WO2012006478A2 - Installation de synthèse de méthanol mobile autonome - Google Patents

Installation de synthèse de méthanol mobile autonome Download PDF

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Publication number
WO2012006478A2
WO2012006478A2 PCT/US2011/043270 US2011043270W WO2012006478A2 WO 2012006478 A2 WO2012006478 A2 WO 2012006478A2 US 2011043270 W US2011043270 W US 2011043270W WO 2012006478 A2 WO2012006478 A2 WO 2012006478A2
Authority
WO
WIPO (PCT)
Prior art keywords
methanol
self
carbon dioxide
mobile
hydrogen gas
Prior art date
Application number
PCT/US2011/043270
Other languages
English (en)
Other versions
WO2012006478A9 (fr
WO2012006478A3 (fr
Inventor
Steven Phillip Atkins
Brandon Doss
Original Assignee
Arizona Board Of Regents, Acting For And On Behalf Of, Northern Arizona University
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
Application filed by Arizona Board Of Regents, Acting For And On Behalf Of, Northern Arizona University filed Critical Arizona Board Of Regents, Acting For And On Behalf Of, Northern Arizona University
Publication of WO2012006478A2 publication Critical patent/WO2012006478A2/fr
Publication of WO2012006478A9 publication Critical patent/WO2012006478A9/fr
Publication of WO2012006478A3 publication Critical patent/WO2012006478A3/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00018—Construction aspects
    • B01J2219/00022—Plants mounted on pallets or skids

Definitions

  • the invention relates to the field of sustainable energy, and the production of methanol, which is useful as a fuel and as a basic chemical.
  • Methanol and compounds which may be made from methanol, such as di-methyl ether, synthetic gasoline and plastics, may be used as direct replacements of their fossil fuel derived equivalents.
  • the present invention relates to a portable, self-contained system and process for producing methanol from carbon dioxide and hydrogen gas.
  • the system is designed to be portable, so that it may be readily transported to and commissioned at various sites wherein carbon dioxide and/or hydrogen gases are produced and/or collected, and those gases reacted to form methanol.
  • the system of the invention is transported to a site where it is permanently or temporarily installed and commissioned (placed into operation).
  • the system of the invention is designed so that various organizations and business establishments could have the system easily and quickly delivered and set up into an operative sate on their premises, to utilize and process into methanol excess gases that may be available at that premises for various reasons.
  • breweries which produce carbon dioxide as a result of the fermentation process in which beer is produced often have a wish to dispose of the carbon dioxide in an environmentally- friendly manner.
  • the system of the present invention provides a way for breweries to readily have a methanol synthesis system installed on or near the brewery premises, to convert process to methanol excess carbon dioxide captured in the fermentation.
  • the invention is a process and apparatus for synthesizing carbon-neutral fuels derived from captured (and preferably concentrated) atmospheric carbon dioxide and hydrogen.
  • the hydrogen gas is ideally obtained from hydrolysis of water and via use of renewable electricity.
  • the system of the invention produces methanol liquid, which is a carbon-neutral transportation fuel, and can be burned in most existing vehicles without modification.
  • the primary synthesis product is methanol, an alcohol with chemical and physical properties that are nearly identical to ethanol.
  • Methanol can be blended with gasoline up to 20% (M20) and burned in any unmodified internal combustion engine or at blends up to 85% (M85) in flex fuel vehicles. While methanol can be used directly as an automotive fuel, the invention can also include a means to further process methanol into di-methyl ether (DME), an excellent diesel fuel and propane substitute, synthetic gasoline and even carbon-negative plastics such as ethylene and propylene.
  • DME di-methyl ether
  • FIGURE 1 is a schematic representation of a process and device according to a preferred embodiment of the invention using a recirculating loop.
  • FIGURE 2 is a schematic representation of a process and device according to an embodiment of the invention without a recirculating loop.
  • FIGURE 5 is a graphical representation of the space-time yield
  • the device of the invention is designed to be self-contained, easily transportable, and may be operated at existing sites that emit carbon dioxide (for example, fermentation plants, breweries, etc.) and/or sites with abundant (renewable), low cost electricity, which may be used to disassociate water in order to obtain the requisite hydrogen.
  • the device of the invention consumes carbon dioxide from the atmosphere or carbon dioxide destined to be emitted into the atmosphere (e.g., from smokestacks, fermentation processes, etc.), water, and electricity only. Its only outputs are methanol, water, and heat, but further processing may convert methanol to DME, gasoline and/or plastics.
  • the portable methanol synthesis plant of the invention is capable of producing a renewable, carbon-neutral, liquid transportation fuel that can be used in all gasoline engines.
  • the invention provides carbon-emitting entities with a new way to sequester carbon dioxide into a valuable product, rather than permitting it to vent to the atmosphere.
  • the invention has the capability to significantly increase the alcohol fuel production capacity of the industry at only a modest capital investment.
  • the invention is designed to operate at various scales, depending on the size of the carbon dioxide and/or hydrogen source and desired methanol output.
  • the smallest, economically viable plant size may be 12,000 gal/yr of methanol production.
  • the entire system is essentially pre- assembled on a platform or some other movable structure, so that once the system is transported to the site where it will be commissioned (operated), very little further assembly will be required to render the system operational.
  • Components may be compartmentalized for easy transport by truck, and for "plug and play" operation at fermentation sites or other sites with a carbon dioxide and/or hydrogen source.
  • the system of the invention is optionally equipped with a storage tank for collecting the methanol produced.
  • the storage tank may be unitary to the system, i.e., incorporated into the system delivered to the site, or it may be external to the system.
  • hoses, tubing and/or piping composed of material that is inert (non- reactive to and non-dissolvable by) to methanol is attached to the exit portal of the system of the gas-liquid separator component of the system, and liquid methanol is collected in the storage tank as it is drawn off from the system.
  • the system of the invention is mobile and transportable, meaning that it can readily be prefabricated and delivered to a site where it is intended to be used, with minimal set-up materials, parts and labor required.
  • no further set-up is required other than providing a source of power such as electricity or a battery to power the components of the system (such as the heater and pressurizing equipment), and to open valves to cause the starting materials (hydrogen and carbon dioxide gases) to flow through the system for reaction in the synthesis reactor.
  • the transportability of the system of the invention is made possible by any means by which most or all of the components of the system can be delivered to the site of operation already assembled together in a single package.
  • the system can be packaged in a shipping container, with the various components actually secured to one or more inner surfaces of the container.
  • the system can be preassembled on a platform that can be placed on the floor of the container.
  • Yet another alternative is to secure the preassembled system onto a wheeled platform, or build the system onto a wheeled platform; in either case, the system can be permanently or removably (temporarily) secured to the wheeled platform.
  • a non limited example of a wheeled platform is a flat bed trailer.
  • Still yet another alternative is to use a trailer having sides and a roof in place of a flat bed trailer.
  • Yet another alternative is to incorporate the system into a truck or other self-propelled vehicle.
  • the system may include a power generating device, such as a generator, for use in powering the system in place of using electricity or for use as an emergency backup should the main source of power fail.
  • a power generating device such as a generator
  • An embodiment of a device of the invention comprises five (5) main components or systems, as follows: a carbon dioxide recovery system, a gas recirculation system, a heat-exchanging system, a synthesis reactor, and a distillation system.
  • the synthesis reactor is provided with a catalyst, preferably a fixed-bed catalyst, to catalyze the reaction between the hydrogen and carbon dioxide gases to form methanol.
  • catalysts which are preferred include Cu/Zn catalysts, particularly Cu/Zn/ A1 2 0 3 .
  • the device further includes a mechanism or loop for recirculating unreacted carbon dioxide and hydrogen gas that exit the methanol synthesis reactor, so that these unreacted gases are transported back into the methanol synthesis reactor as starting materials for the synthesis of methanol.
  • the mechanism for recirculating includes pipes and pumps, as well as pressure regulators and check valves to facilitate the return of unreacted CO 2 and 3 ⁇ 4 to the synthesis reactor.
  • Figure 1 is a schematic illustration of an embodiment of the invention including a recirculating loop.
  • Figure 2 is a schematic illustration of a methanol synthesis device without the recirculating loop.
  • the device further comprises a hydrogen electrolyzer system for hydrolyzing water (such as with electricity) to cause it to break into hydrogen gas and oxygen gas.
  • a hydrogen electrolyzer system for hydrolyzing water (such as with electricity) to cause it to break into hydrogen gas and oxygen gas.
  • the hydrogen gas produced thereby is then used in the methanol synthesis device and process of the invention.
  • Components may be compartmentalized for easy transport by truck, and for plug-and-play operation at fermentation sites or other sites with a CO 2 and/or hydrogen/electricity source.
  • the conversion of carbon dioxide to methanol is estimated to be 95% or greater, and product purity is estimated to be 99.5% or greater.
  • the synthesis reactor typically operates in the range of about 1400 to about 1800 psi.
  • One typical operating condition would be about 1400 psi at about 240 °C.
  • the synthesis reactor is operated at 1800 psi at 240 °C.
  • the cylindrical reactor was constructed in- house from 316SS with 12 inches length and an internal diameter of 1 inch. All pressurized gas lines were 316SS 0.25 inch o.d. tubing and sealed with Swagelok fittings. Gas flow rates were regulated using Brooks 5850 mass flow controllers, which were calibrated with a certified mass flow meter from Alicat Scientific. Reactor pressure was maintained by a back pressure regulator monitored via a pressure transducer with digital display. The reactor temperature was maintained by an external, electrical heating block and a PID temperature controller. The catalyst bed temperature was measured during reactions using a type K thermocouple positioned within the reactor itself, near the center of the catalyst bed.
  • Figure 2 shows a schematic of the reactor system described here.
  • Synthesis products were purified by simple distillation to determine conversion efficiency, reported as molar CO 2 conversion and space-time yield (STY).
  • Sample distillates were first analyzed by FT-IR to confirm methanol as the major product, then by capillary gas chromatography to identify and to quantify any byproducts that may be present in the finished sample.
  • the FT-IR was a Varian Excalibur 3100 with a single bounce Pike ATR accessory.
  • the two gas chromatographs used for purity analysis were a Varian Saturn 2100T for identification of byproducts by mass spectrometry and a Shimadzu GC-14A with a flame ionization detector for quantification of byproducts.
  • the reactor exhaust stream was analyzed by FT-IR spectroscopy to determine the amount of carbon monoxide (CO) that was formed.
  • the synthesized methanol was analyzed for purity and presence of byproducts by capillary gas chromatography. Following simple distillation, 1.0 ⁇ ., of product methanol was injected onto a DB-5 GC column. Comparison was made to reagent grade methanol (Fisher Scientific) and to a calibration solution made of reagent methanol spiked with 0.01% (v/v) each of ethanol, isopropanol, isopentanol, and 0.05% (v/v) 1-butanol as an internal standard. For quantitative analysis, the synthetic methanol was also spiked with 0.05% (v/v) 1-butanol as an internal standard prior to injection.
  • FIG. 6 Representative chromatograms ( Figure 6) show the presence of 6 minor byproducts in the distillate methanol that, after quantification, represent a total concentration less than 0.05% (v/v).
  • the trace impurities were identified as ethanol, isopropanol, 1-propanol, 2-butanol, 1-butanol, and 2-methyl-l-propanol, all of which are acceptable byproducts that should have little or no effect on combustion properties or engine performance when used in modern vehicles.
  • H 2 conversion calculated as molar ratio of methanol produced to total 3 ⁇ 4 flow through rreeaaccttoorr..
  • bb CC00 22 ccconversion calculated as molar ratio of methanol produced to total CO 2 flow through reactor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un système et un procédé portable, autonome pour produire du méthanol à partir de dioxyde de carbone et de gaz d'hydrogène. Le système est conçu pour être portable, de sorte qu'il puisse être aisément transporté vers et mis en œuvre à différents sites dans lesquels des gaz de dioxyde de carbone et/ou hydrogène sont produits et/ou collectés, et ces gaz réagissent pour former du méthanol. Dans un mode de réalisation préféré, le système de l'invention est transporté à un site où il est installé de façon permanente ou temporaire et mis en fonctionnement.
PCT/US2011/043270 2010-07-07 2011-07-07 Installation de synthèse de méthanol mobile autonome WO2012006478A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36223910P 2010-07-07 2010-07-07
US61/362,239 2010-07-07

Publications (3)

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WO2012006478A2 true WO2012006478A2 (fr) 2012-01-12
WO2012006478A9 WO2012006478A9 (fr) 2012-03-01
WO2012006478A3 WO2012006478A3 (fr) 2014-03-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9027566B2 (en) 2010-10-15 2015-05-12 Celanese Acetate Llc Apparatuses, systems, and associated methods for forming porous masses for smoke filter
US9380807B2 (en) 2013-06-28 2016-07-05 Celanese Acetate Llc Modified filter rod feeding trays for porous masses
US9386803B2 (en) 2010-01-06 2016-07-12 Celanese Acetate Llc Tobacco smoke filter for smoking device with porous mass of active particulate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013111897B4 (de) 2013-10-29 2020-10-22 Karlsruher Institut für Technologie Anlage zur Synthese von Kohlenwasserstoffen aus Synthesegas
EP3759289A4 (fr) 2018-03-02 2021-12-01 Modular Plant Solutions LLC Système structural modulaire d'installation de traitement

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0933251A2 (fr) * 1998-01-28 1999-08-04 Heinrich Torwesten Spedition Véhicule de transport, particulièrement pour l'industrie de la bière et de la brasserie
US20030037487A1 (en) * 2001-07-06 2003-02-27 Amendola Steven C. Portable hydrogen generator
US20040162357A1 (en) * 2001-05-30 2004-08-19 Davy Process Technology Limited Pre-converter for methanol synthesis
US20070254966A1 (en) * 2006-05-01 2007-11-01 Lpp Combustion Llc Integrated system and method for production and vaporization of liquid hydrocarbon fuels for combustion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0933251A2 (fr) * 1998-01-28 1999-08-04 Heinrich Torwesten Spedition Véhicule de transport, particulièrement pour l'industrie de la bière et de la brasserie
US20040162357A1 (en) * 2001-05-30 2004-08-19 Davy Process Technology Limited Pre-converter for methanol synthesis
US20030037487A1 (en) * 2001-07-06 2003-02-27 Amendola Steven C. Portable hydrogen generator
US20070254966A1 (en) * 2006-05-01 2007-11-01 Lpp Combustion Llc Integrated system and method for production and vaporization of liquid hydrocarbon fuels for combustion

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9386803B2 (en) 2010-01-06 2016-07-12 Celanese Acetate Llc Tobacco smoke filter for smoking device with porous mass of active particulate
US9027566B2 (en) 2010-10-15 2015-05-12 Celanese Acetate Llc Apparatuses, systems, and associated methods for forming porous masses for smoke filter
US9138017B2 (en) 2010-10-15 2015-09-22 Celanese Acetate Llc Apparatuses, systems, and associated methods for forming porous masses for smoke filter
US9149069B2 (en) 2010-10-15 2015-10-06 Celanese Acetate Llc Apparatuses, systems, and associated methods for forming porous masses for smoke filter
US9179708B2 (en) 2010-10-15 2015-11-10 Celanese Acetate Llc Apparatuses, systems, and associated methods for forming porous masses for smoke filter
US9380807B2 (en) 2013-06-28 2016-07-05 Celanese Acetate Llc Modified filter rod feeding trays for porous masses

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WO2012006478A9 (fr) 2012-03-01
WO2012006478A3 (fr) 2014-03-20

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