WO2006109294A1 - Systemes et procedes pour la production d’hydrogene - Google Patents

Systemes et procedes pour la production d’hydrogene Download PDF

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Publication number
WO2006109294A1
WO2006109294A1 PCT/IL2006/000435 IL2006000435W WO2006109294A1 WO 2006109294 A1 WO2006109294 A1 WO 2006109294A1 IL 2006000435 W IL2006000435 W IL 2006000435W WO 2006109294 A1 WO2006109294 A1 WO 2006109294A1
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Prior art keywords
hydrogen
gases
carbon monoxide
converting
waste
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PCT/IL2006/000435
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English (en)
Inventor
Valery G. Gnedenko
Igor V. Goryachev
David Pegaz
Zeev Bargil
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C. En. Limited
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Publication date
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Publication of WO2006109294A1 publication Critical patent/WO2006109294A1/fr

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    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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    • 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
    • C01B3/38—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 using catalysts
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    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
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Definitions

  • This invention relates to the production of hydrogen. More specifically, the invention is concerned with the production of hydrogen from the gas products resulting from the processing of waste matter, in particular via pyrolyzation and/or gasification thereof. The invention is also concerned with the production of hydrogen from water using recirculated carbon monoxide.
  • Waste processing systems for converting waste into, inter alia, product gases are well known.
  • the product gases comprise relatively large proportions of hydrogen, and in some systems, molecular hydrogen can be extracted by itself or in combination with other fuel gases.
  • the hydrogen whether harvested from the product gases by itself or included in a fuel gas, can constitute an important resource.
  • a vessel which converts waste into a molten material that can be removed from the vessel, and product gases, by means of a plasma torch system.
  • the product gases are subjected to a ceramic filtration system which removes molecular hydrogen from the product gases.
  • the fuel gas is combusted in gas turbine generators to produce electricity.
  • Exhaust gases from the turbine are processed in another chamber comprising incandescent coke, to convert the exhaust gases into hydrogen, carbon monoxide and some methane.
  • the resulting fuel gas may be fed into the turbines, or alternatively the hydrogen removed and the carbon monoxide converted in another chamber to methane and oxygen, the oxygen being used in the turbines.
  • product gases resulting from pyrolysis of waste contains hydrogen which may be separated and stored in nanotubes.
  • the present invention relates to a system for producing hydrogen, comprising: processing apparatus for processing waste into at least product gases based on at least one of pyrolysis and gasification of said waste, said product gases comprising at least carbon monoxide; post processing apparatus operatively connected to said processing apparatus and to a source of water, and adapted for producing hydrogen, said post-processing apparatus comprising first converting apparatus, separating apparatus and second converting apparatus, wherein: said first converting apparatus comprises arrangement for receiving product gases from said processing apparatus and for receiving carbon monoxide from said second converting apparatus, and reaction arrangement for reacting carbon monoxide with water to produce output gases including hydrogen and carbon dioxide; said separating apparatus configured for selectively separating at least hydrogen from said output gases received from said first converting apparatus, and for directing at least said carbon dioxide to said second converting apparatus; said second converting apparatus configured for converting carbon dioxide to carbon monoxide and for directing at least said carbon monoxide to said first converting apparatus.
  • the waste processing apparatus typically comprises: a waste converting chamber for accommodating a column of said waste, said chamber having an upper part and a lower part; at least one primary plasma torch arrangement for generating a hot gas jet at an output end thereof and for directing said jet towards said lower part of said chamber; at least one waste inlet arrangement at said upper part of said chamber; at least one liquid product outlet arrangement at said lower part for removing liquid product from said chamber; and at least one product gas outlet arrangement for directing product gases out of said chamber and into said post processing arrangement.
  • the waste is comprises substantially solid waste, including for example at least one of municipal waste and industrial waste.
  • the system preferably further comprises gas cleaning arrangement upstream of said first converting apparatus, said gas cleaning arrangement being adapted for removing predetermined components - such as for example one or more of pitch, tar, dust, water, HCl, H 2 S, and so on - from said product gases, and for subsequently directing said product gases to said first converting apparatus.
  • predetermined components such as for example one or more of pitch, tar, dust, water, HCl, H 2 S, and so on - from said product gases, and for subsequently directing said product gases to said first converting apparatus.
  • the product gases typically further comprise at least one of H 2 , CO 2 , N 2 , C n H m , wherein n and m are each integers.
  • the reaction arrangement typically comprises a suitable reaction vessel configured for running therein a water-gas shift reaction in the presence of suitable catalysts comprised therein.
  • the catalysts may comprise a zinc-copper- chromium catalyst, and wherein said water-gas shift reaction is run at a temperature typically in the range of about 35O 0 C to about 380 0 C.
  • the second converting apparatus typically comprises a suitable UHF discharge device coupled to a DC electrical power source.
  • the first converting apparatus advantageously further comprises a suitable heat exchanger for cooling said output gases.
  • the heat exchanger is typically further configured for preheating water from said water source prior to being reacted in said first converting apparatus.
  • the system may further comprise suitable hydrocarbon converter arrangement for converting hydrocarbons comprised in said product gases such as to provide hydrogen therefrom.
  • the hydrocarbon converter arrangement typically comprises a suitable reaction vessel configured for carrying out therein a steam conversion reaction on said hydrocarbons in the presence of a suitable catalyst, e.g. an iron-chromium catalyst to produce hydrogen and carbon monoxide.
  • a suitable catalyst e.g. an iron-chromium catalyst to produce hydrogen and carbon monoxide.
  • the hydrogen produced by said hydrocarbon converter arrangement may be separated via said separating apparatus.
  • a cooler may be provided for cooling gases output from said hydrocarbon converter prior to separating hydrogen therefrom.
  • the hydrocarbon converter arrangement comprises a suitable reaction vessel configured for carrying out therein a decomposition reaction for decomposing hydrocarbons to carbon and hydrogen.
  • the separation apparatus typically comprises at least one separation unit comprising membrane arrangement for separating hydrogen from said output gases by selectively allowing hydrogen to diffuse through said membrane.
  • the separation apparatus may comprise further separation units for separating other gases from said output gases.
  • One such separation unit may be adapted for separating carbon dioxide from said output gases, and for directing said carbon dioxide to said second converting apparatus.
  • Other arrangement for separating the hydrogen and/or other desired gases may be provided, as described herein for example.
  • the present invention also relates to an apparatus for producing hydrogen, comprising: first converting apparatus operatively connectable to a source of water, separating apparatus and second converting apparatus, wherein: said first converting apparatus comprises arrangement for receiving carbon monoxide from said second converting apparatus, and reaction arrangement for reacting carbon monoxide with water to produce output gases including hydrogen and carbon dioxide; said separating apparatus configured for selectively separating at least hydrogen from said output gases received from said first converting apparatus, and for directing at least said carbon dioxide to said second converting apparatus; said second converting apparatus configured for converting carbon dioxide to carbon monoxide and for directing at least said carbon monoxide to said first converting apparatus.
  • the reaction arrangement comprises a suitable reaction vessel configured for running therein a water-gas shift reaction in the presence of suitable catalysts comprised therein, for example said catalysts may comprise a zinc-copper- chromium catalyst, and wherein said water-gas shift reaction is run at a temperature in the range of about 350 0 C to about 380 0 C.
  • the second converting apparatus typically comprises a suitable UHF discharge device coupled to a DC electrical power source.
  • the first converting apparatus typically further comprises a suitable heat exchanger for cooling said output gases, and the heat exchanger may be further configured for preheating water from said water source prior to being reacted in said first converting apparatus.
  • the separation apparatus comprises at least one separation unit typically comprising membrane arrangement for separating hydrogen from said output gases by selectively allowing hydrogen to diffuse through said membrane.
  • Other arrangement for separating the hydrogen may be provided, as described herein for example.
  • the apparatus further comprises a supply of carbon dioxide or carbon dioxide for maintaining the level of carbon monoxide within the apparatus within predetermined thresholds.
  • the present invention also relates to a method for producing hydrogen, comprising:
  • step (c) converting carbon dioxide contained in the output gases in step (b) to carbon monoxide and recycling at least said carbon monoxide to said product gases produced by said waste processing apparatus to be processed according to step (a);
  • step (a) carbon monoxide and steam are reacted together in a water-gas shift reaction to produce carbon dioxide and hydrogen, typically under the presence of suitable catalysts - for example a zinc-copper-chromium catalyst- the water-gas shift reaction being typically run at elevated temperatures, for example a temperature in the range of about 350 0 C to about 38O 0 C.
  • suitable catalysts for example a zinc-copper-chromium catalyst- the water-gas shift reaction being typically run at elevated temperatures, for example a temperature in the range of about 350 0 C to about 38O 0 C.
  • any suitable separation process may be used, for example based on using polymeric or metal diffusing membranes, physical absorption or adsorption processes, cryogenic methods, and so on.
  • Step (c) typically involves providing a suitable UHF discharge to carbon dioxide at below ambient pressure, typically increasing the gas temperatures to greater than 1000 0 C, and the conversion efficiency is kept as high as possible but within safety limits, for example at less than 40% by weight.
  • the method optionally further comprises converting hydrocarbons in the product gases to hydrogen and carbon (which is subsequently converted to carbon monoxide or dioxide) or carbon monoxide; the hydrogen is removed, and the carbon monoxide reacted with water to produce more hydrogen and carbon dioxide.
  • the carbon dioxide may then be recycled in step (c).
  • the present invention also relates to a method for producing hydrogen, from water, comprising:
  • step (d) converting carbon dioxide contained in the output gases in step (c) to carbon monoxide and recycling at least said carbon monoxide to be processed according to step (a);
  • step (e) repeating steps (b) to (d).
  • carbon monoxide may be provided already prepared, for example in pressurized containers, or alternatively may be provided by combusting coke or the like in a low oxygen atmosphere.
  • a carbon dioxide supply for example liquefied carbon dioxide with arrangement for gasifying an amount thereof on demand, is processed according to step (d), and applying steps (b) to (e) to the resulting carbon monoxide.
  • step (b) carbon monoxide and steam are reacted together in a water-gas shift reaction to produce carbon dioxide and hydrogen, typically under the presence of suitable catalysts - for example a zinc-copper-chromium catalyst- the water-gas shift reaction being typically run at elevated temperatures, for example a temperature in the range of about 350 0 C to about 38O 0 C.
  • suitable catalysts for example a zinc-copper-chromium catalyst- the water-gas shift reaction being typically run at elevated temperatures, for example a temperature in the range of about 350 0 C to about 38O 0 C.
  • any suitable separation process may be used, for example based on using polymeric or metal diffusing membranes, physical absorption or adsorption processes, cryogenic methods, and so on.
  • Step (d) typically involves providing a suitable UHF discharge to carbon dioxide at below ambient pressure, typically increasing the gas temperatures to greater than 1000 0 C, and the conversion efficiency is kept as high as possible but within safety limits, for example at less than 40% by weight.
  • step (e) it is possible to check the amount of carbon monoxide in the system, and if below a threshold amount, for example due to leakage, additional carbon monoxide may be provided via step (a).
  • Fig. 1 is a schematic representation of the system according to a first embodiment of a first aspect of the invention.
  • Fig. 2 is a cross-sectional view of the waste processing plant of Fig. 1.
  • Fig. 3 is a schematic representation of the post-processing arrangement of
  • Fig. 4 is a schematic representation of an embodiment of the hydrogen separation unit of Fig. 3.
  • Fig. 5 is a schematic representation of a process for extracting hydrogen via physical absorption.
  • Fig. 6 is a schematic representation of the system according to a first embodiment of the first aspect the invention.
  • Fig. 7 is a schematic representation of the system according to a first embodiment of a second aspect of the invention.
  • Fig. 8 is an alternative schematic representation of the system according to a first embodiment of a second aspect of the invention
  • Fig. 9 is a schematic representation of the method according to a first embodiment of a first aspect of the invention.
  • a system for producing hydrogen according to a first embodiment of the present invention is generally designated with the numeral 150, and comprises a waste processing plant 100 for processing waste, and post-processing arrangement 200 operatively connected thereto for producing hydrogen.
  • the waste processing plant 100 is illustrated in more detail. It should be understood that the waste processing plant 100 illustrated in Fig. 2 and described below is only illustrative, and any suitable waste processing plant may be used with the system 150 and that produces at least carbon monoxide (CO).
  • the plant 100 is adapted for producing at least product gases, and typically also solid waste, such as for example slag and/or metal residues, and exemplary waste processing plants are described in US 6,763,772, US 6,820,564, US 6,807,913, WO 02/070412, WO 03/078897, and WO 03/069227, the contents of each of which are incorporated herein in their entirety. In these references, and also referring to Fig.
  • the plant 100 comprises a processing chamber 10, in which a suitable feeding system 20 introduces waste to the chamber via an air lock arrangement 30, typically comprising an upper valve 32 and a lower valve 34 defining a loading chamber 36 therebetween, the operation of which may be controlled by a human and/or automated controller (not shown).
  • the waste may include solid, liquid or mixed waste, including medical, municipal, industrial, agricultural, and any other type of waste.
  • metallic waste such as iron and aluminium, and other recyclable materials including glass may be removed prior to providing the waste to the chamber 10.
  • the hot gases support the temperature gradient set up in the chamber 10, and is sufficient for converting the waste into product gases that are channeled away from the chamber via outlet 50, and into a liquid material 33 that may include molten metal and/or slag, which may be periodically or continuously collected from the lower end of the chamber 10 via one or more outlets 60.
  • Oxidising fluid source 70 provides oxidizing fluid such as oxygen, air or steam, typically at the lower end of the chamber 10 for converting carbon, produced in the process from organic waste, into product gases including CO and hydrogen (H 2 ).
  • a disinfectant spraying system 31 may be provided for periodically or continuously spraying the inlet end or hop arrangement 39 with disinfectant, as required, particularly when medical waste is being processed by the plant 100.
  • the said controller may be adapted to control the input of waste into the chamber 10, for example substantially as disclosed in WO 03/078897.
  • the chamber 10 may comprise an oxidizing fluid distribution and mixing chamber incorporated therein, for example as disclosed in WO 02/070412.
  • the processing plant 10 may further comprise a dedicated liquid waste feeding system (not shown), for example as disclosed in US 6,763,772.
  • the plant 100 may further comprise a first decongesting system (not shown) for the removal of, and for the prevention of the formation of, bridging phenomena in the chamber 10, for example as disclosed in US 6,807913.
  • a first decongesting system (not shown) for the removal of, and for the prevention of the formation of, bridging phenomena in the chamber 10, for example as disclosed in US 6,807913.
  • the plant 100 may further comprise a second decongestion system (not shown) for the removal of, and for the prevention of the formation of, unprocessed solid deposition within the chamber 10 and/or for dealing with high viscosity liquid product produced by the plant 100, for example as disclosed in US 6,820,564.
  • a second decongestion system (not shown) for the removal of, and for the prevention of the formation of, unprocessed solid deposition within the chamber 10 and/or for dealing with high viscosity liquid product produced by the plant 100, for example as disclosed in US 6,820,564.
  • the plant 100 may further comprise a recycling system (not shown) for recycling non-gaseous residues, such as for example flyash, generated by the plant 100, in order to reduce the eventual volume of residues, and to dispose of at least a part of the heavy metals produced by the plant 100, by encasing the compounds and complexes of metals in the slag melt, i.e., when the slag is still molten, for example substantially as disclosed in WO 03/069227.
  • a recycling system for recycling non-gaseous residues, such as for example flyash, generated by the plant 100, in order to reduce the eventual volume of residues, and to dispose of at least a part of the heavy metals produced by the plant 100, by encasing the compounds and complexes of metals in the slag melt, i.e., when the slag is still molten, for example substantially as disclosed in WO 03/069227.
  • the system 150 comprises a scrubber system 130, operatively connected to the outlet 50 for removing particulate matter and/or liquid droplets, including tar, pitch and dust for example, as well as any undesired gases (for example HCl, H 2 S, and so on) from the product gas stream. Scrubbers capable of performing such tasks are well known and shall not be further described herein.
  • the post-processing arrangement 200 is adapted for producing hydrogen from the product gases P produced by the gasification of the waste by means of the plant 100 and from water by reaction thereof with CO, and for enabling the hydrogen to be removed for further exploitation.
  • the hydrogen may be removed after purification, or together with other combustible gases in a hydrogen-enriched syngases.
  • the product gases P 5 after being cleaned by the scrubber 130 and prior to post-processing by means of post-processing arrangement 200 typically comprise H 2 , CO, CO 2 , N 2 , and hydrocarbons designated herein as C n H m , wherein n and m are each integers . 5
  • the post-processing arrangement 200 provides
  • post-processing arrangement 200 comprises a conduit or conduits for transporting the product gases P to a steam converter 230, in which carbon 15 monoxide, from the product gases P and/or as recycled within the postprocessing arrangement 200, as will be further described hereinbelow, is reacted with steam to produce hydrogen in a water-gas shift reaction: -
  • the water-gas shift reaction is typically run in the presence of suitable 20 catalysts comprised in the steam converter 230 and at a suitable temperature, for example a zinc-copper-chromium catalyst at a temperature in the range of about 35O 0 C to about 380 0 C.
  • a suitable temperature for example a zinc-copper-chromium catalyst at a temperature in the range of about 35O 0 C to about 380 0 C.
  • the water-gas shift reaction is exothermic, and the temperature of the resulting gases, designated P2 in Fig. 3, is higher than that of the pre-reacted gases, usually higher than 400 0 C, and typically between about 25 430° and about 45O 0 C.
  • the output gases P2 have higher concentrations of H 2 and CO 2 than in the product gases P, but still contain the other original gases in P, notably N 2 , C n H m , as well as unreacted CO and H 2 O.
  • Steam converters are well known and are manufactured by many different companies, for example Linde, Uhde (Germany), Marubeni (Japan), KTI (England) and so on.
  • unwanted gases in P are removed therefrom prior to being channeled to the steam converter 230, for example using suitable membrane units, as described below, mutatis mutandis, so that only CO (and possibly also the H 2 in the product gases P) is supplied to the steam converter 230.
  • the output gases P2 are passed through a suitable heat exchanger 240, in which steam from a suitable source 245, such as a steam generator, for example, is heated by the output gases P2 prior to being supplied to the steam converter 230.
  • a suitable source 245 such as a steam generator, for example
  • the output gases P2 are then directed to a hydrocarbon converter 250 for converting hydrocarbons present in the output gases to hydrogen in any suitable manner.
  • the hydrocarbon converter 250 may be based on steam reforming reactions, for example, in which the hydrocarbons are converted to hydrogen and carbon monoxide, exemplified as follows for methane and other hydrocarbons :-
  • the steam reforming reactions are typically run in the presence of a suitable catalyst, and at relatively high temperatures and pressures, for example an iron-chromium catalyst, at a temperature of between about 800 0 C to about 900°C, and at pressure in the order of about 2.5MPa absolute.
  • a suitable catalyst for example an iron-chromium catalyst, at a temperature of between about 800 0 C to about 900°C, and at pressure in the order of about 2.5MPa absolute.
  • a suitable steam source typically source 245 or alternatively a different source (not shown), provides steam for the reactions.
  • the hydrocarbon converter 250 operates by decomposing the hydrocarbons into hydrogen and carbon, for example as follows for methane :-
  • the hydrocarbon converter 250 may comprise a suitable plasma catalytic reactor, for example, for applying a plasma catalysis process for converting hydrocarbons to produce hydrogen.
  • a plasma catalytic reactor for example, for applying a plasma catalysis process for converting hydrocarbons to produce hydrogen.
  • Such a process is based on subjecting the hydrocarbons to an electric plasma discharge rated at a frequency in the microwave range, and having suitable discharge energy for dissociating the C-C and C-H bonds the microwave plasma discharge acting as a catalyst.
  • the plasma for the catalytic process is typically provided by means of a suitable super-high-frequency plasma torch.
  • Suitable plasma torches of this type are described in the following publications, the contents or which are incorporated herein in their entirety by reference:-
  • plasma torches configured for converting hydrocarbons into carbon and hydrogen are commercially available from many sources, for example: KVAERNER ENGINEERING S. A. (Norway); CONSULECTRA, EES, HGS (Germany); HOLDOR TOPSH (Holland).
  • the output gases P3 exiting the hydrocarbon converter 250 are thus further enriched in hydrogen, and also contain substantial amounts of carbon monoxide, which is recycled in the post-processing means 200, as will be further described herein.
  • the CO may be separated from the H 2 and other gases, and the CO is directly channeled to the steam converter 230 for converting more steam into H 2 .
  • the output gases P3 are cooled in cooler 260 using any suitable heat exchanger system, for example, based on a water coolant supply 265.
  • the cooler 260 reduces the temperature of the output gases to a temperature in the range of about 2O 0 C to about 5O 0 C, typically to about 25°C.
  • the output gases P2 from the steam converter 230 typically contain only small percentages of hydrocarbons, typically of the order of about 3% to about 4%, for example, and it may be more economical or preferred in some hydrogen production systems according to the invention to omit the said hydrocarbon converter 250 altogether.
  • the output gases P2 can be directed from the steam converter 230 or heat exchanger 240 directly to the next component in the post-processing arrangement 200, i.e., the hydrogen separator 270 (illustrated in Fig. 3 as dotted line 241) to extract the hydrogen, as well as these gaseous hydrocarbons which may optionally be taken off. stored and used (for example for combustion to generate heat or power) at some convenient point.
  • the post-processing arrangement may be used to provide a fuel gas comprising hydrocarbons and that is hydrogen enriched, in which case the hydrocarbon converter 250 is omitted, and the output gas P2 further processed in the hydrogen extractor 270 to remove therefrom the fuel gases comprising the hydrocarbons together with the hydrogen.
  • the remaining gases typically N 2 , CO and CO 2 are further processed, for example as described below regarding the hydrogen separating unit 270, mutatis mutandis.
  • the hydrocarbons present in the product gases P may be separated therefrom, for example using a suitable separating membrane unit, and the hydrocarbons routed directly to the hydrocarbon converter 250 (illustrated in
  • the output gases P3 (or output gases P2 if the hydrocarbon converter 250 is omitted) are then directed to a hydrogen separating unit 270, which purifies the hydrogen (optionally together with hydrocarbons, or alternatively and optionally also the hydrocarbons separately to the hydrogen) in the output gases and diverts the hydrogen (and/or hydrocarbons) to a suitable storage facility and/or to a consumer pipeline (not shown) and/or to a user facility.
  • some of the hydrogen and/or hydrocarbons may be diverted for power and/or heat for at least a part of the system 150.
  • the hydrogen separation unit 270 is based on diffusion separation processes, and typically comprises a membrane separator of any suitable configuration, though any other separation arrangements may be implemented for separating and purifying the hydrogen in the output gases and optionally also for separating hydrocarbon gases (together with or separately from the hydrogen).
  • the hydrogen separating unit 270 may comprise a series of membrane separating units, for example the three units 272, 274, 276 exemplified in Fig. 4, each of which separates out a particular effluent of interest.
  • the first separation stage unit 272 comprises membrane 273 that is adapted for separating a first effluent, such as for example nitrogen or hydrocarbon gases (from P2), which can then be channeled off and stored or used.
  • Suitable membranes for use as membrane 273 are well known, and may comprise, for example, polysiloxan or other polymer flat composite types or as marketed under the name "MEM", for example.
  • the unit 272 may have any suitable construction, for example comprising a plurality of separation modules, each in the form of a cylindrical housing having an internal cylindrically disposed membrane separating the housing into an outer and an inner chamber. Raw gases are fed into the outer chamber and under pressure the effluent is separated off into the inner chamber and removed from the unit. Many other forms for unit 272 are possible within the spirit of the invention.
  • unit 274 comprises membrane 275 which is adapted for separating out hydrogen, which is also channeled off and stored or used.
  • Suitable membranes for use as membrane 275 are also well known, and may comprise, for example, polysulfon or other hollow fiber axisymmetric types, for example as marketed under the name “Medal” by the company "Air Liquid” of Argentina.
  • the unit 274 may have any suitable construction, for example comprising a plurality of porous polymer fibers, with a suitable gas separating layer applied to the outer surface.
  • the porous fibers have a complex asymmetric structure, and the polymer's density increases towards the outer surface of the fibers.
  • the membrane unit 274 may optionally comprise a removable membrane cartridge construction, allowing membranes to be easily replaced.
  • the gas flow after unit 274 is further purified via unit 276, which comprise membrane 277 adapted for this purpose, and the remaining gases, designated P4 and comprising (typically a relatively low proportion of) CO and (typically a relatively high proportion of) CO 2 are then directed to oxidizer 280.
  • Unit 276 and membrane 277 may be similar to the other units and membranes of the hydrogen separation unit 270, as described herein mutatis mutandis.
  • the third unit 276 recycles residual gases through the separator 270 continuously via feedback line 271 after having separated out output gases P4.
  • a suitable compressor arrangement 273 pressurises the separator 270 and provides the required pressure head upstream of the first unit 272 to operate the separating membranes at optimum efficiencies.
  • the separating units 272, 274, 276 are configured for serially and selectively separating target gases from the input gas flow, in a predetermined sequence or order correlated to the properties of each membrane viz-a-viz the mixture of gases flowing through the unit 27Oe. These properties typically relate to the solubility of the gases and their capability of diffusing through the material of the membranes.
  • Membrane separation units have certain advantages over other separation systems, for example: low initial investment and maintenance costs; low energy consumption; simplicity of use and construction; reliability; operation thereof is potentially capable of being automated; flexibility in operation — e.g., scaling can be achieved by adding more units.
  • a membrane separation unit 270 performs the function of preliminary enrichment of a particular target gas in a mixture, the target gas typically being H 2 (but for some separation units may comprise CO, CO 2 , N 2 , and so on), and an additional separation unit (not shown), for example based on cryogenic separation, or absorption separation, or adsorption separation (e.g. pressure swing adsorption) carries out final purification of the target gas.
  • an additional separation unit for example based on cryogenic separation, or absorption separation, or adsorption separation (e.g. pressure swing adsorption) carries out final purification of the target gas.
  • metallic membranes may be used, for example based on Palladium alloys, for separating hydrogen to a high degree of purity.
  • the process of separating hydrogen using Palladium alloy membranes is typically carried out at high temperatures, in the order of about 500 0 C to about 600°C, and high pressures, in the order of at least 2MPa. Examples of such membranes are manufactured by the firm Reb Research & consulting of Ferndale, MI 48220.
  • one or more of the membrane separation units may be replaced with any other suitable separation arrangement.
  • separation processes based on physical absorption may be used.
  • absorption separation unit 220 CO 2 , CO and hydrocarbons may be separated from an inlet gas also comprising hydrogen in the separator regenerator unit 224.
  • CO can be removed using a mixture of aluminium tetrachloride and copper tetrachloride; CO 2 can be removed by using monoethanolamin (NH 2 CH 2 CH 2 OH), for example.
  • monoethanolamin NH 2 CH 2 CH 2 OH
  • the unwanted gases CO 2 , CO and hydrocarbons come out of solution and are siphoned away at 227 via cooler 222 and compressor 223, while the absorbent agent is recycled to the absorber 221. Accordingly, the hydrogen in the absorber 221 becomes more and more purified, and the hydrogen can be removed from the absorber for use or storage.
  • suitable separation units based on physical adsorption methods for example pressure swing adsorption (PSA) or short cycle heatless adsorption (SCA) may be used.
  • PSA pressure swing adsorption
  • SCA short cycle heatless adsorption
  • separation units based on cryogenic methods may be used.
  • oxidizer unit 280 air, oxygen or other oxidizer is provided from source 285 to convert the relatively small proportions of CO in P4 to CO 2 , and the resulting output gas P5, comprising substantially pure CO 2 is directed to a carbon monoxide generator 290.
  • the oxidizer unit 280 may be omitted, and instead the CO is separated from the CO 2 , for example in separation unit 270 or another separating unit, the CO 2 being directed to the carbon monoxide generator 290, while the CO is recycled directly to the steam converter 230.
  • the first option of converting the CO to CO 2 is typically more advantageous.
  • the oxidizer unit 280 may be omitted, and the gas mixture including CO and CO 2 is directed to carbon monoxide generator 290.
  • Carbon monoxide generator 290 is adapted for generating carbon monoxide from carbon dioxide.
  • the said carbon monoxide generator 290 comprises a microwave plasma torch reactor or plasmatron which is based on providing non-equilibrium microwave supersonic discharges to the W
  • a UHF discharge is maintained in the plasmatron for the purpose of breaking down the CO 2 , and gas temperatures in the discharge can reach 1,500 0 C to about 2,000 0 C.
  • the UHF discharge is maintained by a high power magnetron connected to a suitable DC electrical supply. Suitable heat exchangers and compressors are provided to maintain the pressure in the plasmatron below atmospheric.
  • the conversion efficiency of the generator 290 is typically kept at between 35% to about 40% by weight, since after decomposition the gas mixture can become explosive if the CO 2 concentration in the mixture is below about 60% by weight.
  • Suitable plasma torch reactors for converting or reforming CO 2 to CO are disclosed in the following publications, the contents of which are incorporated herein by reference:-
  • the resultant output gases P6, comprising a mixture of CO 2 , CO, and O 2 5 of varying proportions is directed to the steam converter 230, so that the CO from output gases P6 is reacted with steam to provide more hydrogen. Effectively, then, carbon monoxide is continually recycled in the post-processing unit 200, producing hydrogen from steam which is continuously provided via source 245. In addition, more CO is also continually provided to the CO recycling loop by
  • a carbon dioxide separator (not shown) may be provided for removing excess CO 2 from the recycling loop past the carbon monoxide generator 290, and this CO 2 may be stored or sold as desired.
  • a separator may be similar to separator 270, and may comprise, for example, a membrane separator, and is particularly adapted for separating CO 2 from the other output
  • any other suitable process may be applied for removing the excess CO 2 , and many such processes are commonly used industrially for this purpose, including for example, chemosorption processes, which may be based on amines such as for example monomethanolamin and/or dimethanolamin, or alternatively may be alkaline-based; physical absorption processes (for example
  • an oxygen separator (not shown) may be provided for removing excess O 2 from the recycling loop past the carbon monoxide generator
  • this O 2 may be stored, and/or sold.
  • at least a part of the oxygen generated by the CO generator 290 may be channeled to the plant 10 and/or to oxidizer unit 280 to be used as oxidizer.
  • One or more compressors (not shown), as well as valves and other suitable hardware, are provided at strategic locations in the system 200 to provide required pressure heads and safety and control apparatus such that gases are caused to flow within the system 200 in the desired directions therein.
  • a chimney, flue or stack (not shown) may be provided for venting excess gases and removing the same from the system 200.
  • a second embodiment of the invention is illustrated in Fig. 6 and comprises all of the elements and features as described with respect to the first embodiment, mutatis mutandis, with some differences as described below.
  • similar components to the first embodiment are shown in Fig. 6 with the same reference numerals.
  • the main distinctions between the second and first embodiments are that in the second embodiment, hydrogen is extracted at a number of separate stages.
  • output gases from the waste processing plant 100 having been filtered and scrubbed by unit 130, are passed through a cooler 283, fed with water from source 286, and the gases are passed through a first separator unit 279a, typically a membrane separator unit as described for the first embodiment, mutatis mutandis, via compressor 282, to separate the hydrogen therein. Residual gases are then passed on to the steam converter 230, which converts CO in the residual gases to CO 2 and H 2 , and to the hydrocarbon converter 250, which converts the hydrogen bound in the hydrocarbons to molecular H 2 .
  • a first separator unit 279a typically a membrane separator unit as described for the first embodiment, mutatis mutandis
  • Another separating unit 279b typically a membrane separator, separates out the hydrogen produced in these conversion units, and the residual gases are passed on to a suitable PSA unit (for example as provided by the Russian firm "GRASIS") or the like, coupled to a third membrane separator 279c for removing substantially the remaining hydrogen gases produced by the system 200'.
  • the residual gases are then passed on directly to the carbon monoxide generator 290, or alternatively the residual gases are first separated out so that only CO and CO 2 are channeled to the carbon monoxide generator 290, which converts CO 2 to CO and feeds this back to the steam converter unit 230 to continue with another hydrogen generation cycle.
  • a suitable separation unit for example a membrane separation unit, can be configured for separating CO from the corresponding gas mixture prior to being channeled to the steam converter 230, so that only CO (and possibly some CO 2 and/or H 2 only) is provided to the steam converter 230.
  • an absorption unit typically similar to that illustrated in Fig. 5 may be used for the extraction of CO from the gas mixture.
  • the gas mixture is input to an absorber unit containing a particular liquid absorbent that selectively absorbs CO.
  • Selective absorption of CO can be provided with an absorbent liquid comprising a solution of mixed slats of copper and aluminium tetrachloride in aromatic hydrocarbons (e.g., in toluene).
  • the absorption process can be carried out at moderate temperatures, such as about 40 0 C, and minimum positive gauge pressures.
  • the remaining gases of the mixture, having been rid of the CO, are then removed from the unit, and after having been cleaned from residual absorbent (by condensers and filters, for example) and supplied to the next component in the system.
  • the absorbent liquid, saturated with CO, is the heated via a heat exchanger to release the CO, and the regenerated absorbent liquid is channeled back to the absorbent unit via the heat exchanger.
  • This desorption can be carried out by heating the absorbent, for example the aforesaid solution of mixed slats of copper and aluminium tetrachloride in aromatic hydrocarbons, up to a temperature of between about 120 0 C and about 14O 0 C.
  • moisture is removed from the gas mixture prior to absorption of CO.
  • the extracted CO is then purified from any remaining drops of absorbent, and supplied to the steam converter 230 for generating hydrogen and CO 2 from steam.
  • the present invention provides a system for producing hydrogen from waste and also from water provided to the system, using the CO and CO 2 in the product gases from the plant 10 in a recycling loop to provide a high efficiency for hydrogen production.
  • the system 400 is similar to the system 200 of the first aspect of the invention, and comprises a steam converter 430, optional heat exchanger 440, hydrogen separation units 470a, 470b, optional oxidizer unit (not shown) with oxygen supply (not shown), carbon monoxide generator 490, similar to the components described above for the system 200, mutatis mutandis, i.e.:- steam converter 230, heat exchanger 240, hydrogen separation unit 270, oxidizer unit 280 with oxygen supply 285, carbon monoxide generator 290.
  • Suitable conduits between the different components as illustrated in Figs. 7 and 8, and water is provided from a water source (not shown), similar to water source 245 as described above, mutatis mutandis.
  • the system 400 differs from the system 200 of the first aspect of the invention in a number of ways.
  • a carbon monoxide source (not shown) provides an initial quantity of CO to the system 400, and replenishes the same with CO as required to compensate for any losses in CO; other than this, substantially the same quantity of CO is constantly recirculated through system 400 during operation thereof.
  • the carbon monoxide source may comprise any suitable arrangement for providing carbon monoxide, and may include, for example, a supply of CO, for example in pressurized bottles, a burner typically configured to burn coke or the like in an oxygen atmosphere in a manner such as to produce CO. If necessary 2
  • CO 2 may be provided to the carbon monoxide generator 490, and the process started thereat (and of course, depletions in CO can also be corrected by topping up with CO 2 at the carbon monoxide generator 490).
  • a liquid CO 2 storage tank 401 provides an initial quantity of gaseous CO 2 to the carbon monoxide generator 490 via gasifier 402, typically a heated diffuser arrangement. Excess gaseous CO 2 may be stored in storage tank 403.
  • the carbon monoxide generator 490 comprises a plasma-chemical reactor 404 and a magnetron 406 comprising a waveguide system directed to said reactor 404, and connected to a suitable DC electrical supply 407.
  • the carbon monoxide generator 490 is typically operated at a conversion efficiency of between about 35% to about 40% for safety reasons.
  • the output gases comprising CO, CO 2 , and O 2 are cooled via heat exchanger 440, which is connected to a vacuum pump 411 to reduce the pressure in the reactor 404 to below atmospheric.
  • the gas mixture is compressed via compressor 412 prior to being fed to a separation unit 470a, which comprises an additional compressor 413 for recirculating the gas mixtures through the separator 470a to boost the separating efficiency thereof.
  • the separator 470a can be a membrane separator, or an absorption separator, for example as described above, mutatis mutandis, and separates out CO from the CO 2 and O 2 .
  • the Oxygen can be converted to CO 2 via afterburner or combustor 418 and recycled to the carbon monoxide generator 490 via conduit 431 and non- return valve 405.
  • Catalytic reactor 435 is provided for converting excess CO, that could not be separated out in the separator 470a, into CO 2 .
  • the CO separated out by the separator unit 470a is channeled to the steam converter 430, which is fed steam from a suitable supply (not shown).
  • the product gases from the steam converter, CO 2 and H 2 are then channeled to a second separator unit 470b, which also comprises a compressor arrangement 417 the gas mixture through the separator 470b to boost the separating efficiency thereof.
  • the separator 470b can be a membrane separator, for example as described above, mutatis mutandis, and separates out H 2 from the CO 2 .
  • system 400 provides hydrogen from a single source, the conversion of CO, which is continually recycled through the system 400. There is also no need in general for hydrocarbon converter or its associated cooler.
  • the oxygen which is produced by the carbon monoxide converter or generator 490 can be removed and stored or sold, for example.
  • the compressors, as well as valves and other suitable hardware, are provided at strategic locations in the system 400 to provide required pressure heads and safety and control apparatus such that gases are caused to flow within the system 400 in the desired directions therein.
  • a suitable control system 419 is provided for monitoring and controlling the monoxide generator 490, and another control unit 420 for controlling and monitoring operation of the separation units 470a and 470b.
  • the hydrogen production method according to a first embodiment comprises the following steps :-
  • Step 310 - providing a core quantity of carbon monoxide, typically CO 2 is provided by the carbon dioxide source 401 and converted to CO by the carbon monoxide generator 490.
  • Step 320 reacting the carbon monoxide with water, typically in the form of steam, to produce hydrogen and carbon dioxide according to a water-gas shift reaction:-
  • This step is carried out substantially as described above via steam converter 430, the reaction product gases being cooled by the heat exchanger 440, which in turn advantageously preheats steam prior to being reacted in the steam converter 430.
  • Step 330 - the hydrogen produced in step 320 is separated from the carbon dioxide, as well as unreacted water and CO. Hydrogen separation is typically via suitable membranes, as described for the first aspect of the invention, mutatis mutandis.
  • Step 340 - the CO 2 in step 330 is converted back to carbon monoxide and recirculated so that step 320 may be reapplied to the CO.
  • a carbon monoxide converter 490 is used for this reaction, and optionally, carbon monoxide left over in the gases leaving the hydrogen separation unit 470 may be first oxidized to CO 2 , as described for the first aspect of the invention, mutatis mutandis.
  • oxygen produced by the conversion of CO 2 to CO may be recirculated within the system to oxidize the residual CO left over after the hydrogen is separated in step 330.
  • the quantity of CO remaining at step 340 is determined, and if depleted can be augmented as required at step 360.
  • water is supplied to the system 400 via a suitable water source, and hydrogen is generated therefrom, the carbon monoxide required for the steam conversion reaction being continually recycled from CO 2 produced by the steam conversion reaction itself.
  • the system 400 may be incorporated into an apparatus having a water inlet and a hydrogen outlet, and may be configured for large scale use, for example industrial, hospital, household and other uses, or may be configured in a transportable configuration.
  • the system may be incorporated in a seafaring ship to produce hydrogen to power the ship from seawater, though the system would typically require suitable arrangement for purifying the water prior to being reacted with the carbon monoxide.
  • systems and methods are provided for producing hydrogen, based on reacting CO with water, and reconverting the resulting carbon dioxide to CO and recycling the same.
  • the system and method are coupled to a waste processing plant.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L’invention concerne des systèmes et procédés de production de l’hydrogène, basés sur la réaction de CO avec l’eau et la reconversion du dioxyde de carbone résultant en CO, qui est alors recyclé. Sous l'un des aspects de l'invention, le système et le procédé sont couplés à une usine de traitement des déchets.
PCT/IL2006/000435 2005-04-12 2006-04-06 Systemes et procedes pour la production d’hydrogene WO2006109294A1 (fr)

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EP2163597A1 (fr) * 2007-07-06 2010-03-17 Aba Research, S. A. De C. V. Procédé et appareil pour la gazéification au plasma de matière carbonique par irradiation micro-ondes
WO2011005984A2 (fr) * 2009-01-01 2011-01-13 Mitchell Andrew G Processus permettant de générer de l’huile algale et de l’électricité à partir de déchets d’origine humaine et animale et d’autres sources d’hydrocarbures
JP2015113265A (ja) * 2013-12-13 2015-06-22 三菱日立パワーシステムズ株式会社 水素製造装置および水素製造方法
AT524186A1 (de) * 2020-08-25 2022-03-15 Gs Gruber Schmidt Erzeugung von Wasserstoff mit Hilfe von Metalloxidreaktoren und plasmaunterstützte Umwandlung von Kohlendioxid zu Synthesegas
AT524185A1 (de) * 2020-08-31 2022-03-15 Gs Gruber Schmidt Erzeugung von Wasserstoff mit Hilfe von solarthermischer Strahlung und Metalloxidreaktoren

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2163597A1 (fr) * 2007-07-06 2010-03-17 Aba Research, S. A. De C. V. Procédé et appareil pour la gazéification au plasma de matière carbonique par irradiation micro-ondes
EP2163597A4 (fr) * 2007-07-06 2012-08-22 Aba Res S A De C V Procédé et appareil pour la gazéification au plasma de matière carbonique par irradiation micro-ondes
WO2011005984A2 (fr) * 2009-01-01 2011-01-13 Mitchell Andrew G Processus permettant de générer de l’huile algale et de l’électricité à partir de déchets d’origine humaine et animale et d’autres sources d’hydrocarbures
WO2011005984A3 (fr) * 2009-01-01 2011-04-28 Mitchell Andrew G Processus permettant de générer de l'huile algale et de l'électricité à partir de déchets d'origine humaine et animale et d'autres sources d'hydrocarbures
JP2015113265A (ja) * 2013-12-13 2015-06-22 三菱日立パワーシステムズ株式会社 水素製造装置および水素製造方法
AT524186A1 (de) * 2020-08-25 2022-03-15 Gs Gruber Schmidt Erzeugung von Wasserstoff mit Hilfe von Metalloxidreaktoren und plasmaunterstützte Umwandlung von Kohlendioxid zu Synthesegas
AT524185A1 (de) * 2020-08-31 2022-03-15 Gs Gruber Schmidt Erzeugung von Wasserstoff mit Hilfe von solarthermischer Strahlung und Metalloxidreaktoren

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