WO1992002448A1 - Conversion de methane et de dioxyde de carbone a l'aide du rayonnement de micro-ondes - Google Patents

Conversion de methane et de dioxyde de carbone a l'aide du rayonnement de micro-ondes Download PDF

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Publication number
WO1992002448A1
WO1992002448A1 PCT/US1991/004622 US9104622W WO9202448A1 WO 1992002448 A1 WO1992002448 A1 WO 1992002448A1 US 9104622 W US9104622 W US 9104622W WO 9202448 A1 WO9202448 A1 WO 9202448A1
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WO
WIPO (PCT)
Prior art keywords
metal
methane
carbon dioxide
plasma
initiator
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Application number
PCT/US1991/004622
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English (en)
Inventor
William J. Murphy
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Exxon Research And Engineering Company
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 Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Publication of WO1992002448A1 publication Critical patent/WO1992002448A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations

Definitions

  • This invention relates to a method for converting methane and carbon dioxide to carbon mono ⁇ xide and hydrogen using microwave radiation.
  • Microwave energy has been used to convert methane to other hydrocarbons.
  • U.S. Patent 4,574,038 discloses that methane can be con ⁇ verted to ethylene and hydrogen in a batch process at pressures of from 0.3 to 1 atmosphere by subjecting the methane to microwave radiation in the presence of a metal powder catalyst.
  • Another example of methane conversion using microwave energy is disclosed in U.S. Patent 3,663,394.
  • This invention concerns the manufacture of synthesis gas (carbon monoxide and hydrogen) from methane and carbon dioxide. More specifically, methane and carbon dioxide can be converted into synthesis gas (i.e. CO + nH2 where n is a function of feed composi ⁇ tion) by irradiating the methane/carbon dioxide mixture with microwave radiation in the presence of at least one elongated plasma initiator that is capable of ini ⁇ tiating an electric discharge in an electromagnetic field.
  • the plasma initiator will comprise a plurality of elongated metal wire seg ⁇ ments arranged in close proximity to one another.
  • This invention requires the presence of methane, carbon dioxide, at least one elongated plasma initiator capable of initiating an electric discharge in an electromagnetic field, and a source of microwave energy.
  • the methane and carbon dioxide may be pure or mixed with other hydrocarbons (e.g.. , methane may be a component of natural gas) , or both may be components of gas streams from a gas producing well.
  • Non-hydrocar ⁇ bons e.g.. H2O, H2S, N2, H2, etc.
  • Both can be added to the reaction zone separately or as a mixture.
  • the plasma initiator may be essentially any material capable of accumulating an electric charge when placed in an electromagnetic field and then dissipating the charge (or initiating an electric discharge) , for example, by ionizing a gas environment.
  • This includes metal initiators, non-metal initiators (including semi-conductors) , and composites of metal and non-metal initiators.
  • composite is meant to include mixtures (or combinations) of metals and non-metals.
  • suitable metal initiators are tungsten, iron, nickel, copper, their alloys, or mixtures thereof.
  • Preferred metal initia ⁇ tors are tungsten, iron, or mixtures thereof, with iron being particularly preferred.
  • non-metal initiators examples include carbon, alumina, manganese dioxide, magnetite, nickel oxide (e.g. NiO) , iron oxide (e.g. F ⁇ 3 ⁇ 4) , calcium aluminate, cobalt oxide, chromium nitride, iron sulfide (e.g. FeS2, Fe ⁇ __ x S) , copper sulfide (e.g. CUS2) , or mixtures thereof.
  • Calcium aluminate, carbon, iron oxide, or their mixtures are preferred non-metal initiators, with carbon being particularly preferred.
  • Silica is not a suitable non-metal initiator. However, silica composited with a metal initiator or another non-metal initiator would be a suitable plasma initiator.
  • methane/carbon dioxide conversion can be effected using onl j>ne plasma initiator, conversion is enhanced if than one ( ⁇ .g. , 6 or more) plasma initiators are used.
  • a plurality of plasma initiators are used.
  • the plasma initiator will comprise a plurality of metal wire segments.
  • Each plasma initiator should be of at least a minimum length that is sufficient to initiate an electric discharge when placed in an electromagnetic field. However, the precise minimum length of each initiator may vary with the frequency of the microwave source as well as the geometry of the reaction zone and of the initiator.
  • a minimum distance should be maintained between each initiator to facilitate dissipation of the electric charge.
  • the minimum distance will vary depending upon the frequency of the microwave source. As an example, the minimum distance should be at least about 0.25 cm, preferably at least about 0.5 cm, for a frequency of 2.45 GHz.
  • the plasma initiators should be elongated, but may be formed, combined, or bent in any convenient shape (e.g., straight, helix, spiral, and the like). Preferably, the initiators should be formed such that there are points or sharp edges at the ends or on the surface of the initiators. Particulate powders are not suitable plasma initiators.
  • the plasma initiators may be stationary within the reaction zone or they may be in motion.
  • the motion can result from the initiators being fluidized by a gas (e.g. the methane feedstock) or by other means (e.g. an external magnetic field gradient) .
  • a gas e.g. the methane feedstock
  • other means e.g. an external magnetic field gradient
  • the frequency of the microwave source can vary broadly.
  • the microwave energy will have a frequency of at least 0.3 GHz, with frequencies centered around 0.915, 2.45, 5.80, or 22.0 GHz being presently preferred in North America; particularly frequencies centered around 0.915, 2.45, or 5.80 GHz; especially frequencies centered around 0.915 or 2.45 GHz.
  • the microwave energy used in this invention may be continuous or pulsed. If pulsed, the duration of on-time pulses can vary broadly, but typically will range from about 1 nanosecond to about 20 seconds, preferably from about 1 millisecond to about 10 sec ⁇ onds, and most preferably from about 0.01 to about 0.2 seconds.
  • the duration of off-time rests can vary broadly as well, but typically will range from about 1 nanosecond to about 100 seconds, preferably from about 0.003 to about 60 seconds, and most preferably from about 0.3 to about 5 seconds. This invention can be practiced at any convenient temperature and pressure, including ambient conditions.
  • a methane/carbon dioxide mixture (1:1 mole ratio) flowing at 20 ml/minute (milliliters/minute) at atmospheric pressure was contacted with 1.5 gm of tungsten wire (about 0.03 inches in diameter and cut into 45 mm lengths) in a reactor fabricated from WR430 waveguide bounded by quartz plate glass wir ⁇ ows and positioned approximately one-quarter waveguide wave ⁇ length from a short circuit plate.
  • the reactor was irradiated with microwave radiation centered at a 2.45 GHz frequency and pulsed in an on/off cycle (0.14 seconds on in a total of 3.5 seconds) with a power ranging from 3.2 to 6.2 watts.
  • Methane conversion was calculated to be 40% using to the following equation:
  • % Methane Conversion wt.% methane in the products wt.% methane in the feed x 100
  • Example l Using the apparatus and procedure of Example l (except that the average power was 6.4 watts), a methane/carbon dioxide mixture (1:2 mole ratio) flowing at 15 ml/min was converted to 47.5 wt% carbon monoxide, 1.7 wt% hydrogen, and 2-3 wt% water. Methane and carbon dioxide conversions were 53.6% and 52.6%, respectively.
  • Example 2 Using the apparatus and procedure of Example 1 (except that the average power was 7.4 watts), a methane/carbon dioxide mixture (1:-18 mole ratio) flowing at 10 ml/min was converted to 43.4 wt% carbon monoxide, 0.7 wt% hydrogen, and 2-3 wt% water. Methane and carbon dioxide conversions were 60% and 46.4%, respectively.
  • a methane/carbon dioxide mixture (1:1.09 mole ratio) was passed through an empty quartz glass tube at a total flow rate of 20 ml/min at atmospheric pressure.
  • the tube was irradiated with up to 1170 watts of microwave radiation centered at a frequency of 2.45 GHz, but no plasma was formed and no conversion prod ⁇ ucts obtained. Attempts to initiate a plasma using the discharge from a Tesla coil also failed.
  • Particulate nickel powder (0.1 g) was then evenly distributed over an approximately 1 cm diameter sintered glass disc contained in a quartz reactor and contacted with the methane/carbon dioxide mixture described above flowing at 20 ml/min through the sintered disc.
  • the reactor was located in a WR430 waveguide positioned approximately one quarter wave ⁇ guide wave-length from a short circuit plate.
  • the reactor was irradiated with pulsed microwave radiation centered at a frequency of 2.45 GHz and having an on/off cycle of 0.14 seconds on in a total of 3.5 seconds.
  • methane and carbon dioxide conversions were calculated to be 1.4% and 1.0%, respectively, with the primary products being 0.7 wt.% carbon monoxide, 0.09 wt.% hydrogen, and 0.15 wt.% water.
  • methane and carbon dioxide conversions were calculated to be 1.2% and 0.45%, respectively, with the primary products being 0.56 wt.% carbon monoxide and 0.07 wt.% hydrogen (no water was detected).
  • the powders glowed but no conversion was obtained.
  • Example 4 show that particulate metal powders are not effective in converting methane and carbon dioxide.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

Un mélange de méthane et de dioxyde de carbone peut être efficacement converti en monoxyde de carbone et en hydrogène en soumettant ledit mélange au rayonnement de micro-ondes, en présence d'au moins une amorce au plasma capable d'amorcer une décharge électrique dans un champ électromagnétique.
PCT/US1991/004622 1990-07-31 1991-06-28 Conversion de methane et de dioxyde de carbone a l'aide du rayonnement de micro-ondes WO1992002448A1 (fr)

Applications Claiming Priority (2)

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US56052290A 1990-07-31 1990-07-31
US560,522 1990-07-31

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WO1992002448A1 true WO1992002448A1 (fr) 1992-02-20

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2689116A1 (fr) * 1992-03-25 1993-10-01 Schwob Yvan Procédé pour la préparation de gaz de synthèse.
EP0601797A1 (fr) * 1992-12-04 1994-06-15 Exxon Research And Engineering Company Conversion de méthane/gaz carbonique en hydrogène/monoxyde de carbone
US5411649A (en) * 1992-10-02 1995-05-02 Electricite De France, Service National Catalytic process for controlled oxidation of methane using microwaves for the synthesis of ethane and ethylene and catalysts used in this process
US5472581A (en) * 1993-06-11 1995-12-05 Queen's University Microwave production of C2 hydrocarbons, using a carbon catalyst
FR2757499A1 (fr) * 1996-12-24 1998-06-26 Etievant Claude Generateur d'hydrogene
DE19757936A1 (de) * 1997-12-27 1999-07-08 Abb Research Ltd Verfahren zur Herstellung eines H2-CO-Gasgemisches
WO2001009031A1 (fr) * 1999-07-29 2001-02-08 David Systems Technology, S.L. Transformateur de plasma de combustibles fossiles en gaz riche en hydrogene
US6322268B1 (en) 1993-11-12 2001-11-27 Avery Dennison Corporation Efficient fluid dispensing utensil
WO2002028771A1 (fr) * 2000-10-05 2002-04-11 David Systems Technology, S.L. Procede et appareil destines a la transformation par voie plasma catalytique de combustibles fossiles en gaz riche en hydrogene
US6413001B1 (en) 1995-08-14 2002-07-02 Dataprint R. Kaufmann Gmbh Liquid applicator implement
ES2174693A1 (es) * 1999-07-29 2002-11-01 David Systems Tecnology S L Mejoras introducidas en la patente de invencion 9901720 por "convertidor de plasma de combustibles fosiles en un gas rico en hidrogeno.
US6637965B1 (en) 2001-06-22 2003-10-28 Avery Dennison Corporation Writing instrument having a reservoir between a tip and a capillary storage
ES2310127A1 (es) * 2007-06-01 2008-12-16 Consejo Superior De Investigaciones Cientificas Procedimiento de produccion de gas de sintesis, dispositivo para su ejecucion y sus aplicaciones.
WO2009093803A1 (fr) * 2007-12-27 2009-07-30 Posco Appareil pour le traitement des gaz à effet de serre
US8021448B2 (en) 2007-01-25 2011-09-20 Eden Energy Ltd. Method and system for producing a hydrogen enriched fuel using microwave assisted methane plasma decomposition on catalyst
US8075869B2 (en) 2007-01-24 2011-12-13 Eden Energy Ltd. Method and system for producing a hydrogen enriched fuel using microwave assisted methane decomposition on catalyst
AT524346A5 (de) * 2018-04-25 2022-03-15 Josef Philipp Franz Vorrichtung zur thermischen und katalytischen Behandlung von kohlenstoffhaltigem Material
CN114988409A (zh) * 2022-04-25 2022-09-02 鲁东大学 一种二氧化碳转化的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8092778B2 (en) 2007-01-24 2012-01-10 Eden Energy Ltd. Method for producing a hydrogen enriched fuel and carbon nanotubes using microwave assisted methane decomposition on catalyst
CN114620685B (zh) * 2020-12-12 2023-07-25 中国科学院大连化学物理研究所 一种提高等离子体重整甲烷转化率的装置及方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GASNER, CHEMICAL ABSTRACTS 106:7281h, 1987. *
HARAGUCHI, CHEMICAL ABSTRACTS 93:70223u, 1980. *
TANAKA, "A Stoicheiometric Conversion of CO2 + CH4 into 2CO + 2H2 by Microwave Discharge", J. CHEM. SOC. 1982, (See entire document). *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2689116A1 (fr) * 1992-03-25 1993-10-01 Schwob Yvan Procédé pour la préparation de gaz de synthèse.
US5411649A (en) * 1992-10-02 1995-05-02 Electricite De France, Service National Catalytic process for controlled oxidation of methane using microwaves for the synthesis of ethane and ethylene and catalysts used in this process
EP0601797A1 (fr) * 1992-12-04 1994-06-15 Exxon Research And Engineering Company Conversion de méthane/gaz carbonique en hydrogène/monoxyde de carbone
US5472581A (en) * 1993-06-11 1995-12-05 Queen's University Microwave production of C2 hydrocarbons, using a carbon catalyst
US6322268B1 (en) 1993-11-12 2001-11-27 Avery Dennison Corporation Efficient fluid dispensing utensil
US6413001B1 (en) 1995-08-14 2002-07-02 Dataprint R. Kaufmann Gmbh Liquid applicator implement
FR2757499A1 (fr) * 1996-12-24 1998-06-26 Etievant Claude Generateur d'hydrogene
WO1998028223A1 (fr) * 1996-12-24 1998-07-02 H2-Tech S.A.R.L. Procede et appareils de production d'hydrogene par reformage a plasma
DE19757936A1 (de) * 1997-12-27 1999-07-08 Abb Research Ltd Verfahren zur Herstellung eines H2-CO-Gasgemisches
DE19757936B4 (de) * 1997-12-27 2005-08-25 Abb Research Ltd. Verfahren zur Herstellung eines H2-CO-Gasgemisches
US6284157B1 (en) 1997-12-27 2001-09-04 Abb Research Ltd. Process for producing an H2-CO gas mixture
ES2174693A1 (es) * 1999-07-29 2002-11-01 David Systems Tecnology S L Mejoras introducidas en la patente de invencion 9901720 por "convertidor de plasma de combustibles fosiles en un gas rico en hidrogeno.
WO2001009031A1 (fr) * 1999-07-29 2001-02-08 David Systems Technology, S.L. Transformateur de plasma de combustibles fossiles en gaz riche en hydrogene
WO2002028771A1 (fr) * 2000-10-05 2002-04-11 David Systems Technology, S.L. Procede et appareil destines a la transformation par voie plasma catalytique de combustibles fossiles en gaz riche en hydrogene
US6637965B1 (en) 2001-06-22 2003-10-28 Avery Dennison Corporation Writing instrument having a reservoir between a tip and a capillary storage
US8075869B2 (en) 2007-01-24 2011-12-13 Eden Energy Ltd. Method and system for producing a hydrogen enriched fuel using microwave assisted methane decomposition on catalyst
US8021448B2 (en) 2007-01-25 2011-09-20 Eden Energy Ltd. Method and system for producing a hydrogen enriched fuel using microwave assisted methane plasma decomposition on catalyst
ES2310127A1 (es) * 2007-06-01 2008-12-16 Consejo Superior De Investigaciones Cientificas Procedimiento de produccion de gas de sintesis, dispositivo para su ejecucion y sus aplicaciones.
WO2009093803A1 (fr) * 2007-12-27 2009-07-30 Posco Appareil pour le traitement des gaz à effet de serre
CN101909724A (zh) * 2007-12-27 2010-12-08 Posco公司 用于处理温室气体的装置
KR101482259B1 (ko) * 2007-12-27 2015-01-13 주식회사 포스코 온실 가스 분해 장치
AT524346A5 (de) * 2018-04-25 2022-03-15 Josef Philipp Franz Vorrichtung zur thermischen und katalytischen Behandlung von kohlenstoffhaltigem Material
AT524346B1 (de) * 2018-04-25 2022-07-15 Josef Philipp Franz Vorrichtung zur thermischen und katalytischen Behandlung von kohlenstoffhaltigem Material
CN114988409A (zh) * 2022-04-25 2022-09-02 鲁东大学 一种二氧化碳转化的方法

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