WO2018128983A1 - Procédé intégré utilisant la chaleur de conversion oxydative de méthane pour la production d'éthylène et de méthanol - Google Patents

Procédé intégré utilisant la chaleur de conversion oxydative de méthane pour la production d'éthylène et de méthanol Download PDF

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WO2018128983A1
WO2018128983A1 PCT/US2018/012067 US2018012067W WO2018128983A1 WO 2018128983 A1 WO2018128983 A1 WO 2018128983A1 US 2018012067 W US2018012067 W US 2018012067W WO 2018128983 A1 WO2018128983 A1 WO 2018128983A1
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stream
temperature
produce
acetylene
pyrolysis reaction
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Aghaddin Mamedov
Nareshkumar HANDAGAMA
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Sabic Global Technologies, B.V.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • 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
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • 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
    • C01B2203/0465—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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • 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
    • C07C2523/72—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present disclosure relates to methods of producing olefins and methanol, more specifically methods of producing ethylene and methanol by integrating hydrocarbon pyrolysis with ethylene and methanol production.
  • Hydrocarbons and specifically olefins such as ethylene
  • ethylene can be typically used to produce a wide range of products, for example, break-resistant containers and packaging materials.
  • ethylene is produced by heating natural gas condensates and petroleum distillates, which include ethane and higher hydrocarbons, and the produced ethylene is separated from a product mixture by using gas separation processes.
  • Methanol is an important chemical building block, which can be used to produce a wide range of products, such as of paints, solvents and plastics, and has found innovative applications in energy, transportation fuel and fuel cells. Methanol is commonly produced from synthesis gas. However, the formation of synthesis gas from natural gas is strongly endothermic and requires high temperatures, which translates in a high energy input.
  • reaction (1) The combustion products having high temperature produced via reaction (1) enter a subsequent reaction zone (having a catalyst bed, in some configurations) where they undergo endothermic reactions (2) and (3) with methane by utilizing the heat of combustion from reaction (1):
  • the overall reaction (4) involves the production of a mixture containing H 2 , CO and C0 2 , as well as H 2 0, given the equilibrium of water gas shift reaction which takes place in the catalyst bed:
  • conversion of methane to acetylene involves (a) combustion of a portion of methane in a combustion zone to produce heat, which is then used for (b) injection of a separate portion of methane feed to the flame produced in combustion zone and conversion to acetylene according to cracking reaction (5), wherein the temperature of the flame can be more than 2500 °C:
  • the cracking reaction products can further undergo fast quenching to stop the reaction at the acetylene production stage, and to prevent coke formation.
  • An overall process involving thermal gas phase water shift reaction (4) and cracking reaction (5) can be described by reaction (6):
  • Acetylene can be further hydrogenated to ethylene via liquid phase hydrogenation using a supported Pd (Pd/Al 2 0 3 ) catalyst according to reaction (7):
  • Methane pyrolysis generally produces C 2 H 4 , CO, H 2 , C0 2 , and H 2 0, wherein a H 2 /CO molar ratio is close to the ratio which can be used for methanol synthesis, thus leaving no excess H 2 .
  • Conversion of C0 2 needs external energy sources for the production of useful chemicals, such as methanol. Conversion of C0 2 with H 2 to methanol is a known process, but this reaction needs an external H 2 source to meet the requirement of a H 2 /C0 2 molar ratio of 3. Recycling heat is quite common in Europe. For example, Denmark gets roughly half of its electricity from recycled heat. According to a report by Lawrence Livermore National Laboratory and the Department of Energy, the U.S. wastes more than half of the produced energy. However, by using this wasted energy, the U.S. could reduce carbon dioxide emissions.
  • a process for producing ethylene comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product, (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction, (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ), (d) cooling at least a portion of the pyrolysis reaction product in a quench zone by heat exchange with a quenching fluid to produce a quenching fluid to produce a
  • Also disclosed herein is a process for producing ethylene and methanol comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product, (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction, (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ), (d) cooling at least a portion of the pyrolysis reaction product in a quench zone by heat exchange with a quenching fluid
  • a process for producing ethylene and methanol comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product, (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction, (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ), (d) quenching at least a portion of the pyrolysis reaction product in a quench zone to produce a quenched
  • Figure 1 displays a schematic of an ethylene and methanol production system
  • Figure 2 displays another schematic of an ethylene and methanol production system
  • Figure 3 displays a graph of product concentration over time for a carbon dioxide to syngas conversion.
  • the process for producing ethylene as disclosed herein can comprise utilizing at least a portion of the heat generated by the combustion process to sustain methane pyrolysis, and also generate electricity to power water electrolysis, wherein water gets split into H 2 and oxygen (0 2 ), according to reaction (8):
  • the 0 2 produced by water splitting reaction (8) can be recycled to the combustion zone as the oxidant gas.
  • the H 2 produced by water splitting reaction (8) can be further used to hydrogenate C0 2 to syngas, which can be further used for methanol production.
  • Utilizing some of the combustion heat to produce electricity for water splitting can prevent or minimize wasting energy produced in the process.
  • a portion of the heat can be captured during the step (d) of cooling at least a portion of the pyrolysis reaction product in a quench zone, which heat would otherwise be lost as quench waste energy.
  • reaction (9) is present in the products in a H 2 / C0 2 molar ratio of 3, and the C0 2 could be further converted to methanol through direct exothermic hydrogenation reaction (10):
  • reaction (9) By accounting for reaction (10), reaction (9) can be written as an overall methane conversion reaction (1 1):
  • Reaction (1 1) provides a pathway of methane conversion to desired chemicals, such as C 2 H 4 and CH 3 OH, which can be achieved in an energy efficient manner and without C0 2 emissions by utilizing the quench waste energy to generate electricity for splitting water.
  • desired chemicals such as C 2 H 4 and CH 3 OH
  • the terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms include any measurable decrease or complete inhibition to achieve a desired result.
  • the term "effective,” means adequate to accomplish a desired, expected, or intended result.
  • the terms “comprising” (and any form of comprising, such as “comprise” and “comprises"), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • the ethylene and methanol production system 101 generally comprises a pyro lysis unit 10 comprising a combustion zone 1 1, a cracking zone 12 (e.g., first reaction zone), and a quench zone 13; an electricity generating unit 15; a first separation unit 16; an electrolysis unit 20; a C0 2 hydrogenation to syngas unit 30; a liquid phase hydrogenation unit 40 (e.g., second reaction zone); a second separation unit 50; and a methanol production reactor 60 (e.g., third reaction zone).
  • a pyro lysis unit 10 comprising a combustion zone 1 1, a cracking zone 12 (e.g., first reaction zone), and a quench zone 13; an electricity generating unit 15; a first separation unit 16; an electrolysis unit 20; a C0 2 hydrogenation to syngas unit 30; a liquid phase hydrogenation unit 40 (e.g., second reaction zone); a second separation unit 50; and a methanol production reactor 60 (e.g., third reaction zone).
  • the ethylene and methanol production system 102 generally comprises a pyro lysis unit 10 comprising a combustion zone 1 1, a cracking zone 12 (e.g., first reaction zone), and a quench zone 13; a heat exchanger 14; an electricity generating unit 15; a first separation unit 16; an electrolysis unit 20; a C0 2 hydrogenation to syngas unit 30; a liquid phase hydrogenation unit 40 (e.g., second reaction zone); a second separation unit 50; and a methanol production reactor 60 (e.g., third reaction zone).
  • a pyro lysis unit 10 comprising a combustion zone 1 1, a cracking zone 12 (e.g., first reaction zone), and a quench zone 13; a heat exchanger 14; an electricity generating unit 15; a first separation unit 16; an electrolysis unit 20; a C0 2 hydrogenation to syngas unit 30; a liquid phase hydrogenation unit 40 (e.g., second reaction zone); a second separation unit 50; and a methanol production reactor
  • ethylene and methanol production system components shown in Figures 1 and 2 can be in fluid communication with each other (as represented by the connecting lines indicating a direction of fluid flow) through any suitable conduits (e.g., pipes, streams, etc.).
  • suitable conduits e.g., pipes, streams, etc.
  • Common reference numerals refer to common components present in one or both of the Figures, and the description of a particular component is generally applicable across respective Figures wherein the component is present, except as otherwise indicated herein.
  • the pyrolysis unit 10 can comprise the combustion zone 1 1 and the cracking zone 12 (e.g., first reaction zone). Impurities and contaminants can be removed from a fuel gas stream and/or a hydrocarbon stream prior to introducing to the combustion zone 11 and/or the cracking zone 12, respectively.
  • the fuel gas stream and the hydrocarbon stream can be the same (e.g., can comprise the same hydrocarbons, for example can be portions of the same gas stream feedstock).
  • the fuel gas stream and the hydrocarbon stream can be different (e.g., can comprise different hydrocarbons, for example originating from different upstream sources).
  • the fuel gas stream and/or the hydrocarbon stream can comprise methane, ethane, propane, natural gas, natural gas liquids, associated gas, well head gas, enriched gas, heavy hydrocarbons, petcoke, naphtha, heavy oil, heavy oil residue, and the like, or combinations thereof.
  • natural gas is a naturally occurring hydrocarbon gas mixture comprising mostly methane, but commonly including varying amounts of other higher alkanes, and sometimes a small percentage of carbon dioxide, nitrogen, hydrogen sulfide, helium, etc.
  • Heavy oil residues generally comprise polyalkylbenzenes such as polyethylbenzenes (PEBs), as well as multi-ring compounds.
  • Petcoke generally refers to a carbonaceous solid produced in oil refinery coker units or other cracking processes.
  • Heavy hydrocarbons generally comprise hydrocarbons which are solid or extremely viscous at standard processing conditions, and can include materials such as, but not limited to, asphaltenes, tars, paraffin waxes, coke, refining residues, and other similar residual hydrocarbon materials.
  • Heavy hydrocarbons can include any material that comprises a majority of hydrocarbon materials with a molecular weight range of about 700 to 2,000,000 Daltons.
  • Heavy oil generally refers to heavy crude, oils sands bitumen, bottom of the barrel and residue left over from refinery processes (e.g., visbreaker bottoms), and any other lower quality material that contains a substantial quantity of high boiling hydrocarbon fractions (e.g., that boil at or above 343 °C, or alternatively at or above about 524 °C).
  • Nonlimiting examples of heavy oil feedstocks include, but are not limited to, Lloydminster heavy oil, Cold Lake bitumen, Athabasca bitumen, atmospheric tower bottoms, vacuum tower bottoms, residuum (or "resid"), resid pitch, vacuum residue, and nonvolatile liquid fractions that remain after subjecting crude oil, bitumen from tar sands, liquefied coal, oil shale, or coal tar feedstocks to distillation, hot separation, and the like; and that contain higher boiling fractions and/or asphaltenes.
  • Naptha generally comprises flammable liquid hydrocarbon mixtures.
  • a process for producing ethylene and methanol as disclosed herein can comprise a step of introducing the fuel gas stream (e.g., comprising methane) and an oxidant gas to the combustion zone 11 to produce a combustion product.
  • the combustion zone 11 can comprise a burner, such as an in-line burner; a furnace; or combinations thereof; wherein the fuel gas stream is burned (e.g., combusted) with the oxidant gas to produce the combustion product.
  • the oxidant gas can comprise oxygen, purified oxygen, air, oxygen- enriched air, and the like, or combinations thereof.
  • the oxidant gas is oxygen-enriched, such as oxygen-enriched air, to minimize NO x production in the combustion zone.
  • NO x products can be acidic and as such would necessitate downstream removal.
  • Water or steam can be further introduced to the combustion zone to lower and thereby control the combustion product temperature.
  • the combustion product generally comprises combustion products, such as carbon monoxide (CO), C0 2 , water (H 2 0), as well as some unconverted hydrocarbons (e.g., hydrocarbons that were present in the fuel gas stream and did not combust).
  • CO carbon monoxide
  • C0 2 water
  • H 2 0 water
  • some unconverted hydrocarbons e.g., hydrocarbons that were present in the fuel gas stream and did not combust.
  • the combustion product may not be isolatable, and it might be introduced as produced to the cracking zone 12.
  • a process for producing ethylene and methanol as disclosed herein can comprise introducing a first reactant mixture to the cracking zone 12 (e.g., first reaction zone), wherein the first reactant mixture comprises the hydrocarbon stream (e.g., comprising methane) and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction; and allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product.
  • the pyrolysis reaction product can comprise unconverted hydrocarbons (e.g., methane), acetylene (C 2 H 2 ), C 2 H 4 , CO, H 2 , water, and C0 2 .
  • the cracking zone 12 (e.g., first reaction zone) zone excludes a catalyst.
  • a catalyst for hydrocarbon pyrolysis
  • the current disclosure does not utilize a catalyst for hydrocarbon pyrolysis; the hydrocarbon pyrolysis as disclosed herein is thermal.
  • the pyrolysis unit 10 can comprise a reactor that contains both the combustion zone 11 and the cracking zone 12.
  • the pyrolysis unit 10 can comprise a furnace that contains the combustion zone 11 ; and a reactor that contains the cracking zone 12 and is configured to receive the combustion product from the furnace comprising the combustion zone 11.
  • a diluent such as an inert gas (e.g., nitrogen, argon, helium, etc.) and/or steam can be further introduced to the cracking zone 12.
  • the hydrocarbon stream can be further pre-heated in pre-heaters (e.g., electrical heaters, heat exchangers, etc.) before being heated to the first temperature (e.g., temperature effective for the pyrolysis reaction) by direct heat exchange through contact with the combustion product.
  • pre-heaters e.g., electrical heaters, heat exchangers, etc.
  • a temperature of the combustion product can be a temperature effective to reach a pyrolysis reaction temperature (e.g., first temperature, cracking zone temperature) of equal to or greater than about 1,000 °C, alternatively equal to or greater than about 1,500 °C, alternatively equal to or greater than about 2,000 °C, alternatively equal to or greater than about 2,250 °C, alternatively equal to or greater than about 2,500 °C, alternatively from about 1,000 °C to about 2,500 °C, alternatively from about 1,500 °C to about 2,500 °C, or alternatively from about 2,000 °C to about 2,500 °C.
  • a pyrolysis reaction temperature e.g., first temperature, cracking zone temperature
  • higher temperatures in the cracking zone 12 favor alkyne (e.g., acetylene) formation, while lower temperatures in the cracking zone 12 favor olefin or alkene (e.g., ethylene) formation.
  • alkyne e.g., acetylene
  • olefin or alkene e.g., ethylene
  • the cracking zone 12 can be characterized by a residence time effective to allow for the conversion of at least a portion of the first reactant mixture to acetylene and ethylene.
  • the cracking zone 12 can be characterized by a residence time of from about 0.1 milliseconds (ms) to 100 ms, alternatively from about 0.5 ms to about 80 ms, or alternatively from about 1 ms to about 50 ms.
  • the hydrocarbon stream that is introduced to the cracking zone 12 can be characterized by a pressure of from about 1 bar to about 20 bar (e.g., from about 100 kPa to about 2,000 kPa), to achieve the desired products.
  • the pyrolysis unit 10 can be designed to accommodate one or more gas feed streams (e.g., fuel gas stream, hydrocarbon stream), which may employ natural gas combined with other gas components including, but not limited to hydrogen, carbon monoxide, carbon dioxide, ethane, and ethylene.
  • the pyrolysis unit 10 can be designed to accommodate one or more oxidant gas streams, such as an oxygen stream and an oxygen- containing stream, for example an air stream, which employ unequal oxidant concentrations for purposes of temperature or composition control.
  • the pyrolysis unit 10 may comprise a single device or multiple devices. Each device of the pyrolysis unit 10 may comprise one or more sections.
  • Products from the combustion zone 1 1 are communicated to the cracking zone 12 via the combustion product stream.
  • the combustion product stream may not be isolatable (for example, in configurations where the combustion zone 11 and the cracking zone 12 are contained within a common vessel or reactor).
  • a process for producing ethylene and methanol as disclosed herein can comprise cooling at least a portion of the pyrolysis reaction product in the quench zone 13 by heat exchange with a quenching fluid to produce a cooled pyrolysis reaction product and a heated quenching fluid, wherein the cooled pyrolysis reaction product is characterized by a second temperature, wherein the second temperature is lower than the first temperature, and wherein a temperature of the heated quenching fluid is greater than a temperature of the quenching fluid.
  • the second temperature can be from about 600 °C to about 1,000 °C, alternatively from about 700 °C to about 950 °C, or alternatively from about 800 °C to about 900 °C.
  • the quenching fluid can be characterized by a temperature (e.g., an inlet temperature) of from about 40 °C to about 80 °C, alternatively from about 45 °C to about 75 °C, or alternatively from about 50 °C to about 70 °C.
  • the heated quenching fluid can be characterized by a temperature (e.g., an outlet temperature) of from about 600 °C to about 800 °C, alternatively from about 625 °C to about 775 °C, or alternatively from about 650 °C to about 750 °C.
  • a temperature e.g., an outlet temperature
  • the pyrolysis unit 10 can further comprise a quench zone 13, wherein the pyrolysis reaction products are quenched prior to exiting the pyrolysis unit 10 via the cooled pyrolysis reaction product.
  • the quench zone 13 can employ any suitable quenching methods, for example spraying a quenching fluid such as steam, water, hydrocarbons, oil, liquid product, and the like, or combinations thereof into a reactor quench zone or chamber; conveying the product stream through or into water, natural gas feed, or liquid products; heat exchange; preheating other streams such as fuel gas stream and/or hydrocarbon stream; generating steam; expanding in a kinetic energy quench, such as a Joule Thompson expander, choke nozzle, turbo expander, etc.; or combinations thereof.
  • a quench zone 13 may be incorporated within a pyrolysis reactor, may comprise a separate vessel or device from the pyrolysis reactor, or both.
  • a process for producing ethylene and methanol as disclosed herein can comprise cooling at least a portion of the pyrolysis reaction product to produce a cooled pyrolysis reaction product and thermal energy, wherein the cooled pyrolysis reaction product is characterized by a second temperature, and wherein the second temperature is lower than the first temperature.
  • the thermal energy can be recovered from the quench zone 13, e.g., the cooling of the pyrolysis reaction product to produce a cooled pyrolysis reaction product occurs substantially in the quench zone 13.
  • a first portion of the thermal energy can be recovered from the quench zone 13, and a second portion of the thermal energy can be recovered in a unit subsequent to the quench zone 13, for example in the heat exchanger 14 positioned downstream of the quench zone 13.
  • thermal energy can be produced by at least a portion of the pyrolysis reaction product exchanging heat with a quenching fluid, a heat exchange fluid, or both a quenching fluid and a heat exchange fluid.
  • thermal energy can be recovered from the quench zone 13 by (i) indirect heat exchange; (ii) direct heat exchange; or (iii) both direct heat exchange and indirect heat exchange.
  • the streams e.g., pyrolysis reaction product, and quenching fluid and/or heat exchange fluid
  • the streams that exchange heat do not contact each other, as they are separated by a wall (usually a metal wall), and the streams exchange heat across the wall.
  • the streams e.g., pyrolysis reaction product, and quenching fluid and/or heat exchange fluid
  • the streams e.g., pyrolysis reaction product, and quenching fluid and/or heat exchange fluid
  • the streams that exchange heat contact each other, and can be further separated from each other, subsequent to exchanging heat with each other.
  • thermal energy (e.g., a first portion of the thermal energy) can be recovered from the quench zone 13 by indirect heat exchange, wherein the quenching fluid (e.g., a heat exchange fluid) can be contained inside heat exchange elements within the quench zone 13, such as pipes running through the quench zone 13.
  • the quenching zone 13 can comprise a heat exchanger.
  • the quenching fluid can be water, and the heated quenching fluid can be recovered as steam from the heat exchange elements.
  • quenching fluid and/or a heat exchange fluid comprising water
  • any suitable quenching fluid and/or heat exchange fluid can be used, such as hydrocarbons, oils, mineral oils, molten salts, etc.
  • the quenching fluid and the heat exchange fluid can be the same or different.
  • the quenching fluid can be a heat exchange fluid.
  • thermal energy (e.g., a first portion of the thermal energy) can be recovered from the quench zone 13 by direct heat exchange, wherein the quenching fluid can be contacted directly with the pyrolysis reaction product within the quench zone 13.
  • the heated quenching fluid and the cooled pyrolysis reaction product can be recovered from the quenching zone 13 as separate (distinct) streams, or as a common stream, wherein the common stream can be further separated into the heated quenching fluid and the cooled pyrolysis reaction product.
  • the quenching fluid can be water, and the heated quenching fluid can be recovered as steam from the quenching zone 13 and/or from the common stream comprising both the heated quenching fluid and the cooled pyrolysis reaction product.
  • a process for producing ethylene and methanol as disclosed herein can comprise (i) quenching at least a portion of the pyrolysis reaction product in the quench zone 13 to produce a quenched pyrolysis reaction product and the first portion of the thermal energy, wherein the quenched pyrolysis reaction product comprises at least a portion of the pyrolysis reaction product, and wherein the quenched pyrolysis reaction product is characterized by the second temperature, wherein the second temperature is lower than the first temperature; and (ii) introducing at least a portion of the quenched pyrolysis reaction product to the heat exchanger 14 to produce a cooled pyrolysis reaction product and the second portion of the thermal energy, wherein the cooled pyrolysis reaction product is characterized by a third temperature, and wherein the third temperature is lower than the second temperature.
  • the cooled pyrolysis product characterized by the second temperature can also be referred to as "quenched pyrolysis reaction product.”
  • the quenched pyrolysis reaction product can be further cooled to produce a cooled pyrolysis reaction product characterized by the third temperature, and the second portion of the thermal energy.
  • the first portion of the thermal energy and/or the second portion of the thermal energy can be recovered as steam.
  • the quenched pyrolysis reaction product can exchange heat with a quenching fluid and/or a heat exchange fluid comprising water to produce the cooled pyrolysis reaction product characterized by the third temperature and a heated quenching fluid and/or a heated heat exchange fluid, respectively (e.g., steam).
  • the third temperature can be from about 100 °C to about 900 °C, alternatively from about 110 °C to about 700 °C, or alternatively from about 120 °C to about 500 °C.
  • the acetylene in the cooled pyrolysis reaction product is meant to be hydrogenated in liquid phase to ethylene, which hydrogenation process generally occurs below about 250 °C, and as such a gas mixture that will be sent to the liquid phase hydrogenation process requires a temperature below about 250 °C (e.g., cooled pyrolysis reaction product characterized by the third temperature).
  • the heated quenching fluid can comprise steam.
  • a water quench is applied for quenching of hot gases having high temperatures (e.g., greater than about 2,000 °C), wherein the water quench can produce high temperature steam.
  • the heated quenching fluid can be introduced to a heat exchanger to produce steam, wherein the heated quenching fluid can exchange heat with a heat exchange fluid such as water to produce steam.
  • the heated quenching fluid and/or the cooled pyrolysis reaction product characterized by the second temperature can be introduced to a heat exchanger to produce steam, wherein the heated quenching fluid and/or the cooled pyrolysis reaction product characterized by the second temperature, respectively can exchange heat with a heat exchange fluid such as water to produce steam.
  • the heated quenching fluid and the cooled pyrolysis reaction product characterized by the second temperature can be separate streams introduced to the heat exchanger.
  • the heated quenching fluid and the cooled pyrolysis reaction product characterized by the second temperature can be part of the same common stream introduced to the heat exchanger, wherein the cooled pyrolysis reaction product can be recovered from the common stream downstream of the heat exchanger, as the cooled pyrolysis reaction product characterized by the third temperature.
  • the cooled pyrolysis reaction product (regardless of its temperature) can comprise unconverted hydrocarbons (e.g., methane), acetylene, ethylene, CO, H 2 , water, and C0 2 .
  • unconverted hydrocarbons e.g., methane
  • acetylene ethylene
  • CO ethylene
  • H 2 ethylene
  • H 2 ethylene
  • H 2 ethylene
  • H 2 e.g., water
  • C0 2 e.g., a quenching fluid
  • the composition of the cooled pyrolysis reaction product is substantially the same as the composition of the pyrolysis reaction product, although some components could have changed phase, for example from a gas phase to a vapor phase or a liquid phase.
  • the composition of the cooled pyrolysis reaction product will also account for the added quenching fluid.
  • the quenching fluid used for direct heat exchange is water or steam
  • the cooled pyrolysis reaction product will have a higher water content as compared to a water content of the pyrolysis reaction product.
  • the cooled pyrolysis reaction product can be further compressed (e.g., via a compressor), for example to a pressure in the range of from about 150 psig to about 300 psig, alternatively about 175 psig to about 275 psig, or alternatively about 200 psig to about 250 psig, followed by optionally feeding the compressed cooled pyrolysis reaction product to a water removal unit.
  • a pressure in the range of from about 150 psig to about 300 psig, alternatively about 175 psig to about 275 psig, or alternatively about 200 psig to about 250 psig.
  • compressing a gas that contains water to increase its pressure will lead to the water condensing at the increased pressure at an increased temperature as compared to a temperature where water of an otherwise similar gas condenses at pressure lower than the increased pressure.
  • the compressed cooled pyrolysis reaction product can be further introduced to a water removal unit (e.g., a water quench vessel and/or a cooling tower), where the compressed cooled pyrolysis reaction product can be further cooled to promote water condensation and removal.
  • a water removal unit e.g., a water quench vessel and/or a cooling tower
  • water can be recovered from the cooled pyrolysis reaction product as steam.
  • a process for producing ethylene and methanol as disclosed herein can comprise converting at least a portion of the thermal energy into electrical energy, for example by feeding at least a portion of the heated quenching fluid and/or a at least a portion of the heated heat exchange fluid to the electricity generator 15 to produce electricity.
  • an electricity generator is a device that converts a type of energy other than electrical energy, such as thermal energy, mechanical energy, etc., into electrical energy (e.g., electricity).
  • the electricity generator can comprise a turbine, a thermoelectric generator, a thermionic converter, and the like, or combinations thereof.
  • a fluid such as steam
  • a turbine wherein the moving part of the turbine rotates (spins), while a shaft connected to the spinning part can be connected to a turbogenerator that can convert the mechanical spinning energy into electricity.
  • the heated quenching fluid and/or the heated heat exchange fluid can comprise steam
  • the turbine can comprise a steam turbine, wherein at least a portion of the steam is fed to the steam turbine to produce electricity.
  • thermoelectric generator also known as a Seebeck generator
  • Seebeck generator is a solid state device that converts heat or thermal energy (temperature differences) directly into electrical energy through a thermoelectric effect known as the Seebeck effect.
  • a thermionic converter has two electrodes, wherein one electrode is raised to a sufficiently high temperature to become a thermionic electron emitter, or "hot plate,” and wherein the other electrode, referred to as a "collector” because it receives the emitted electrons, is operated at a significantly lower temperature than the temperature of the thermionic electron emitter.
  • the movement of electrons between the two electrodes generates electricity.
  • the space between the electrodes can be vacuum, or it can be filled with a low pressure vapor or gas.
  • Thermionic converters are solid state devices with no moving parts.
  • the step of cooling the pyrolysis product in the quench zone to produce thermal energy and the step of converting at least a portion of the thermal energy into electrical energy occur about concurrently, for example by co-generating steam and electricity.
  • a process for producing ethylene and methanol as disclosed herein can comprise using at least a portion of the electricity for water electrolysis (e.g., splitting water) in the electrolysis unit 20 to produce a hydrogen stream and an oxygen stream.
  • at least a portion of the oxygen stream can be recycled to the combustion zone 1 1.
  • water electrolysis can be conducted under conventional conditions, for example wherein liquid water can be split into hydrogen and oxygen.
  • Water electrolysis cells or units typically employ stainless steel or nickel-based electrodes which operate in a potassium hydroxide solution at a concentration range of 6-9 molar and a temperature range of 60-80 °C.
  • high temperature steam can be subjected to electrolysis to produce hydrogen and oxygen.
  • the steam generated in the quench zone 13 and/or the heat exchanger 14 can be used for electricity generation in the electricity generator 15, a portion of the steam generated in the quench zone 13 and/or the heat exchanger 14 could be used for electrolysis.
  • a process for producing ethylene and methanol as disclosed herein can comprise separating at least a portion of the cooled pyro lysis reaction product in the first separation unit 16 into a C0 2 stream and an acetylene stream, wherein the acetylene stream comprises unconverted hydrocarbons (e.g., methane), C 2 H 2 , C2H4, CO, and H 2 .
  • unconverted hydrocarbons e.g., methane
  • C0 2 can be removed from the cooled pyrolysis reaction product by using a C0 2 separator to produce a C0 2 stream.
  • the C0 2 separator can comprise C0 2 removal by amine (e.g., monoethanolamine) absorption (e.g., amine scrubbing), pressure swing adsorption, temperature swing adsorption, gas separation membranes (e.g., porous inorganic membranes, palladium membranes, polymeric membranes, zeolites, etc.), and the like, or combinations thereof.
  • the C0 2 separator can comprise C0 2 removal by amine absorption.
  • a process for producing ethylene and methanol as disclosed herein can comprise contacting at least a portion of the hydrogen stream and at least a portion of the C0 2 stream with a C0 2 hydrogenation catalyst in the C0 2 hydrogenation to syngas unit 30 to produce a first syngas stream, wherein the first syngas stream comprises H 2 and CO.
  • the first syngas stream can be characterized by a H 2 /CO molar ratio of from about 1 : 1 to about 2: 1, alternatively from about 1.1 : 1 to about 1.95: 1, or alternatively from about 1.2: 1 to about 1.9: 1.
  • C0 2 can be converted to syngas by using a hydrogenating agent, e.g., hydrogen or any suitable compound that can provide hydrogen for hydrogenation reaction.
  • a hydrogenating agent e.g., hydrogen or any suitable compound that can provide hydrogen for hydrogenation reaction.
  • Hydrogenation of C0 2 to syngas composition can be described by reactions (12)-(14):
  • reaction (12) is an equilibrium controlled reaction which depends on the H 2 /C0 2 ratio, as it can be seen from reactions (13) and (14).
  • a catalyst for C0 2 hydrogenation to syngas can comprise mixed oxides of redox types, for example chromium (Cr), iron (Fe), manganese (Mn), or copper (Cu) based oxides.
  • the hydrogenation of carbon dioxide to syngas can be conducted in the presence of a CATOFIN catalyst, which is a chromium (Cr) based catalyst commercially available from Clariant, wherein the resulting syngas composition is suitable for methanol and/or olefins synthesis.
  • the composition of syngas produced by C0 2 hydrogenation is dependent upon the H 2 /C0 2 ratio and on a C0 2 hydrogenation temperature.
  • the C0 2 hydrogenation temperature can be from about 500 °C to about 700 °C, alternatively from about 600 °C to about 650 °C, or alternatively about 630 °C.
  • a process for producing ethylene and methanol as disclosed herein can comprise introducing at least a portion of the acetylene stream and a polar aprotic solvent to the liquid phase hydrogenation unit 40 (e.g., second reaction zone), wherein the liquid phase hydrogenation unit 40 comprises an acetylene hydrogenation catalyst; and allowing at least a portion of the acetylene in the acetylene stream to undergo hydrogenation to ethylene to produce a second reaction zone effluent, wherein the second reaction zone effluent comprises unconverted hydrocarbons (e.g., methane), C 2 H 4 , CO, and H 2 , and wherein an amount of C 2 H 4 in the second reaction zone effluent is greater than an amount of C 2 H 4 in the acetylene stream. At least a portion of the H 2 in the acetylene stream hydrogenates at least a portion of the acetylene of the acetylene stream to produce ethylene.
  • the liquid phase hydrogenation unit 40 comprises
  • Nonlimiting examples of polar aprotic solvents suitable for use in the present disclosure include N- methyl-2-pyrrolidone (NMP), ⁇ , ⁇ -dimethylformamide (DMF), acetone, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), and the like, or combinations thereof.
  • NMP N- methyl-2-pyrrolidone
  • DMF ⁇ , ⁇ -dimethylformamide
  • THF tetrahydrofuran
  • DMSO dimethylsulfoxide
  • the liquid phase hydrogenation unit 40 can be any suitable liquid phase hydrogenation reactor, such as a fixed bed catalytic reactor (typically operated adiabatically); and/or a tubular reactor (typically operated isothermally).
  • the liquid phase hydrogenation unit 40 comprises an acetylene hydrogenation catalyst, such as a palladium (Pd) based catalyst, which can be supported on alumina, zeolites, etc.
  • the hydrogenation catalyst can further comprise other metals, such as platinum, silver, nickel, etc.
  • the acetylene hydrogenation catalyst can comprise Pd/Al 2 0 3 . Liquid phase hydrogenation of acetylene processes are described in more detail in U.S. Patent No. 4,128,595, which is incorporated by reference herein in its entirety.
  • a process for producing ethylene and methanol as disclosed herein can comprise separating at least a portion of the second reaction zone effluent in the second separation unit 50 into an ethylene stream and a second syngas stream, wherein the second syngas stream comprises H 2 and CO.
  • the second syngas stream can be characterized by a H 2 /CO molar ratio of from about 1 : 1 to about 2: 1, alternatively from about 1.1 : 1 to about 1.95: 1, or alternatively from about 1.2: 1 to about 1.9: 1.
  • the second separation unit 50 can employ distillation and/or cryogenic distillation to produce the ethylene stream and the second syngas stream.
  • Other components present in the effluent from the first and/or second reaction zones may be recovered via one or more additional streams produced in the first separation unit and/or the second separation unit, respectively.
  • a process for producing ethylene and methanol as disclosed herein can comprise introducing at least a portion of the first syngas stream and/or at least a portion of the second syngas stream to the methanol production reactor 60 (e.g., third reaction zone) comprising a methanol production catalyst to produce a methanol stream.
  • the methanol production reactor 60 can comprise any reactor suitable for a methanol synthesis reaction from CO and H 2 , such as for example an isothermal reactor, an adiabatic reactor, a slurry reactor, a cooled multi tubular reactor, and the like, or combinations thereof.
  • At least a portion of the first syngas stream and/or at least a portion of the second syngas stream could be mixed with methane steam reforming syngas (e.g., syngas produced by steam reforming of methane), and subsequently fed to methanol synthesis (e.g., methanol production reactor 60; third reaction zone).
  • a feed stream (e.g., the first syngas stream and/or the second syngas stream) to the methanol production reactor 60 can be characterized by a H 2 /CO molar ratio of about 2: 1, alternatively about 2.1 : 1, alternatively from about 1.5: 1 to about 2.5: 1, alternatively from about 1.8: 1 to about 2.3 : 1, or alternatively from about 2.0: 1 to about 2.1 : 1.
  • the H 2 /CO molar ratio of the feed stream to the methanol production reactor 60 can be adjusted as necessary to meet the requirements of the methanol production reactor 60, for example by mixing with methane steam reforming syngas.
  • At least a portion of the CO and at least a portion of the H 2 of a feed stream to the methanol production reactor 60 can undergo a methanol synthesis reaction.
  • Methanol synthesis from CO and H 2 is a catalytic process, and is most often conducted in the presence of copper based catalysts.
  • the methanol production reactor 60 can comprise a methanol production catalyst, such as any suitable commercial catalyst used for methanol synthesis.
  • Nonlimiting examples of methanol production catalysts suitable for use in the methanol production reactor 60 in the current disclosure include Cu, Cu/ZnO, Cu/Th0 2 , Cu/Zn/Al 2 0 3 , Cu/ZnO/Al 2 0 3 , Cu/Zr, and the like, or combinations thereof.
  • a process for producing ethylene and methanol can comprise the steps of (a) introducing a fuel gas stream (e.g., comprising methane) and an oxidant gas to a combustion zone to produce a combustion product and combustion heat; (b) reacting a first reactant mixture in a cracking zone, wherein the first reactant mixture comprises a hydrocarbon stream (e.g., comprising methane) and at least a portion of the combustion product, wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction to produce a pyrolysis reaction product, wherein the first temperature is equal to or greater than about 2,000 °C, and wherein the pyrolysis reaction product comprises unconverted hydrocarbons (e.g., methane), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ); (c)
  • a process for producing ethylene and methanol as disclosed herein can advantageously display improvements in one or more process characteristics when compared to an otherwise similar process that does not integrate hydrocarbon pyrolysis with other processes for producing desired products.
  • the process for producing ethylene and methanol as disclosed herein can advantageously use waste energy from the quench zone for generation of electricity, which electricity can be advantageously used for water electrolysis to produce hydrogen and oxygen.
  • the hydrogen produced by electrolysis can be used to hydrogenate carbon dioxide from combustion and pyrolysis to syngas, thereby increasing the overall efficiency of the process, while minimizing C0 2 emissions.
  • a synthesis gas (e.g., H 2 and CO) to methanol conversion process as disclosed herein can increase further the overall efficiency of the process by producing methanol from the H 2 and CO obtained from hydrocarbon pyrolysis, as well as C0 2 hydrogenation.
  • Methanol can be advantageously used as a liquid fuel, and can be easily transported, as compared to transporting gases. Additional advantages of the process for producing ethylene and methanol as disclosed herein can be apparent to one of skill in the art viewing this disclosure.
  • the hydrogenation of C0 2 was investigated in a metal reactor at a temperature of 630 °C, and the data are displayed in Figure 3.
  • the flow rates were 3490.2 cc/min for hydrogen, and 873.7 cc/min for C0 2 .
  • the reactor used had a diameter of 1.5 inches and a length of 1.5 meters.
  • the catalyst used was a CATOFIN catalyst, at a loading of 123.7 ml. In different experiments, various amounts of catalyst were used, for the purpose of scaling up the process (e.g., the higher the catalyst loading, the higher the scale).
  • composition of the gas effluent recovered from the reactor was similar to the composition of syngas produced via a methane steam reforming process.
  • the produced syngas could be mixed with methane steam reforming syngas and subsequently fed for methanol synthesis.
  • a first aspect which is a process for producing ethylene comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product; (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction; (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ); (d) cooling at least a portion of the pyrolysis reaction product in a quench zone by heat exchange with a quenching fluid to produce a quenching
  • a second aspect which is the process of the first aspect, wherein the quenching fluid comprises water, hydrocarbons, oil, or combinations thereof.
  • a third aspect which is the process of any one of the first and the second aspects, wherein the electricity generator comprises a turbine, a thermoelectric generator, a thermionic convertor, or combinations thereof.
  • a fourth aspect which is the process of the third aspect, wherein the heated quenching fluid comprises steam, and wherein the turbine comprises a steam turbine.
  • a fifth aspect which is the process of any one of the first through the fourth aspects, wherein the quench zone comprises a heat exchanger.
  • a sixth aspect which is the process of any one of the first through the fifth aspects, wherein steps (d) and (e) occur about concurrently.
  • a seventh aspect which is the process of the sixth aspect further comprising co-generating steam and electricity.
  • step (e) further comprises (i) introducing the heated quenching fluid to a heat exchanger to produce steam; and (ii) feeding at least a portion of the steam to a steam turbine to produce electricity.
  • step (e) further comprises (i) introducing the cooled pyrolysis reaction product characterized by the second temperature, the heated quenching fluid, or both to a heat exchanger to produce steam; and (ii) feeding at least a portion of the steam to a steam turbine to produce electricity.
  • a tenth aspect which is the process of the ninth aspect, wherein a temperature of the cooled pyrolysis reaction product is decreased from the second temperature to a third temperature, and wherein the third temperature is from about 100 °C to about 900 °C.
  • An eleventh aspect which is the process of any one of the first through the tenth aspects further comprising using at least a portion of the electricity for water electrolysis to produce a hydrogen stream and an oxygen stream.
  • a twelfth aspect which is the process of the eleventh aspect, wherein at least a portion of the oxygen stream is recycled to the step (a) as the oxidant gas.
  • a thirteenth aspect which is the process of any one of the first through the twelfth aspects further comprising (i) separating at least a portion of the cooled pyrolysis reaction product into a C0 2 stream and an acetylene stream, wherein the acetylene stream comprises unconverted hydrocarbons, C 2 H 2 , C 2 H , CO, and H 2 ; and (ii) contacting at least a portion of the hydrogen stream and at least a portion of the C0 2 stream with a C0 2 hydrogenation catalyst to produce a first syngas stream, wherein the first syngas stream comprises H 2 and CO.
  • a fourteenth aspect which is the process of the thirteenth aspect, wherein the C0 2 hydrogenation catalyst comprises one or more oxides of a metal selected from the group consisting of chromium (Cr), iron (Fe), manganese (Mn), and copper (Cu).
  • a fifteenth aspect which is the process of any one of the first through the fourteenth aspects, wherein the first C0 2 stream is separated from the cooled pyrolysis reaction product by amine absorption.
  • a sixteenth aspect which is the process of any one of the first through the fifteenth aspects further comprising ( 1 ) introducing at least a portion of the acetylene stream and a polar aprotic solvent to a second reaction zone, wherein the second reaction zone comprises an acetylene hydrogenation catalyst; (2) allowing at least a portion of the acetylene in the acetylene stream to undergo hydrogenation to ethylene to produce a second reaction zone effluent, wherein the second reaction zone effluent comprises unconverted hydrocarbons, C 2 H 4 , CO, and H 2 , and wherein an amount of C 2 H 4 in the second reaction zone effluent is greater than an amount of C 2 H 4 in the acetylene stream; and (3) separating at least a portion of the second reaction zone effluent into an ethylene stream and a second syngas stream, wherein the second syngas stream comprises H 2 and CO.
  • a seventeenth aspect which is the process of the sixteenth aspect, wherein the polar aprotic solvent comprises N-methyl-2-pyrrolidone (NMP), ⁇ , ⁇ -dimethylformamide (DMF), acetone, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), or combinations thereof.
  • NMP N-methyl-2-pyrrolidone
  • DMF ⁇ , ⁇ -dimethylformamide
  • THF acetone
  • THF tetrahydrofuran
  • DMSO dimethylsulfoxide
  • An eighteenth aspect which is the process of any one of the first through the seventeenth aspects, wherein the acetylene hydrogenation catalyst comprises palladium (Pd).
  • a nineteenth aspect which is the process of any one of the first through the eighteenth aspects, wherein the first syngas stream and/or the second syngas stream are characterized by a H 2 /CO molar ratio of from about 1 : 1 to about 2: 1.
  • a twentieth aspect which is the process of any one of the first through the nineteenth aspects further comprising introducing at least a portion of the first syngas stream and/or at least a portion of the second syngas stream to a third reaction zone comprising a methanol production catalyst to produce a methanol stream.
  • a twenty-first aspect which is the process of the twentieth aspect, wherein the methanol production catalyst comprises Cu, Cu/ZnO, Cu/Th0 2 , Cu/Zn/Al 2 0 3 , Cu/ZnO/Al 2 0 3 , Cu/Zr, or combinations thereof.
  • a twenty-second aspect which is the process of any one of the first through the twenty-first aspects, wherein the first temperature is equal to or greater than about 2,000 °C.
  • a twenty-third aspect which is the process of any one of the first through the twenty-second aspects, wherein the second temperature is from about 600 °C to about 1,000 °C.
  • a twenty-fourth aspect which is the process of any one of the first through the twenty-third aspects, wherein the quenching fluid is characterized by an inlet temperature of from about 40 °C to about 80 °C.
  • a twenty-fifth aspect which is the process of any one of the first through the twenty-fourth aspects, wherein the heated quenching fluid is characterized by a temperature of from about 600 °C to about 800 °C.
  • a twenty-sixth aspect which is the process of any one of the first through the twenty-fifth aspects, wherein the fuel gas stream and the hydrocarbon stream are the same or different.
  • a twenty-seventh aspect which is the process of any one of the first through the twenty-sixth aspects, wherein the fuel gas stream and/or the hydrocarbon stream comprise methane, ethane, propane, natural gas, natural gas liquids, associated gas, well head gas, enriched gas, heavy hydrocarbons, petcoke, naphtha, heavy oil, heavy oil residue, or combinations thereof.
  • a twenty-eighth aspect which is the process of any one of the first through the twenty-seventh aspects, wherein the oxidant gas comprises oxygen, purified oxygen, air, oxygen-enriched air, or combinations thereof.
  • a twenty-ninth aspect which is a process for producing ethylene and methanol comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product; (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction; (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ); (d) cooling at least a portion of the pyrolysis reaction product in a quench zone by heat exchange with
  • a thirtieth aspect which is a process for producing ethylene and methanol comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product; (b) introducing a first reactant mixture to a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, and wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction; (c) allowing at least a portion of the first reactant mixture to react via the pyrolysis reaction and produce a pyrolysis reaction product, wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ); (d) quenching at least a portion of the pyrolysis reaction product in a quench zone to produce a quench zone to produce
  • a thirty-first aspect which is a process for producing ethylene and methanol comprising (a) introducing a fuel gas stream and an oxidant gas to a combustion zone to produce a combustion product and combustion heat; (b) reacting a first reactant mixture in a first reaction zone, wherein the first reactant mixture comprises a hydrocarbon stream and at least a portion of the combustion product, wherein the combustion product heats the hydrocarbon stream to a first temperature effective for a pyrolysis reaction to produce a pyrolysis reaction product, and wherein the pyrolysis reaction product comprises unconverted hydrocarbons, acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), carbon monoxide (CO), hydrogen (H 2 ), water (H 2 0), and carbon dioxide (C0 2 ); (c) cooling at least a portion of the pyrolysis reaction product to produce a cooled pyrolysis reaction product and thermal energy, wherein the cooled pyrolysis reaction product is characterized by a second temperature,
  • a thirty-second aspect which is the process of the thirty-first aspect, wherein the thermal energy is produced by at least a portion of the pyrolysis reaction product exchanging heat with a quenching fluid to produce the cooled pyrolysis reaction product and a heated quenching fluid.
  • a thirty-third aspect which is the process of the thirty-second aspect, wherein the heated quenching fluid comprises steam.
  • step (d) further comprises introducing at least a portion of the heated quenching fluid to a turbine to generate electricity.
  • a thirty-fifth aspect which is the process of any one of the thirty-first through the thirty-fourth aspects, wherein the thermal energy is produced by at least a portion of the pyrolysis reaction product exchanging heat with a heat exchange fluid.
  • a thirty-sixth aspect which is the process of the thirty-fifth aspect, wherein the heat exchange fluid comprises water, and wherein exchanging heat with a heat exchange fluid comprises converting at least a portion of the water to steam.
  • a thirty-seventh aspect which is the process of the thirty-sixth aspect, wherein step (d) further comprises introducing at least a portion of the steam to a steam turbine to generate electricity.
  • step (d) further comprises introducing at least a portion of the steam to a steam turbine to generate electricity.
  • step (d) further comprises introducing at least a portion of the steam to a steam turbine to generate electricity.
  • step (e) further comprises introducing at least a portion of the steam to a steam turbine to generate electricity.
  • a thirty-eighth aspect which is the process of any one of the thirty-first through the thirty- seventh aspect, wherein the thermal energy is produced by at least a portion of the pyrolysis reaction product exchanging heat with a quenching fluid, a heat exchange fluid, or both.

Abstract

La présente invention concerne un procédé de production d'éthylène comprenant les étapes consistant à : introduire un gaz combustible et un gaz oxydant dans une zone de combustion pour produire un produit de combustion ; introduire dans une première zone de réaction un premier mélange réactif comprenant des hydrocarbures et le produit de combustion, le produit de combustion chauffant les hydrocarbures à une première température efficace pour la pyrolyse ; permettre au premier mélange réactif de réagir par pyrolyse et de produire un produit de pyrolyse comprenant des hydrocarbures non convertis, C2H2, C2H4, CO, H2, H2O et CO2 ; refroidir le produit de pyrolyse dans une zone de refroidissement par échange de chaleur avec un fluide de refroidissement afin de produire un produit de réaction de pyrolyse refroidi et un fluide de refroidissement chauffé, le produit de réaction de pyrolyse refroidi étant caractérisé par une seconde température, la seconde température étant inférieure à la première température, et la température du fluide de refroidissement chauffé étant supérieure à la température du fluide de refroidissement ; et diriger le fluide de refroidissement chauffé vers un générateur d'électricité pour produire de l'électricité.
PCT/US2018/012067 2017-01-06 2018-01-02 Procédé intégré utilisant la chaleur de conversion oxydative de méthane pour la production d'éthylène et de méthanol WO2018128983A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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