a rate of 25,000 barrels per working day (BPSD).

[0107] The reactor inlet temperature was then increased from 110°C to 238°C at a rate of 17°C / hr.

[0108] Operation of the DMDS conversion reactor: DMDS and hydrogen were injected into the DMDS conversion reactor at a rate of 3,000 L / h in a hydrogen:DMDS molar ratio of 3:1. The DMDS conversion reactor had an internal diameter of 0.75 meters and a height of 2 meters. The reactor was operated at a pressure of 30 bar (3 MPa) and 220°C. DMDS was completely converted to hydrogen sulfide, producing 1,134 L / h of hydrogen sulfide. The resulting gas mixture was fed to a commercial reactor to sulfide the catalyst. Breakthrough was reached when 45,000 kg of DMDS had been injected.

[0109] It should also be noted that references herein to "at least one" component, element, etc. should not be used to create an inference that the use of the alternative articles "a" or "an" should be limited to one component, element, etc.

[0110] Although the subject matter of the present disclosure has been described in detail with reference to particular embodiments thereof, the various details disclosed herein should not be construed to imply that these details relate to elements that are essential components of the various embodiments described herein, even if a particular element is shown in each of the drawings accompanying this description. Moreover, it will be apparent that modifications and variations are possible without departing from the scope of the present disclosure, including, but not limited to, the embodiments defined in the appended claims. More particularly, although certain aspects of the present disclosure have been identified herein as preferred or particularly advantageous, the present disclosure is not necessarily limited to these aspects.

[0111] Please note that one or more of the following claims utilize the term "herein" as a transitional phrase. Please note that for purposes of defining the invention, this term is introduced in the claims as an open-ended transitional phrase used to introduce the recitation of a series of features of a structure, and should be interpreted in the same manner as the more commonly used open-ended predicate term "comprising." Preferred embodiments of the present invention will be described below in detail. Embodiment 1 1. A process for modifying a hydrogenation catalyst, comprising: introducing a precursor agent into a conversion reactor; introducing hydrogen gas into said conversion reactor; contacting the precursor reactant with a conversion catalyst in the conversion reactor, thereby producing an active reactant; introducing the active agent into a production reactor; and contacting the active agent with a hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst; and the precursor agent is introduced into the conversion reactor as a liquid; The process wherein the active agent is introduced into the production reactor as a gas. Embodiment 2 2. The process of embodiment 1, wherein the precursor agent comprises a sulfide precursor and the precursor conversion catalyst comprises a sulfide conversion catalyst. Embodiment 3 3. The process of embodiment 2, wherein the sulfide precursor comprises one or more organic monosulfides or polysulfides. Embodiment 4 4. The process of any one of embodiments 1 to 3, wherein the precursor agent is disulfide oil (DSO). Embodiment 5 5. The process of any one of embodiments 1 to 4, wherein the precursor agent comprises an ammonia precursor and the precursor conversion catalyst comprises an ammonia conversion catalyst. Embodiment 6 6. The process of embodiment 5, wherein the ammonia precursor comprises one or more organic compounds containing nitrogen. Embodiment 7 the precursor agent comprises a sulfide precursor; The process comprises: introducing an ammonia precursor into the conversion reactor; introducing hydrogen gas into said conversion reactor; contacting the ammonia precursor with the conversion catalyst in the conversion reactor, thereby producing ammonia gas; introducing the ammonia gas into the production reactor; and contacting the ammonia gas with the modified hydrogenation catalyst in the production reactor, thereby producing a sulfided and passivated hydrogenation catalyst; further comprising the ammonia precursor is introduced into the conversion reactor as a liquid; 5. The process of any one of embodiments 1 to 4, wherein the ammonia gas is introduced into the production reactor as a gas. Embodiment 8 8. The process of any one of the preceding embodiments, further comprising introducing hydrogen gas into the production reactor. Embodiment 9 9. The process of any one of embodiments 1 to 8, further comprising introducing a hydrocarbon feedstock into the conversion reactor. Embodiment 10 10. The process of any one of the preceding claims, further comprising separating the production reactor outlet stream into a liquid effluent and a gaseous effluent, and recycling at least a portion of the gaseous effluent back to the production reactor. Embodiment 11 11. The process of embodiment 10, further comprising recycling at least a portion of the liquid effluent back to the production reactor. Embodiment 12 12. The process of any one of the preceding embodiments, wherein the hydrogenation catalyst comprises alumina, silica-alumina, zeolite, or a combination thereof. Embodiment 13 13. The process of any one of embodiments 1 to 12, further comprising continuing to introduce the precursor agent into the conversion reactor after breakthrough is achieved in the conversion reactor. Embodiment 14 14. The process of any one of embodiments 1 to 13, wherein the combined mass of all contaminants in the modified hydrogenation catalyst is less than 1 wt. % of the total mass of the modified hydrogenation catalyst. Embodiment 15 15. The process of any one of the preceding embodiments, further comprising contacting the modified hydrogenation catalyst with a hydrotreating material in a hydrotreating process, wherein the hydrotreating material does not contact the conversion catalyst.

Claims

1. 1. A process for modifying a hydrogenation catalyst, comprising: introducing a precursor agent comprising at least one of a sulfide precursor, an ammonia precursor, or a combination thereof into a conversion reactor; introducing hydrogen gas into said conversion reactor; contacting the precursor reactant with a conversion catalyst in the conversion reactor, thereby producing an active reactant comprising sulfide, ammonia, or a combination thereof; introducing the active agent into a production reactor; contacting the active agent with a hydrogenation catalyst in the production reactor, thereby producing a modified hydrogenation catalyst; contacting the hydrogenation catalyst with a hydrocarbon feedstock in the production reactor to produce an outlet stream; and separating the outlet stream of the production reactor into a liquid effluent and a gaseous effluent; and the precursor agent is introduced into the conversion reactor as a liquid; The process wherein the active agent is introduced into the production reactor as a gas.

2. The process of claim 1 , wherein the precursor agent comprises a sulfide precursor and the precursor conversion catalyst comprises a sulfide conversion catalyst.

3. 3. The process of claim 2, wherein the sulfide precursor comprises one or more organic monosulfides or polysulfides.

4. 2. The process of claim 1, wherein the precursor agent is disulfide oil (DSO).

5. The process of claim 1 , wherein the precursor agent comprises an ammonia precursor and the precursor conversion catalyst comprises an ammonia conversion catalyst.

6. The process of claim 5 , wherein the ammonia precursor comprises one or more organic compounds containing nitrogen.

7. the precursor agent comprises a sulfide precursor and an ammonia precursor; The process comprises: introducing said precursor agent into said conversion reactor; introducing hydrogen gas into said conversion reactor; contacting the precursor reactant with the conversion catalyst in the conversion reactor, thereby producing the active reactant comprising sulfide gas and ammonia gas; introducing the sulfide gas and the ammonia gas into the production reactor; and contacting the sulfide gas with the modified hydrogenation catalyst in the production reactor, thereby producing a sulfided and passivated hydrogenation catalyst; further comprising 7. The process of claim 1, wherein the ammonia precursor is introduced into the conversion reactor as a liquid.

8. 8. The process of claim 7, further comprising introducing hydrogen gas into the production reactor.

9. The process of claim 7 further comprising the step of introducing a hydrocarbon feedstock into the conversion reactor.

10. The process of claim 7, further comprising recycling at least a portion of the gaseous effluent back to the production reactor.

11. The process of claim 10 further comprising recycling at least a portion of the liquid effluent back to the production reactor.

12. The process of claim 7, wherein the hydrogenation catalyst comprises alumina, silica-alumina, zeolite, or a combination thereof.

13. 8. The process of claim 7, further comprising continuing to introduce the precursor agent into the conversion reactor after breakthrough is achieved in the conversion reactor.

14. 8. The process of claim 7, wherein the combined mass of all contaminants in the modified hydrogenation catalyst is less than 1 wt. % of the total mass of the modified hydrogenation catalyst.

15. 8. The process of claim 7, further comprising contacting the modified hydrogenation catalyst with a hydrotreating material in a hydrotreating process, wherein the hydrotreating material does not contact the conversion catalyst.

16. The process of claim 7, wherein the conversion catalyst is not sulfided.

17. The process of claim 7, wherein the sulfide conversion catalyst comprises one or more of Co, Mo, W, Ni, and alumina.

18. The process of claim 7, wherein the ammonia conversion catalyst comprises one or more of Co, Mo, W, Ni, and alumina.

19. The process of claim 7, wherein the hydrogenation catalyst comprises one or more of Mo, W, Co, and Ni.

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