WO1992002448A1 - Conversion of methane and carbon dioxide using microwave radiation - Google Patents

Conversion of methane and carbon dioxide using microwave radiation 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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Prior art keywords
metal
methane
carbon dioxide
plasma
initiator
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PCT/US1991/004622
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French (fr)
Inventor
William J. Murphy
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Exxon Research And Engineering Company
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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.

Abstract

A mixture of methane and carbon dioxide can be effectively converted to carbon monoxide and hydrogen by subjecting the mixture to microwave radiation in the presence of at least one plasma initiator that is capable of initiating an electric discharge in an electromagnetic field.

Description

CONVERSION OF METHANE AND CARBON DIOXIDE USING MICROWAVE RADIATION
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for converting methane and carbon dioxide to carbon mono¬ xide and hydrogen using microwave radiation.
2. Description of Related Art
Microwave energy has been used to convert methane to other hydrocarbons. For example, 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.
In addition, the conversion of methane and carbon dioxide into carbon monoxide and hydrogen using a microwave discharge at -5 torr pressure has been disclosed by Tana a et al, J. Chem. Soc, Chem. Comm. , pp. 921-922, (1982).
However, neither publication suggests the particular conversion process described below, which requires the presence of a plasma initiator.
SUMMARY OF THE INVENTION
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. In a preferred embodiment, the plasma initiator will comprise a plurality of elongated metal wire seg¬ ments arranged in close proximity to one another.
DETAILED DESCRIPTION OF THE INVENTION
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.) may be present in either or both as well. 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. As used herein, "composite" is meant to include mixtures (or combinations) of metals and non-metals. Examples of 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. Examples of suitable non-metal initiators include carbon, alumina, manganese dioxide, magnetite, nickel oxide (e.g. NiO) , iron oxide (e.g. Fβ3θ4) , calcium aluminate, cobalt oxide, chromium nitride, iron sulfide (e.g. FeS2, Feτ__xS) , 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.
Although methane/carbon dioxide conversion can be effected using onl j>ne plasma initiator, conversion is enhanced if
Figure imgf000005_0001
than one (≤.g. , 6 or more) plasma initiators are used. Preferably, a plurality of plasma initiators are used. Most prefer¬ ably, 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.
If more than one plasma initiator is used, a minimum distance should be maintained between each initiator to facilitate dissipation of the electric charge. However, 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) .
The frequency of the microwave source can vary broadly. Typically, 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.
This invention will be further understood by reference to the following Examples which are not intended to restrict the scope of the claims appended hereto.
Example l - Conversion of Methane and Carbon Dioxide Using Plasma Initiators
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 wirάows 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
Figure imgf000007_0001
Similarly, carbon dioxide conversion was calculated to be 43% using the following equation:
% Carbon Dioxide = wt.% carbon dioxide in the products Conversion wt.% carbon dioxide in the feed x 100
Figure imgf000007_0002
The primary products produced were 35.7% carbon mono¬ xide, 2.9 wt% hydrogen, and 2-3 wt% water. Example 2 - Conversion of Methane and Carbon Dioxide Using Plasma Initiators
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 3 - Conversion of Methane and Carbon Dioxide Using Plasma Initiators
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.
Example 4 - Conversion of Methane and Carbon Dioxide Using Particulate Metal Powder
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. After 18 minutes onstream at an average power of 1.4 watts, 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. After an additional 18 minutes onstream, 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). At higher average power (e.g. 2.6 watts) , the powders glowed but no conversion was obtained.
The data in Example 4 show that particulate metal powders are not effective in converting methane and carbon dioxide.

Claims

CLAIMS :
1. A method for converting methane and carbon dioxide to carbon monoxide and hydrogen which comprises:
(a) introducing methane and carbon dioxide into a reaction zone that contains at least one plasma initiator capable of initiating an electric discharge in an electromagnetic field, and
(b) subjecting the methane, carbon dioxide, and plasma initiator to microwave radiation for a period of time suffi¬ cient to convert at least a portion of the methane and carbon dioxide to carbon monoxide and hydrogen.
2. The method of claim 1 wherein the plasma initiator is a metal.
3. The method of claim 2 wherein the metal is tungsten, iron, nickel, copper, their alloys, or mixtures thereof.
4. The method of claim 3 wherein the metal is tungsten, iron, or mixtures thereof.
5. The method of claim 1 wherein the plasma initiator is a non-metal other than silica.
6. The method of claim 5 wherein the non- metal is calcium aluminate, carbon, iron oxide, or mixtures thereof.
7. The method of claim 1 wherein the plasma initiator is a composite of a metal initiator and a non-metal initiator.
8. The method of claim 1 wherein a plurality of plasma initiators are present in the reaction zone.
9. The method of claim 8 wherein the plasma initiators are elongated.
10. The method of claim 1 wherein the fre¬ quency of the microwave radiation is at least 0.3 GHz.
11. A method for converting methane and carbon dioxide to carbon monoxide and hydrogen which comprises:
(a) introducing methane and carbon dioxide into a reaction zone that contains at least one elongated plasma initiator capable of initiating an electric discharge in an electromagnetic field, and
(b) subjecting the methane, carbon dioxide, and plasma initiator to microwave radiation having a frequency of at least 0.3 GHz for a period of time sufficient to convert at least a portion of the methane and carbon dioxide to carbon monoxide and hydrogen.
12. The method of claim 11 wherein a plural¬ ity of plasma initiators are present in the reaction zone.
13. The method of claim 12 wherein the plasma initiators are a metal and the metal is tung¬ sten, iron, nickel, copper, their alloys, or mixtures thereof.
14. The method of claim 13 wherein the metal is tungsten, iron, or mixtures thereof.
15. The method of claim 14 wherein the frequency of microwave radiation is centered around 0.915, 2.45, or 5.8 GHz.
16. The method of claim 11 wherein at least one plasma initiator is a metal.
17. The method of claim 16 wherein the metal is tungsten, iron, nickel, copper, their alloys, or mixtures thereof.
18. The method of claim 17 wherein the metal comprises tungsten, iron, or mixtures thereof.
19. The method of claim 16 wherein the plasma initiator is a plurality of metal wires.
20. The method of claim 11 wherein at least one plasma initiator is a non-metal other than silica.
21. The method of claim 20 wherein the non-metal is calcium aluminate, carbon, iron oxide, or mixtures thereof.
22. The method of claim 11 wherein at least one plasma initiator is a composite of a metal initia¬ tor and a non-metal initiator.
PCT/US1991/004622 1990-07-31 1991-06-28 Conversion of methane and carbon dioxide using microwave radiation WO1992002448A1 (en)

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FR2689116A1 (en) * 1992-03-25 1993-10-01 Schwob Yvan Prepn. of synthesis gas - by an auto-thermal reaction between methane water vapour and carbon di:oxide in a plasma gas
EP0601797A1 (en) * 1992-12-04 1994-06-15 Exxon Research And Engineering Company Methane/carbon dioxide conversion to hydrogen/carbon monoxide
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FR2689116A1 (en) * 1992-03-25 1993-10-01 Schwob Yvan Prepn. of synthesis gas - by an auto-thermal reaction between methane water vapour and carbon di:oxide in a plasma gas
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 (en) * 1992-12-04 1994-06-15 Exxon Research And Engineering Company Methane/carbon dioxide conversion to hydrogen/carbon monoxide
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 (en) * 1996-12-24 1998-06-26 Etievant Claude HYDROGEN GENERATOR
WO1998028223A1 (en) * 1996-12-24 1998-07-02 H2-Tech S.A.R.L. Method and devices for producing hydrogen by plasma reformer
DE19757936A1 (en) * 1997-12-27 1999-07-08 Abb Research Ltd Production of synthesis gas with given hydrogen to carbon monoxide ratio in silent discharge
DE19757936B4 (en) * 1997-12-27 2005-08-25 Abb Research Ltd. Process for producing a H2-CO gas mixture
US6284157B1 (en) 1997-12-27 2001-09-04 Abb Research Ltd. Process for producing an H2-CO gas mixture
ES2174693A1 (en) * 1999-07-29 2002-11-01 David Systems Tecnology S L Plasma fuel convertor for producing hydrogen-rich gas, used e.g. for vehicle engines, includes pseudo-corona discharge generated by microwaves
WO2001009031A1 (en) * 1999-07-29 2001-02-08 David Systems Technology, S.L. Plasma transformer for the transformation of fossil fuels into hydrogen-rich gas
WO2002028771A1 (en) * 2000-10-05 2002-04-11 David Systems Technology, S.L. Method and apparatus for plasma-catalytic conversion of fossil fuels into a hydrogen-rich gas
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 (en) * 2007-06-01 2008-12-16 Consejo Superior De Investigaciones Cientificas Synthesis gas production procedure, device for its execution and its applications (Machine-translation by Google Translate, not legally binding)
WO2009093803A1 (en) * 2007-12-27 2009-07-30 Posco Apparatus for treating green house gases
CN101909724A (en) * 2007-12-27 2010-12-08 Posco公司 Apparatus for treating green house gases
KR101482259B1 (en) * 2007-12-27 2015-01-13 주식회사 포스코 Apparatus for treating green house gases
AT524346A5 (en) * 2018-04-25 2022-03-15 Josef Philipp Franz Device for thermal and catalytic treatment of carbonaceous material
AT524346B1 (en) * 2018-04-25 2022-07-15 Josef Philipp Franz Device for thermal and catalytic treatment of carbonaceous material
CN114988409A (en) * 2022-04-25 2022-09-02 鲁东大学 Method for converting carbon dioxide

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