EP4469393A2 - Systeme, vorrichtungen und verfahren zur eingangs- und ausgangsdruckverwaltung von reformern für luftatmungsmotoren - Google Patents

Systeme, vorrichtungen und verfahren zur eingangs- und ausgangsdruckverwaltung von reformern für luftatmungsmotoren

Info

Publication number
EP4469393A2
EP4469393A2 EP23747922.5A EP23747922A EP4469393A2 EP 4469393 A2 EP4469393 A2 EP 4469393A2 EP 23747922 A EP23747922 A EP 23747922A EP 4469393 A2 EP4469393 A2 EP 4469393A2
Authority
EP
European Patent Office
Prior art keywords
engine
systems
gas
methods
methanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23747922.5A
Other languages
English (en)
French (fr)
Other versions
EP4469393A4 (de
Inventor
Paul E. YELVINGTON
John Anthony DEAN
Andrew L. RANDOLPH
Joshua B. BROWNE
Doug C. HOFER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
M2X Energy Inc
Original Assignee
M2X Energy Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US17/746,942 external-priority patent/US11649201B2/en
Priority claimed from US17/953,056 external-priority patent/US20230212098A1/en
Priority claimed from US17/984,126 external-priority patent/US20230279802A1/en
Application filed by M2X Energy Inc filed Critical M2X Energy Inc
Publication of EP4469393A2 publication Critical patent/EP4469393A2/de
Publication of EP4469393A4 publication Critical patent/EP4469393A4/de
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/869—Multiple step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using oxygen; using mixtures containing oxygen as gasifying agents
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using oxygen; using mixtures containing oxygen as gasifying agents
    • C01B3/366—Partial combustion in internal-combustion engines
    • 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; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by diffusion
    • 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; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification at low temperatures
    • 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; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • 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; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • 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
    • C07C29/152—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 characterised by the reactor used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • 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
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B37/00—Engines characterised by provision of pumps driven at least for part of the time by exhaust
    • F02B37/004—Engines characterised by provision of pumps driven at least for part of the time by exhaust with exhaust drives arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B37/00—Engines characterised by provision of pumps driven at least for part of the time by exhaust
    • F02B37/013—Engines characterised by provision of pumps driven at least for part of the time by exhaust with exhaust-driven pumps arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B75/00—Other engines
    • F02B75/02—Engines characterised by their cycles, e.g. six-stroke
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B75/00—Other engines
    • F02B75/04—Engines with variable distances between pistons at top dead-centre positions and cylinder heads
    • F02B75/045—Engines with variable distances between pistons at top dead-centre positions and cylinder heads by means of a variable connecting rod length
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D13/00—Controlling the engine output power by varying inlet or exhaust valve operating characteristics, e.g. timing
    • F02D13/02—Controlling the engine output power by varying inlet or exhaust valve operating characteristics, e.g. timing during engine operation
    • F02D13/0203—Variable control of intake and exhaust valves
    • F02D13/0215—Variable control of intake and exhaust valves changing the valve timing only
    • F02D13/0219—Variable control of intake and exhaust valves changing the valve timing only by shifting the phase, i.e. the opening periods of the valves are constant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D13/00—Controlling the engine output power by varying inlet or exhaust valve operating characteristics, e.g. timing
    • F02D13/02—Controlling the engine output power by varying inlet or exhaust valve operating characteristics, e.g. timing during engine operation
    • F02D13/0269—Controlling the valves to perform a Miller-Atkinson cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D15/00—Varying compression ratio
    • F02D15/02—Varying compression ratio by alteration or displacement of piston stroke
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D15/00—Varying compression ratio
    • F02D15/04—Varying compression ratio by alteration of volume of compression space without changing piston stroke
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0626—Measuring or estimating parameters related to the fuel supply system
    • F02D19/0634—Determining a density, viscosity, composition or concentration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0642—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions
    • F02D19/0644—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions the gaseous fuel being hydrogen, ammonia or carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0663—Details on the fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F02D19/0668—Treating or cleaning means; Fuel filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0663—Details on the fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F02D19/0668—Treating or cleaning means; Fuel filters
    • F02D19/0671—Means to generate or modify a fuel, e.g. reformers, electrolytic cells or membranes
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    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D35/00—Controlling engines, dependent on conditions exterior or interior to engines, not otherwise provided for
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    • F02D35/02—Controlling engines, dependent on conditions exterior or interior to engines, not otherwise provided for on interior conditions
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    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/0025—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D41/0027—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures the fuel being gaseous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F02D41/14—Introducing closed-loop corrections
    • F02D41/1438—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor
    • F02D41/1444—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases
    • F02D41/1446—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being exhaust temperatures
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    • F02D41/14—Introducing closed-loop corrections
    • F02D41/1438—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor
    • F02D41/1444—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases
    • F02D41/1454—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being an oxygen content or concentration or the air-fuel ratio
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    • F02D41/1473—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the regulation method
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F02D41/1438—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor
    • F02D41/1473—Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the regulation method
    • F02D41/1475—Regulating the air fuel ratio at a value other than stoichiometry
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    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0215—Mixtures of gaseous fuels; Natural gas; Biogas; Mine gas; Landfill gas
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    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0218—Details on the gaseous fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F02M21/0227—Means to treat or clean gaseous fuels or fuel systems, e.g. removal of tar, cracking, reforming or enriching
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    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present inventions relate to new and improved methods, devices and systems for operating engines, in particular air-breathing reformers, for use in gas-to-liquids systems and processes.
  • flare gas gas generated, created, associated or produced by or from oil and gas production, hydrocarbon wells (including conventional and unconventional wells), petrochemical processing, refining, landfills, wastewater treatment, dairies, livestock production, and other municipal, chemical and industrial processes.
  • flare gas and waste gas would include stranded gas, associated gas, landfill gas, vented gas, biogas, digester gas, smallpocket gas, and remote gas.
  • the composition of flare gas is a mixture of different gases.
  • the composition can depend upon the source of the flare gas.
  • gases released during oil and gas production mainly contain natural gas.
  • Natural gas is more than 90% methane (CH4) with ethane and smaller amounts of other hydrocarbons, water, N2 and CO2 may also be present.
  • Flare gas from refineries and other chemical or manufacturing operations typically can be a mixture of hydrocarbons and in some cases H2.
  • Landfill gas, biogas or digester gas typically can be a mixture of CH4 and CO2, as well as small amounts of other inert gases.
  • flare gas can contain one or more of the following gases: methane, ethane, propane, n-butane, isobutane, n- pentane, isopentane, n-hexane, ethylene, propylene, 1 -butene, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen, oxygen, nitrogen, and water.
  • flare gas is produced from smaller, individual point sources, such as a number of oil or gas wells in an oil field, a landfill, or a chemical plant.
  • flare gas and in particular flare gas generated from hydrocarbon producing wells and other smaller point sources, was burned to destroy it, and in some instances may have been vented directly into the atmosphere. This flare gas could not be economically recovered and used.
  • the burning or venting of flare gas both from hydrocarbon production and other endeavors, raises serious concerns about pollution and the production greenhouse gases.
  • gas and “synthesis gas” and similar such terms should be given their broadest possible meaning and would include gases having as their primary components a mixture of H2 and CO; and may also contain CO2, N2, and water, as well as, small amounts of other materials.
  • CC e is used to define carbon dioxide equivalence of other, more potent greenhouse gases, to carbon dioxide (e.g., methane and nitrous oxide) on a global warming potential basis of 20 or 100 years, based on Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5) methodology.
  • carbon intensity is taken to mean the lifecycle CO2e generated per unit mass of a product.
  • % and mol % are used interchangeably and refer to the moles of a first component as a percentage of the moles of the total, e.g., formulation, mixture, material or product.
  • FIG. 8 is a schematic flow diagram of an embodiment of a system and process having a recuperator and turbo-expander in accordance with the present inventions.
  • FIG. 12 is a table showing global warming potential values.
  • FIG. 13 is a T-S diagram showing an embodiment of a process, operating conditions and thermodynamic state points for converting flag gas to syngas to methanol, using the system of FIG. 8 having a spark ignition reciprocating engine in accordance with the present inventions.
  • embodiments of the present inventions relate to systems and methods having gas-to-liquids systems and processes, e.g., for processing flare gas to methanol.
  • an air-breathing engine reformer produces a syngas intermediate that is further converted to methanol in a downstream synthesis step.
  • Examples of these gas-to-liquid systems are taught and disclosed in US patent publication no. 2022/0388930 and in US patent application serial numbers 17/953,056 (filed 09/26/2022) and 17/984,126 (filed 11/152022), the entire disclosure of each of which is incorporated herein by reference.
  • embodiments of the present inventions relate to devices, systems and methods to improve and enhance the pressure differential associated with the air-breathing engine reformer in these gas-to- liquids systems and processes, and thus reduce compressor work need for operation of these systems.
  • embodiments of the present devices and system to reduce compressor work required for reciprocating engine reformer-based hydrocarbon processing systems are utilized with, or as a part of, these gas-to-liquid systems.
  • systems and methods reduce the gas compression requirements for synthesis of methanol (or other downstream product such as ammonia or F-T liquids) in an integrated system with an engine-based reformer for small, modular, distributed conversion of stranded gas to products, preferably value-added, easily transported products (such as methanol, ethanol, ammonia, dimethyl-ether, F-T liquids, and other fuels or chemicals).
  • the gas compression requirements contribute to the overall capx and opex of the process and impact the overall profitability of the modular plant.
  • Compressors for increasing the pressure of the syngas exiting the engine reformer to values for downstream methanol synthesis can account for nearly half of the overall plant capex.
  • the plant be self-sufficient with little or no external power requirements. Power requirements are dominated by power required to drive the compressors and therefore compressor work can be linked to opex and self-sufficiency of the plant.
  • methanol plants operate the methanol synthesis at elevated pressures of nominally 50 bar, much higher than the nominal exhaust pressure from an enginebased reformer, and in particular, air-breathing engine-based reformers.
  • This high pressure requires substantial compression work and the associated high capex and opex.
  • the single-pass conversion is still rather low and therefore there can be the use of recycle loops to increase the overall conversion at the expense of larger reactors and more complex and costly downstream separations.
  • the one or more of the devices and processes to reduce compressor work is used as part of a small, modular, distributed, self-sufficient plant for conversion of stranded gas to fungible, easily transportable products using an engine-based reformer and syngas intermediate.
  • An objective of embodiments of the present inventions is to reduce the compressor work required for the conversion of otherwise uneconomic hydrocarbon-based fuel (e.g., stranded, associated, landfill, flared, small-pocket, remote gas) to value-added, easily transported products (such as methanol, ethanol, ammonia, dimethyl-ether, F-T liquids, and other fuels or chemicals) using an autonomous, modular system.
  • otherwise uneconomic hydrocarbon-based fuel e.g., stranded, associated, landfill, flared, small-pocket, remote gas
  • value-added, easily transported products such as methanol, ethanol, ammonia, dimethyl-ether, F-T liquids, and other fuels or chemicals
  • Conventional air-breathing reciprocating engines typically are designed to operate using fuels with a narrow fuel specification.
  • the compression ratio of automotive gasoline engines is selected for the quality of fuel used.
  • the “regular’ gasoline in the United States has an octane rating of 86-87.
  • a higher performance (e.g., higher compression ratio) engine may require premium gasoline with octane rating of 91-94.
  • Embodiments of the present inventions can be used to take uneconomic hydrocarbon-based fuels at a well-head and remote locations that are primarily gaseous hydrocarbons and convert them to a more valuable easily condensable gas or liquid compound, such as methanol.
  • One source of fuel could be associated gas or flare gas, which is produced as a byproduct at oil wells.
  • Another source is flare gas produced by industrial processes, such as refinery flare gas.
  • Another source could be biogas from landfill or anaerobic digesters.
  • Embodiments of the present inventions can be incorporated into one or more modular, interconnected skids or containers that are built at a central fabricator shop location and then installed at a field location.
  • a system comprises a small number of modules and when connected at site they form an integrated system.
  • the modular nature of the assembly enables application to remote locations under a range of inlet gas feed volumes, with a minimum of field labor.
  • FIG. 3 there is shown a generalized embodiment of a system and method for the conversion of a waste gas, e.g., flare gas, into a value-added product, e.g., methanol.
  • the system 100 has a reformer stage 101 and a synthesis stage 102.
  • the system 100 has an air intake 110, that feeds air through into a compressor 111 , which compresses the air.
  • the compressed air is feed through heat exchanger 120a into a mixer 113.
  • the system has a waste gas, e.g., flare gas, intake 114.
  • the waste gas flows through a heat exchanger 120b into the mixer 113.
  • the mixer 113 provides a predetermined mix of air and waste gas, as taught and disclosed in this specification, to a reformer 114.
  • the fuel-air mixture that is formed in mixer 113 is preferably rich, more preferably having an overall fuel/air equivalence ratio (d) or ER) greater than 1 , greater than 1 .5, greater than 2, greater than 3, from about 1 .5 to about 4.0, about 1 .1 to about 3.5, about 2 to about 4.5, and about 1 .1 to about 3, and greater values.
  • d fuel/air equivalence ratio
  • ER overall fuel/air equivalence ratio
  • the reformer 114 combusts the predetermined mixture of waste gas and air (e.g., flare gas and air) to form a reprocessed gas (e.g., syngas).
  • a reprocessed gas e.g., syngas
  • the syngas flows through heat exchangers 120a, 120b and into a filter 115, e.g., a particulate filter.
  • the reprocessed gas (e.g., syngas) flows to heat exchanger 120c.
  • the reprocessed gas (e.g., syngas) then flows from heat exchanger 120c to a water removal unit 118, e.g., a water knockout drum, demister, dryer, membrane, cyclone, desiccant or similar devices, where water is removed from the reprocessed gas (e.g., syngas).
  • a water removal unit 118 e.g., a water knockout drum, demister, dryer, membrane, cyclone, desiccant or similar devices, where water is removed from the reprocessed gas (e.g., syngas).
  • the reprocessed gas e.g., syngas
  • the reprocessed gas upon leaving unit 118 should have less than about 5% water by weight, less than about 2%, less than about 1 % and less than about 0.1 % water.
  • minor constituents in the gas exiting the reformer can include water vapor, CO 2 , and various unburned hydrocarbons.
  • the now dry reprocessed gas (e.g., syngas) is in the synthesis stage 102.
  • the now dry reprocessed gas e.g., syngas
  • Assembly 130 provides for the controlled addition of hydrogen from line 131 into the now dry reprocessed gas (e.g., syngas). In this manner the ratio of the syngas components can be adjusted and controlled to a predetermined ratio.
  • the hydrogen is provided from hydrogen separation unit 139.
  • the ratio-adjusted dry reprocessed gas leaves assembly 130 and flow to compressor 132.
  • the synthesis unit 133 converts the ratio-adjusted dry reprocessed gas (e.g., syngas) into a value-added product (e.g., methanol, ethanol, mixed alcohols, ammonia, dimethyl-ether, F-T liquids, and other fuels or chemicals).
  • a value-added product e.g., methanol, ethanol, mixed alcohols, ammonia, dimethyl-ether, F-T liquids, and other fuels or chemicals.
  • the value-added product e.g, methanol, etc.
  • the value-added product flows to a collection unit 140.
  • the collection unit 140 collects the value-added product (e.g, methanol, etc.) and flows it through line 141 for sale, holding, or further processing.
  • the methanol synthesis window 211 defines the region of temperature and pressure where the methanol synthesis reactions take place.
  • the region defines the reaction conditions that lead to reasonable equilibrium conversion for this equilibrium-limited reaction. For this exothermic process, lower temperatures are favored for equilibrium conversion but are constrained on the low end by ensuring sufficient catalyst activity. Higher pressures yield higher equilibrium concentrations due to the net decrease in moles in the reaction but require the cost of compression and design for high pressure. While FIG. 11 specifically shows a methanol synthesis window, it is understood that other possible downstream synthesis reactions, e.g. Fischer-Tropsch synthesis, require similar conditions.
  • the syngas flows to a guard bed reactor assembly, optionally having two guard bed reactors.
  • the syngas flows to a deoxo reactor.
  • the deoxo reactor removes excess oxygen from the reprocessed gas (e.g., syngas).
  • the system has a cooling system, which uses a cooling fluid, e.g., cooling water, that is flowed through cooling lines.
  • a cooling fluid e.g., cooling water
  • Other means of cooling for example direct air cooling, are also contemplated.
  • the collection unit 1640 also has a line that flows unreacted gas separated from the methanol to a tee-connector, where it is sent to hydrogen separation unit 1639, to a recycle loop or both.
  • the recycle loop has a compressor and a valve to feed the methanol back into the synthesis unit 1633.
  • the reciprocating engine 1814 partially combusts the predetermined mixture of flare gas and air to form syngas.
  • the syngas flows through heat exchangers and into a filter, e.g., a particulate filter.
  • the syngas flows to a guard bed reactor assembly, optionally having two guard bed reactors.
  • the syngas flows to a deoxo reactor.
  • the deoxo reactor removes excess oxygen from the reprocessed gas (e.g., syngas).
  • the system has a cooling system, which uses a cooling fluid, e.g., cooling water, that is flowed through cooling lines.
  • a cooling fluid e.g., cooling water
  • Other means of cooling for example direct air cooling, are also contemplated.
  • the syngas After leaving the deoxo reactor, the syngas flows to a heat exchanger to cool the gas.
  • the reprocessed gas e.g., syngas
  • a water removal unit e.g., a water knockout drum, demister, dryer, membrane, cyclone, desiccant or similar, where water is removed from the syngas.
  • the syngas upon leaving unit the water removal unit should have less than about 5% water by weight, less than about 2%, less than about 1% and less than about 0.1% water.
  • the now dry syngas is in the synthesis stage 1802.
  • the now dry syngas flows to an assembly that provides for the controlled addition of a hydrogen-rich gas into the now dry syngas.
  • the hydrogen is provided from hydrogen separation unit 1839.
  • the ratio-adjusted dry syngas leaves the assembly and flows to compressor 1832.
  • Compressor 1832 compresses the syngas to an optimal pressure as taught and disclosed in this specification, for use the synthesis unit 1833, which is optionally a two-stage unit with a first reactor unit 1833a and a second reactor unit 1833b.
  • Synthesis unit 1833 also has a recuperative heat exchanger.
  • the synthesis unit 1833 converts the ratio-adjusted dry syngas into a value-added product, e.g., methanol.
  • methanol flows into to heat exchanger (i.e., cooler) and then to a collection unit 1840.
  • the collection unit 1840 collects the condensed methanol and flows it through a line for sale, holding, or further processing.
  • the collection unit 1840 also has a line that flows unreacted gas separated from the methanol to a tee-connector, where it is sent to hydrogen separation unit 1839, to a recycle loop or both.
  • the recycle loop has a compressor and a valve to feed the methanol back into the synthesis unit 1833.
  • Stage 1802 has a line 1883 for taking depleted methanol from unit 1833b and sending it through heat exchanger 1820d .
  • the stage 1802 has a methanol desorber 1880 that has pump 1881.
  • Line 1882 for desorber 1880 flows methanol rich product to heat exchanger 1820g.
  • the preferred process uses a two- stage methanol synthesis reactor with reactive separation in the second stage (Rxtr 2) 1833b only.
  • the first stage (Rxtr 1 ) 1833a is generally far from equilibrium and does not warrant reactive separation.
  • the example shown in this figure is reactive absorption or membrane separation with a liquid sweep. Methanol is selectively removed from the reactor in situ resulting in a methanol-depleted gaseous stream containing primarily unreacted syngas and a methanol-rich absorbent stream.
  • the primary recycle loop is not used because of the improved single-pass conversion.
  • the methane-rich absorbent stream passes through a valve to reduce the pressure and desorb the methanol which is then condensed and sent to the product stream.
  • the absorbent now in a regenerated state, is pumped back to the synthesis pressure and recirculated to the reactor.
  • the pumping work for the absorbent is minimal compared to the syngas compressor work because the liquid absorbent is nearly incompressible.
  • the reactor could be a trickle bed or a membrane reactor with the liquid absorbent (sweep) on the permeate side of the membrane. Any methanol that does not partition into the absorbent is condensed out of the gas phase in a downstream separation step and combined with the methanol product stream.
  • the fuel-air mixture that is formed in the mixer is preferably rich, more preferably having an overall fuel/air equivalence ratio ( ⁇ J> or ER) greater than 1 , greater than 1 .5, greater than 2, greater than 3, from about 1 .5 to about 4.0, about 1 .1 to about 3.5, about 2 to about 4.5, and about 1 .1 to about 3, and greater values.
  • ⁇ J> or ER overall fuel/air equivalence ratio
  • the reciprocating engine 1914 partially combusts the predetermined mixture of flare gas and air to form syngas.
  • the syngas flows through heat exchangers and into a filter, e.g., a particulate filter.
  • the syngas flows to a guard bed reactor assembly, optionally having two guard bed reactors.
  • the syngas flows to a deoxo reactor.
  • the deoxo reactor removes excess oxygen from the reprocessed gas (e.g., syngas).
  • the system has a cooling system, which uses a cooling fluid, e.g., cooling water, that is flowed through cooling lines.
  • a cooling fluid e.g., cooling water
  • Other means of cooling for example direct air cooling, are also contemplated.
  • the syngas After leaving the deoxo reactor, the syngas flows to a heat exchanger to cool the gas.
  • the reprocessed gas e.g., syngas
  • a water removal unit e.g., a water knockout drum, demister, dryer, membrane, cyclone, desiccant or similar, where water is removed from the syngas.
  • the syngas upon leaving unit the water removal unit should have less than about 5% water by weight, less than about 2%, less than about 1 % and less than about 0.1 % water.
  • the now dry syngas is in the synthesis stage 1902.
  • stage 1902 the now dry syngas flows to an assembly that provides for the controlled addition of a hydrogen-rich gas from line into the now dry syngas.
  • the hydrogen is provided from hydrogen separation unit 1939.
  • the ratio-adjusted dry syngas leaves the assembly and flows to compressor 1932.
  • Compressor 1932 compresses the syngas to an optimal pressure as taught and disclosed in this specification, for use the synthesis unit 1933, which is optionally a two-stage unit with a first reactor unit 1933a and a second reactor unit 1933b.
  • Synthesis unit 1933 also has recuperative heat exchanger 1920e.
  • the synthesis unit 1933 converts the ratio-adjusted dry syngas into a value-added product, e.g., methanol.
  • methanol flows into to heat exchanger (i.e., cooler) and then to a collection unit 1940.
  • the collection unit 1940 collects the condensed methanol and flows it through a line for sale, holding, or further processing.
  • the collection unit 1940 also has a line that flows unreacted gas separated from the methanol to a tee-connector, where it is sent to hydrogen separation unit 1939, to a recycle loop or both.
  • the recycle loop has a compressor and a valve to feed the methanol back into the synthesis unit 1933.
  • Stage 1902 has a line 1983 for taking water-depleted methanol from unit 1933b and sending it through heat exchanger 1920d .
  • the stage 1902 has a line 1987 from unit 1833b that removes water-rich product.
  • the system 1900 is for the gas-to-liquids process with reactive separation of byproducts.
  • the process uses a two-stage methanol synthesis reactor with reactive separation in the second stage (Rxtr 2) 1933b only.
  • the first stage (Rxtr 1) 1833a is generally far from equilibrium and does not warrant reactive separation.
  • the example shown in this figure is membrane separation with a gaseous sweep. Water (a byproduct of CO2 hydrogenation to methanol) is selectively removed from the reactor 1833b (via line 1987) in situ resulting in a water-depleted gaseous stream containing primarily unreacted syngas and a water-rich sweep gas.
  • a primary recycle loop is not use because of the improved single-pass conversion.
  • regeneration of the sweep stream (e.g., air in this embodiment) is not performed.
  • the membrane reactor could use a polymeric or ceramic membrane material that is perm-selective to water and a sweep gas (e.g., air) on the permeate side of the membrane. Removing the water shifts the equilibrium towards the products.
  • the reverse water-gas shift reaction converts CO2 to CO, and so this approach also helps convert CO2 to more reactive CO. As such, this approach is especially attractive for CO2-rich syngas streams such as those produced from partial oxidation.
  • Methanol is condensed out of the gas phase in a downstream separation step and combined with the methanol product stream.
  • the system and process of FIG. 7 may have one or more of the devices and processes to reduce compressor work.
  • the system and process of FIG. 7 can have or use one or more of: (a) reducing the amount of nitrogen; (b) increasing back-pressure of the engine from standard 1 or 2 bar, to up to 5 bar; (c) use a turbo-expander to recover much of the compression work, thus lowering the cost, among other efficiencies, to operate a plant; and (d) utilizing an intensified synthesis loop to achieve acceptable methanol synthesis at lower overall pressure.
  • These devices and processes to reduce compressor work can be used in conjunction with the system and process of FIG. 7, as a part of (e.g., modular, integral, and combinations thereof) the system and process of FIG. 7, and combinations and variations of this manner of association.
  • the systems and processes utilize reactive separation of byproducts.
  • the process uses a two-stage methanol synthesis reactor with reactive separation in the second stage (Rxtr 2) only.
  • the first stage (Rxtr 1 ) is generally far from equilibrium and does not warrant reactive separation.
  • the example shown in this figure is membrane separation with a gaseous sweep. Water (a byproduct of CO2 hydrogenation to methanol) is selectively removed from the reactor in situ resulting in a water-depleted gaseous stream containing primarily unreacted syngas and a water-rich sweep gas.
  • the primary recycle loop may not be and preferably is not required because of the improved single-pass conversion.
  • regeneration of the sweep stream may not be and preferably is not required.
  • the membrane reactor could use a polymeric or ceramic membrane material that is perm-selective to water and a sweep gas (e.g., air) on the permeate side of the membrane. Removing the water shifts the equilibrium towards the products.
  • the reverse water-gas shift reaction converts CO2 to CO, and so this approach also helps convert CO2 to more reactive CO. As such, this approach is especially attractive for CO2-rich syngas streams such as those produced from partial oxidation.
  • Methanol is condensed out of the gas phase in a downstream separation step and combined with the methanol product stream. This system and process may have one or more of the devices and processes to reduce compressor work.
  • FIG. 8 there is shown an embodiment of a system and method for the conversion of flare gas into a value-added product.
  • the system 800 has a reformer stage 801 and a synthesis stage 802.
  • the system 800 has an air intake 810, that feeds air into a compressor 811 , which compresses the air.
  • the compressed air is fed through heat exchanger 820a into a mixer 813.
  • the system has a flare gas intake 884.
  • the flare gas flows through a heat exchanger 820b into the mixer 813.
  • the mixer 813 provides a predetermined mix of air and flare gas, as disclosed and taught in greater detail in this specification, to a reformer 814, which is a reciprocating engine.
  • the fuel-air mixture that is formed in mixer 813 is preferably rich, more preferably having an overall fuel/air equivalence ratio ( ⁇ J> or ER) greater than 1 , greater than 1 .5, greater than 2, greater than 3, from about 1 .5 to about 4.0, about 1 .1 to about 3.5, about 2 to about 4.5, and about 1 .1 to about 3, and greater values.
  • ⁇ J> or ER overall fuel/air equivalence ratio
  • oxygen can be added to the air.
  • Water or steam may also be injected into the mixture of air and fuel, or to air or fuel individually. From about 1 to about 20% (molar) water can be injected, from about 10 to about 15% (molar water), from about 5 to about 17% (molar) water, more than 5% (molar) water, more than 10% (molar) water, more than 15% (molar) water, and less than 25% (molar) water, water can be injected. Following oxygen enrichment, the combustion air can have from about 21% (molar) to about 90% (molar) oxygen.
  • “Air-breathing” reformers, and air breathing engines as used herein are understood to also include engines using air modified with the addition of water, oxygen or both.
  • the reciprocating engine 814 partially combusts the predetermined mixture of flare gas and air to form syngas.
  • the syngas flows through heat exchangers 820a, 820b and into a filter 815, e.g., a particulate filter.
  • the syngas flows to a guard bed reactor assembly 816, optionally having two guard bed reactors 816a, 816b.
  • the guard bed reactor 816 has materials, e.g., catalysts, that remove contaminates and other materials from the syngas that would harm, inhibit or foul later apparatus and processes in the system.
  • the guard bed reactor 816 may contain catalyst or other materials to remove sulfur (e.g., iron sponge, zinc oxide or similar) and halogenated compounds.
  • the syngas flows to a deoxo reactor 817.
  • the deoxo reactor 817 removes excess oxygen from the reprocessed gas (e.g., syngas) by oxidizing combustible compounds in the mixture such as methane, CO, and H2, where the oxygen is converted to water.
  • Catalyst for the deoxo reaction are platinum, palladium, and other active materials supported on alumina or other catalyst support materials.
  • the system 800 has a cooling system 850, which uses a cooling fluid, e.g., cooling water, that is flowed through cooling lines, e.g., 851 .
  • a cooling fluid e.g., cooling water
  • Other means of cooling for example direct air cooling, are also contemplated.
  • the syngas flows to heat exchanger 820c to cool the gas.
  • the reprocessed gas e.g., syngas
  • a water removal unit 818 e.g., a water knockout drum, demister, dryer, membrane, cyclone, desiccant or similar, where water is removed from the syngas.
  • the syngas upon leaving unit 818 should have less than about 5% water by weight, less than about 2%, less than about 1 % and less than about 0.1% water.
  • the now dry syngas is in the synthesis stage 802.
  • stage 802 the now dry syngas flows to an assembly 830.
  • Assembly 830 provides for the controlled addition of a hydrogen-rich gas from line 831 into the now dry syngas. In this manner the ratio of the syngas components can be adjusted and controlled to a predetermined ratio.
  • the hydrogen is provided from hydrogen separation unit 839.
  • the ratio-adjusted dry syngas leaves assembly 830 and flow to compressor 832.
  • Compressor 832 compresses the syngas to an optimal pressure as taught and disclosed in this specification, for use the synthesis unit 833.
  • the synthesis unit 833 is optionally a two-stage unit with a first reactor unit 833a and a second reactor unit 833b.
  • Synthesis unit 833 also has recuperative heat exchanger 820e.
  • the synthesis unit 833 converts the ratio-adjusted dry syngas into a value-added product, methanol.
  • the methanol flows into to heat exchanger (i.e., cooler) 820d.
  • the methanol flows to a collection unit 840.
  • the collection unit 840 collects the condensed methanol and flows it through line 841 for sale, holding, or further processing.
  • the syngas is compressed to a pressure of about 15 to about 100 bar and preferably 30-50 bar, and about 25 to about 80 bar, at least about 10 bar, at least about 25 bar and at least about 50 bar, and greater and lower pressures.
  • the temperature of the pressurized syngas is adjusted to a temperature of about 150 °C to about 350 °C and preferably 250 °C, about 200 °C to about 300 °C, about 250 °C to about 375 °C, greater than 125 °C, greater than 150 °C, greater than 200 °C, greater than 250 °C, greater than 350 °C, and less than 400 °C, and higher and lower temperatures.
  • methanol is produced using the overall reaction of syngas to methanol via reactions for hydrogenation of CO, hydrogenation of CO2, and reverse water-gas shift using actively cooled reactors, such as a heat-exchanged reactor or boiling water reactor, and a copper containing catalyst such as Cu/ZnO/AhOs or the like.
  • the characteristic length scale of the reactors used in this system are sufficiently small (e.g., micro-channel or mini-channels) that they can be shaped into unconventional shapes and topologies using new 3D printing techniques for metals and other high-temperature materials, thus allowing compact packaging and tight control over reaction conditions.
  • Other strategies for intensification of the downstream synthesis reactions can also be considered, such as selectively removing the product from the reactor in-situ, or in a closely coupled fashion, to shift the equilibrium-limited reaction to higher conversion. This process intensification may minimize the need for large recycle streams or allow the reaction to proceed at milder conditions (e.g., lower pressure) thereby increasing process safety margins and providing other benefits.
  • the ratio of H2/CO in the syngas produced by the engine can be tailored to the downstream conversion process.
  • the ideal H2/CO ratio is 2-3.
  • the maximum possible H2/CO ratio is desirable and can be enhanced by, for example, steam addition to promote the water-gas shift reaction.
  • the CO is not required by the downstream synthesis. As such, CO and CO2 byproducts can be collected, sequestered, stored or utilized for other purposes.
  • the collection unit 840 also has a line that flows gas separated from the methanol to a tee-connector 835, where it is sent to hydrogen separation unit 839, to a recycle loop or both.
  • the recycle loop has compressor 834 and valve 838 to feed the methanol back into the synthesis unit 833.
  • Hydrogen separation can be achieved by via membrane separation or pressure swing absorption (PSA) or the like in the hydrogen separation unit 839.
  • PSA pressure swing absorption
  • the remaining gas after hydrogen separation is sent through loop 890 and through heat exchanger 820f to turbo-expander 891 , where the gas is then sent to exhaust.
  • the turbo-expander generates power that offsets some of the compressor power requirements.
  • the reformer 814 is a spark ignition (otto cycle) reciprocating engine.
  • This system can be preferably operated as set forth in the T-S diagram of FIG. 13.
  • the reference points correspond to process conditions, i.e., state points, at those locations in the system of FIG. 8, and those process conditions are shown by corresponding reference points in FIG. 13.
  • the line from state point 84a’ to 84b’ represents a reduction in compression ratio that occurs in response to a more reactive flare gas fuel.
  • State point 85b relates to the syngas exiting the syngas reformer after the expansion of the turbocharger.
  • the expansion from 85 to 85b occurs within the turbocharger.
  • the starting specific entropy for this process is at points 81 , 82 (6.9 kJ/kg °C) and the final specific entropy point for this process is 89 (6.95 kJ/kg °C).
  • the difference between the start and final specific entropy is 0.05 kJ/kg °C.
  • the reformer 814 is a compression ignition (diesel cycle) reciprocating engine. This system can be preferably operated as set forth in the T-S diagram of FIG. 14.
  • the reference points correspond to process conditions, i.e., state points, at those locations in the system of FIG. 8, and those process conditions are shown by corresponding reference points in FIG. 14.
  • the line from state point 84a’ to 84b’ represents a reduction in compression ratio that occurs in response to a more reactive flare gas fuel.
  • State point 85b relates to the syngas exiting the syngas reformer after the expansion of the turbocharger. The expansion from 85 to 85b occurs within the turbocharger.
  • the starting specific entropy for this process is at points 81 , 82 (6.9 kJ/kg °C) and the final specific entropy point for this process is 89 (6.95 kJ/kg °C).
  • the difference between the start and final specific entropy is 0.05 kJ/kg °C.
  • the spark ignition (otto cycle) reciprocating engine and compression ignition (diesel cycle) reciprocating engine embodiment of the system and process of FIG. 8, have one or more of the devices and processes to reduce compressor.
  • the systems and processes of FIG. 8 can have or use one or more of: (a) reducing the amount of nitrogen; (b) increasing back-pressure of the engine from standard 1 or 2 bar, to up to 5 bar; (c) use a turbo-expander to recover much of the compression work, thus lowering the cost, among other efficiencies, to operate a plant; and (d) utilizing an intensified synthesis loop to achieve acceptable methanol synthesis at lower overall pressure.
  • These devices and processes to reduce compressor work can be used in conjunction with the systems and processes of FIG. 8, as a part of (e.g., modular, integral, and combinations thereof) the systems and processes of FIG. 8, and combinations and variations of this manner of association.
  • FIG. 10 there is shown an embodiment of a turbo-expander heat exchanger system for reducing the compressor work required for reformer-based hydrocarbon processing systems, such as gas-to-liquid systems.
  • the system 1000 has three stages, 1100, 1200, 1300. Each stage has compressor and turbine assembly and a heat exchanger.
  • Stage 1100 has compressor 1101 that is driven by turbine 1102 and a heat exchanger 1103.
  • Stage 1200 has compressor 1201 that is driven by turbine 1202 and a heat exchanger 1203.
  • Stage 1300 has compressor 1301 that is driven by turbine 1302 and a heat exchanger 1303.
  • a product 600 which typically can be tail gas that is separated out by the gas-to-liquid system, is feed into stage 1300.
  • the product 600 can have a pressure above 50 bar and a temperature less than 250 C.
  • the product 600 flows through stages 1300, 1200 and 1100 as shown in the figure.
  • Reactants 500 which can be the materials provided by the output of the reformer, e.g., syngas, is feed into stage 1100, and flows through stage 1200 and 1300 as shown in the figure exiting near 250 °C and 50 bar.
  • Graph 1000b shows the pressure, and pressure changes, of the product 600b and reactants 500b as they move through the stages 1100a, 1200a, 1300a.
  • Graph 1000c shows the temperature, and temperature changes, of the product 600c and reactants 500c as they move through the stages 1100a, 1200a, 1300a.
  • the 1 and 5 on the axis of graph 1000b indicate pressure in units of bar.
  • FIG. 10 has three stages, a single stage, two stages, four stages, five stages or more are contemplated.
  • the system 1000 can be an integral part of a gas-to-liquid system, such as the systems of FIGS 3, 4, 6, 7, or 8. It can be a separate module(s), e.g., skid mounted, that is operationally connected (e.g., pipes, valves, control systems) to the gas-to-liquid system.
  • the system 100 of FIG. 3 has a turbo-expander- compressor-heat exchanger system, such as shown for example in FIG. 10 as the compressor 132.
  • the product 600 in FIG. 10 is the tail gas from hydrogen separation unit 139.
  • the reactants 500 in FIG. 10 would be the ratio adjusted dry reprocessed gas (e.g., syngas) leaving assembly 830.
  • the high-pressure liquid and gaseous product streams are expanded through valves (or backpressure regulators) in a Joule-Thompson (substantially isenthalphic) expansion process.
  • auxiliary power is required for compression as there is not sufficient power for self-sufficiency.
  • the system 1600 of FIG. 4 has a turbo-expander- compressor-heat exchanger system, such as shown for example in FIG. 10 as the compressor 1632.
  • the product 600 in FIG. 10 is the tail gas from hydrogen separation unit 1639.
  • the reactants 500 in FIG. 10 would be the ratio adjusted dry reprocessed gas (e.g., syngas) feeding compressor 1632.
  • the system 800 of FIG. 8 has a turbo-expandercompressor-heat exchanger system, such as shown for example in FIG. 10 as the compressor 832.
  • the product 600 in FIG. 10 is the tail gas from hydrogen separation unit 839.
  • the reactants 500 in FIG. 10 would be the ratio adjusted dry reprocessed gas (e.g., syngas) leaving assembly 830.
  • the turbo-expander 891 may not be used in this embodiment, or still may be used for excess tail gas that is not utilized for the operation of the turbo-expander-compressor-heat-exchanger of FIG. 10.
  • the system and method utilize a nominally air-breathing engine that is operated under rich conditions and having means to produce pressurized syngas.
  • the syngas can have pressure exiting the engine reformer greater than 1 bar, greater than 2 bar, greater than 3 bar, greater than 4 bar, greater than 5 bar, from about 2 bar to about 5 bar, from about 3 bar to about 5 bar.
  • the syngas exiting the water knockout and entering the compressor is at temperature of about 50 °C, from 40 °C to 60°C, or higher or lower.
  • the system and method utilize a nominally air-breathing engine that is operated under rich conditions and having means to produce pressurized syngas.
  • the system further has a means to reduce the amount of nitrogen, such as an oxygen enrichment unit, or an air separation unit, or a nitrogen rejection unit from the syngas. In this system for example where the nitrogen is reduced by 10% or 20% or more.
  • the system and method utilize a nominally air-breathing engine that is operated under rich conditions and having means to produce pressurized syngas.
  • the system further has a turbo-expander or expansion turbine, such as a turbine-driven shaft using excess high pressure gas that is expanded to produce work.
  • a turbo-expander or expansion turbine such as a turbine-driven shaft using excess high pressure gas that is expanded to produce work.
  • the turbine inlet is at about 50 bar and the turbine exit is at about 3 bar.
  • the system and method utilize a nominally air-breathing engine that is operated under rich conditions and having means to produce pressurized syngas.
  • the system further has an intensified synthesis loop for methanol synthesis at lower pressures, such as via reactive separation of the products or by-products. In this system for example where the single-pass methanol synthesis conversion increases by 5% or 10% or more or less.
  • the exhaust backpressure of the engine reformer is increased to reduce the downstream syngas compression requirements. It is anticipated that the exhaust pressure could reasonably be increased from typical values near atmospheric pressure (ca. 1 bar) up to 5 bar or higher. Considering that the downstream synthesis pressure is set nominally to 50 bar, increasing the engine reformer exhaust backpressure reduces the overall pressure ratio for syngas compression and reduces the compressor work (kJ/kg) or power (kW). Because the engine reformer is self- sustaining, increasing the exhaust backpressure does not directly impact upstream compression work. Increasing the backpressure does however impact the volumetric efficiency of the engine and the net brake power of the engine. These trades suggest an optimal backpressure at some intermediate value. The backpressure is determined by the resistance to flow of the downstream processes. Various engine modifications (e.g., turbocharging the engine reformer inlet air, modification of the engine valve timing to reduce or eliminate valve overlap) are anticipated to maintain acceptable engine performance with elevated exhaust backpressure.
  • engine modifications e.g., turbocharging the engine reformer inlet air, modification of the engine valve timing to reduce
  • reactive separation is used to selectively remove the products (or byproducts) of the reaction to shift the equilibrium towards the products according to Le Chatelier’s principle.
  • the products e.g., methanol
  • byproducts e.g., water
  • Close-coupled means in a loop without an expensive and energy intensive downstream separation.
  • the separation can be accomplished through adsorption, absorption, membrane separation, distillation, or the like.
  • the reactive separation enables good single-pass conversion and reduces or eliminates the need for an energy- intensive and capital-intensive separation and recycle loop.
  • the adsorption separation can use a variety of adsorbents (e.g., silica- alumina) that are selective to methanol or water and various adsorption equipment (e.g., packed beds, moving beds, simulated moving beds).
  • adsorbents e.g., silica- alumina
  • various adsorption equipment e.g., packed beds, moving beds, simulated moving beds.
  • the absorption separation can use a variety of absorbents (e.g., tetraethylene glycol dimethyl ether, commonly TGDE or tetraglyme, or squalane) in various absorption equipment (e.g., trickle beds, bubble columns).
  • Membrane separations can use a variety of polymeric materials (e.g., sulfonated tetrafluoroethylene based fluoropolymer-copolymer such as Nafion®) or ceramic materials (e.g., zeolites) to selectively remove methanol or water in a variety of membrane module configurations (e.g., hollow fiber bundles, spiral wound, plate frame).
  • the membrane separation can use a sweep stream on the permeate side that is a gas (e.g., air) or liquid (e.g., TGDE).
  • Reactive distillation (RD) can also be used selectively remove methanol from the reactants based on differences in volatility.
  • the RD can use various improved (e.g., dividing wall column distillation) or hybrid (e.g., extractive distillation with TGDE or the like) distillation approaches.
  • a turbo-expander is used to generate shaft work to partially offset the compression work requirements.
  • the turbo-expander can export shaft work directly to another rotating machine (e.g., compressor) or generate electrical power or pneumatic/hydraulic pressure that can be used elsewhere in the process (e.g., to drive compressors or pumps).
  • a heat exchanger can beneficially recover heat from other parts of the process (e.g., the hot syngas stream) to increase the enthalpy of the stream going to the turbo-expander and increase the amount of work produced by the turbo-expander.
  • recuperative heat exchanger can use either direct heat exchange or indirect heat exchange through some other heat transfer medium (e.g., steam, or heat transfer fluid). If an indirect heat transfer loop is used, optionally the loop can incorporate thermal energy storage (e.g., as sensible heat in tank of the heat transfer medium or latent heat in a phase change material).
  • an integrated turbo-expander is envisioned with inter-stage heat exchange as part of a multi-stage compressor with the turbine directly driving the compressor in each stage.
  • the coupled turbine-compressor can be an industrial compressor-expander (“compander”) or automotive turbocharger.
  • a small-scale plant targeting 3,000,000 scfd (standard cubic feet per day) of inlet gas.
  • the size of such a plant could vary from 50,000 scfd to 15,000,000 scfd.
  • the plant is incorporated into one or more modular, interconnected skids or containers that are built at a central fabricator shop location and then installed at a field location.
  • the system comprises a small number of modules that when connected at site form an integrated system.
  • the modular nature of the assembly enables application to remote locations under a range of inlet gas feed volumes, with a minimum of field labor.
  • the modular nature further improves flexibility to deploy or redeploy these assets, reduces initial capital outlay and project financial risks, allows matching of the process throughput to the flare gas supply, and reduces time-to-market by allowing module fabrication and site preparation to occur in parallel.
  • the plant has one or more of (a) reducing the amount of nitrogen; (b) increasing back-pressure of the engine from standard 1 or 2 bar, to up to 5 bar; (c) use of a turbo-expander to recover much of the compression work, thus lowering the cost, among other efficiencies, to operate a plant; and (d) utilizing an intensified synthesis loop to achieve acceptable methanol synthesis at lower overall pressure.
  • FIGS 15, and FIGS. 15A to 15C there is shown a schematic of a system and process system utilizing the embodiments of Examples 10 and 13 in a gas-to-liquid system 1400.
  • the system and process 1400 has a reformer subsystem 1440, a methanol subsystem 1460 and a turbo-expander (e.g., turbo compressor) subsystem 1480.
  • An enlarged view of the reformer subsystem 1440, (and other components) are shown in FIG. 15A.
  • An enlarged view of the methanol subsystem 1460 is shown in FIG. 15B.
  • An enlarged view of the turbo-expander subsystem 1480 is shown in FIG. 15C.
  • Reformer subsystem 1440 has an air intake 1445 for receiving a flow of air and a hydrocarbon gas intake 1446 (e.g., flare gas intake) for receiving a flow of hydrocarbon gas (e.g., flare gas).
  • the reformer subsection has a supercharger 1441 , an air preheater 1442, an air breathing reformer 1449, a mixer 1444 and a desulfur unit 1447.
  • a DeOxo unit 1433 on the line from the reformer subsystem 1440 to the turbo-expander subsystem 1460. Arrows show the direction of flow in the system and process.
  • methanol syntheses subsystem 1460 has a compressor 1461 , mixer 1462, CO2 membrane unit 1463, and hydrogen membrane unit 1464.
  • the subsystem 1460 has reactor unit 1469, heat exchanger 1474.
  • the subsystem 1460 also has heat exchangers 1471 , 1472 and methanol condenser 1465, and methanol degasser 1466.
  • the system has tail gas oxidizer unit 1467 that air in feed 1468, and an associated heat exchanger 1475.
  • the system 1460 has compressor 1473, heat exchanger 1474, and mixer 1470.
  • the system has arrows show the direction of flow in the system and process.
  • the turbo-expander subsystem 1480 has a heat exchanger 1481 , a heat exchanger 1481 and a knock-out drum 1483.
  • the subsystem 1480 has a compressor 1484 and a turbine 1485.
  • the turbine (turbo-expander) 1485 also has associated with it a balancing valve 1486 and a mixer 1487.
  • the subsystem 1480 has a heat exchanger 1488, and a water knock-out drum 1439.
  • the subsystem 1480 has a compressor 1490 and turbine (turbo-extractor) 1493, which has a balancing valve 1491 and a heat exchanger 1492 associated with it.
  • the subsystem 1480 also has a splitter 1494, a heat exchanger 1495, a heat exchanger 1496 and a water knockout drum 1497.
  • the system has arrows show the direction of flow in the system and process.
  • This system utilizes high-pressure stream from the chemical process and thermal energy (heat) available in the process to create shaft work via turboexpanders.
  • the shaft work drives the initial compression system for the incoming process stream. Additional turbine work is generated by the addition of reheat between stages on the turbine side. Compression work is reduced by intercooling between stages of compression. Individual bypass (wastegate) control valves are used for turbocompressor control.
  • the outlet pressure of the initial compression system is matched to the outlet pressure of the retentate (tail gas) from the hydrogen separation unit, allowing the streams to be combined into a single compression device to raise the pressure to pressure needed for the methanol process.
  • this turbo-compressor system reduces the external shaft power, such as that provided by an electric motor, from 98 kW e to 60 kW e .
  • the condensing temperature of the process streams is raised from 30°C to 60°C, resulting in reduction of chiller load from 258 kWth to 20 kWth.
  • the various embodiments of devices, systems, activities, methods and operations set forth in this specification may be used with, in or by, various processes, industries and operations, in addition to those embodiments of the figures and disclosed in this specification.
  • the various embodiments of devices, systems, methods, activities, and operations set forth in this specification may be used with other processes industries and operations that may be developed in the future; with existing processes industries and operations, which may be modified, in-part, based on the teachings of this specification; and with other types of gas recovery and valorization systems and methods.
  • the various embodiments of devices, systems, activities, methods and operations set forth in this specification may be used with each other in different and various combinations.
  • the configurations provided in the various embodiments of this specification may be used with each other.
  • the components of an embodiment having A, A’ and B and the components of an embodiment having A”, C and D can be used alone or with each other in various combination, e.g., A, C, D, and A, A”, C, D, and A’, B, and D, etc., in accordance with the teaching of this specification.
  • the scope of protection afforded the present inventions should not be limited to a particular embodiment, configuration or arrangement that is set forth in a particular embodiment, example, or in an embodiment in a particular figure.

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EP23747922.5A 2022-01-28 2023-01-28 Systeme, vorrichtungen und verfahren zur eingangs- und ausgangsdruckverwaltung von reformern für luftatmungsmotoren Pending EP4469393A4 (de)

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US202263304463P 2022-01-28 2022-01-28
US202263304471P 2022-01-28 2022-01-28
US202263304475P 2022-01-28 2022-01-28
US17/746,942 US11649201B2 (en) 2021-05-18 2022-05-17 Autonomous modular flare gas conversion systems and methods
US17/953,056 US20230212098A1 (en) 2021-09-26 2022-09-26 Modular Methanol Upgrading Hub Methods and Systems
US17/984,126 US20230279802A1 (en) 2021-11-09 2022-11-09 Pre-Chamber Combustion Systems and Methods
PCT/US2023/061523 WO2023147525A2 (en) 2022-01-28 2023-01-28 Systems, devices and methods for input and output pressure management of air breathing engine reformers

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EP4469398A1 (de) 2024-12-04
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CA3243239A1 (en) 2023-08-03
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EP4469398A4 (de) 2026-01-28
CA3243250A1 (en) 2023-08-03
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AU2023211693A1 (en) 2024-08-08

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