Method for operating an integrated chemical processing system to produce olefins - Patent Application 20070122997
The use of a wide-temperature-range first hydrogenation catalyst and a downstream second catalyst in integrated olefin production systems addresses thermal runaway risks, maintaining stability and safety in acetylene hydrogenation units.
Patent Information
- Application Number
- JP2021576990
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-06-24
- Filing Date
- 2020-06-08
- Publication Date
- 2025-09-12
- Estimated Expiration
- 2040-06-08
AI Technical Summary
Integrated olefin production processes face thermal runaway risks in acetylene hydrogenation units due to sudden changes in carbon monoxide concentration, leading to catalyst degradation and safety hazards.
Employing a first hydrogenation catalyst with a wide temperature operating range and a second hydrogenation catalyst downstream to manage sudden CO concentration fluctuations, reducing thermal runaway and MA/PD concentrations.
Prevents thermal runaway and maintains catalyst activity by stabilizing the acetylene hydrogenation unit, ensuring safe and efficient olefin production.
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Abstract
Description
[Technical Field]
[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 865,597, filed June 24, 2020, the entire disclosure of which is incorporated herein by reference. [Background technology]
[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to chemical processing systems and their operation for producing olefins, and more particularly to methods for operating an integrated olefin production process to remove by-products of the olefin production process.
[0003] Background technology Light olefins can be used as base materials to produce many types of goods and materials. For example, ethylene can be used to make polyethylene, ethylene chloride, or ethylene oxide. Such products can be used in packaging products, construction, fibers, etc. Therefore, there is an industrial demand for light olefins such as ethylene, propylene, and butene. Summary of the Invention [Problem to be solved by the invention]
[0004] Light olefins can be produced by different reaction processes depending on a given chemical feed stream, such as natural gas condensate or product streams from petrochemical companies. For example, olefins can be produced from hydrocarbon streams using hydrocarbon cracking (e.g., steam cracking), catalytic dehydrogenation, methanol-to-olefins processes, dehydration processes, or other processes. However, hydrocarbon cracking and other processes for producing light olefins can also produce by-products and impurities, such as acetylenic and allenic compounds, which can reduce the effectiveness of downstream processes and catalysts. In addition, the presence of high concentrations of acetylenic and allenic compounds can pose safety concerns in downstream processes due to the reactivity of these compounds. Acetylene, methylacetylene, propadiene, and other impurities and by-products can be removed from olefin-containing hydrocarbon cracked effluents or other process effluents by hydrogenation in a selective hydrogenation process or other olefin production process downstream of the hydrocarbon cracker. Additional product olefins, such as ethylene and propylene, can also be recovered by selective hydrogenation of acetylenic and allenic compounds in hydrocarbon cracked effluents or other process effluents.
[0005] In some olefin production processes, light olefins such as ethylene and propylene can be produced by one or more olefin production processes, such as steam cracking, fluid catalytic dehydrogenation (FCDh), methanol-to-oil processes, dehydration processes, or a combination of other olefin production processes. Because the effluents from these processes have similar compositions, two or more of these separate olefin production processes can be integrated to use a single effluent treatment system operable to purify and separate the effluent streams. For example, a steam cracking system and an FCDh system can be integrated, such that the cracked gas from the steam cracking system and at least a portion of the FCDh effluent from the FCDh system can be combined and processed in a common effluent treatment system downstream of the steam cracking system and the FCDh system. The effluent treatment system can include various separation and purification systems to separate products and / or recycle streams and remove unwanted contaminants and reaction by-products. The effluent treatment system can include an acetylene hydrogenation unit operable to hydrogenate acetylene produced in the steam cracker or other olefin production process.
[0006] The acetylene hydrogenator may be sensitive to the concentration of carbon monoxide (CO) in the feed stream to the acetylene hydrogenator. Without intending to be limited by any particular theory, it is believed that CO may interact with the hydrogenation catalyst in the acetylene hydrogenator, reducing the activity of the hydrogenation catalyst for hydrogenating acetylene. Conversely, reducing the CO concentration in the acetylene hydrogenator may increase the activity of the hydrogenation catalyst. A sudden decrease in the CO concentration in the hydrogenation feed to the acetylene hydrogenator may increase the activity of the hydrogenation catalyst, which may lead to increased hydrogenation of olefin products in the hydrogenation feed, such as ethylene and propylene, and reduced olefin selectivity. Olefin hydrogenation is exothermic. Therefore, a rapid increase in the hydrogenation of olefins, such as ethylene and propylene, may lead to thermal runaway in the acetylene hydrogenator due to the rapid heat release from the olefin hydrogenation reaction.
[0007] In one or more embodiments, the effluent from a first olefin production process can have a higher CO concentration than the CO concentration in the effluent from a second olefin production process integrated with the first olefin production process. For example, the FCDh effluent from an FCDh process can have a higher CO concentration than the CO concentration in the cracked gas from a steam cracker. Thus, when an integrated process for producing olefins is operating with both the cracked gas and at least a portion of the FCDh effluent routed to an effluent treatment system, the CO concentration in the feed to the acetylene hydrogenation unit can be substantially higher (e.g., at least 25% higher, or even 100% or more higher) than the CO concentration from the cracked gas alone. When the FCDh system is interrupted, such as during an unexpected FCDh trip, the flow of FCDh effluent to the effluent treatment system can be suddenly reduced or completely lost. This can lead to a sudden and significant decrease in the CO concentration of the hydrogenation feed. As previously mentioned, a sudden drop in CO concentration can lead to thermal runaway in the acetylene hydrogenation unit due to a sudden increase in olefin product hydrogenation and the generation of heat from the exothermic hydrogenation reaction. Therefore, a sudden reduction or complete loss of FCDh effluent or other olefin production process effluent flow to the effluent treatment system can lead to thermal runaway in the acetylene hydrogenation reactor. A sudden reduction or loss of FCDh effluent flow to the effluent treatment system can also reduce the total reactant flow rate through the acetylene hydrogenation unit, resulting in a lower gas hourly space velocity (GHSV) or a longer residence time for the hydrogenation feedstock, which can also increase olefin conversion and lead to thermal runaway. During thermal runaway, a temperature rise of over 200°C can occur, causing the acetylene hydrogenation unit to trip and the system to restart. Additionally, a temperature rise of over 200°C can damage the hydrogenation catalyst and equipment, such as the reactor, meters, heat exchangers, and other devices, and can also pose a safety risk. In many runaway situations, severe loss of catalyst performance due to thermal runaway can require catalyst replacement, which leads to significant equipment downtime.Thermal runaway can also increase olefin product losses due to over-hydrogenation of ethylene and propylene.
[0008] The methods disclosed herein can reduce or prevent thermal runaway in an acetylene hydrogenation unit of an integrated process for producing olefins, such as an integrated process combining a steam cracking system and an FCDh system, in response to a sudden decrease in CO concentration due to the loss of an effluent stream from one of the integrated olefin processes. In particular, the methods disclosed herein can reduce or prevent thermal runaway in an acetylene hydrogenation unit by utilizing a first hydrogenation catalyst having a temperature operating range of 40°C or greater for a given hydrogenation feed composition. The temperature operating range of the first hydrogenation catalyst can be the difference between the cleanup temperature and the runaway temperature, within which 3 wt% of the ethylene in the hydrogenation feed is hydrogenated in the acetylene hydrogenation unit. The cleanup temperature can be the temperature at which the acetylene concentration in the hydrogenation effluent is equal to a target acetylene concentration set by a downstream user or customer, such as parts per million per volume, or another value set by the downstream user or customer. A larger temperature operating range of the first hydrogenation catalyst may make the first hydrogenation catalyst less responsive to sudden changes in carbon monoxide concentration in the hydrogenation feedstock and may allow the operation of the acetylene hydrogenation unit to be modified within a wide temperature operating range without causing thermal runaway of the acetylene hydrogenation unit.
[0009] The first hydrogenation catalyst is effective in reducing or preventing thermal runaway in the acetylene hydrogenation unit, but may have reduced activity for hydrogenating methylacetylene (MA) and propadiene (PD), which may be produced in one or more integrated olefin processes, such as a steam cracking process, and may be present in the hydrogenation feedstock. MA and PD can produce coke when a stream containing MA and / or PD is recycled back to an olefin production process, such as an FCDh system, or sent to a downstream process. In addition, specifications from olefin users may require that the concentrations of MA and PD be reduced below threshold concentrations of these compounds. The systems and methods disclosed herein may further include a methylacetylene / propadiene hydrogenation unit (MAPD hydrogenation unit) downstream of the acetylene hydrogenation unit. The MAPD hydrogenation unit may be operable to contact at least a portion of the hydrogenation effluent from the acetylene hydrogenation unit with a second hydrogenation catalyst to produce a MAPD hydrogenation effluent.
[0010] According to one currently described embodiment, a method for operating an integrated system for producing olefins includes contacting a hydrogenation feedstock with a first hydrogenation catalyst to produce a hydrogenation effluent. The hydrogenation feedstock can include at least a portion of a first process effluent from a first olefin production process and at least a portion of a second process effluent from a second olefin production process. The hydrogenation feedstock can include at least hydrogen, ethylene, carbon monoxide, acetylene, methyl acetylene, and propadiene. The first hydrogenation catalyst has a temperature operating range of at least 40 degrees Celsius. The temperature operating range can be the difference between a runaway temperature and a cleanup temperature for a given hydrogenation feed composition, where the runaway temperature is the temperature at which 3% of the ethylene in the hydrogenation feedstock reacts, and the cleanup temperature is the temperature at which the acetylene concentration in the hydrogenation effluent equals a threshold acetylene concentration. The hydrogenation effluent can include methyl acetylene (MA), propadiene (PD), or both. The method can further include contacting at least a portion of the hydrogenation effluent with a second hydrogenation catalyst, which can hydrogenate at least a portion of the methylacetylene, propadiene, or both from the hydrogenation effluent to produce a MAPD hydrogenation effluent having a reduced concentration of methylacetylene, propadiene, or both, compared to the portion of the hydrogenation effluent prior to contact with the second hydrogenation catalyst. [Brief explanation of the drawings]
[0011] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, in which like structure is indicated with like reference numerals and in which: [Figure 1] FIG. 1 illustrates a schematic of an integrated process for producing olefins, including an FCDh system integrated with a steam cracking system and a shared effluent treatment system, according to one or more embodiments shown and described herein. [Figure 2]FIG. 2 illustrates a schematic of a steam cracking system for the integrated process of FIG. 1 according to one or more embodiments shown and described herein. [Figure 3] FIG. 3 illustrates a schematic diagram of an FCDh system for the integrated process of FIG. 1 according to one or more embodiments shown and described herein. [Figure 4] FIG. 4 schematically illustrates a portion of a product processing system of the integrated process of FIG. 1 according to one or more embodiments shown and described herein. [Figure 5] FIG. 5 is a graph of the acetylene concentration (left y-axis) and ethylene selectivity (right y-axis) of the acetylene hydrogenation unit as a function of the temperature of the hydrogenation feed sent to the acetylene hydrogenation unit (x-axis) according to one or more embodiments shown and described herein. [Figure 6] FIG. 6 illustrates schematically another integrated process for producing olefins, including an FCDh system integrated with a steam cracking system and a shared effluent treatment system, according to one or more embodiments shown and described herein. [Figure 7] FIG. 7 illustrates a schematic of a stand-alone FCDh system with a dedicated effluent treatment system according to one or more embodiments shown and described herein.
[0012] It should be understood that the drawings are schematic in nature and may not include some components of reactor systems commonly used in the art, such as, without limitation, sensors, temperature transmitters, pressure transmitters, flow meters, pumps, valves, heat exchangers, internal reactor structures, etc. These components would be known to be within the spirit and scope of the disclosed embodiments. However, operational components such as those described in this disclosure may be added to the embodiments described in this disclosure.
[0013] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. DETAILED DESCRIPTION OF THE INVENTION
[0014] One or more embodiments of the present disclosure are directed to systems and methods for operating an integrated process for producing olefins, including multiple olefin production processes that utilize a common effluent treatment system to purify and separate multiple effluent streams from the olefin production processes. Specifically, one or more embodiments of the present disclosure are directed to systems and methods for operating an integrated process for producing olefins that can reduce or prevent thermal runaway of an acetylene hydrogenation unit in response to a sudden decrease in carbon monoxide (CO) concentration in the hydrogenation feedstock due to a sudden decrease and / or loss of effluent flow from one of the olefin production processes. In some embodiments of the present disclosure, a method for operating an integrated system for producing olefins can include contacting a hydrogenation feedstock with a first hydrogenation catalyst to produce a hydrogenation effluent. The hydrogenation feedstock can include at least a portion of a first process effluent from the first olefin production process and at least a portion of a second process effluent from the second olefin production process. The hydrogenation feedstock can include at least hydrogen, ethylene, carbon monoxide, acetylene, methylacetylene, and propadiene. The first hydrogenation catalyst may be a hydrogenation catalyst having a temperature operating range of at least 40°C, the temperature operating range being the difference between the runaway temperature and the cleanup temperature for a given hydrogenation feed composition, where the runaway temperature is the temperature at which 3% of the ethylene in the hydrogenation feed reacts, and the cleanup temperature is the temperature at which the acetylene concentration in the hydrogenation effluent is equal to a threshold acetylene concentration set by a downstream user or customer, such as equal to 1 ppm, or another threshold acetylene concentration set by the downstream user / customer. The hydrogenation effluent may include methylacetylene (MA), propadiene (PD), or both (MAPD). The method may further include contacting at least a portion of the hydrogenation effluent with a second hydrogenation catalyst, whereby at least a portion of the methylacetylene, propadiene, or both from the hydrogenation effluent is hydrogenated to produce a MAPD hydrogenation effluent.
[0015] By contacting the hydrogenation feedstock with a first hydrogenation catalyst having a wide temperature operating range for a given hydrogenation feed composition, the response of the acetylene hydrogenation unit to a sudden decrease in CO concentration due to a sudden reduction or complete loss of flow in one of the first or second olefin production processes of an integrated system for producing olefins can be reduced, thereby reducing or preventing thermal runaway of the acetylene hydrogenation unit. In addition, by contacting at least a portion of the hydrogenation effluent with a second hydrogenation catalyst downstream of the acetylene hydrogenation unit, the concentrations of MA and PD can be reduced below a threshold MAPD concentration to produce a MAPD hydrogenation effluent, which can be recycled back to the first or second olefin production process. Reducing the MAPD concentration in the MAPD hydrogenation effluent can potentially reduce coke formation in the first or second olefin production process.
[0016] Described herein is one example of an integrated process for producing olefins that involves steam cracking combined with FCDh and utilizes a single shared effluent treatment system with an acetylene hydrogenation unit. This integrated process is used to provide context for the presently disclosed method of operating an acetylene hydrogenation unit, which can reduce or prevent acetylene breakthrough to downstream processes. It should be understood that the schematics in Figures 1-4, 6, and 7 are merely exemplary systems, and other systems suitable for producing olefins are contemplated herein, and the concepts described herein can be utilized in such alternative systems. For example, the concepts described herein are equally applicable to other integrated systems with alternative reactor and regenerator equipment, such as those operating under non-flow conditions or those that are downers rather than risers. Additionally, the presently described methods and processes for treating chemical streams in a reactor system should not be limited solely to embodiments of a reactor system designed to produce light olefins by steam cracking integrated with fluidized catalytic dehydrogenation, such as the reactor system described with reference to Figure 1, as other processes for producing olefins (e.g., utilizing different feedstocks) are contemplated. Additionally, other processes for producing olefins, such as, but not limited to, methanol-to-olefins and dehydration processes, can be included in the integrated system either in situ or in addition to one or both of the steam cracker or FCDh system.
[0017] A system and method for operating an integrated system for producing olefins will now be described in further detail with reference to Figure 1. The chemical stream to be treated may be referred to as a feed stream or simply feedstock, which is treated by reaction, separation, or other processes to form a product stream, reactor effluent, or simply effluent. The feedstock may have a composition, and depending on the feed composition, an appropriate catalyst may be utilized to convert the contents of the feedstock into an effluent that may include light olefins or other chemical products.
[0018] As used herein, "start-up" can generally refer to the time when reactor temperature, reactor pressure, flow rates (e.g., flow rates of reactor feed gases (hydrocarbon and / or inert gases), fuel gas and air for catalyst regeneration, catalyst stripping and fluidizing gases, oxygen-containing gas for oxygenating the catalyst, etc.), catalyst recycle rate, or combinations thereof, have been established but have not yet reached the desired values for stable operation of a given reaction.
[0019] As used herein, "shutdown" can generally refer to the time during which the temperature, pressure, flow rate, and / or catalyst recycle rate of a reactor system (e.g., reactor and / or regenerator) are reduced prior to the end of the process reaction.
[0020] As used herein, the term "system recycle" can refer to the operation of a reactor system in which at least a portion of the reactor effluent (e.g., FCDh effluent) can be recycled back to the hydrocarbon feedstock or directly to the reactor. System recycle can be part of normal operation, such as when one or more streams from an effluent treatment system are recycled back to one or more olefin production processes to increase the yield of olefins. In addition, system recycle events can include off-spec product events in which the reactor system is operated in system recycle mode until the reactor effluent and / or reactor operating conditions return to target or normal operating conditions. A reactor system can also be operated in system recycle mode in response to a planned or unplanned shutdown of the operation of another reactor system, such as the interruption of operation of a steam cracking system integrated with the reactor system disclosed herein. In some embodiments, system recycle can reduce the reactor temperature to a low temperature (i.e., <550°C). In other circumstances, system recycle can include circulating an inert gas through the reactor to maintain the catalyst in a fluidized state.
[0021] As used herein, the term "unit trip" can refer to a condition in which a reactor unit shuts down completely, for example, due to a runaway condition during chemical processing, or a condition in which the temperature drops and / or the flow rate of one or more streams is reduced or diverted. Unit trips can include different levels of unit trips, such as a severe unit trip in which the entire reactor system shuts down completely, or an intermediate-level trip in which the temperature drops, the pressure drops, or one or more streams are diverted. As used herein, low-temperature reaction conditions, such as those present during startup, shutdown, system recycle, or unit trip, and conditions in which inert gas circulates through a reactor system without a hydrocarbon feed stream, may be referred to as abnormal operating conditions. Normal operating conditions refer to elevated, steady-state conditions, such as temperatures above 550°C or temperatures favorable for catalytic reactions of a given reactant.
[0022] As used herein, the term "hydrogenation feedstock" can refer to the effluent from the separation system sent to the acetylene hydrogenation unit, which comprises at least 95% by mass of acetylene from the cracked gas introduced into the separation system.
[0023] As used herein, the term "acetylene-depleted stream" can refer to a separate effluent stream from a separation system that is different from the hydrogenation feedstock and that contains less than 5% by weight of acetylene from the cracked gas sent to the separation system.
[0024] As used herein, the terms "upstream" and "downstream" refer to the direction of material flow through an integrated process. For example, if one or more streams of material flow from a first equipment operation to a second equipment operation, the first equipment operation is upstream of the second equipment operation. If one or more streams of material flow from the second equipment operation to the first equipment operation, the first equipment operation is downstream of the second equipment operation.
[0025] As used herein, the term "selectivity" can refer to the ratio of moles of the desired product to moles of all products in the reactor effluent, all products normalized to the same carbon number. For example, the ethylene selectivity of an acetylene hydrogenation unit can be the ratio of the moles of ethylene further produced in the hydrogenation effluent divided by the total moles of all products produced during the hydrogenation reaction. For example, if all acetylene is converted to ethylene, the selectivity is 100%. If all acetylene is converted to ethane, the selectivity is 0 (zero). If all acetylene and some of the inflowing ethylene are converted to ethane, the selectivity is negative.
[0026] As used herein, the term "breakthrough" can refer to the transmission of a particular reactant, such as, but not limited to, acetylene, methylacetylene, propadiene, or other compounds, from one processing unit to another downstream processing unit in an amount greater than an olefin user-specified threshold, e.g., parts per million per volume (ppmv). In one example, breakthrough can occur when a particular reactant undergoes substantially incomplete conversion in a reaction system such that the effluent from the reaction system has a concentration of the particular reactant greater than 1 ppmv or greater than 2 ppmv, depending on the olefin user and its location.
[0027] As used herein, the term "threshold acetylene concentration" can refer to the concentration of acetylene in the hydrogenation effluent from an acetylene hydrogenation unit at or below which the acetylene concentration is considered to be within the product purity specifications provided by an olefin user and / or does not cause catalyst fouling or other disruption in downstream processes.
[0028] As used herein, the term "thermal runaway" can refer to a condition in a process where a gradual increase in the temperature of the process changes the operating conditions in a way that creates or generates heat, thereby causing a further increase in temperature.
[0029] As used herein, the term "normal operating conditions" can refer to elevated steady-state temperatures, such as temperatures suitable for catalysis of a given reaction, such as temperatures suitable for conducting an acetylene hydrogenation reaction in an acetylene hydrogenation unit. A suitable temperature in a hydrogenation unit may be a temperature within the temperature operating range of a hydrogenation catalyst of a given composition.
[0030] As used herein, the term "temperature operating range" of a hydrogenation catalyst can refer to the difference between the runaway temperature and the cleanup temperature for a given system configuration at a given composition of hydrogenation feedstock.
[0031] As used herein, the term "cleanup temperature" can refer to the operating temperature of an acetylene hydrogenation unit at which, for a given hydrogenation catalyst and at a given composition of the hydrogenation feedstock, the acetylene concentration in the hydrogenation effluent is equal to a threshold acetylene concentration set by a downstream user or customer. For example, the cleanup temperature can be the operating temperature of an acetylene hydrogenation unit at which, for a given hydrogenation catalyst and at a given composition of the hydrogenation feedstock, the acetylene concentration in the hydrogenation effluent is equal to 1 ppmv or other threshold acetylene concentration set by a downstream user and / or customer.
[0032] As used herein, the term "runaway temperature" may refer to the operating temperature of an acetylene hydrogenator at which 3% of the ethylene from the hydrogenation feedstock reacts in the acetylene hydrogenator for a given hydrogenation catalyst and at a given composition of the hydrogenation feedstock.
[0033] Referring to Figure 1, an integrated process 10 for producing olefins is shown schematically. The integrated process 10 may include a steam cracking system 20, a fluid catalytic cracking (FCDh) system 30, and an effluent treatment system 38 that may be operable to treat effluents from the steam cracking system 20 and the FCDh system 30. The steam cracking system 20 may be operable to convert at least a portion of a first hydrocarbon feedstock 22 to produce a cracked gas 28 comprising at least hydrogen, carbon monoxide (CO), acetylene, and at least one steam cracker product. The FCDh system 30 may be operable to convert at least a portion of a second hydrocarbon feedstock 32 to produce an FCDh effluent 34 comprising at least hydrogen, CO, and at least one FCDh product. At least a portion of the cracked gas 28, or the cracked gas 28 and the FCDh effluent 34, may be sent to an effluent treatment system 38, which may be operable to treat the cracked gas 28 and / or the FCDh effluent 34 to produce one or more component streams (not shown), such as an ethylene stream 72, a propylene stream 74, a propane stream 76, or other component streams. The effluent treatment system 38 may include at least a first separation system 40, an acetylene hydrogenation unit 50 downstream of the first separation system 40, a heat exchanger 60 disposed between the first separation system 40 and the acetylene hydrogenation unit 50, a second separation system 70 downstream of the acetylene hydrogenation unit 50, and a MAPD hydrogenation unit 80. The effluent treatment system 38 may also include additional separation and / or purification processes (not shown) disposed downstream of the acetylene hydrogenation unit 50.
[0034] Referring to FIG. 2 , one embodiment of a steam cracking system 20 is shown schematically. The steam cracking system 20 can include one or more of a steam cracker 110, an oil quencher 120, a water quencher 130, a compressor system 140, or a combination thereof. In some embodiments, the steam cracking system 20 can also include an acid gas removal unit (not shown). A first hydrocarbon feedstock 22 can be introduced into the steam cracker 110 to crack one or more hydrocarbon components of the first hydrocarbon feedstock 22 to produce one or more olefins. The first hydrocarbon feedstock 22 can be any hydrocarbon stream, such as a product stream from a petrochemical process, or naphtha from a crude oil refining process, natural gas liquids (NGLs), or other hydrocarbon sources. In some embodiments, the first hydrocarbon feedstock 22 can include multiple different hydrocarbon streams combined prior to or within the steam cracker 110. In some embodiments, the first hydrocarbon feedstock 22 may be a light hydrocarbon feedstock, such as a feedstock comprising ethane, propane, butane, naphtha, other light hydrocarbons, or combinations thereof.
[0035] The steam cracker 110 may be operable to receive the first hydrocarbon feedstock 22 and crack one or more components of the first hydrocarbon feedstock 22 to produce a cracker effluent 112. The steam cracker 110 may be operable to contact the first hydrocarbon feedstock 22 with steam at a temperature between 500°C and 850°C to produce the cracker effluent 112. The sulfur-containing composition 24, the methanol-containing stream 26, or both, may also be introduced into the hydrocarbon cracker 110. The sulfur-containing composition 24, the methanol-containing stream 26, or both, may be introduced directly into the steam cracker 110 or may be combined with the first hydrocarbon feedstock 22 upstream of the steam cracker 110. The sulfur-containing composition 24 may include one or more sulfur-containing compounds, such as, but not limited to, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), diethyl disulfide (DES), methyl mercaptan (MM), or combinations thereof. The sulfur-containing compounds from sulfur-containing composition 24 can passivate heating coils in the steam cracking furnace of steam cracker 110 to manage coke formation in steam cracker 110. Increasing or decreasing the sulfur-containing compounds can change the amount of CO generated in steam cracker 110, which can change the CO concentration (e.g., CO amount) in cracker effluent 112.
[0036] Ethane, propane, naphtha, and other hydrocarbons present in the first hydrocarbon feedstock 22 can be steam cracked in the steam cracker 110 to produce at least one or more light olefins, such as, but not limited to, ethylene, propylene, butenes, or combinations thereof. The steam cracker 110 can be operated under conditions (i.e., temperature, pressure, residence time, etc.) sufficient to produce one or more light olefins, such as ethylene and propylene, from the hydrocarbons in the first hydrocarbon feedstock 22. In some embodiments, the steam cracker 110 can be operated at temperatures between 500°C and 850°C, between 500°C and 810°C, between 550°C and 850°C, between 550°C and 810°C, between 600°C and 850°C, or between 600°C and 810°C. The temperature of the steam cracker 110 can depend on the composition of the first hydrocarbon feedstock 22 introduced into the steam cracker 110. Other suitable operating conditions for hydrocarbon cracking processes are known in the art.
[0037] The cracker effluent 112 may include one or more cracking reaction products, such as, but not limited to, ethylene, propylene, butenes (e.g., 1-butene, trans-2-butene, cis-2-butene, isobutene), ethane, propane, other light hydrocarbons, or combinations thereof. The cracker effluent 112 may also include hydrogen, CO, acetylene, methylacetylene, propadiene, methane, other compounds produced in the steam cracker 110, unreacted components of the first hydrocarbon feedstock 22, or combinations thereof. For example, the cracking reaction in the steam cracker 110 may produce by-products such as hydrogen and carbon monoxide (CO), and by-products such as acetylene, methylacetylene (MA), propadiene (PD), other by-products, or combinations thereof. Additionally, unreacted hydrocarbons and / or other components of the first hydrocarbon feedstock 22 may pass through the steam cracker 110 without undergoing reaction, such that the cracker effluent 112 includes these unreacted components of the first hydrocarbon feedstock 22. Acid and alcohol gases may also be produced in the steam cracker 110.
[0038] 2 , the cracker effluent 112 may be routed from the steam cracker 110 to an oil quencher 120 downstream of the steam cracker 110. The oil quencher 120 may be operable to quench the cracker effluent 112 with a hydrocarbon quench liquid 122 to reduce the temperature of the cracker effluent 112 and remove heavy hydrocarbon components to produce an oil quench effluent 126. The oil quench effluent 126 may be routed from the oil quencher 120 to a water quencher 130 downstream of the oil quencher 120. The water quencher 130 may be operable to quench the cracker effluent 112 with liquid water to further reduce the temperature of the oil quench effluent 126 and remove steam to produce cracked gases 28. 2 as being downstream of the oil quencher 120, it is understood that the water quencher 130 may alternatively be positioned upstream of the oil quencher 120. The steam cracking system 20 may optionally include an acid gas removal system (not shown) for removing acid gases from the cracked gases 28. Alternatively, in some embodiments, the acid gas removal system may be incorporated into the effluent treatment system 38 (FIG. 1). The cracked gases 28 may be routed to a compression system 140 operable to reduce the volume of the cracked gases 28 upstream of the effluent treatment system 38.
[0039] Referring now to FIG. 3 , an FCDh system 30 may be operable to receive a second hydrocarbon feedstock 32 and contact the second hydrocarbon feedstock 32 with a dehydrogenation catalyst to produce an FCDh effluent 34. The second hydrocarbon feedstock 32 to the FCDh system 30 may comprise at least one of propane, n-butane, isobutane, ethane, or ethylbenzene. The second hydrocarbon feedstock 32 may comprise one or more hydrocarbon streams from a hydrocarbon processing facility. The second hydrocarbon feedstock 32 may be the same as or different from the first hydrocarbon feedstock 22. In some embodiments, the second hydrocarbon feedstock 32 may comprise a propane or ethane stream (e.g., propane stream 76 in FIG. 1 ) recovered from the effluent treatment system 38 and recycled back to the FCDh system 30. In the FCDh system 30, at least a portion of the second hydrocarbon feedstock 32 may be converted to light olefins or other products by dehydrogenation in the presence of a dehydrogenation catalyst. The dehydrogenation catalyst can be any catalyst known in the art for dehydrogenating hydrocarbons to produce olefins. The FCDh effluent 34 can include at least CO, hydrogen, and at least one FCDh product. The at least one FCDh product can include one or more of ethylene, propylene, or a combination thereof.
[0040] Referring to Figure 3, an exemplary FCDh system 30 is shown schematically. The FCDh system 30 can include a reactor section 200 and a catalyst treatment section 300. As used herein in the context of Figure 3, the reactor section 200 can refer to the portion of the FCDh system 30 where the primary process reactions occur. For example, the second hydrocarbon feedstock 32 can be dehydrogenated in the presence of a dehydrogenation catalyst in the reactor section 200 of the FCDh system 30. The reactor section 200 includes a reactor 202, which can include a downstream reactor section 230, an upstream reactor section 250, and a catalyst separation section 210 that serves to separate the catalyst from the chemical products formed in the reactor 202.
[0041] Also, as used herein, catalytic treater section 300 of FCDh system 30 of FIG. 3 generally refers to the portion of FCDh system 30 where, during normal operation of FCDh system 30, the catalyst is in some way processed, such as to remove coke deposits, heat the catalyst, reactivate the catalyst, other treatment operations, or a combination thereof. In some embodiments, catalytic treater section 300 can include combustor 350, riser 330, catalyst separation section 310, and oxygen treatment zone 370. Combustor 350 of catalytic treater section 300 can include one or more lower combustor inlet ports 352 and can be in fluid communication with riser 330. Combustor 350 can be in fluid communication with catalyst separation section 210 via transfer line 426, which can supply deactivated catalyst (during normal operating conditions) from reactor section 200 to catalytic treater section 300 for catalyst treatment (e.g., coke removal, heating, reactivation, etc.). The oxygen treatment zone 370 may be in fluid communication with the upstream reactor section 250 (e.g., via a transfer line 424 and a transfer riser 430) to supply treated catalyst from the catalyst treatment section 300 back to the reactor section 200. The combustor 350 may include a lower combustor inlet port 352 connecting an air flow inlet 428 to the combustor 350. The air flow inlet 428 may supply air or other reactive gases, such as oxygen-containing gases, to the combustor 350. Air and / or other reactive gases may be introduced into the combustor 350 to aid in the combustion of the auxiliary fuel. The combustor 350 may also include a fuel flow inlet 354. The fuel flow inlet 354 may supply a fuel, such as a hydrocarbon stream 356, to the combustor 350. The oxygen treatment zone 370 may include an oxygen-containing gas flow inlet 372 that may supply an oxygen-containing gas 374 to the oxygen treatment zone 370 for oxygen treatment of the catalyst.
[0042] 3, the general operation of the FCDh system 30 for conducting continuous reactions under normal operating conditions is described. During operation of the reactor section 200 of the FCDh system 30, the second hydrocarbon feedstock 32 can enter the transfer riser 430, and the FCDh effluent 34 can exit the FCDh system 30 via the pipe 420. According to one or more embodiments, the FCDh system 30 can operate by feeding the second hydrocarbon feedstock 32 and a fluidized dehydrogenation catalyst to the upstream reactor section 250. The hydrocarbons in the second hydrocarbon feedstock 32 can contact the dehydrogenation catalyst in the upstream reactor section 250, each of which can flow upward through the downstream reactor section 230 to produce at least one FCDh product under normal operating conditions.
[0043] The FCDh effluent 34 and dehydrogenation catalyst can be sent downstream from the reactor section 230 to a separation device 220 in the catalyst separation section 210. The FCDh effluent 34 can include hydrogen, CO, and at least one FCDh product. The FCDh effluent 34 can also include an unreacted portion of the second hydrocarbon feedstock 32, a fluidization gas, by-products, reaction intermediates, other gases, or a combination thereof. The at least one FCDh product can include ethylene, propylene, or other light olefins. The FCDh effluent 34 can have a CO concentration higher than the CO concentration in the cracked gas 28 from the steam cracking system 20. The FCDh effluent 34 can have a CO concentration from 500 parts per million per volume (ppmv) to 2400 ppmv, such as from 1000 ppmv to 2000 ppmv. The FCDh effluent 34 may include acetylene, methylacetylene (MA), propadiene (PD), or a combination thereof. The acetylene concentration in the FCDh effluent 34 may be less than 50 ppmv. The MA concentration in the FCDh effluent 34 may be less than or equal to 300 ppmv. The PD concentration in the FCDh effluent 34 may be less than or equal to 100 ppmv.
[0044] The dehydrogenation catalyst can be separated from the FCDh effluent 34 in separation device 220. The FCDh effluent 34 can then be transported from the catalyst separation section 210. For example, the separated vapor of the FCDh effluent 34 can be removed from the FCDh system 30 via pipe 420 at a gas outlet port of the catalyst separation section 210. In some embodiments, separation device 220 can be a powder separation system that can include two or more stages of powder separation.
[0045] According to some embodiments, following separation of the FCDh effluent 34 from the vapor in separation device 220, the dehydrogenation catalyst may generally travel through stripper 224 to reactor catalyst outlet port 222, where it may be transferred from reactor section 200 to catalyst treater 300 via transfer line 426. Optionally, the dehydrogenation catalyst may also be transferred directly back to upstream reactor section 250 via standpipe 422. In some embodiments, recycled dehydrogenation catalyst from stripper 224 may be premixed with treated dehydrogenation catalyst from catalyst treater 300 in transfer riser 430.
[0046] The separated dehydrogenation catalyst can be sent from the catalyst separation section 210 to the combustor 350 of the catalytic treatment section 300. The dehydrogenation catalyst can be treated in the catalytic treatment section 300 during normal operation to remove coke deposits, heat the catalyst, reactivate the catalyst, other catalytic treatments, or any combination thereof. As previously described, treating the dehydrogenation catalyst in the catalytic treatment section 300 can include removing coke deposits from the catalyst, increasing the temperature of the catalyst by burning a combustion fuel source, reactivating the catalyst, removing one or more components from the catalyst, other treatment operations, or combinations thereof. In some embodiments, treating the dehydrogenation catalyst in the treatment section 300 can include burning a combustion fuel source in the presence of the dehydrogenation catalyst in the combustor 350 to remove coke deposits and / or heat the dehydrogenation catalyst to produce a heated catalyst. The heated dehydrogenation catalyst can be separated from the combustion gas in the catalyst separation section 310.
[0047] In some embodiments, the heated dehydrogenation catalyst can then be reactivated by oxygenating the heated dehydrogenation catalyst. The oxygenating can include exposing the heated dehydrogenation catalyst to an oxygen-containing gas 374 for a period of time sufficient to reactivate the dehydrogenation catalyst. The oxygenating to reactivate the dehydrogenation catalyst can occur after combustion of the auxiliary fuel to heat the dehydrogenation catalyst. The oxygenating can include treating the heated dehydrogenation catalyst with the oxygen-containing gas 374 for at least two minutes, thereby reactivating the dehydrogenation catalyst to produce a reactivated dehydrogenation catalyst. The oxygen-containing gas 374 can include an oxygen content of 5 mole % to 100 mole %, based on the total molar flow rate of the oxygen-containing gas 374. In some embodiments, the oxygenating of the dehydrogenation catalyst can include maintaining the dehydrogenation catalyst at a temperature of at least 660° C. while exposing the dehydrogenation catalyst to a flow of oxygen-containing gas 374 for a period of more than two minutes and sufficient to produce a reactivated dehydrogenation catalyst having greater catalytic activity than the heated dehydrogenation catalyst after being heated by combustion of the auxiliary fuel. The oxygen treatment can occur in an oxygen treatment zone 370 which can be downstream of the catalyst separation section 310 of the catalytic treatment section 300 .
[0048] Combustion gases from the combustion of coke and / or auxiliary fuel during the treatment of the dehydrogenation catalyst, or other gases introduced into the dehydrogenation catalyst during catalyst treatment and catalyst reactivation, can be removed from the catalyst treatment section 300 via the regenerator effluent outlet 432.
[0049] 3 and the foregoing description present one embodiment of a system for catalytically dehydrogenating hydrocarbons to produce light olefins. However, it is understood that other reactor system configurations may be used for the catalytic dehydrogenation of hydrocarbons to produce light olefins without departing from the scope of the present disclosure. For example, in some embodiments, the FCDh system 30 may include any type of flow reactor system operable to contact the second hydrocarbon feedstock 32 with the catalyst in a fluidized regime, such as a bubble regime, a slug flow regime, a turbulent flow regime, a fast fluidized regime, a pneumatic entrainment regime, or a combination thereof.
[0050] Referring again to FIG. 3 , the FCDh system 30 can be operated in system recycle mode, in which at least a portion of the FCDh effluent 34 is recycled back to the reactor section 200 of the FCDh system 30. The FCDh system 30 can be operated in system recycle mode during start-up of the FCDh system 30 or in response to an out-of-specification event in which the composition of the FCDh effluent 34 does not meet product stream target standards. In these situations, the FCDh effluent 34 can be recycled back to the FCDh system 30 while adjustments are made to the FCDh system 30 to bring the composition of the FCDh effluent 34 back into compliance. System recycle can also occur when the reactor system is integrated with another reactor system (e.g., steam cracking system 20) and the other reactor system experiences a shutdown (e.g., a planned event, such as planned maintenance, or an unplanned event, such as an unexpected failure of equipment, such as a furnace, compressor, or other equipment). During system recycle operation, at least a portion or all of the FCDh effluent 34 may be recycled back to the FCDh system 30 in the FCDh effluent recycle 36. The FCDh effluent recycle 36 may be combined with the second hydrocarbon feedstock 32 upstream of the transfer riser 430, as shown in Figure 3. In some embodiments, the FCDh effluent recycle 36 may be sent directly to the transfer riser 430, where it is then combined with the second hydrocarbon feedstock 32 and the dehydrogenation catalyst.
[0051] 1 as integrating a steam cracking system 20 and an FCDh system 30, it is contemplated that other processes for producing olefins may be included in the integrated system 10 in addition to, or as an alternative to, the steam cracking system 20 or the FCDh system 30. Examples of other olefin production systems that may be included in the integrated system may include a methanol-to-olefins process, an alcohol dehydration process, or other olefin production processes.
[0052] 4 , as previously described, the effluent treatment system 38 may include at least a first separation system 40, an acetylene hydrogenation unit 50 downstream of the first separation system 40, a heat exchanger 60 disposed between the first separation system 40 and the acetylene hydrogenation unit 50, a second separation system 70, and an MAPD hydrogenation unit 80. The cracked gas 28, at least a portion of the FCDh effluent 34, or both, may be sent to the first separation system 40. In some embodiments, the cracked gas 28 and the FCDh effluent 34 may be sent independently directly to the first separation system 40. In some embodiments, the cracked gas 28 and the FCDh effluent 34 may be combined upstream of the first separation system 40 and sent as a combined stream 39. The FCDh effluent 34 may be combined with the cracked gas 28 at any point downstream of the water quench unit 130 and the oil quench unit 120 of the steam cracking system 20.
[0053] The first separation system 40 may be operable to produce at least the hydrogenation feedstock 42 and the acetylene-depleted stream 44 from the cracked gas 28, a portion of the FCDh effluent 34, or both. The first separation system 40 may include one or more separation devices. The first separation system 40 may include any type of separation device operable to produce the hydrogenation feedstock 42 from the cracked gas 28, the FCDh effluent 34, or both. In some embodiments, the first separation system 40 may include a distillation device in which the cracked gas 34, the FCDh effluent 34, or both, may be separated into the hydrogenation feedstock 42 and the acetylene-depleted stream 44 based on differences in the boiling point temperatures of the components. In some embodiments, the first separation system 40 may be a multi-stage distillation column. Separating the components of the cracked gas 28, the FCDh effluent 34, or both, based on differences in boiling point temperatures may include initially cooling the cracked gas 28, the FCDh effluent 34, or both, to a temperature below the boiling point temperatures of one or more of the components. Thus, the first separation system 40 may include a condenser (not shown) operable to condense one or more components of the cracked gas 28, the FCDh effluent 34, or both, upstream of the distillation apparatus. The first separation system 40 is not limited to distillation processes. It is understood that other methods and processes for producing the hydrogenation feedstock 42 from the cracked gas 28, the FCDh effluent 34, or both, are contemplated.
[0054] As previously mentioned, the hydrogenation feedstock 42 can comprise at least 95% by weight of the acetylene from the cracked gas 28 sent to the first separation system 40. The hydrogenation feedstock 42 can comprise saturated and unsaturated hydrocarbons, such as, but not limited to, ethylene (C2H4), propylene (C3H6), acetylene (C2H2), methylacetylene (HC-C≡CH), propadiene (HC=C=CH2), methane (CH4), ethane (C2H6), propane (C3H8), or combinations thereof. The hydrogenation feedstock 42 can also comprise non-hydrocarbon gases, such as, but not limited to, hydrogen, CO, carbon dioxide (CO2), inert gases, or combinations thereof. The inert gases can include nitrogen, argon, or other inert gases present in the steam cracking system 20, the FCDh system 30, or both. In some embodiments, the hydrogenation feedstock 42 can comprise at least acetylene, hydrogen, CO, MA, and PD. The hydrogenation feedstock 42 may include at least 95%, or even at least 99%, of the CO from the cracked gas and a portion of the FCDh effluent sent to the first separation system 40. The hydrogenation feedstock 42 may also include one or more product olefins, which may include, but are not limited to, propylene, ethylene, or combinations thereof. The hydrogenation feedstock 42 may also include other hydrocarbons, such as, but not limited to, methane, ethane, propane, or combinations thereof.
[0055] The acetylene-depleted stream 44 may contain less than 5% by weight of acetylene from the cracked gas 28. The acetylene-depleted stream 44 may contain a higher weight percentage of higher boiling point hydrocarbons compared to the hydrogenation feedstock 42. These higher boiling point hydrocarbons may include saturated and unsaturated hydrocarbons, such as, but not limited to, butane, butene, butadiene, pentane, or other higher boiling point temperature hydrocarbons.
[0056] The first separation system 40 may be a depropanizer for a front-end steam cracking system (FEDP). When the first separation system 40 is configured as a FEDP, the hydrogenation feedstock 42 may contain C3 and C3-hydrocarbons and non-hydrocarbon gases. The C3 and C3-hydrocarbons may include, but are not limited to, methane, ethane, propane, ethylene, propylene, acetylene, methylacetylene, propadiene, and combinations thereof. The light gases in the hydrogenation feedstock 42 may include hydrogen, CO, carbon dioxide, nitrogen, or other non-hydrocarbon gases. When the first separation system 40 is a FEDP, the acetylene-depleted stream 44 may include C4 and C4+ hydrocarbons, such as butane, butene, butadiene, pentane, pentenes (i.e., one or more of the various isomers of pentene), and other C4 and C4+ hydrocarbons. When the first separation system 40 is a FEDP, the hydrogenation feedstock 42 can have at least 95% of the acetylene, MA, and PD from the cracked gas 28 and a portion of the FCDh effluent 34. For more information on various front-end configurations for acetylene hydrogenation in olefin production processes, see "Overview on C2 and C3 Selective Hydrogenation in Ethylene Plants" by Edgar L. Mohundro. th Ethylene Produces Conference, 2003 AICHE Spring National Meeting, New Orleans, LA, the entire contents of which are incorporated herein by reference.
[0057] Referring to FIG. 4 , the effluent treatment system 38 may include an acetylene hydrogenation unit 50 downstream of the first separation system 40. The acetylene hydrogenation unit 50 may be positioned to receive the hydrogenation feedstock 42 from the first separation system 40. The hydrogenation feedstock 42 may be sent to the acetylene hydrogenation unit 50 from the first separation system 40. The hydrogenation feedstock 42 may be contacted with a first hydrogenation catalyst in the acetylene hydrogenation unit 50. Contacting the hydrogenation feedstock 42 with the first hydrogenation catalyst may hydrogenate at least a portion of the acetylene in the hydrogenation feedstock 42 to produce a hydrogenated effluent 52, which may have a reduced acetylene concentration compared to the hydrogenation feedstock 42. The hydrogenation effluent 52 may include reaction products from the hydrogenation reaction and unreacted components of the hydrogenation feedstock 42. The acetylene hydrogenation unit 50 can include one or more hydrogenation reactors, such as one, two, three, or more than three hydrogenation reactors. The hydrogenation reactor of the acetylene hydrogenation unit 50 can be a fixed-bed reactor including a fixed bed of a first hydrogenation catalyst. The hydrogenation reactor of the acetylene hydrogenation unit 50 can be a gas-phase reactor operable to conduct a hydrogenation reaction by contacting the first hydrogenation catalyst (solid) with a reactant in a gas phase.
[0058] 4, in some embodiments, the acetylene hydrogenation unit 50 can include multiple hydrogenation reactors arranged in series (e.g., a first hydrogenation reactor 150, a second hydrogenation reactor 160, and a third hydrogenation reactor 170). Referring to FIG. 4, in one embodiment, the acetylene hydrogenation unit 50 can include at least the first hydrogenation reactor 150 and a second hydrogenation reactor 160 downstream of the first hydrogenation reactor 150. The acetylene hydrogenation unit 50 can also include a third hydrogenation reactor 170 downstream of the second hydrogenation reactor 160. Typically, the first hydrogenation reactor 150 removes a majority of the acetylene in the hydrogenation feedstock, while the second reactor 160 removes the remainder of the acetylene, and the third reactor 170 functions as a polishing bed to prevent the hydrogenation effluent from being out of specification for acetylene concentration. The acetylene hydrogenation apparatus 50 may also optionally include a heat exchanger 180 disposed between each of the hydrogenation reactors. Each of the heat exchangers 180 may be located downstream of one of the hydrogenation reactors 150, 160, 170 and may be operable to remove heat generated from the exothermic hydrogenation reaction in each of the hydrogenation reactors 150, 160, 170.
[0059] The hydrogenation feedstock 42 may be sent to a first hydrogenation reactor 150, which may be operable to hydrogenate at least acetylene from the hydrogenation feedstock 42 to produce a first hydrogenation effluent 152. The first hydrogenation effluent 152 may have an acetylene concentration lower than the acetylene concentration in the hydrogenation feedstock 42. The first hydrogenation reactor 150 may have an acetylene conversion of 85% or greater, 90% or greater, or 95% or greater during normal operating conditions of the acetylene hydrogenation unit 50 to maintain the acetylene concentration in the hydrogenation effluent 52 below a threshold acetylene concentration. Heat may be removed from the first hydrogenation effluent 152 by sending the first hydrogenation effluent 152 to a heat exchanger 180. The first hydrogenation effluent 152 may be sent to a second hydrogenation reactor 160, which may be operable to further hydrogenate the acetylene in the first hydrogenation effluent 152 to produce a second hydrogenation effluent 162. Heat may be removed from the second hydrogenation effluent 162 by sending the second hydrogenation effluent 162 to a heat exchanger 180. The second hydrogenation effluent 162 may be sent to a third hydrogenation reactor 170, which may be operable to further hydrogenate the acetylene in the second hydrogenation effluent 162 to produce a third hydrogenation effluent 172. Heat may be removed from the third hydrogenation effluent 172 by sending the third hydrogenation effluent 172 to a heat exchanger 180. The third hydrogenation reactor effluent 172 may exit the acetylene hydrogenation unit 50 as the hydrogenation effluent 52.
[0060] Although not shown in the figure, the acetylene hydrogenation unit 50 may include one or more temperature sensors, pressure sensors, flow meters, or combinations thereof to measure temperature, pressure, or gas flow rate at one or more locations in the acetylene hydrogenation unit 50. The temperature, pressure, and / or gas flow rate may be determined for one or more of the multiple acetylene hydrogenation reactors in the acetylene hydrogenation unit 50 and / or for the hydrogenation feedstock 42 introduced to the acetylene hydrogenation unit 50. A method of operating the acetylene hydrogenation unit 50 may include determining the temperature of the acetylene hydrogenation unit 50, the temperature of the hydrogenation feedstock 42 delivered to the acetylene hydrogenation unit 50, or both.
[0061] The acetylene hydrogenation unit 50 may also include one or more analyzers, such as a GC analyzer, operable to measure the concentration of CO, hydrogen, or other components in the hydrogenation feed 42, the hydrogenation effluent 52, an intermediate effluent from one or more of the hydrogenation reactors of the acetylene hydrogenation unit 50, or a combination thereof. In some embodiments, a stream for compositional analysis may be removed from the hydrogenation feed 42 prior to introducing the hydrogenation feed 42 into the acetylene hydrogenation unit 50. Alternatively, or additionally, a stream for compositional analysis may be removed from the hydrogenation effluent 52 exiting the acetylene hydrogenation unit 50. In some embodiments, a stream for compositional analysis may be removed from one or more intermediate effluent streams exiting one of the hydrogenation reactors of the acetylene hydrogenation unit 50. A method of operating the acetylene hydrogenation unit 50 may include determining the concentration of CO, hydrogen, or other components in the acetylene hydrogenation unit 50.
[0062] The acetylene hydrogenation unit 50 can be operated under conditions where catalytic hydrogenation is selective for the hydrogenation of acetylene over the hydrogenation of propylene and ethylene. The first hydrogenation catalyst can be an acetylene hydrogenation catalyst that is selective for the hydrogenation of acetylene relative to the product compounds in the hydrogenation feedstock 42. The acetylene hydrogenation unit 50 can be operated at a temperature sufficient to hydrogenate acetylene at a conversion rate that prevents breakthrough of acetylene to downstream processes, but below a temperature that would result in increased olefin hydrogenation and thermal runaway of the acetylene hydrogenation unit 50. As described in further detail herein, the operating temperature of the acetylene hydrogenation unit 50 can depend on the composition of the hydrogenation feedstock 42, but the operating temperature of the acetylene hydrogenation unit 50 can be between 10°C and 200°C, such as between 10°C and 100°C. Other factors that affect the operating temperature of the acetylene hydrogenation unit 50 can include, but are not limited to, the type of hydrogenation catalyst, the age / activity of the hydrogenation catalyst, the flow rate, the inlet acetylene concentration, the CO concentration, the presence of contaminants or toxic substances, other factors, or combinations thereof. The acetylene hydrogenation unit 50 can be operated at pressures from 100 pounds per square inch gauge (psig) to 1000 psig (i.e., from about 690 kilopascals (kPa) to about 6900 kPa). The acetylene hydrogenation unit 50 can further be operated at gas hourly space velocities (GHSV) (volumes per volume of catalyst per hour) from 1,000 to 14,000.
[0063] When operated under normal operating conditions, the acetylene conversion in the first hydrogenation reactor 150 of the acetylene hydrogenation unit 50 may be sufficient to maintain the acetylene concentration in the hydrogenation effluent 52 at or below a threshold acetylene concentration. In some embodiments, the acetylene conversion in the first hydrogenation reactor 150 may be 85% or greater, such as 88% or greater, 90% or greater, or even 95% or greater, under normal operating conditions. Under normal operating conditions, this refers to operation of the acetylene hydrogenation unit 50 at steady state, where the acetylene concentration in the hydrogenation effluent 52 is at or below the threshold acetylene concentration. In some embodiments, under normal operating conditions, the acetylene conversion in the first hydrogenation reactor 150 may be between 85% and 95%, or between 88% and 92%.
[0064] The hydrogenation effluent 52 may refer to an effluent or composition exiting the acetylene hydrogenation unit 50, such as from the final hydrogenation reactor of the acetylene hydrogenation unit 50. The hydrogenation effluent 52 may have an acetylene concentration that is lower than the acetylene concentration of the hydrogenation feedstock 42. The hydrogenation effluent 52 may have an acetylene concentration at or below a threshold acetylene concentration that may be specified by a downstream olefin product user or customer. In some embodiments, the hydrogenation effluent 52 may have an acetylene concentration of 2 parts per million per volume (ppmv) or less, 1 ppmv or less, 0.5 ppmv or less, or even 0.1 ppmv or less. The first hydrogenation catalyst and operating conditions of the acetylene hydrogenation unit 50 may be selective for hydrogenating acetylene relative to the hydrogenation of product compounds such as propylene and ethylene produced in the steam cracking system 20 and / or the FCDh system 30.
[0065] 4, the effluent treatment process 38 may include a heat exchanger 60 disposed between the first separation system 40 and the acetylene hydrogenation unit 50. The heat exchanger 60 may include a bypass 62 having a control valve 64. By controlling the amount of hydrogenation feedstock 42 passing through the heat exchanger 60 and the amount of hydrogenation feedstock 42 passing through the heat exchanger 60 via the bypass 62, the temperature of the hydrogenation feedstock 42 at the inlet to the acetylene hydrogenation unit 50 can be increased or decreased. By controlling the amount of hydrogenation feedstock 42 passing through the bypass of the heat exchanger 60, it is possible to increase or decrease the temperature of the hydrogenation feedstock 42 at the inlet to the acetylene hydrogenation unit 50. The heat exchanger 60 for the hydrogenation feedstock 42 may be any type of heat exchanger known in the chemical industry.
[0066] The hydrogenation effluent 52 may be sent to a second separation system 70. The second separation system 70 may include one or more unit operations operable to separate the hydrogenation effluent 52 into multiple component streams, such as, but not limited to, an ethylene stream 72, a propylene stream 74, a propane stream 76, other component streams, or combinations thereof. The largest portion (e.g., greater than 90%) of the MAPD from the hydrogenation effluent 52 may be included in the propane stream 76 exiting the second separation system 70. One or more of the component streams may be sent to one or more unit operations and / or processes downstream of the second separation system 70 for further processing of the hydrogenation effluent 52 or as a product stream. Downstream processes may include vapor compression, separation, drying, or other operations and processes. One or more of the component streams may be sent as a reactant or feedstock to a further production process, such as a polymer production process. In some embodiments, the propane stream 76 or other component streams may be sent or recycled back to the steam cracking system 20 and / or the FCDh system 30 as at least a portion of the first hydrocarbon feedstock 22 and / or the second hydrocarbon feedstock 32, respectively.
[0067] Referring now to FIG. 5 , the acetylene concentration in the hydrogenation effluent 52 (left y-axis) and the ethylene selectivity of the acetylene hydrogenation unit 50 (right y-axis) are shown as a function of the temperature (x-axis) of the hydrogenation feed 42 at the inlet to the acetylene hydrogenation unit 50. Line 502 in FIG. 5 represents the threshold acetylene concentration in the hydrogenation effluent 52, below which the acetylene is deemed to have degraded to a level sufficient to meet the requirements of olefin users and / or prevent or reduce catalyst fouling, off-specification product streams, or other problems in downstream processes. As shown in FIG. 5 , the acetylene concentration in the hydrogenation effluent 52 (curve 510) decreases with increasing inlet temperature for a given composition of the hydrogenation feed 42. FIG. 5 illustrates that the acetylene concentration 510 in the hydrogenation effluent 52 can be increased or decreased by decreasing or increasing the inlet temperature to the acetylene hydrogenation unit 50, respectively. The temperature T1 of the curve 510 for a given composition of the hydrogenation feedstock 42 can be defined as the lowest temperature at which the acetylene concentration in the hydrogenation effluent 52 is less than or equal to the threshold acetylene concentration 502. At temperatures of the hydrogenation feedstock 42 greater than T1, the acetylene concentration (510) in the hydrogenation effluent 52 is less than the threshold acetylene concentration. For temperatures of the hydrogenation feedstock 42 less than T1, the acetylene concentration (510) in the hydrogenation effluent 52 can be greater than the threshold acetylene concentration. The temperature T1 in FIG. 5 can be considered the cleanup temperature of a particular catalyst for a given composition of the hydrogenation feedstock.
[0068] FIG. 5 also shows the ethylene selectivity (curve 520) of the acetylene hydrogenation unit 50 as a function of inlet temperature for the same composition of the hydrogenation feedstock 42 as curve 510. As shown in FIG. 5, the ethylene selectivity (curve 520) decreases with increasing inlet temperature. Therefore, as the inlet temperature to the acetylene hydrogenation unit 50 increases, the ethylene selectivity of the acetylene hydrogenation unit 50 decreases, indicating that more acetylene and / or some more ethylene is converted to ethylene, which may be caused by increased hydrogenation of ethylene within the acetylene hydrogenation unit 50. Increased ethylene hydrogenation can lead to thermal runaway. For example, at temperatures of the hydrogenation feedstock 42 greater than temperature T2, ethylene selectivity may decrease to the point where an unacceptable amount of ethylene undergoes hydrogenation. For example, temperature T2 may be the runaway temperature at which 3% of the ethylene from the hydrogenation feedstock 42 reacts in the acetylene hydrogenation unit 50.
[0069] Because the ethylene hydrogenation reaction is exothermic, the additional heat released from the increased hydrogenation of ethylene and other olefins can further increase the temperature within the acetylene hydrogenation unit 50, further shifting the hydrogenation reaction toward ethylene and propylene hydrogenation. The increased heat generated from the increased hydrogenation of ethylene and other olefins can lead to thermal runaway in the acetylene hydrogenation unit 50. As previously mentioned, during thermal runaway, a temperature increase of over 200°C can occur, potentially tripping the acetylene hydrogenation unit and requiring a system restart. Additionally, a temperature increase of over 200°C can damage the hydrogenation catalyst and other equipment, such as the reactor, meters, heat exchangers, and other devices, and can also pose a safety risk. In many runaway situations, severe loss of catalyst performance due to thermal runaway can require catalyst replacement, leading to significant unit downtime. Thermal runaway can also increase olefin product loss due to overhydrogenation of ethylene and propylene.
[0070] Referring again to FIG. 5 , the temperature operating window of the acetylene hydrogenation unit 50 for a given composition of the hydrogenation feedstock 42 can be defined between a cleanup temperature (e.g., temperature T1 in FIG. 5 , below which the acetylene concentration in the hydrogenation effluent 52 becomes higher than the threshold acetylene concentration 502) and a runaway temperature (e.g., temperature T2, above which ethylene selectivity decreases and hydrogenation of the olefin product can lead to thermal runaway of the acetylene hydrogenation unit 50).
[0071] Varying the CO concentration of the hydrogenation feedstock 42 can change the operating window of the acetylene hydrogenation unit 50. Increasing the CO concentration in the hydrogenation feedstock 42 widens the process window, potentially shifting the process window relative to the temperature of the hydrogenation feedstock 42 toward higher temperatures. In FIG. 5 , curve 512 represents the acetylene concentration in the hydrogenation effluent 52 as a function of the inlet temperature of the hydrogenation feedstock 42 for operating the acetylene hydrogenation unit 50 at a higher CO concentration, such as when the FCDh effluent is integrated into the product processing system 38 (e.g., when only the cracked gas 28 is sent to the product processing system 38), compared to the CO concentration of curve 510. At a given temperature of the hydrogenation feedstock 42, increasing the CO concentration decreases the acetylene conversion. By increasing the CO concentration in the acetylene hydrogenation unit 50, the inlet temperature T3 at which the acetylene concentration in the hydrogenation effluent 52 equals the threshold acetylene concentration 502 becomes higher than the corresponding temperature T1 of the hydrogenation feedstock 42 in curve 510 (which has a lower CO concentration).
[0072] Additionally, increasing the CO concentration in the acetylene hydrogenation unit 50 can shift the ethylene selectivity curve toward higher inlet temperatures. Referring to FIG. 5 , curve 522 represents the ethylene selectivity of the acetylene hydrogenation unit 50 as a function of the inlet temperature of the hydrogenation feedstock for higher CO concentrations (e.g., when the FCDh effluent 34 is integrated into the product processing system 38) compared to the CO concentration of curve 520 (e.g., when only the cracked gas 28 is sent to the product processing system 38). As shown in FIG. 5 , increasing the CO concentration in the acetylene hydrogenation unit 50 (curve 522) can increase the ethylene selectivity at a given temperature. This can enable operation of the acetylene hydrogenation unit 50 at higher inlet temperatures compared to operating the acetylene hydrogenation unit 50 at lower CO concentrations. However, a sudden decrease in CO concentration in the hydrogenation feedstock due to a sudden reduction or complete loss of the flow of FCDh effluent 34 can not only potentially shift the process toward lower olefin selectivity, but can also significantly increase catalyst activity within the hydrogenation unit at the same temperature, increasing the hydrogenation of olefin products such as ethylene and / or propylene, which can lead to thermal runaway, as previously described herein.
[0073] 1 , the steam cracking system 20 and the FCDh system 30 can be integrated such that the processes share a common effluent treatment system 38, which can include at least a first separation system 40, an acetylene hydrogenation unit 50, a second separation system 70, and an MAPD hydrogenation unit 80. The steam cracking system 20 can be operated, and the cracked gas 28 can be sent to the product treatment system 38. The FCDh system 30 can also be operated, and at least a portion of the FCDh effluent 34 from the FCDh system 30 can be integrated into the product treatment system 38. A portion of the FCDh effluent 34 can be integrated into the product treatment system 38 by sending a portion of the FCDh effluent 34 to the first separation system 40, combining a portion of the FCDh effluent 34 with the cracked gas 28 upstream of the first separation system 40, or both. In some embodiments, the entire FCDh effluent 34 can be sent to the first separation system 40, combined with the cracked gas 28, or both. In some embodiments, only a portion of the FCDh effluent 34 can be sent to the first separation system 40, combined with the cracked gas 28, or both. The remaining FCDh effluent can be recycled back to the FCDh system 30 or combined with the second hydrocarbon feedstock 32 via the FCDh effluent recycle 36. Additionally, in some embodiments, the portion of the FCDh effluent 34 sent to the first separation system 40, combined with the cracked gas 28, or both, can be a second portion of the FCDh effluent that supplements the first portion of the FCDh effluent that has already entered the product processing system 38.
[0074] As previously mentioned, the CO concentration in the FCDh effluent 34 may be higher than the CO concentration in the cracked gas 28. The cracked gas 28 may have a CO concentration of 50 ppmv to 400 ppmv. The FCDh effluent 34 may have a CO concentration of 500 ppmv to 2400 ppmv, such as 1000 ppmv to 2000 ppmv. When both the cracked gas 28 and a portion of the FCDh effluent 34 are sent to the effluent treatment system 38, the amount of CO in the hydrogenation feedstock 42 may be higher than the amount of CO in the cracked gas 28.
[0075] An equipment trip of FCDh system 30 can shut down FCDh system 30 completely, or can recycle a majority of FCDh effluent 34 back to FCDh system 30 through FCDh recycle 36. When this occurs, the flow of FCDh effluent 34 to product treatment system 38 can be suddenly reduced (e.g., by increasing the recycle back to FCDh system 30) or eliminated (e.g., by completely shutting down FCDh system 30 and suddenly reducing the flow rate of FCDh effluent 34 to zero, or by completely disconnecting FCDh system 30 from effluent treatment system 38). A sudden substantial reduction or complete loss of the flow of a portion of FCDh effluent 34 to first separation system 40 (e.g., directly or in combination with cracked gas 28) can result in a sudden decrease in the CO concentration in hydrogenation feedstock 42 to acetylene hydrogenation unit 50.
[0076] As previously mentioned, reducing the CO concentration in the hydrogenation feedstock 42 reduces the CO concentration in the acetylene hydrogenation unit 50, potentially increasing the hydrogenation of ethylene and other olefin products in the acetylene hydrogenation unit 50 and thereby decreasing ethylene selectivity. A sudden decrease in the CO concentration in the hydrogenation feedstock 42 due to a sudden reduction or complete loss of the flow of the FCDh effluent 34 to the effluent treatment system 38 can increase the activity of the hydrogenation catalyst and increase the reaction rate of the acetylene hydrogenation reaction at a constant temperature. The increased reaction rate can increase the hydrogenation of ethylene and other product olefins and decrease ethylene selectivity. A sudden reduction or complete loss of the flow of the FCDh effluent 34 can also result in a sudden decrease in the mass flow rate of the hydrogenation feedstock 42 and the mass flow rate through the acetylene hydrogenation unit 50. This can lead to a smaller gas space velocity or residence time of the hydrogenation feedstock, which can also increase the hydrogenation of ethylene and other product olefins in the acetylene hydrogenation unit 50. As previously mentioned, increased hydrogenation of ethylene and other olefins in acetylene hydrogenation unit 50 can lead to thermal runaway of acetylene hydrogenation unit 50, which can reduce the yield of product olefins and damage equipment and catalysts, as previously described herein.
[0077] The first hydrogenation catalyst in the acetylene hydrogenation unit 50 may be a hydrogenation catalyst with reduced sensitivity to changes in CO concentration. For example, the first hydrogenation catalyst may have a wide temperature operating range, which may reduce the sensitivity of the first hydrogenation catalyst to sudden increases and / or decreases in CO concentration in the hydrogenation feedstock 42. Temperature operating range, as used herein, may refer to the difference between the cleanup temperature and the runaway temperature of the acetylene hydrogenation unit 50 of the integrated process 10, which includes the cracker 20, the FCDh unit 30, and the first separation system 40 having a front-end depropanizer (FEDP). The wide temperature operating range of the first hydrogenation catalyst may allow for a greater increase in temperature in the acetylene hydrogenation unit 50 in response to a sudden decrease in CO concentration without reaching a temperature at which at least 3% of the ethylene in the hydrogenation feedstock 42 is hydrogenated. In some embodiments, the first hydrogenation catalyst may have a temperature operating range sufficient to reduce or prevent thermal runaway of the acetylene hydrogenation unit 50 in response to a sudden loss of flow of the FCDh effluent 34 from the FCDh system 30. In some embodiments, the first hydrogenation catalyst may have a temperature operating range of 40° C. or greater, 45° C. or greater, or even 50° C. or greater for a given composition of the hydrogenation feedstock 42 when used in the acetylene hydrogenation unit 50 of an integrated system 10 in which the first separation system 40 has a FEDP configuration.
[0078] In some embodiments, the first hydrogenation catalyst can be a commercially available Pd-Ag-based selective hydrogenation catalyst with a wide temperature operating window. In some embodiments, the first hydrogenation catalyst can be an acetylene hydrogenation catalyst commercially available for acetylene hydrogenation in effluent treatment systems with a front-end deethanizer (FEDE) configuration. These types of selective hydrogenation catalysts with a wide temperature operating window have not currently been applied to the selective hydrogenation of the integrated process 10 having a steam cracker 20 and a first separation system 40 with a front-end depropanizer (FEDP) configuration because their activity for hydrogenating MAPD is insufficient. For the integrated process 10 having a steam cracker 20 and a first separation system 40 with a front-end deethanizer (FEDE) configuration, selective acetylene hydrogenation catalysts with a wide temperature operating range are commercially available because their activity is acceptable for acetylene removal when the hydrogenation feedstock 42 does not have a significant concentration of MAPD. In some embodiments, the first hydrogenation catalyst can be a selective hydrogenation catalyst for a cracker system having a FEDP configuration or a selective hydrogenation catalyst for a cracker system having a FEDE configuration.
[0079] Utilizing a first hydrogenation catalyst having a temperature operating range of 40°C or greater can reduce or prevent thermal runaway of the acetylene hydrogenation unit 50 in response to loss of the flow of FCDh effluent 34 from the FCDh system 30. However, a first hydrogenation catalyst with a wide operating window may be less effective for hydrogenating methylacetylene (MA) and propadiene (PD) compared to other acetylene hydrogenation catalysts. Contacting the hydrogenation feedstock 42 with the first hydrogenation catalyst in the acetylene hydrogenation unit 50 may result in a conversion of MA in the acetylene hydrogenation unit 50 of 80% or less, such as 75% or less, 70% or less, 60% or less, or even 40% or less. Similarly, contacting the hydrogenation feedstock 42 with the first hydrogenation catalyst in the acetylene hydrogenation unit 50 may result in a conversion of PD in the acetylene hydrogenation unit 50 of 10% or less, such as 8% or less, 5% or less, or even 1% or less. Compared to conventional hydrogenation catalysts, the reduction in conversion of MA and PD due to the first hydrogenation does not pose a problem when the effluent treatment system 38 has a FEDE configuration because, in the FEDE configuration, the first separation system 40 separates the MA and PD into an acetylene-depleted stream that is not sent to the acetylene hydrogenation unit 50. Thus, in the FEDE configuration, the MA and PD are not sent to the acetylene hydrogenation unit 50. However, when the effluent treatment system 38 has a FEDP configuration, the first separation system 40 separates the majority of the MA and PD into the hydrogenation feedstock 42, which is then sent to the acetylene hydrogenation unit 50. When a first hydrogenation catalyst having a temperature operating range of 40° C. or greater is used, low conversion of MA and PD in acetylene hydrogenation unit 50 can result in significant amounts of MA and PD in hydrogenation effluent 52. MAPD in hydrogenation effluent 52 can increase coke production when the stream containing MA and / or PD is recycled back to an olefin production process, such as FCDh system 30, or sent to a downstream process. Additionally, specifications from olefin users may require that the concentrations of MA and PD be below threshold concentrations for these compounds.
[0080] 1 , as previously mentioned, the effluent treatment system 38 may include a MAPD hydrogenation unit 80 downstream of the acetylene hydrogenation unit 50. The MAPD hydrogenation unit 80 may be operable to contact at least a portion of the hydrogenated effluent 52 with a second hydrogenation catalyst. At least a portion of the hydrogenated effluent 52 sent to the MAPD hydrogenation unit 80 may have a combined MA and PD concentration of 10 wt.% or less, such as 8 wt.% or less, or even 6 wt.% or less. The portion of the hydrogenated effluent 52 sent to the MAPD hydrogenation unit 80 may include, but is not limited to, one or more of propane, propylene, or a combination thereof.
[0081] Contacting the portion of the hydrogenation effluent 52 with the second hydrogenation catalyst can be performed in the presence of hydrogen. Contacting the portion of the hydrogenation effluent 52 with the second hydrogenation catalyst can hydrogenate at least a portion of the MA and PD in the portion of the hydrogenation effluent 52 to produce a MAPD hydrogenation effluent 82. In some embodiments, the portion of the hydrogenation effluent 52 sent to the MAPD hydrogenation unit 80 can include hydrogen. In other embodiments, a supplemental hydrogen stream 79 can be sent to the MAPD hydrogenation unit 80.
[0082] MAPD hydrogenation unit 80 can include one or more MAPD hydrogenation reactors, such as one, two, three, or more than three MAPD hydrogenation reactors. Each of the MAPD hydrogenation reactors can be a fixed-bed reactor including a fixed bed of a second hydrogenation catalyst. The MAPD hydrogenation reactors of MAPD hydrogenation unit 80 can be gas-phase reactors operable to conduct a hydrogenation reaction by contacting a gas-phase reactant with the second hydrogenation catalyst (solid).
[0083] The second hydrogenation catalyst may be a catalyst operable to hydrogenate MA and PD. The second hydrogenation catalyst may be any commercially available hydrogenation catalyst effective for hydrogenating MA and PD to propylene, propane, or a combination of both. The second hydrogenation catalyst may be a conventional full-hydrogenation catalyst, such as, but not limited to, a Ni-, Pd-, Pt-, or Cu-based supported catalyst, or a combination thereof. In some embodiments, the second hydrogenation catalyst is different from the first hydrogenation catalyst. The MAPD hydrogenation unit 80 may be operated under conditions sufficient to hydrogenate at least a portion of the MA and PD from the hydrogenation effluent 52 (e.g., the MA / PD in the propane stream 76 from the second separation system 70) to produce an MA / PD-depleted stream 82. The MAPD hydrogenation unit 80 may be operated at a temperature sufficient to hydrogenate the MA / PD at a conversion rate that prevents breakthrough of the MA / PD to downstream processes. The operating temperature of the MAPD hydrogenation unit 80 may be between 10°C and 200°C, such as between 10°C and 100°C, although the operating temperature of the MAPD hydrogenation unit 80 may depend on the composition of the portion of the hydrogenation effluent 52 sent to the MAPD hydrogenation unit 80. Other factors that affect the operating temperature of the MAPD hydrogenation unit 80 may include, but are not limited to, the type of second hydrogenation catalyst, the age / activity of the second hydrogenation catalyst, the flow rate, the influent concentrations of MA and PD, the presence of contaminants or toxic substances, other factors, or combinations thereof. The MAPD hydrogenation unit 80 may be operated at pressures between 100 pounds per square inch gauge (psig) and 1000 psig (i.e., about 690 kilopascals (kPa) and about 6900 kPa) using the second hydrogenation catalyst.
[0084] 1 , in some embodiments, the portion of the hydrogenated effluent 52 sent to the MAPD hydrogenation unit 80 may include one or more effluent streams from the second separation system 70, such as a propane stream 76. The hydrogenated effluent 52 may be sent to the second separation system 70, which may be operable to separate the hydrogenated effluent 52 into at least an ethylene stream 72, a propylene stream 74, and a propane stream 76. The propane stream 76 may include MA and PD and may be the portion of the hydrogenated effluent 52 sent to the MAPD hydrogenation unit 80. The MAPD hydrogenation unit 80 may be operable to contact the propane stream 76 with a second hydrogenation catalyst in the presence of hydrogen to hydrogenate at least a portion of the MA and PD from the propane stream 76 to produce a MAPD hydrogenated effluent 82. In some embodiments, the MAPD hydrogenation effluent 82 can be sent to the FCDh system 30 as a recycle propane stream, combined with a second hydrocarbon stream 32 upstream of the FCDh system 30, or both. In some embodiments, the MAPD hydrogenation effluent 82 can be combined with an auxiliary hydrocarbon stream 84, such as an auxiliary propane stream, upstream of the FCDh system 30 to produce a combined stream 86, which can be sent to the FCDh system 30 or combined with the second hydrocarbon feedstock 32 upstream of the FCDh system 30. In some embodiments, the second hydrocarbon feedstock 32 can be the auxiliary hydrocarbon stream 84, and the MAPD hydrogenation effluent 82 can be combined therewith upstream of the FCDh system 30. As shown in FIG. 1 , at least a portion of the auxiliary hydrocarbon stream 84 can be sent to the steam cracker 20.
[0085] Referring now to FIG. 6 , in some embodiments, the auxiliary hydrocarbon stream 84 can also be sent to the MAPD hydrogenation unit 80 and contacted with a second hydrogenation catalyst before being sent to the FCDh system 30. Depending on the source of the auxiliary hydrocarbon stream 84, the auxiliary hydrocarbon stream 84 can contain various unsaturated hydrocarbon compounds, including, but not limited to, various alkenes, alkynes, aromatics, or combinations thereof. In some embodiments, the auxiliary hydrocarbon stream 84 can contain MA, PD, or both. These unsaturated hydrocarbon impurities in the auxiliary hydrocarbon stream 84 can produce coke within the FCDh system 30 at operating conditions. The additional coke produced by the unsaturated hydrocarbon impurities in the auxiliary hydrocarbon stream 84 can reduce the activity of the catalyst in the FCDh system 30, thereby reducing the yield, selectivity, or both of the FCDh system 30. The additional coke formation can also lead to operating difficulties in the long term. The auxiliary hydrocarbon stream 84 may be contacted with a second hydrogenation catalyst in the MAPD hydrogenation unit 80 to hydrogenate at least a portion of the unsaturated hydrocarbon impurities in the auxiliary hydrocarbon stream 84, thereby reducing the amount of unsaturated hydrocarbon impurities entering the FCDh system 30.
[0086] 6 , in some embodiments, the auxiliary hydrocarbon stream 84 can be combined with at least a portion of the hydrogenation effluent 52 (e.g., propane stream 76) upstream of the MAPD hydrogenation unit 80. In other embodiments, the auxiliary hydrocarbon stream 84 and a portion of the hydrogenation effluent 52 can be sent separately to the MAPD hydrogenation unit 80. The MAPD hydrogenation effluent 82 can then be sent from the MAPD hydrogenation unit 80 to the FCDh system 30. In some embodiments, the MAPD hydrogenation effluent 82 can be combined with the second hydrocarbon feedstock 32 upstream of the FCDh system 30, or can be sent to the FCDh system 30 separately from the second hydrocarbon feedstock 32. In some embodiments, the MAPD hydrogenation effluent 82 can be the second hydrocarbon feedstock 32 sent to the FCDh system 30.
[0087] In some embodiments, at least a portion of the auxiliary hydrocarbon stream 84 may be sent to the steam cracking system 20. The portion of the auxiliary hydrocarbon stream 84 may be combined with the first hydrocarbon feedstock 22 upstream of the steam cracking system 20 or may be sent separately to the steam cracking system 20. The portion of the auxiliary hydrocarbon stream 84 may be sent to the steam cracking system 20 without passing through the MAPD hydrogenation unit 80.
[0088] Referring now to FIG. 7, an FCDh olefin production process 100 is illustrated schematically. The process illustrated in FIG. 7 includes an FCDh system 30 with a dedicated effluent treatment system 138 that is not integrated with the steam cracking system 20, or any other olefin production process. In the process 100, at least a portion of the FCDh effluent 34 from the FCDh system 30 can be sent to a hydrogenation unit 150 as a hydrogenation feedstock 142. The hydrogenation feedstock 142 can include at least CO, hydrogen, acetylene, MA, and PD. The hydrogenation feedstock 142 can further include olefinic compounds and / or other gases. The hydrogenation feedstock 142 can have any of the compositions, components, or properties described herein above for the hydrogenation feedstock 42. The hydrogenation feedstock 142 can be passed through a heat exchanger 160 and sent to the hydrogenation unit 150.
[0089] In a stand-alone FCDh process 100 in which the FCDh system 30 is not integrated with the steam cracking system 20, sudden changes in CO concentration in the hydrogenation feed 142 to the hydrogenation unit 150 are no longer an issue. In the case of a stand-alone FCDh process 100 with a dedicated effluent treatment system 138, the hydrogenation unit 150 can include a third hydrogenation catalyst, which can be a high-criticality selective hydrogenation catalyst that is selective for hydrogenating acetylene, MA, and PD. The third hydrogenation catalyst can include any commercially available high-criticality selective hydrogenation catalyst. The hydrogenation feed 142 can be contacted with the third hydrogenation catalyst in the hydrogenation unit 150 to produce a hydrogenated effluent 152. Contacting the hydrogenation feed 142 with the third hydrogenation catalyst can hydrogenate at least a portion of the acetylene, MA, and PD from the hydrogenation feed 142 to produce a hydrogenated effluent 152 having concentrations of acetylene, MA, and PD below threshold concentrations of these compounds.
[0090] The hydrogenated effluent 152 may be sent to a second separation system 170, which may be operable to separate the hydrogenated effluent 152 into multiple hydrocarbon vapors, such as, but not limited to, an ethylene stream 172, a propylene stream 174, a propane stream 176, other streams, or combinations of these streams. Because a highly selective hydrogenation catalyst may be used, the dedicated effluent treatment system 138 of the stand-alone FCDh process 100 may not include an additional hydrogenation unit to further remove MA and PD from the propane stream 176 before sending it back to the FCDh system 30.
[0091] 1 , a method for operating the integrated system 10 to produce olefins can include contacting a hydrogenation feedstock 42 with a first hydrogenation catalyst to produce a hydrogenation effluent 52. The hydrogenation feedstock 42 can include at least a portion of a first process effluent from a first olefin production process and at least a portion of a second process effluent from a second olefin production process. The hydrogenation feedstock 42 can include at least hydrogen, ethylene, carbon monoxide, acetylene, methylacetylene, and propadiene. The hydrogenation feedstock 42 can have any other composition, properties, or characteristics described herein above for the hydrogenation feedstock 42. In some embodiments, the hydrogenation feedstock 42 can include at least 95% of the CO from the first process effluent (e.g., cracked gas 28), the second process effluent (e.g., a portion of the FCDh effluent 34), or both. The first hydrogenation catalyst can include a hydrogenation catalyst having a temperature operating range of at least 40° C., where the temperature range is the difference between the runaway temperature and the cleanup temperature for a given hydrogenation feed composition, where the runaway temperature is the temperature at which 3% of the ethylene in the hydrogenation feedstock 42 reacts, and the cleanup temperature is the temperature at which the acetylene concentration in the hydrogenation effluent 52 is equal to 1 ppm or other threshold acetylene concentration set by a downstream olefin user or customer. The hydrogenation effluent 52 can include MA, PD, or both. The hydrogenation effluent 52 can have any other components, properties, or characteristics described herein for the hydrogenation effluent 52. A first hydrogenation catalyst having a temperature operating range of 40° C. or greater can reduce or prevent thermal runaway of the acetylene hydrogenation unit 50 in response to an interruption in the flow of the first process effluent or the second process effluent.
[0092] The method can further include contacting at least a portion of the hydrogenation effluent 52 with a second hydrogenation catalyst, which hydrogenates at least a portion of the MA, PD, or both from the hydrogenation effluent 52 to produce a MAPD hydrogenation effluent 82. In some embodiments, the combined concentration of MA and PD in the portion of the hydrogenation effluent 52 contacted with the second hydrogenation catalyst can be 10 wt % or less. The MAPD hydrogenation effluent 82 can have any of the compositions, properties, or characteristics described herein above for the MAPD hydrogenation effluent 82.
[0093] 1 , in some embodiments, the first process effluent can include a cracked gas 28 produced by cracking at least a portion of the first hydrocarbon feedstock 22 in a steam cracking system 20. The cracked gas 28 can include at least hydrogen, carbon monoxide, acetylene, methyl acetylene, and propadiene. In some embodiments, the second process effluent can include at least a portion of an FCDh effluent 34 produced by dehydrogenating at least a portion of the second hydrocarbon feedstock 32 in an FCDh system 30. The portion of the FCDh effluent 34 can include at least hydrogen and carbon monoxide. In some embodiments, the method can include cracking at least a portion of the first hydrocarbon feedstock 22 in the steam cracking system 20 to produce a cracked gas 28 including at least hydrogen, carbon monoxide, acetylene, methyl acetylene, and propadiene. In some embodiments, the method can further include dehydrogenating at least a portion of the second hydrocarbon feedstock 32 in the FCDh system 30 to produce an FCDh effluent 34 comprising at least hydrogen and carbon monoxide. The steam cracking system 20 and the FCDh system 30 can have any of the features, characteristics, or operating conditions described herein for these systems. The first hydrocarbon feedstock 22, the second hydrocarbon feedstock 32, the cracked gas 28, and the FCDh effluent 34 can each have any of the compositions, properties, or characteristics described herein for these streams.
[0094] As previously mentioned, the hydrogenation feedstock 42 may be contacted with a first hydrogenation catalyst in the acetylene hydrogenation unit 50. In some embodiments, the method may further include passing the hydrogenation feedstock 42 to the acetylene hydrogenation unit 50. In some embodiments, contacting the hydrogenation feedstock 42 with the first hydrogenation catalyst in the acetylene hydrogenation unit 50 may produce a conversion of MA from the hydrogenation feedstock 42 of less than 80%. In some embodiments, contacting the hydrogenation feedstock 42 with the first hydrogenation catalyst may produce a conversion of PD from the hydrogenation feedstock 42 of less than 10%.
[0095] 1 , in some embodiments, the method may further include sending at least a portion of the MAPD hydrogenation effluent 82 to the FCDh system 30. In some embodiments, the MAPD hydrogenation effluent 82 may include a propane stream. In some embodiments, the method may further include sending a supplemental hydrogen stream 79 to the MAPD hydrogenation unit 80. In some embodiments, the method may further include combining at least a portion of the second hydrocarbon feedstock 32 with the portion of the hydrogenation effluent 52 (e.g., the propane stream 76) before or during contacting the portion of the hydrogenation effluent 52 with a second hydrogenation catalyst in the MAPD hydrogenation unit 80.
[0096] In some embodiments, the method may further include separating the first process effluent and the second process effluent (e.g., cracked gas 28 and a portion of FCDh effluent 34) into a hydrogenation feedstock 42 and an acetylene-depleted stream 44. The first separation system 40 for separating the first process effluent and the second process effluent into the hydrogenation feedstock 42 and the acetylene-depleted stream 44 may have a FEDP configuration. [Example]
[0097] Embodiments of the present disclosure are further clarified by the following examples, which should not be construed as limiting the presently described disclosure and / or claimed embodiments.
[0098] Example 1: Generation and analysis of FCDh effluent In Example 1, an FCDh effluent was generated and analyzed for its composition in terms of C3+ and C3- compounds. Propane dehydrogenation was carried out in a modified Davison Circulating Riser (DCR) pilot unit, which employs in-situ fuel combustion in the regeneration section. Approximately 4,100 grams of Ga-Pt supported catalyst was loaded into the circulation system, and approximately 90 g of catalyst was calculated to be present in the reactor at any given time. The inlet temperature to the riser (reactor) was controlled at 630°C, and the pressure was set at 90 kilopascals (kPa) gauge (13 psig or 191 kPa / 27.7 psia absolute). High-purity propane was injected into the system to achieve a propane weight hourly space velocity (WHSV) of approximately 3.5. Nitrogen (N2) was co-fed into the system primarily as a catalyst carrier gas. The propane partial pressure was approximately 30 kPa (4.3 psig) gauge. The temperature for catalyst regeneration ranged from 700 to 750° C. High-purity methane (CH4) was used as fuel gas in the regenerator and was injected at a rate of 50 standard liters per hour.
[0099] The reactor system was operated for a period sufficient to achieve steady-state operation, at which point a sample of the FCDh effluent from the reactor system was collected and analyzed for composition using an online Maxum GC. Specifically, the FCDh effluent contained CO, carbon dioxide (CO), C, and C. 2- The compounds were analyzed to determine the concentrations of C3 compounds (including hydrogen), and C4 compounds. The results are shown in Table 1 below. [Table 1]
[0100] The data indicate that the CO concentration in the FCDh effluent can be much higher than the CO concentration in a typical hydrogenation feed to an acetylene hydrogenator, which contains only cracked gas from the steam cracking system. Typical concentrations of CO in the hydrogenation feed when only cracked gas is introduced into the separator are shown in Table 2 for the front-end deethanizer (FEDE) and front-end depropanizer (FEDP) configurations. Additionally, the acetylene concentration in the FCDh effluent was less than 50 ppmv, and the methylacetylene (MA) and propadiene (PD) concentrations (not listed in Table 1) in the FCDh effluent were less than 300 ppmv and less than 100 ppmv, respectively.
[0101] Therefore, the amount of these highly unsaturated molecules provided by the FCDh effluent was found to be substantially less than the amount of acetylene, MA, and PD provided by the cracked gas from the steam cracking system. Table 2 below shows typical concentrations of acetylene and MA / PD in the hydrogenation feed when only the cracked gas is introduced into the first separation system. Table 2 also shows data for front-end deethanizer (FEDE) and front-end depropanizer (FEDP) configurations. [Table 2]
[0102] Experimental Preparation for Selective Hydrogenation Reactions in Examples 2 to 4 and Comparative Examples 5 to 7 In the following examples and comparative examples, selective hydrogenation of hydrogenation feedstocks containing acetylene, MA, and PD was carried out in an isothermal acetylene hydrogenation system using two identical 1 / 2-inch internal diameter reactors (the first reactor and the second reactor) operated in parallel. Thirty to forty grams of hydrogenation catalyst was placed in each of the first and second reactors. Each of the first and second reactors contained ten evenly distributed thermocouples to monitor the temperature profile and determine whether isothermal temperature distribution conditions were achieved. Nitrogen was used as the internal standard, and methane (CH4) was used as the equilibrium gas.
[0103] The composition of the hydrocarbon feedstock from the cracker unit obtained in the first separation system having the FEDP configuration is shown in Table 3 below. [Table 3]
[0104] Overall GHSV of the acetylene hydrogenation unit is 5000 hours without FCDh effluent -1 The composition of the FCDh effluent from Example 1 is used as the composition of the FCDh effluent. For simplicity, the CO concentration in the hydrogenation feedstock from the FCDh effluent was 1200 ppm. Acetylene, MA, and PD, which were contributed by the FCDh effluent, were not included due to their relatively low levels compared to the amounts contributed by the cracked gases.
[0105] Examples 2-4: Hydrogenation of Hydrogenation Feedstocks Using a First Hydrogenation Catalyst Having a Wide Temperature Operating Range In Examples 2 to 4, the hydrogenation of the hydrogenation feedstock (Table 3) was carried out using a first hydrogenation catalyst (Catalyst A) with a wide temperature operating range exceeding 40°C. The temperature operating range of the first hydrogenation catalyst depends on the composition of the hydrogenation feedstock. The temperature operating range of each catalyst for each hydrogenation feedstock composition is shown in Table 4 below. In Example 2, the hydrogenation feedstock contained only components derived from the cracked gas. The composition of the hydrogenation feedstock for Example 2 is shown in Table 3 above. For Example 3, the hydrogenation feedstock was determined based on a 2:1 flow ratio, which is the ratio of the amount of C3 / C3 components derived from the cracked gas to the amount of C3 / C3 components derived from the FCDh effluent. For Example 4, the hydrogenation feedstock was determined based on a 12:1 flow ratio. For Examples 3 and 4, the unit tripping of the FCDh system was simulated by eliminating the components derived from the FCDh system.
[0106] For each of Examples 2-4, the reactor system was operated for a period sufficient to achieve steady-state operation, at which point samples of the hydrogenation effluent from the reactor system were collected and analyzed for composition using techniques known in the art. Specifically, the hydrogenation effluent composition was analyzed to determine ethylene selectivity, MA conversion, and PD conversion. In addition, the cleanup temperature and temperature operating range of the first hydrogenation catalyst were determined for each hydrogenation feed composition in Examples 2-4. For Examples 3 and 4, the change in reactor delta T (ΔT) during a simulated FCDh system unit trip was determined. Table 4 shows the change in ethylene selectivity, MA conversion, PD conversion, cleanup temperature, temperature operating range of the first hydrogenation catalyst, and reactor delta T for each of Examples 2-4.
[0107] Comparative Examples 5 to 7: Hydrogenation of Hydrogenated Feedstocks Using Conventional Hydrogenation Catalysts In Comparative Examples 5 to 7, the hydrogenation of the hydrogenation feedstock was carried out using a conventional hydrogenation catalyst (Catalyst B). The temperature operating range of the first hydrogenation catalyst depends on the composition of the hydrogenation feedstock. The temperature operating range of each catalyst for each hydrogenation feedstock composition is shown in Table 4 below. In Comparative Example 5, the hydrogenation feedstock contained only C3 / C3-components derived from the cracked gas. The composition of the hydrogenation feedstock for Comparative Example 5 is shown in Table 3 above. For Comparative Example 6, the hydrogenation feedstock was determined based on a 2:1 flow ratio, and for Comparative Example 7, the hydrogenation feedstock was determined based on a 12:1 flow ratio. For Comparative Examples 6 and 7, the unit trips of the FCDh system were simulated by excluding the components derived from the FCDh system.
[0108] For each of Comparative Examples 5 through 7, the reactor system was operated for a period sufficient to achieve steady-state operation, at which point a sample of the hydrogenation effluent from the reactor system was collected and analyzed for composition using GC. Specifically, the hydrogenation effluent composition was analyzed to determine ethylene selectivity, MA conversion, and PD conversion. In addition, the cleanup temperature and temperature operating range of the conventional hydrogenation catalyst were determined for each hydrogenation feed composition of Comparative Examples 5 through 7. For each of Comparative Examples 6 and 7, the change in reactor delta T during a simulated FCDh system unit trip was determined. Table 4 shows the change in ethylene selectivity, MA conversion, PD conversion, cleanup temperature, temperature operating range of the conventional hydrogenation catalyst, and reactor delta T for each of Comparative Examples 5 through 7.
[0109] Comparison of Examples 2 to 4 with Comparative Examples 5 to 7 Table 4 shows the changes in ethylene selectivity, MA conversion, PD conversion, cleanup temperature, catalyst temperature operating range, and reactor delta T for each of Examples 2-4 and Comparative Examples 5-7. [Table 4] [Table 5]
[0110] As shown in Table 4 above, the first hydrogenation catalyst, Catalyst A, had a substantially larger temperature operating range than Catalyst B. The results in Table 4 also show that Catalyst A, with its larger temperature operating range, experienced a reactor delta T change of less than 1 in response to a simulated FCDh system unit trip. This change in delta T for Catalyst A was smaller than the change in delta T for Catalyst B in Comparative Examples 6 and 7 in response to a simulated FCDh system unit trip. This indicates that Catalyst A is less sensitive to changes in CO concentration and can reduce or prevent the possibility of thermal runaway of an acetylene hydrogenation reactor in response to a sudden loss of FCDh effluent flow, such as during an FCDh system unit trip. Catalyst A in Examples 2-4 also provided higher ethylene selectivity than Catalyst B in Comparative Examples 5-7.
[0111] Table 4 also shows that Catalyst A, which has a larger temperature operating range, can provide lower conversion of MA and PD. Therefore, an additional hydrogenation step, such as sending a portion of the hydrogenation effluent to a MAPD hydrogenator, can help further convert MA and PD to ethylene and / or ethane, reducing the concentration of these components in the hydrogenation effluent.
[0112] It should be noted that one or more of the following claims utilize the term "herein" as a transitional phrase. It should be noted 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 structure, and should be interpreted in a similar manner to the more commonly used open-ended preamble term "comprising."
[0113] Generally, the "inlet port" and "outlet port" of any system device of process 10 described herein refer to an opening, hole, channel, aperture, gap, or other similar mechanical feature of the system device. For example, an inlet port allows material to enter a particular system device, and an outlet port allows material to exit a particular system device. Generally, an outlet port or inlet port defines an area of a system device of process 10 to which a pipe, conduit, tube, hose, material transfer line, or similar mechanical feature is attached, or a portion of a system device to which another system device is directly attached. Although inlet ports and outlet ports may be described herein functionally in operation, they can have similar or identical physical features, and their respective functions in an operating system should not be construed as limiting their physical structure.
[0114] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the present invention. Since combinations, subcombinations, and variations of the disclosed embodiments that incorporate the spirit and substance of the present invention may occur to those skilled in the art, the present invention should be construed as including all that come within the scope of the appended claims and their equivalents. The inventions described in the original claims of this application are set forth below. [1] A method for operating an integrated system for producing olefins, comprising: contacting a hydrogenation feedstock with a first hydrogenation catalyst to produce a hydrogenation effluent, wherein the hydrogenation feedstock comprises at least a portion of a first process effluent from a first olefin production process and at least a portion of a second process effluent from a second olefin production process; the hydrogenation feedstock comprises at least hydrogen, ethylene, carbon monoxide, acetylene, methylacetylene, and propadiene; the first hydrogenation catalyst has a temperature operating range of at least 40 degrees Celsius, the temperature operating range being the difference between a runaway temperature and a clean-up temperature for a given hydrogenation feed composition, the runaway temperature being the temperature at which 3% of the ethylene in the hydrogenation feed reacts, and the clean-up temperature being the temperature at which the acetylene concentration in the hydrogenation effluent is equal to a threshold acetylene concentration; contacting the hydrogenation effluent with methylacetylene (MA), propadiene (PD), or both; contacting at least a portion of the hydrogenation effluent with a second hydrogenation catalyst, wherein said contacting hydrogenates at least a portion of the methyl acetylene, propadiene, or both from the hydrogenation effluent to produce a MAPD hydrogenation effluent having a reduced concentration of methyl acetylene, propadiene, or both, compared to said portion of the hydrogenation effluent before contacting with the second hydrogenation catalyst. [2] The method of [1], wherein the first process effluent comprises cracked gas produced by cracking at least a portion of a first hydrocarbon feedstock in a steam cracking system, the cracked gas comprising at least hydrogen, carbon monoxide, acetylene, methylacetylene, and propadiene. [3] The method of either [1] or [2], wherein the second process effluent comprises a fluid catalytic dehydrogenation (FCDh) effluent, the FCDh effluent being produced by dehydrogenating at least a portion of a second hydrocarbon feedstock in an FCDh system, the FCDh effluent comprising at least hydrogen and carbon monoxide. [4] The method according to any one of [1] to [3], wherein the total concentration of methylacetylene and propadiene in the portion of the hydrogenation effluent that contacts the second hydrogenation catalyst is 10% by weight or less. [5] The method according to any one of [1] to [4], further comprising sending at least a portion of the MAPD hydrogenation effluent to the FCDh system. [6] The method according to any one of [1] to [5], wherein the MAPD hydrogenation effluent contains propane. [7] The method according to any one of [1] to [6], further comprising combining at least a portion of the second hydrocarbon feedstock with the portion of the hydrogenation effluent before or during contact of the portion of the hydrogenation effluent with the second hydrogenation catalyst. [8] The method according to any one of [1] to [7], wherein the hydrogenation feedstock contains at least 95% of the carbon monoxide from the first process effluent and the second process effluent. [9] The method according to any one of [1] to [8], wherein contacting the hydrogenation feedstock with the first hydrogenation catalyst produces a conversion of methylacetylene in the hydrogenation feedstock of less than 80%.
[10] The method according to any one of [1] to [9], wherein contacting the hydrogenation feedstock with the first hydrogenation catalyst produces a conversion of propadiene in the hydrogenation feedstock of less than 10%.
[11] The method according to any one of [1] to
[10] , wherein the hydrogenation feedstock is contacted with the first hydrogenation catalyst in an acetylene hydrogenation unit.
[12] The method of
[11] , wherein the first hydrogenation catalyst having a temperature operating range of 40°C or greater reduces or prevents thermal runaway of the acetylene hydrogenation unit in response to an interruption in the flow of the first process effluent or the second process effluent.
[13] The method according to any one of [1] to
[12] , further comprising separating the first process effluent and the second process effluent into the hydrogenation feedstock and an acetylene-depleted stream.
[14] The method of
[13] , wherein the first separation system for separating the first process effluent and the second process effluent into the hydrogenation feedstock and an acetylene-depleted stream has a front-end depropanizer configuration.
[15] The method of [1], wherein the threshold acetylene concentration is 1 part per million by volume.
Claims
1. 1. A method for operating an integrated system for producing olefins, comprising: contacting the hydrogenation feedstock with a first hydrogenation catalyst to produce a hydrogenation effluent; wherein said hydrogenation feedstock comprises at least a portion of a first process effluent from a first olefin production process and at least a portion of a second process effluent from a second olefin production process; the hydrogenation feedstock comprises at least hydrogen, ethylene, carbon monoxide, acetylene, methylacetylene, and propadiene; the first hydrogenation catalyst has a temperature operating range of at least 40 degrees Celsius, the temperature operating range being the difference between a runaway temperature and a clean-up temperature for a given hydrogenation feed composition, the runaway temperature being the temperature at which 3% of the ethylene in the hydrogenation feed reacts, and the clean-up temperature being the temperature at which the acetylene concentration in the hydrogenation effluent equals a threshold acetylene concentration; the hydrogenation effluent comprises methylacetylene (MA), propadiene (PD), or both; contacting at least a portion of the hydrogenation effluent with a second hydrogenation catalyst; wherein said contacting hydrogenates at least a portion of said methylacetylene, propadiene, or both from said hydrogenation effluent to produce a MAPD hydrogenation effluent having a reduced concentration of methylacetylene, propadiene, or both, compared to said portion of said hydrogenation effluent prior to contacting with said second hydrogenation catalyst. A method comprising:
2. 10. The method of claim 1, wherein the first process effluent comprises cracked gas produced by cracking at least a portion of a first hydrocarbon feedstock in a steam cracking system, the cracked gas comprising at least hydrogen, carbon monoxide, acetylene, methylacetylene, and propadiene.
3. 3. The method of claim 1, wherein the second process effluent comprises a fluid catalytic dehydrogenation (FCDh) effluent, the FCDh effluent being produced by dehydrogenating at least a portion of a second hydrocarbon feedstock in an FCDh system, the FCDh effluent comprising at least hydrogen and carbon monoxide.
4. 4. The process of claim 1, wherein the combined concentration of methylacetylene and propadiene in the portion of the hydrogenation effluent that contacts the second hydrogenation catalyst is 10 wt. % or less.
5. 4. The method of claim 3, further comprising sending at least a portion of said MAPD hydrogenation effluent to said FCDh system.
6. The process of any one of claims 1 to 5, wherein the MAPD hydrogenation effluent comprises propane.
7. 6. The method of claim 3 or 5, further comprising combining at least a portion of the second hydrocarbon feedstock with said portion of the hydrogenation effluent before or during contacting said portion of the hydrogenation effluent with said second hydrogenation catalyst.
8. 8. The process of any one of claims 1 to 7, wherein the hydrogenation feedstock comprises at least 95% of the carbon monoxide from the first process effluent and the second process effluent.
9. 9. The process of any one of claims 1 to 8, wherein contacting the hydrogenation feedstock with the first hydrogenation catalyst results in a conversion of methyl acetylene in the hydrogenation feedstock of less than 80%.
10. 10. The process of any one of claims 1 to 9, wherein contacting the hydrogenation feedstock with the first hydrogenation catalyst results in a conversion of propadiene in the hydrogenation feedstock of less than 10%.
11. The process of any one of claims 1 to 10, wherein the hydrogenation feedstock contacts the first hydrogenation catalyst in an acetylene hydrogenation unit.
12. 12. The method of claim 11, wherein the first hydrogenation catalyst having a temperature operating range of 40°C or greater reduces or prevents thermal runaway of the acetylene hydrogenation unit in response to an interruption in the flow of the first process effluent or the second process effluent.
13. 13. The process of any one of claims 1 to 12, further comprising separating the first process effluent and the second process effluent into the hydrogenation feedstock and an acetylene-depleted stream.
14. 14. The method of claim 13, wherein the first separation system for separating the first process effluent and the second process effluent into the hydrogenation feedstock and the acetylene-depleted stream has a front-end depropanizer configuration.
15. 10. The method of claim 1, wherein the threshold acetylene concentration is 1 part per million by volume.
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