WO2019021131A1 - Appareil et méthode liés à l'utilisation de gaz de synthèse dans la production d'oléfines - Google Patents

Appareil et méthode liés à l'utilisation de gaz de synthèse dans la production d'oléfines Download PDF

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WO2019021131A1
WO2019021131A1 PCT/IB2018/055400 IB2018055400W WO2019021131A1 WO 2019021131 A1 WO2019021131 A1 WO 2019021131A1 IB 2018055400 W IB2018055400 W IB 2018055400W WO 2019021131 A1 WO2019021131 A1 WO 2019021131A1
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gas
heat exchange
reformer
synthesis gas
heat
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PCT/IB2018/055400
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English (en)
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Mohammed Nadim SHAIK
Khalid Karim
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Sabic Global Technologies B.V.
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • Syngas mixtures of H 2 and CO
  • synthesis gas can be readily produced from a carbon source, such as either coal or methane (natural gas) by methods well known in the art and widely commercially practiced around the world.
  • a carbon source such as either coal or methane (natural gas)
  • a number of well-known industrial processes use syngas for producing various hydrocarbons and oxygenated organic chemicals.
  • the Fischer-Tropsch catalytic process for catalytically producing hydrocarbons from syngas was initially discovered and developed in the 1920's, and was used in South Africa for many years to produce gasoline range hydrocarbons as automotive fuels.
  • the catalysts typically comprised iron or cobalt supported on alumina or titania, and promoters were sometimes used with cobalt catalysts to improve various aspects of catalytic performance.
  • the products were typically gasoline-range hydrocarbon liquids having six or more carbon atoms, along with other heavier hydrocarbon products.
  • the composition of synthesis gas used in the Fisher-Tropsch olefin production is an important consideration. It is known that the synthesis gas produced from processes where solid feedstocks are used is usually deficient in hydrogen. Thus, there is a need to enrich the synthesis gas in hydrogen. Conventionally, this short fall in hydrogen is compensated by subjecting at least a portion of the gasification derived synthesis gas to CO Shift process. However, this process can result in the unwanted formation of CO 2 and use of excess steam.
  • a method comprising the steps of: a) converting a first synthesis gas to a product stream comprising methane, ethane and propane, wherein the converting comprises a Fisher Tropsch synthesis reaction; b) separating the product stream to produce a tail gas comprising methane, a tail gas comprising ethane, and a tail gas comprising propane; c) subjecting the tail gas comprising methane to a sufficient heat in a first heat exchange reformer, wherein the first heat exchange reformer is configured to receive a feed of a second synthesis gas having a temperature of at least 900 °C, and wherein the sufficient heat is provided by heat exchange with the second synthesis gas, thereby producing from the tail gas comprising methane a reformed gas comprising synthesis gas and whereby cooling of the second synthesis gas produces a third synthesis gas having a temperature from about 500 °C to about 900 °C; d) subjecting the tail gas comprising ethane
  • an apparatus comprising: a) synthesis gas generation unit; b) a first heat exchange reformer, wherein the first heat exchange reformer is in fluid
  • a second heat exchange pre-reformer wherein the second heat exchange pre-reformer is in fluid communication with the first heat exchange reformer and/or a third heat exchanger unit, wherein the second heat exchange pre- reformer is configured in series to the first heat exchange reformer and/or the third heat exchanger unit; d) the third heat exchanger unit, wherein the third heat exchanger unit is in fluid communication with the second heat exchange pre-reformer and/or the first heat exchange reformer, and wherein the third heat exchanger unit is configured in series to the second heat exchange pre-reformer and/or the first heat exchange reformer; and e) a Fischer- Tropsch reactor, wherein the reactor is in fluid communication with the third heat exchanger unit or the second heat exchange pre-reformer, and wherein the apparatus does not comprise a CO shift reaction unit.
  • FIG. 1A and IB show exemplary flow diagrams of an apparatus and a method described herein.
  • FIG. 2 shows schematics of a first heat exchanger.
  • the terms "about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value "10” is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • first means any order, quantity, or importance, and are used to distinguish one element from another, unless specifically stated otherwise.
  • X and Y are present at a weight ratio of 2:5, and are present in such a ratio regardless of whether additional components are contained in the compound.
  • Synthesis gas derived from gasification of solid materials is usually deficient in hydrogen and thus not directly suitable for Fischer-Tropsch synthesis. This is especially so when the synthesis gas is derived from a gas generator where the syngas exits at a high temperature, a temperature not less than 900 °C.
  • the syngas ratio (H 2 /CO) in the syngas derived from these high temperature gas generators may vary between 0.3 and 1.0.
  • the syngas is processed in a CO Shift unit.
  • the syngas is reacted with steam over a catalyst producing H 2 and CO 2 . This process has several disadvantages since CO 2 is produced and usually excess steam (more than the stoichiometric requirement) is required in the CO Shift unit.
  • hydrocarbons produced include, for example, C1-C3 paraffins, such as methane, ethane and propane, C2-C3 olefins (ethylene and propylene), C4+ hydrocarbons, and wax (i.e. C20+ hydrocarbons).
  • the light paraffins, such as methane, ethane and propane, are conventionally routed to a fuel system, which results in an overall low yield of ethylene and propylene.
  • Disclosed herein are an apparatus and a method that utilize a Fischer-Tropsch based process to maximize the production of ethylene and propylene by reducing or substantially eliminating a need for CO shift unit, by utilization of byproducts such as methane, ethane and propane in an energy efficient manner and increasing the yield of desired product such as ethylene and propylene.
  • the apparatus and a method disclosed herein also have the capabilities of simultaneously reforming methane to synthesis gas in an energy efficient manner.
  • ethylene and propylene are produced by steam cracking of ethane, propane, and naphtha.
  • feedstocks have been sought for, for the production of ethylene and propylene.
  • feedstocks include natural gas, coal, biomass and liquid hydrocarbon feedstocks.
  • a manner to convert these feedstocks to ethylene and propylene is via Fischer Tropsch synthesis.
  • the carbonaceous feed is first converted into synthesis gas.
  • CO and H 2 are converted to hydrocarbons via Fischer Tropsch synthesis.
  • the desired hydrocarbons (ethylene and propylene) are then recovered from the Fischer Tropsch synthesis products.
  • the synthesis gas produced from processes where solid feedstocks are used are usually deficient in hydrogen. In order to make this gas suitable for FT synthesis, a CO Shift process is used. This results in the unwanted formation of CO 2 and use of excess steam.
  • Methane, ethane and propane are amongst the products formed via the Fischer Tropsch reaction and separated when ethylene and propylene are recovered.
  • the apparatus and methods disclosed herein utilize methane, ethane and propane to produce reformed gas comprising syngas and pre-reformed gas comprising methane in an energy efficient manner and thus increase the desired ethylene and propylene product yield, when the reformed gas comprising synthesis gas is converted to products, including ethylene and propylene, in a Fischer Tropsch reaction.
  • the feed of carbonaceous containing material is converted to synthesis gas at a temperature above at least about 900 °C.
  • the resulting synthesis gas also has a temperature above at least 900 °C.
  • This synthesis gas needs to be cooled before it is used in a Fischer- Tropsch reaction, which usually operates at a temperature from about 220 °C to about 380 °C, such as for example from about 220 °C to about 270 °C.
  • the synthesis gas with a temperature above at least about 900 °C is cooled in a steam generating unit, which produces steam that can be used in various processes.
  • the apparatus and method disclosed herein can also simultaneously utilize the heat from the synthesis gas with a temperature above at least about 900 °C to drive the reformation process of methane to produce new synthesis gas, which in turn can be used to produce more ethylene and propylene in a Fischer Tropsch reaction.
  • the synthesis gas can be cooled by converting methane to synthesis gas and by converting by converting ethane and propane to a mixture of methane and syngas.
  • the apparatus and method disclosed herein are more energy efficient than a conventional syngas process, since the energy in the synthesis gas having a temperature above at least about 900 °C is used to drive chemical reactions instead of only generating steam.
  • an apparatus comprising: a) synthesis gas generation unit; b) a first heat exchange reformer, wherein the first heat exchange reformer is in fluid communication with the synthesis gas generation unit; c) a second heat exchange pre-reformer, wherein the second heat exchange pre-reformer is in fluid communication with the first heat exchange reformer and/or a third heat exchanger unit, wherein the second heat exchange pre-reformer is configured in series to the first heat exchange reformer and/or the third heat exchanger unit; d) the third heat exchanger unit, wherein the third heat exchanger unit is in fluid communication with the second heat exchange pre-reformer and/or the first heat exchange reformer, and wherein the third heat exchanger unit is configured in series to the second heat exchange pre- reformer and/or the first heat exchange reformer; and e) a Fischer-Tropsch reactor, wherein the reactor is in fluid communication with the third heat exchanger unit or the second heat exchange pre-reformer, and wherein the apparatus does not comprise
  • the Fisher Tropsch reactor of the disclosed apparatus is in fluid communication with the first and the second heat exchange pre-reformers.
  • the heat exchanger units are known in the art.
  • any of the heat exchanger units disclosed herein can comprise one or more heat exchanger units.
  • any of the heat exchanger units disclosed herein can comprise at least two heat exchanger units.
  • heat exchanger unit refers to any unit built for efficient heat transfer from one medium to another.
  • the media can be separated by a solid wall to prevent mixing.
  • the media can be in direct contact. It is understood that any known in the art heat exchanger units can be used in the method disclosed herein.
  • the heat exchanger units can be classified according to their flow arrangements. In the aspects, where two fluids enter the exchanger at the same end, and travel in parallel to one another to the other side, the heat exchanger unit is classified as parallel-flow heat exchanger. In the aspects, where two fluids enter the exchanger from opposite ends is classified as a counter-flow heat exchanger unit. In the aspects, wherein two fluids travel perpendicular to one another through the exchange, the heat exchanger unit is classified as a cross-flow heat exchanger.
  • At least one of the first heat exchange reformer and the second heat exchange pre-reformer comprises a catalyst.
  • the first heat exchange reformer comprises a catalyst.
  • the second heat exchange pre-reformer comprises a catalyst.
  • the third heat exchanger unit is a heat recovery and a steam generation unit. It is understood that the heat recovery and a steam generation units are known in the art, and any applicable unit can be utilized in this disclosure.
  • the third heat exchanger unit can be positioned downstream from the first heat exchange reformer and upstream from the second heat exchange pre-reformer.
  • the third heat exchanger unit is in further fluid communication with an acid gas removal unit.
  • the acid gas removal unit is utilized to remove CO2 gas and sulfur from the synthesis gas entering the Fisher-Tropsch reactor. It is understood that the acid gas removal units are known in the art, and any applicable unit can be utilized in this disclosure.
  • the acid gas removal unit is in further fluid communication with the Fisher Tropsch reactor.
  • the apparatus comprises a syngas generation unit that can convert a solid feedstock to syngas. It is understood that any units known in the art capable of generating a synthesis gas (syngas) can be used in this disclosure.
  • the syngas generation unit is configured to receive a solid carbon source that can be converted to syngas in the syngas generation unit. It is understood that the syngas can be generated from a variety of different materials that contain carbon. In some aspects, the syngas can be generated from biomass, plastics, coal, or municipal waste, or any combination thereof. In some aspects, the syngas is generated by steam reforming.
  • Fischer-Tropsch reactor any known in the art Fischer-Tropsch reactor can be used.
  • isothermal and/or adiabatic fixed bed reactors can be used as a Fischer- Tropsch reactor, which can carry out the Fischer-Tropsch process.
  • the Fischer-Tropsch reactor can comprise a catalyst, such as, for example, one or more Fischer-Tropsch catalysts.
  • Fischer-Tropsch catalysts are known in the art and can, for example, be Fe based catalysts and/or Co based catalysts and/or Ru based catalysts.
  • the reactor comprises a Co/Mn catalyst or a Co/Mo catalyst, or a combination thereof. For example, U.S.
  • patent 9,416,067 discloses a promoted Co/Mn catalyst for use in a Fischer-Tropsch process, which is hereby incorporated in its entirety, specifically for its disclosure of a promoted Co/Mn catalyst.
  • U.S. patent 9,381,499 discloses a supported Co/Mo catalyst for use in a Fischer- Tropsch process, which is hereby incorporated in its entirety, specifically for its disclosure of a supported Co/Mo catalyst.
  • the disclosed system can be operated or configured on an industrial scale.
  • the reactors described herein can each be an industrial size reactor.
  • the syngas generation unit can be an industrial size reactor.
  • the Fischer-Tropsch reactor can be an industrial size reactor.
  • the first heat exchange reformer, the second heat exchange pre-reformer, and/or the third heat exchanger unit can be an industrial size reactor.
  • the reactors, units, and vessels disclosed herein can have a volume of at least about 1,000 liters, about 2,000 liters, about 5,000 liters, or about 20,000 liters.
  • the reactor can have a volume from about 1,000 liter to about 100,000 liters.
  • the syngas generation unit can have a volume of at least about 1,000 liters, about 2,000 liters, about 5,000 liters, or about 20,000 liters.
  • the syngas generation unit can have a volume from about 1,000 liter to about 100,000 liters.
  • the Fischer-Tropsch reactor can have a volume of at least about 1,000 liters, about 2,000 liters, about 5,000 liters, or about 20,000 liters.
  • the Fischer- Tropsch reactor can have a volume from about 1,000 liter to about 100,000 liters.
  • the first heat exchange reformer, the second heat exchange pre-reformer, and/or the third heat exchanger unit can have a volume of at least about 1,000 liters, about 2,000 liters, about 5,000 liters, or about 20,000 liters.
  • the first heat exchange reformer, the second heat exchange pre-reformer, and/or the third heat exchanger unit can have a volume from about 1,000 liter to about 100,000 liters.
  • FIG. 1A and IB show an apparatus 100.
  • the apparatus has a Fisher Tropsch synthesis reaction unit 102 for production and separation of olefins.
  • the Fisher Tropsch (FT) synthesis reaction unit 102 comprises a FT reactor 134 is in fluid communication with an acid gas removal unit 128, a FT Gas CO 2 removal and FT Gas Dryer unit 136, and Olefin Rich Gas dryer unit 138.
  • the FT reactor 134 is in further fluid communication with Olefin conversion unit 140.
  • the FT reactor 134 is further in fluid communication with the first heat exchange reformer 112, the second heat exchange pre- reformer 120, and the third heat exchanger unit 126.
  • the FT gas CO 2 removal and FT gas dryer unit 136 and Olefin Rich Gas dryer unit 138 are in fluid communication with the Light Ends Recovery 130 and Pressure Swing Absorption unit 130.
  • the Light Ends Recovery unit 130 separates methane and forming a tail gas comprising methane 106.
  • the Light Ends Recovery 130 and Pressure Swing Absorption unit 130 is further in fluid communication with a product separation unit 144 where a product stream comprising ethylene and propylene is formed and a product stream comprising a tail gas comprising ethane 110 and a tail gas comprising propane 108 are formed.
  • the olefin conversion unit 140 is in fluid communication with an aromatics extraction unit 142.
  • the first heat exchange reformer 112 is in fluid communication with a synthesis gas formation unit, for example a coal gasifier unit 148.
  • the first heat exchange reformer 112 is in further fluid communication with an incoming feed of the tail gas comprising methane 106, an incoming feed of a pre-reformed gas comprising methane 122, and an outgoing feed of a reformed gas comprising synthesis gas 116.
  • the first heat exchange reformer 112 is also in fluid communication with the second heat exchange pre- reformer 120.
  • the first heat exchange reformer 112 is also in fluid communication with the third heat exchanger unit 126.
  • the second heat exchange pre-reformer 120 is in fluid communication with an incoming feed of the tail gas comprising ethane 110 and the tail gas comprising propane 108.
  • the second heat exchange pre-reformer 120 is in further communication with an outgoing feed of pre-reformed gas comprising methane 122.
  • the second heat exchange pre-reformer 120 is in further communication with the third heat exchanger unit 126.
  • the third heat exchanger unit 126 is in fluid communication with an incoming feed of the reformed gas comprising synthesis gas 116.
  • the third heat exchanger unit 126 is in optional fluid communication with a CO shift unit 146.
  • the third heat exchanger unit is in further fluid communication with an acid gas removal unit 128.
  • a method comprising the steps of: a) converting a first synthesis gas to a product stream comprising methane, ethane and propane, wherein the converting comprises a Fisher Tropsch synthesis reaction; b) separating the product stream to produce a tail gas comprising methane, a tail gas comprising ethane, and a tail gas comprising propane; c) subjecting the tail gas comprising methane to a sufficient heat in a first heat exchange reformer, wherein the first heat exchange reformer is configured to receive a feed of a second synthesis gas having a temperature of at least 900 °C, and wherein the sufficient heat is provided by heat exchange with the second synthesis gas, thereby producing from the tail gas comprising methane a reformed gas comprising synthesis gas and whereby cooling of the second synthesis gas produces a third synthesis gas having a temperature from about 500 °C to about 900 °C; d) subjecting the tail gas comprising ethane
  • the method disclosed herein is schematically illustrated in FIG. 1A and IB.
  • the first syngas 104 is converted to a product stream comprising methane, ethane and propane in the Fischer Tropsch synthesis reaction unit 102.
  • the Fisher Tropsch synthesis reaction unit 102 can comprise a Fisher Tropsch (FT) reactor 134, a FT CO 2 removal and a FT gas dryer 136, an olefin rich gas dryer 138, a unit for a Light Ends Recovery 130 and pressure swing absorption, an Olefin Conversion Unit 140, an aromatics extraction unit 142, a product separation unit 144 and the like.
  • FT Fisher Tropsch
  • Fischer-Tropsch catalytic process for producing hydrocarbons from syngas is known in the art.
  • Several reactions can take place in a Fischer-Tropsch process, such as, a Fischer-Tropsch (FT) reaction, a water gas shift reaction, and a hydrogen methanation, as shown in Scheme 1.
  • FT Fischer-Tropsch
  • Scheme 1 The Fischer-Tropsch catalytic process for producing hydrocarbons from syngas is known in the art.
  • FT Fischer-Tropsch
  • a Fischer-Tropsch process that targets the production of light olefins is desired and such process can produce a significant amount of C2-C4 hydrocarbons.
  • the FT process can further comprise a product stream comprising C2-C4, C4+ olefins, or any combination thereof. It is further understood that the product stream comprising methane, ethane and propane is also formed.
  • the desirable olefins are separated and the tail gases comprising methane, ethane and propane are formed.
  • the product stream is separated to produce a tail gas comprising methane 104, a tail gas comprising ethane 110, and a tail gas comprising propane 108.
  • the tail gas comprising methane 104 is conveyed by any known in the art means to a first heat exchange reformer 112.
  • the first heat exchange reformer is further configured to receive a feed of a second synthesis gas 114 having a temperature of at least about 900 °C, at least about 950 °C, at least about 1,000 °C, at least about 1,100 °C, at least about 1,200 °C, at least about 1,300 °C, at least about 1,400 °C, or at least about 1,500 °C.
  • the second synthesis gas can have a temperature from about 900 °C to about 1,600 °C.
  • the second synthesis gas is generated from a solid carbon containing feed. It is understood that the second syngas can be generated from a variety of different sources that contain carbon. In some aspects, the syngas can be generated from solid feedstock, for example, biomass, plastics, coal, or municipal waste, or any combination thereof.
  • the sufficient heat used to heat the tail gas comprising methane is provided by heat exchange with the second synthesis gas in the first heat exchange reformer, thereby producing from the tail gas comprising methane a reformed gas comprising synthesis gas 116 and a third synthesis gas 118 having a temperature from about 500 °C to about 900 °C.
  • the third synthesis gas can have a temperature of about 550 °C, about 600 °C, about 650 °C, about 700 °C, about 750 °C, about 800 °C, or about 850 °C.
  • the step of producing the reformed gas comprising synthesis gas from the tail gas comprising methane can be based on steam reforming.
  • the heat exchange with the second synthesis gas in the first heat exchange reformer drives endothermic steam methane reforming reactions, thereby producing the third synthesis gas having a temperature lower than the second synthesis gas and the reform gas.
  • the tail gas comprising ethane and the tail gas comprising propane can be combined into one stream.
  • the exemplary first heat exchange reformer is schematically illustrated in FIG. 2.
  • the first heat exchange reformer 112 comprises a plurality of catalyst filled tubes.
  • the catalyst used in the reforming of the tail gas comprising methane can be any catalyst known in the art.
  • the catalyst is a nickel based catalyst.
  • the catalyst is a cobalt based catalyst.
  • the catalyst is an alloy metal based catalyst.
  • the catalyst is non-metallic catalyst.
  • the shape of the catalyst pellets can be optimized to achieve maximum activity with minimum increase in a pressure drop. In certain aspects, the pressure drop can depend on the void fraction of the packed bed and decrease with increasing particle size.
  • the reformed gas comprising synthesis gas (reformed gas) 116 (FIG. 1A and IB) and the third synthesis gas (warm syngas) 118 (FIG. 1A and IB) exists the first heat exchange unit for further processing.
  • the tail gas comprising ethane 110 and propane 108 are conveyed by any means known in the art to a second heat exchange pre-reformer 120.
  • the tail gas comprising ethane and the tail gas comprising propane are subjected to a sufficient heat in the second heat exchange pre-reformer.
  • the second heat exchange pre-reformer is configured to receive a feed of the third synthesis gas.
  • the sufficient heat is provided by heat exchange with the third synthesis gas, thereby producing from the tail gas comprising ethane and the tail gas comprising propane a pre- reformed gas comprising methane and whereby cooling of the third synthesis gas produces a fourth synthesis gas.
  • the step of subjecting the tail gas comprising ethane and the tail gas comprising propane to a sufficient heat comprises heating the tail gas comprising ethane and the tail gas comprising propane to a temperature form about 350 °C to about 550 °C, for example, form about 400 °C to about 500 °C, including exemplary values of about 410 °C, about 420 °C, about 430 °C, about 440 °C, about 450 °C, about 460 °C, about 470 °C, about 480 °C, and about 490 °C.
  • the fourth synthesis gas can have a temperature from about 350 °C to about 550 °C, including exemplary values of about 410 °C, about 420 °C, about 430 °C, about 440 °C, about 450 °C, about 460 °C, about 470 °C, about 480 °C, and about 490 °C.
  • the second heat exchange pre-reformer 120 comprises a plurality of catalyst filled tubes.
  • the catalyst used in the forming of the pre-reform gas from the tail gas comprising ethane and from the tail gas comprising propane can be any catalyst known in the art.
  • the catalyst is a nickel based catalyst.
  • the catalyst is a cobalt based catalyst.
  • the catalyst is an alloy metal based catalyst.
  • the catalyst is non-metallic catalyst.
  • the pre-reformed gas comprising methane is formed from the tail gas comprising ethane and from the tail gas comprising propane in an adiabatic catalytic reaction.
  • the pre-reformed gas comprising methane (122, FIGs. 1A and IB) and the fourth syngas (warm syngas) (124, FIG. 1A and IB) leave the second heat exchanger for further processing.
  • the pre-reformed gas comprising methane 122 (FIG. 1A and IB) is further introduced to the first heat exchange reformer 112.
  • the pre- reformed gas comprising methane is subjected to a sufficient heat in the first exchanger unit to further form the reformed gas comprising synthesis gas 116.
  • the heat is provided by a heat exchange with the second synthesis gas.
  • the efficiency of the Fisher- Tropsch synthesis reaction depends on the synthesis gas composition.
  • the second synthesis gas, the third synthesis gas and the fourth synthesis gas have a ratio of 3 ⁇ 4 to CO from about 0.3 to about 1.0, including exemplary values of about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, and about 0.9.
  • the composition of the reform gas comprises a ratio of H 2 to CO from about 2.7 to about 6.0, including exemplary values of about 2.8, about 2.9, about 3.0, about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, about 4.0, about 4.1, about 4.2, about 4.3, about 4.4, about 4.5, about 4.6, about 4.7, about 4.8, about 4.9, about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, and about 5.9.
  • the reformed gas comprising synthesis gas 116 (FIGs. 1A and IB) is further introduced to a third heat exchanger unit 126, where it can be cooled by heat exchange to assist in the production of steam or by heat exchange with other process streams.
  • the third exchanger unit 126 is further configured to receive a feed of the fourth synthesis gas 124.
  • the fourth synthesis gas 124 can be cooled by heat exchange to assist in the production of steam or by heat exchange with other process streams, thereby producing the first synthesis gas 104. It is understood that in some aspects, the reformed gas comprising synthesis gas is provided separately from the feed of the fourth synthesis gas.
  • the reformed gas comprising synthesis gas comprises substantially no impurities. In yet other aspects, the reformed gas comprising synthesis gas comprises substantially no sulfur. In still further aspects, the reformed gas comprising synthesis gas is substantially free of sulfur.
  • the third heat exchanger unit 126 is a heat recovery and steam generation unit.
  • the steam generated in the third heat exchanger unit 126 can be fed back to the first heat exchange reformer 112 and the second heat exchange pre-reformer 120.
  • the steam formed in the third heat exchanger unit and fed back to the first and the second heat exchange pre-reformers is used as a reactant in reforming of the tail gas comprising methane and pre-reforming the tail gas comprising ethane and the tail gas comprising propane.
  • the reformed gas comprising synthesis gas is cooled in the third heat exchanger unit by generation of steam.
  • the first synthesis gas is produced by mixing the reformed gas comprising synthesis gas exiting the third heat exchanger unit with unreacted syngas 132 generated in the Light Ends Recovery (LER) unit 130, and a cooled in the third exchanger unit the fourth synthesis gas to form the first synthesis gas that is fed to a Fischer Tropsch synthesis reactor 134.
  • the cooled fourth synthesis gas existing the third heat exchanger unit has a temperature from about 30 °C to about 270 °C, such as from about 30 °C to about 100 °C, or from about 150 °C to about 270 °C.
  • the first synthesis gas has a composition comprising a ratio of H 2 to CO from about 1.0 to about 2.0, including exemplary values of about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, and about 1.9.
  • the first synthesis gas has a temperature from about 220 °C to about 380 °C, such as from about 220 °C to about 270 °C, including exemplary values of about 230 °C, about 240 °C, about 250 °C, and about 260 °C.
  • the inventive method does not comprise a CO shift reaction unit.
  • the CO shift reaction unit is commonly used to increase hydrogen composition in the synthesis gas. It is understood that the inventive method allows increase of the hydrogen composition without presence of the CO shift unit.
  • the method can further comprise a CO shift reaction unit 146.
  • the CO shift unit is optionally present the cooled fourth synthesis gas is processed in the CO shift unit prior to the mixing with the reform gas.
  • the method further comprises removing an acid gas prior to the mixing with the reform gas in the acid gas removal unit 128.
  • the acid gas removal unit is used to remove carbon dioxide and sulfur from the synthesis gas prior to combining it with the reformed gas comprising synthesis gas and recycle synthesis gas to form a firth synthesis gas that is fed into FT reactor.
  • the acid gas units are known in the art and can comprise one or more units depending on a desirable application.
  • the first syngas is converted to hydrocarbons in the FT synthesis reactor 104.
  • the FT product gas is cooled yielding several streams.
  • the first product stream is wax
  • the second is FT water
  • the third is FT condensate
  • the last is FT gas.
  • the FT gas is then processed in a carbon dioxide removal unit 136. Carbon dioxide is removed from the FT gas since it will freeze in the separation unit where low temperatures are prevalent in order to achieve separation and recovery of the ethylene and propylene.
  • downstream of the FT gas carbon dioxide removal unit 136 the FT gas is dried before it is processed in the Light Ends Recovery (LER) unit 130.
  • LER Light Ends Recovery
  • the FT water stream is distilled to separate dissolved oxygenates from the water.
  • the oxygenates and FT condensate are routed to the Olefin Conversion Unit (OCU) 140 where they are catalytically cracked to ethylene and propylene.
  • OCU Olefin Conversion Unit
  • a catalytic cracker in the OCU 140 a catalytic cracker is employed which converts the hydrocarbon condensate (FT condensate) and oxygenates from the FT unit into to ethylene and propylene.
  • FT condensate hydrocarbon condensate
  • oxygenates from the FT unit into to ethylene and propylene.
  • the olefin rich gas from the OCU is then processed in a dryer before separation takes place.
  • both the dried FT gas and olefin rich gas are processed in the LER unit 130.
  • light gases such as CO, H 2 , N 2 , Ar and methane are separated from the C2+ hydrocarbons.
  • methane is separated from a mixture of CO, 3 ⁇ 4, N 2 and Ar to form a tail gas comprising methane 106.
  • This tail gas comprising methane 106 is fed to the first heat exchange reformer 112 as described above (methane reformer).
  • a portion of the syngas with inert gases is recycled to the FT synthesis unit 134.
  • PSU Product Separation Unit
  • ethane, propane, ethylene, propylene and C4+ hydrocarbons are obtained as separate product streams.
  • the C4+ hydrocarbons are recycled to the OCU where the C4+ hydrocarbons are catalytically cracked to ethylene and propylene.
  • the tail gases comprising ethane 110 and propane 108 are fed to the second heat exchange unit 120 as described herein, where they are heated and then pre-reformed to methane and syngas.
  • the apparatus and method disclosed herein have several benefits, including a lower capital cost, decrease in volumetric flow of gases to the reactor, decrease in compressor duty, and decrease in steam consumption.
  • the reforming of methane and pre-reforming of ethane and propane in these disclosed heat exchanger units also has the advantage of being more energy efficient than the use of a standalone steam reformer and pre-reformer. These benefits are achieved by eliminating an external sources of heat used in the standalone steam reformers to drive the endothermic chemical reactions.
  • a Fischer-Tropsch reactor that targets the production of light olefins (C2-C8 olefins) is desired and such process can produce a significant amount of C2-C3 hydrocarbons, and methane.
  • the first product can comprise hydrogen, CO, CO 2 , methane, ethylene, ethane, propylene, propane, butene, butane, mixture of nitrogen and argon, C2-C7 hydrocarbons, or any combination thereof.
  • An exemplary non-limiting composition of the first product is shown in Table 1. The values shown in Table 1 were simulated using Aspen HYSYS V8.4. The values in Table 1 of the first product were calculated after removal of CO 2 and upgrade of C4-C9 hydrocarbons (olefins) via a catalytic conversion unit before being integrated with the remainder of the apparatus disclosed herein.
  • a method comprising the steps of: a) converting a first synthesis gas to a product stream comprising methane, ethane and propane, wherein the converting comprises a Fisher Tropsch synthesis reaction; b) separating the product stream to produce a tail gas comprising methane, a tail gas comprising ethane, and a tail gas comprising propane; c) subjecting the tail gas comprising methane to a sufficient heat in a first heat exchange reformer, wherein the first heat exchange reformer is configured to receive a feed of a second synthesis gas having a temperature of at least about 900 °C, and wherein the sufficient heat is provided by heat exchange with the second synthesis gas, thereby producing from the tail gas comprising methane a reformed gas comprising synthesis gas and whereby cooling of the second synthesis gas produces a third synthesis gas having a temperature from about 500 °C to about 900 °C; d) subjecting the tail gas comprising ethane and
  • Aspect 2 The method of aspect 1, wherein the pre-reformed gas comprising methane is further subjected to a sufficient heat in the first heat exchange reformer to form the reformed gas comprising synthesis gas, and wherein the heat is provided by a heat exchange with the second synthesis gas.
  • Aspect 3 The method of aspects 1 or 2, wherein the reformed gas comprising synthesis gas is cooled in a third heat exchanger unit, wherein the third heat exchanger unit is configured to receive a feed of the fourth synthesis gas, and wherein the fourth synthesis gas cooled in a third heat exchanger unit, thereby producing the first synthesis gas.
  • Aspect 4 The method of any one of aspects 1-3, wherein the second, the third and the fourth synthesis gas comprises H 2 and CO in a ratio of H 2 :CO from about 0.3 to about 1.0.
  • Aspect 5 The method of any one of aspects 1-4, wherein the reformed gas comprises 3 ⁇ 4 and CO at the ratio of H2:CO from about 2.7 to about 6.0.
  • Aspect 6 The method of any one of aspects 1-5, wherein the first synthesis gas comprises H 2 and CO at the ratio of H 2 :CO from about 1.0 to about 2.0.
  • Aspect 7 The method of any one of aspects 1-6, wherein the tail gas comprising ethane and the tail gas comprising propane are combined into one stream and provided as one stream.
  • Aspect 8 The method of any one of aspects 1-7, wherein the step of subjecting the tail gas comprising ethane and the tail gas comprising propane to a sufficient heat comprises heating the tail gas comprising ethane and the tail gas comprising propane to a temperature from about 350 °C to about 500 °C.
  • Aspect 9 The method of any one of aspects 1-8, wherein the method does not comprise a CO shift reaction.
  • Aspect 10 The method of any one of aspects 1-9, wherein the first heat exchange reformer comprises a catalyst.
  • Aspect 11 The method of any one of aspects 1-10, wherein the second heat exchange pre-reformer comprises a catalyst.
  • Aspect 12 The method of any one of aspects 1-11, wherein the step of converting the tail gas comprising ethane and the tail gas comprising propane to the pre-reformed gas comprising methane comprises an adiabatic catalytic reaction.
  • Aspect 13 The method of any one of aspects 1-12, wherein the third exchanger unit is a heat recovery and steam generation unit.
  • Aspect 14 The method of any one of aspects 1-13, wherein a Fisher Tropsch synthesis reaction further comprises formation of a product stream comprising C2-C4 olefins, C4+ olefins, or any combination thereof.
  • Aspect 15 The method of any one of aspects 1-14, wherein the method further comprises removing acid gas prior to forming the first synthesis gas.
  • Aspect 16 An apparatus comprising: a) synthesis gas generation unit; b) a first heat exchange reformer, wherein the first heat exchange reformer is in fluid communication with the synthesis gas generation unit; c) a second heat exchange pre-reformer, wherein the second heat exchange pre-reformer is in fluid communication with the first heat exchange reformer and/or a third heat exchanger unit, wherein the second heat exchange pre-reformer is configured in series to the first heat exchange reformer and/or the third heat exchanger unit; d) the third heat exchanger unit, wherein the third heat exchanger unit is in fluid communication with the second heat exchange pre-reformer and/or the first heat exchange reformer, and wherein the third heat exchanger unit is configured in series to the second heat exchange pre- reformer and/or the first heat exchange reformer; and e) a Fischer-Tropsch
  • Aspect 17 The apparatus of aspect 16, wherein the Fisher Tropsch reactor is in fluid communication with the first and the second heat exchange pre-reformers.
  • Aspect 18 The apparatus of aspects 16 or 17, wherein the third heat exchanger units is a heat recovery and a steam generation unit.
  • Aspect 19 The apparatus of any one of aspects 16-18, wherein the third heat exchanger unit is in further fluid communication with an acid gas removal unit.
  • Aspect 20 The apparatus of aspect 19, wherein the acid gas removal unit is in further fluid communication with the Fisher Tropsch reactor.

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Abstract

Selon la présente invention, l'invention concerne un appareil et une méthode pour enrichir un gaz de synthèse en utilisant des sous-produits de la réaction de Fisher-Tropsch et en mélangeant des gaz de reformage avec un gaz de synthèse obtenu à partir d'une charge contenant du carbone.
PCT/IB2018/055400 2017-07-27 2018-07-19 Appareil et méthode liés à l'utilisation de gaz de synthèse dans la production d'oléfines WO2019021131A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010051662A1 (en) * 2000-02-15 2001-12-13 Arcuri Kym B. System and method for preparing a synthesis gas stream and converting hydrocarbons
EP1403216A1 (fr) * 2002-09-26 2004-03-31 Haldor Topsoe A/S Procédé pour la préparation de gaz de synthèse
EP1413547A1 (fr) * 2002-09-26 2004-04-28 Haldor Topsoe A/S Procédé pour la production de gas de synthèse
WO2009113006A2 (fr) * 2008-03-12 2009-09-17 Sasol Technology (Proprietary) Limited Synthèse d'hydrocarbures
US9381499B2 (en) 2011-04-19 2016-07-05 Saudi Basic Industries Corporation Carbon supported cobalt and molybdenum catalyst
US9416067B2 (en) 2010-12-22 2016-08-16 Saudi Basic Industries Corporation Catalyst useful in fisher-tropsch synthesis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010051662A1 (en) * 2000-02-15 2001-12-13 Arcuri Kym B. System and method for preparing a synthesis gas stream and converting hydrocarbons
EP1403216A1 (fr) * 2002-09-26 2004-03-31 Haldor Topsoe A/S Procédé pour la préparation de gaz de synthèse
EP1413547A1 (fr) * 2002-09-26 2004-04-28 Haldor Topsoe A/S Procédé pour la production de gas de synthèse
WO2009113006A2 (fr) * 2008-03-12 2009-09-17 Sasol Technology (Proprietary) Limited Synthèse d'hydrocarbures
US9416067B2 (en) 2010-12-22 2016-08-16 Saudi Basic Industries Corporation Catalyst useful in fisher-tropsch synthesis
US9381499B2 (en) 2011-04-19 2016-07-05 Saudi Basic Industries Corporation Carbon supported cobalt and molybdenum catalyst

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