US20060272956A1 - Dual hydrogen production apparatus - Google Patents

Dual hydrogen production apparatus Download PDF

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US20060272956A1
US20060272956A1 US11/443,889 US44388906A US2006272956A1 US 20060272956 A1 US20060272956 A1 US 20060272956A1 US 44388906 A US44388906 A US 44388906A US 2006272956 A1 US2006272956 A1 US 2006272956A1
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hydrogen
hydrogen production
feed material
bioreactor
production apparatus
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Mitchell Felder
Justin Felder
Harry Diz
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
    • C12M41/26—Means for regulation, monitoring, measurement or control, e.g. flow regulation of pH
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
    • C12M41/28—Means for regulation, monitoring, measurement or control, e.g. flow regulation of redox potential
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00—Means for pre-treatment of biological substances
    • C12M45/20—Heating; Cooling
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
    • C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates generally to a combination apparatus for concentrated production of hydrogen from hydrogen producing microorganism cultures. More particularly, the invention relates to a method that dually combines a primary hydrogen production apparatus with a secondary hydrogen production apparatus that is different than the primary hydrogen production apparatus.
  • the primary hydrogen production apparatus uses heat or uses heat waste that is produced during typical usage of the secondary hydrogen production apparatus, thereby reducing energy costs of the primary hydrogen production apparatus and conserving energy.
  • One possible method is to create hydrogen in a biological system by converting organic matter into hydrogen gas.
  • the creation of a biogas that is substantially hydrogen can theoretically be achieved in a bioreactor, wherein hydrogen producing microorganisms and an organic feed material are held in an environment favorable to hydrogen production.
  • Substantial and useful creation of hydrogen gas from microorganisms is problematic.
  • the primary obstacle to sustained production of useful quantities of hydrogen by micro-organisms has been the eventual stoppage of hydrogen production generally coinciding with the appearance of methane. This occurs when methanogenic microorganisms invades the bioreactor environment converting hydrogen to methane. This process occurs naturally in anaerobic environments such as marshes, swamps, and pond sediments.
  • continuous production of hydrogen from hydrogen producing micro-organisms has been unsuccessful in the past.
  • Microbiologists have for many years known of organisms which generate hydrogen as a metabolic by-product. Two reviews of this body of knowledge are Kosaric and Lyng (1988) and Nandi and Sengupta (1998).
  • the heterotrophic facultative anaerobes are of interest in this study, particularly those in the group known as the enteric microorganisms. Within this group are the mixed-acid fermenters, whose most well known member is Escherichia coli .
  • one mole of glucose produces two moles of hydrogen gas.
  • acetic and lactic acids also produced during the process are acetic and lactic acids, and minor amounts of succinic acid and ethanol.
  • Other enteric microorganisms use a different enzyme pathway which causes additional CO 2 generation resulting in a 6:1 ratio of carbon dioxide to hydrogen production (Madigan et al., 1997).
  • the hydrogen is typically converted into methane by methanogens.
  • waste organic matter there are many sources of waste organic matter which could serve as a substrate for this microbial process.
  • One such material would be organic-rich industrial wastewaters, particularly sugar-rich waters, such as fruit and vegetable processing wastes.
  • Other sources include agricultural residues and other organic waste such as sewage and manures.
  • Electrolysis is generally a chemical process in which chemically bonded elements are separated by passing an electrical current through them.
  • An important application of electrolysis is in the separation of water into hydrogen and oxygen by the equation 2H 2 O ⁇ 2H 2 +O 2 .
  • This reaction can occur on a highly simplified level, for example, by running two leads from a typical battery into water held in a cup. In this instance, as electricity is passed from one lead to another, preferably with the aid of a water soluble electrolyte, hydrogen and oxygen bubbles can be seen bubbling up from the water.
  • electrolysis can create hydrogen on a larger scale in an electrolyzer. While an electrolyzer is functional at room temperature, doing so at an efficient level requires a high level of electrical energy. High temperature electrolyzers are more efficient than traditional room-temperature electrolyzers because some of the energy is supplied as heat, which is cheaper than electricity, and because the electrolysis reaction is more efficient at higher temperatures. Indeed, at 2500° C., electrical input is unnecessary because water breaks down to hydrogen and oxygen through thermolysis. As such temperatures are impractical, however; high temperature electrolyzers operate at about 100 to 1000° C. At higher temperature operating rates, lower levels of energy are required.
  • Typical high temperature electrolyzers convey steam or super-heated water into an electrolytic cell having an anode and a cathode. This may occur in combination with hydrogen, for example, at about a 50-50 ratio of steam to hydrogen.
  • the steam or water is split within the cell such that oxygen moves toward the anode and hydrogen moves toward the cathode.
  • Remaining steam (if used), prior existing hydrogen and produced hydrogen exit the cell together, wherein hydrogen which can be separated from the steam by a condenser or other like apparatus. In either case, there is never a 100% efficient conversion of the water or steam to hydrogen, resulting in left over heated steam, water and/or oxygen.
  • New apparatuses for hydrogen generation are therefore needed that produce substantial and useful levels of hydrogen in an inexpensive, environmentally sound apparatus that additionally dually combine differing hydrogen production apparatuses.
  • An apparatus for dually producing hydrogen comprising: a secondary hydrogen production apparatus including an apparatus that breaks down chemical compounds, wherein hydrogen is produced from one or a series of reactions using heated liquids, vapors or gases, a primary hydrogen production apparatus operably combined with the secondary hydrogen production apparatus, the primary hydrogen production apparatus including a bioreactor adapted to produce hydrogen from microorganisms metabolizing an organic feed material, and a heat exchanger operably associated with the primary and secondary hydrogen production apparatuses such that heat from the secondary hydrogen production apparatus is transferred to the primary hydrogen production apparatus.
  • FIG. 1 is a plan view of a primary hydrogen production apparatus proximate the secondary hydrogen production apparatus.
  • FIG. 2 is a side view of one embodiment of the bioreactor.
  • FIG. 3 is a plan view the bioreactor.
  • FIG. 4 is a plan view of a secondary hydrogen production apparatus proximate the primary hydrogen production apparatus.
  • FIG. 5 is a plan view of a high temperature secondary hydrogen production apparatus proximate the primary hydrogen production apparatus.
  • microorganisms include bacteria and substantially microscopic cellular organisms.
  • hydrophilicity As used herein, the term “hydrogen producing microorganisms” includes microorganisms that metabolize an organic substrate in one or a series of reactions that ultimately form hydrogen as one of the end products.
  • methanogens refers to microorganisms that metabolize hydrogen in one or a series of reactions that produce methane as one of the end products.
  • primary hydrogen production apparatus refers to a hydrogen producing process from hydrogen producing microorganisms in a bioreactor and related preparatory steps.
  • secondary hydrogen production apparatus refers to a hydrogen producing process other than a bioreactor hydrogen producing process wherein heat waste resultant from the dual hydrogen producing process is used in the primary hydrogen production apparatus.
  • heat waste refers to heat that is produced by dual hydrogen producing process that is otherwise not recycled into the dual hydrogen producing process such as excess heat or aqueous or gaseous compounds that have elevated temperatures, wherein some of the heat is diverted into another hydrogen producing process.
  • FIG. 1 A dual hydrogen producing apparatus 100 in accordance with the present invention is shown in FIG. 1 , wherein primary hydrogen production apparatus 96 is shown in detail.
  • primary hydrogen production apparatus 96 includes bioreactor 10 , heat exchanger 12 , optional equalization tank 14 and reservoir 16 .
  • Apparatus 100 further includes secondary hydrogen production apparatus 50 , and passage 44 bridging primary hydrogen production apparatus 96 and secondary hydrogen production apparatus 50 .
  • Apparatus 100 produces gas in bioreactor 10 , wherein the produced gas contains hydrogen and does not substantially include any methane.
  • the hydrogen containing gas is produced by the metabolism of an organic feed material by hydrogen producing microorganisms.
  • organic feed material is a sugar containing organic feed material.
  • the organic feed material is industrial wastewater or effluent product that is produced during routine formation of fruit and/or vegetable juices, such as grape juice.
  • wastewaters rich not only in sugars but also in protein and fats could be used, such as milk product wastes.
  • the most complex potential source of energy for this process would be sewage-related wastes, such as municipal sewage sludge and animal manures.
  • any feed containing organic material is usable in hydrogen production apparatus 100 .
  • Hydrogen producing microorganisms can metabolize the sugars in the organic feed material under the reactions: Glucose ⁇ 2 Pyruvate (1) 2 Pyruvate+2 Coenzyme A ⁇ 2 Acetyl-CoA+2 HCOOH (2) 2 HCOOH ⁇ 2H 2 +2 CO 2 (3)
  • one mole of glucose produces two moles of hydrogen gas and carbon dioxide.
  • other organic feed materials include agricultural residues and other organic wastes such as sewage and manures. Typical hydrogen producing microorganisms are adept at metabolizing the high sugar organic waste into bacterial waste products.
  • the wastewater may be further treated by aerating, diluting the solution with water or other dilutants, adding compounds that can control the pH of the solution or other treatment step.
  • the solution may be supplemented with phosphorus (NaH 2 PO 4 ) or yeast extract.
  • Organic feed material provides a plentiful feeding ground for hydrogen producing microorganisms and is naturally infested with these microorganisms. While hydrogen producing microorganisms typically occur naturally in an organic feed material, the organic feed material is preferably further inoculated with hydrogen producing microorganisms in an inoculation step. The inoculation may be an initial, one-time addition to bioreactor 10 at the beginning of the hydrogen production process. Further inoculations, however, may be added as desired. The added hydrogen producing microorganisms may include the same types of microorganisms that occur naturally in the organic feed material.
  • the hydrogen producing microorganisms are preferably microorganisms that thrive in pH levels of about 3.5 to 6.0 and can survive in temperature of 60-100° F. or, more preferably, 60-75°.
  • These hydrogen producing microorganisms include, but are not limited to, Clostridium sporogenes, Bacillus licheniformis and Kleibsiella oxytoca .
  • Hydrogen producing microorganisms can be obtained from a microorganismal culture lab or like source. Other hydrogen producing microorganisms or microorganisms known in the art, however, can be used within the spirit of the invention.
  • the inoculation step can occur in bioreactor 10 or elsewhere in the apparatus, for example, recirculation system 58 .
  • Reservoir 16 is a container known in the art that can contain an organic feed material.
  • the size, shape, and material of reservoir 16 can vary widely within the spirit of the invention.
  • reservoir 16 is one or a multiplicity of storage tanks that are adaptable to receive, hold and store the organic feed material when not in use, wherein the one or a multiplicity of storage tanks may be mobile.
  • reservoir 16 is a wastewater well that is adaptable to receive and contain wastewater and/or effluent from an industrial facility 50 .
  • reservoir 16 is adaptable to receive and contain wastewater that is effluent from a juice manufacturing industrial facility 50 , such that the effluent held in the reservoir is a sugar rich juice sludge.
  • Organic feed material contained in reservoir 16 can be removed through passage 22 with pump 28 .
  • Pump 28 is in operable relation to reservoir 16 such that it aids removal movement of organic feed material 16 into passage 22 at a desired, adjustable flow rate, wherein pump 28 can be any pump known in the art suitable for pumping liquids.
  • pump 28 is a submersible sump pump.
  • Reservoir 16 may further include a low pH cutoff device 52 , such that exiting movement into passage 22 of the organic feed material is ceased if the pH of the organic feed material is outside of a desired range.
  • the pH cutoff device 52 is a device known in the art operably related to reservoir 16 and pump 28 .
  • the device ceases operation of pump 28 .
  • the pH cut off in reservoir 16 is typically greater than the preferred pH of bioreactor 10 .
  • the pH cutoff 52 is set between about 7 and 8 pH. In alternate embodiments, particularly when reservoir 16 is not adapted to receive effluent from an industrial facility 50 , the pH cutoff device is not used.
  • Equalization tank is an optional intermediary container for holding organic feed material between reservoir 16 and heat exchanger 12 .
  • Equalization tank 14 provides an intermediary container that can help control the flow rates of organic feed material into heat exchanger 12 by providing a slower flow rate into passage 20 than the flow rate of organic feed material into the equalization tank through passage 22 .
  • the equalization tank can be formed of an), material suitable for holding and treating the organic feed material.
  • equalization tank 14 is constructed of high density polyethylene materials. Other materials include, but are not limited to, metals or acrylics. Additionally, the size and shape of equalization tank 14 can vary widely within the spirit of the invention depending on throughput and output and location limitations.
  • equalization tank 14 further includes a low level cut-off point device 56 .
  • the low-level cut-off point device ceases operation of pump 26 if organic feed material contained in equalization tank 14 falls below a predetermined level. This prevents air from entering passage 20 .
  • Organic feed material can be removed through passage 20 or through passage 24 .
  • Passage 20 provides removal access from equalization tank 14 and entry access into heat exchanger 12 .
  • Passage 24 provides removal access from equalization tank 14 of solution back to reservoir 16 .
  • Passage 24 provides a removal system for excess organic feed material that exceeds the cut-off point of equalization tank 14 .
  • Both passage 20 and passage 24 may further be operably related to pumps to facilitate movement of the organic feed material.
  • equalization tank 14 is not used and organic feed material moves directly from reservoir 16 to heat exchanger 12 . In these embodiments, passages connecting reservoir 16 and heat exchanger 12 are arranged accordingly.
  • the organic feed material is heated prior to conveyance into the bioreactor.
  • the heating can occur anywhere upstream.
  • the heating is achieved in one or a multiplicity of heat exchangers 12 , wherein the organic feed material is heated within the heat exchanger 12 by liquids or gasses of elevated temperatures from secondary hydrogen production apparatus 50 conveyed through passage 44 .
  • Passage 44 may further be associated with a pump device to control flow rates.
  • gases or liquids originally conveyed through passage 44 may be discarded through an effluent pipe (not pictured) or recycled back into the secondary hydrogen production apparatus.
  • Organic feed solution can be additionally heated at additional or alternate locations in the hydrogen production apparatus.
  • Passage 20 provides entry access to heat exchanger 12 , wherein heat exchanger 12 is any apparatus known in the art that can contain and heat contents held within it. Passage 20 is preferably operably related to pump 26 . Pump 26 aids the conveyance of solution from equalization tank 14 or reservoir 16 into heat exchanger 12 through passage 20 , wherein pump 26 is any pump known in the art suitable for this purpose. In preferred embodiments, pump 26 is an air driven pump for ideal safety reasons. However, motorized pumps are also found to be safe and are likewise usable.
  • methanogens contained within the organic feed material are substantially killed or deactivated.
  • the methanogens are substantially killed or deactivated prior to entry into the bioreactor.
  • methanogens contained within the organic feed material are substantially killed or deactivated by being heated under elevated temperatures in heat exchanger 12 .
  • Methanogens are substantially killed or deactivated by elevated temperatures. Methanogens are generally deactivated when heated to temperatures of about 60-75° C. for a period of at least 15 minutes. Additionally, methanogens are generally damaged or killed when heated to temperatures above about 90° C.
  • Heat exchanger 12 enables heating of the organic feed material to temperature of about 60-100° C. in order to substantially deactivate or kill the methanogens while leaving any hydrogen producing microorganisms substantially functional. This effectively pasteurizes or sterilizes the contents of the organic feed material from active methanogens while leaving the hydrogen producing microorganisms intact, thus allowing the produced biogas to include hydrogen without subsequent conversion to methane.
  • the size, shape and numbers of heat exchangers 12 can vary widely within the spirit of the invention depending on throughput and output required and location limitations.
  • retention time in heat exchanger 12 is at least 20 minutes. Retention time marks the average time any particular part of organic feed material is retained in heat exchanger 12 .
  • At least one temperature sensor 48 monitors a temperature indicative of the organic feed material temperature, preferably the temperature levels of equalization tank 14 and/or heat exchanger 12 .
  • an electronic controller is provided having at least one microprocessor adapted to process signals from one or a plurality of devices providing organic feed material parameter information, wherein the electronic controller is operably related to the at least one actuatable terminal and is arranged to control the operation of and to controllably heat the heat exchanger 12 and/or any contents therein.
  • the electronic controller is located or coupled to heat exchanger 12 or equalization tank 14 , or can alternatively be at a third or remote location. In alternate embodiments, the controller for controlling the temperature of heat exchanger 12 is not operably related to temperature sensor 48 .
  • Passage 18 connects heat exchanger 12 with bioreactor 10 .
  • Organic feed material is conveyed into the bioreactor through transport passage 18 at a desired flow rate.
  • System 100 is a continuous flow system with organic feed material in constant motion between containers such as reservoir 16 , heat exchanger 12 , bioreactor 10 , equalization tank 14 if applicable, and so forth.
  • Flow rates between the container can vary depending on retention time desired in any particular container. For example, in preferred embodiments, retention time in bioreactor 10 is between about 6 and 12 hours. To meet this retention time, the flow rate of passage 18 and effluent passage 36 are adjustable as known in the art so that organic feed material, on average, stays in bioreactor 10 for this period of time.
  • passage 18 having a first and second end, wherein passage 18 provides entry access to the bioreactor at a first end of passage 18 and providing removal access to the heat exchanger 12 at a second end of passage 18 .
  • Any type of passage known in the art can be used, such as a pipe or flexible tube.
  • the transport passage may abut or extend within the bioreactor and/or the heat exchanger 12 .
  • Passage 18 can generally provide access to bioreactor 10 at any location along the bioreactor. However, in preferred embodiments, passage 18 provides access at an upper portion of bioreactor 10 .
  • Bioreactor 10 provides an anaerobic environment conducive for hydrogen producing microorganisms to grow, metabolize organic feed material, and produce hydrogen. While the bioreactor is beneficial to the growth of hydrogen producing microorganisms and the corresponding metabolism of organic feed material by the hydrogen producing microorganisms, it is preferably restrictive to the proliferation of unwanted microorganisms such as methanogens, wherein methanogens are microorganisms that metabolize carbon dioxide and hydrogen to produce methane and water. Methanogens are obviously unwanted as they metabolize hydrogen. If methanogens were to exist in substantial quantities in bioreactor 10 , hydrogen produced by the hydrogen producing bacteria will subsequently be converted to methane, reducing the percentage of hydrogen in the produced gas.
  • methanogens were to exist in substantial quantities in bioreactor 10 , hydrogen produced by the hydrogen producing bacteria will subsequently be converted to methane, reducing the percentage of hydrogen in the produced gas.
  • Bioreactor 10 can be any receptacle known in the art for holding an organic feed material.
  • Bioreactor 10 is substantially airtight, providing an anaerobic environment.
  • Bioreactor 10 itself may contain several openings. However, these openings are covered with substantially airtight coverings or connections, such as passage 18 , thereby keeping the environment in bioreactor 10 substantially anaerobic.
  • the receptacle will be a limiting factor for material that can be produced. The larger the receptacle, the more hydrogen producing bacteria containing organic feed material, and, by extension, hydrogen, can be produced. Therefore, the size and shape of the bioreactor can vary widely within the sprit of the invention depending on throughput and output and location limitations.
  • Bioreactor 80 can be formed of any material suitable for holding an organic feed material and that can further create an airtight, anaerobic environment.
  • bioreactor 10 is constructed of high density polyethylene materials. Other materials, including but not limited to metals or plastics can similarly be used.
  • a generally silo-shaped bioreactor 80 has about a 300 gallon capacity with a generally conical bottom 84 .
  • Stand 82 is adapted to hold cone bottom 84 and thereby hold bioreactor 80 in an upright position.
  • the bioreactor 80 preferably includes one or a multiplicity of openings that provide a passage for supplying or removing contents from within the bioreactor.
  • bioreactor 80 preferably includes a central opening covered by lid 86 .
  • the capacity of bioreactor 80 can be readily scaled upward or downward depending on needs or space limitations.
  • the bioreactor preferably provides a system to remove excess solution, as shown in FIGS. 1 and 3 .
  • the bioreactor includes effluent passage 36 having an open first and second end that provides a passage from inside bioreactor 10 to outside the bioreactor.
  • the first end of effluent passage 36 may abut bioreactor 10 or extend into the interior of bioreactor 10 . If effluent passage 36 extends into the interior of passage 10 , the effluent passage preferably extends upwards to generally upper portion of bioreactor 10 .
  • Effluent passage 36 preferably extends from bioreactor 10 into a suitable location for effluent, such as a sewer or effluent container, wherein the excess organic feed material will be deposited through the open second end.
  • Bioreactor 10 preferably contains one or a multiplicity of substrates 90 for providing surface area for attachment and growth of bacterial biofilms. Sizes and shapes of the one or a multiplicity of substrates 90 can vary widely, including but not limited to flat surfaces, pipes, rods, beads, slats, tubes, slides, screens, honeycombs, spheres, object with latticework, or other objects with holes bored through the surface. Numerous substrates can be used, for example, hundreds, as needed. The more successful the biofilm growth on the substrates, the more fixed state hydrogen production will be achieved. The fixed nature of the hydrogen producing microorganisms provide the sustain production of hydrogen in the bioreactor.
  • Substrates 90 preferably are substantially free of interior spaces that potentially fill with gas.
  • the bioreactor comprises about 100-300 pieces of 1′′ plastic media to provide surface area for attachment of the bacterial biofilm.
  • substrates 90 are FlexiringTM Random Packing (Koch-Glitsch.) Some substrates 90 may be retained below the liquid surface by a retaining device, for example, a perforated acrylic plate. In this embodiment, substrates 90 have buoyancy, and float on the organic feed material.
  • the buoyant substrates stay at the same general horizontal level while the organic feed material circulates, whereby providing greater access to the organic feed material by hydrogen producing microorganism- and nonparaffinophilic microorganism-containing biofilm growing on the substrates.
  • a recirculation system 58 is provided in operable relation to bioreactor 10 .
  • Recirculation system 58 enables circulation of organic feed material contained within bioreactor 10 by removing orgYanic feed material at one location in bioreactor 10 and reintroduces the removed organic feed material at a separate location in bioreactor 10 , thereby creating a directional flow in the bioreactor.
  • the directional flow aids the microorganisms within the organic feed material in finding food sources and substrates on which to grown biofilms.
  • removing organic feed material from a lower region of bioreactor 10 and reintroducing it at an upper region of bioreactor 10 would create a downward flow in bioreactor 10 .
  • Removing organic feed material from an upper region of bioreactor 10 and reintroducing it at a lower region would create an up-flow in bioreactor 10 .
  • recirculation system 58 is arranged to produce an up-flow of any solution contained in bioreactor 10 .
  • Passage 60 provides removal access at a higher point than passage 62 provides entry access.
  • Pump 30 facilitates movement from bioreactor 10 into passage 60 , from passage 60 into passage 62 , and from passage 62 back into bioreactor 10 , creating up-flow movement in bioreactor 10 .
  • Pump 30 can be any pump known in the art for pumping organic feed material.
  • pump 30 is an air driven centrifugal pump. Other arrangements can be used, however, while maintaining the spirit of the invention.
  • a pump could be operably related to a single passage that extends from one located of the bioreactor to another.
  • Bioreactor 10 may optionally be operably related to one or a multiplicity of treatment apparatuses for treating organic feed material contained within bioreactor 10 for the purpose of making the organic feed material more conducive to proliferation of hydrogen producing microorganisms.
  • the one or a multiplicity of treatment apparatuses perform operations that include, but are to limited to, aerating the organic feed material, diluting the organic feed material with water or other dilutant, controlling the pH of the organic feed material, and adding additional chemical compounds to the organic feed material.
  • the apparatus coupled to the bioreactor can be any apparatuses known in the art for incorporating these treatments.
  • a dilution apparatus is a tank having a passage providing controllable entry access of a dilutant, such as water, into bioreactor 10 .
  • An aerating apparatus is an apparatus known in the art that provides a flow of gas into bioreactor 10 , wherein the gas is typically air.
  • a pH control apparatus is an apparatus known in the art for controlling a pH of a solution.
  • chemical compounds added by treatment apparatuses include anti-fungal agents, phosphorous supplements, yeast extract or hydrogen producing microorganism inoculation.
  • the one or a multiplicity of treatment apparatuses may be operably related to other parts of the bioreactor system.
  • the treatment apparatuses are operably related to equalization tank 14 or recirculation system 58 .
  • multiple treatment apparatus of the same type may be located at various points in the bioreactor system to provide treatments at desired locations.
  • pH controller 34 monitors the pH level of contents contained within bioreactor 10 .
  • the pH of the organic feed material in bioreactor 10 is maintained at about 3.5 to 6.0 pH, most preferably at about 4.5 to 5.5 pH, as shown in Table 2.
  • pH controller 34 controllably monitors the pH level of the organic feed material and adjustably controls the pH of the solution if the solution falls out of or is in danger of falling out of the desired range. As shown in FIG.
  • pH controller 34 monitors the pH level of contents contained in passage 62 , such as organic feed material, with pH sensor 64 .
  • pH controller 34 can be operably related to any additional or alternative location that potentially holds organic feed material, for example, passage 60 , passage 62 or bioreactor 10 as shown in FIG. 3 .
  • the pH of the organic feed material falls out of a desired range, the pH is preferably adjusted back into the desired range. Precise control of a pH level is necessary to provide an environment that enables at least some hydrogen producing bacteria to function while similarly providing an environment unfavorable to methanogens. This enables the novel concept of allowing microorganism reactions to create hydrogen without subsequently being overrun by methanogens that convert the hydrogen to methane.
  • Control of pH of the organic feed material in the bioreactor can be achieved by any means known in the art.
  • a pH controller 34 monitors the pH and can add a pH control solution from container 54 in an automated manner if the pH of the bioreactor solution moves out of a desired range.
  • the pH monitor controls the bioreactor solution's pH through automated addition of a sodium or potassium hydroxide solution.
  • a sodium or potassium hydroxide solution is an Etatron DLX pH monitoring device.
  • Preferred ranges of pH for the bioreactor solution is between about 3.5 and 6.0, with a more preferred range between about 4.0 and 5.5 pH.
  • the hydrogen producing reactions of hydrogen producing bacteria metabolizing organic feed material in bioreactor 10 can further be monitored by oxidation-reduction potential (ORP) sensor 32 .
  • ORP sensor 32 monitors redox potential of organic feed material contained within bioreactor 10 . Once ORP drops below about ⁇ 200 mV, gas production commences. Subsequently while operating in a continuous flow mode, the ORP was typically in the range of ⁇ 300 to ⁇ 450 mV.
  • the wastewater is a grape juice solution prepared using Welch's Concord Grape JuiceTM diluted in tap water at approximately 32 mL of juice per Liter.
  • the solution uses chlorine-free tap water or is aerated previously for 24 hours to substantially remove chlorine. Due to the acidity of the juice, the pH of the organic feed material is typically around 4.0.
  • the constitutional make-up of the grape juice solution is shown in Table 1. TABLE 1 Composition of concord grape juice. Source: Welch's Company, personal comm., 2005.
  • Bioreactor 10 further preferably includes an overflow cut-off switch 66 to turn off pump 26 if the solution exceeds or falls below a certain level in the bioreactor.
  • Bioreactor 10 further includes an apparatus for capturing the hydrogen containing gas produced by the hydrogen producing bacteria. Capture and cleaning methods can vary widely within the spirit of the invention.
  • gas is removed from bioreactor 10 through passage 38 , wherein passage 38 is any passage known in the art suitable for conveying a gaseous product.
  • Pump 40 is operably related to passage 38 to aid the removal of gas from bioreactor 10 while maintaining a slight negative pressure in the bioreactor.
  • pump 40 is an air driven pump.
  • the gas is conveyed to gas scrubber 42 , where hydrogen is separated from carbon dioxide. Other apparatuses for separating hydrogen from carbon dioxide may likewise be used.
  • the volume of collected gas can be measured by water displacement before and after scrubbing with concentrated NaOH.
  • Samples of scrubbed and dried gas may be analyzed for hydrogen and methane by gas chromatography with a thermal conductivity detector (TCD) and/or with a flame ionization detector (FID). Both hydrogen and methane respond in the TCD, but the response to methane is improved in the FID (hydrogen is not detected by an FID, which uses hydrogen as a fuel for the flame).
  • TCD thermal conductivity detector
  • FID flame ionization detector
  • Exhaust system 70 exhausts gas. Any exhaust system known in the art can be used. In a preferred embodiment, as shown in FIG. 1 , exhaust system includes exhaust passage 72 , backflow preventing device 74 , gas flow measurement and totalizer 76 , and air blower 46 .
  • the organic feed material may be further inoculated in an initial inoculation step with one or a multiplicity of hydrogen producing bacteria, such as Clostridium sporogenes, Bacillus licheniformiis and Kleibsiella oxytoca , while contained in bioreactor 10 .
  • hydrogen producing bacteria are obtained from a bacterial culture lab or like source.
  • the hydrogen producing bacteria that occur naturally in the waste solution can be used without inoculating the solution.
  • additional inoculations can occur in bioreactor 10 or other locations of the apparatus, for example, heat exchanger 12 , equalization tank 14 and reservoir 16 .
  • the preferred hydrogen producing bacteria is Kleibsiella oxytoca , a facultative enteric bacterium capable of hydrogen generation.
  • Kleibsiella oxytoca produces a substantially 1:1 ratio of hydrogen to carbon dioxide through organic feed material metabolization, not including impurities.
  • the source of both the Kleibsiella ocytoca may be obtained from a source such yeast extract.
  • the continuous input of seed organisms from the yeast extract in the waste solution results in a culture of Kleibsiella oxytoca in the bioreactor solution.
  • the bioreactor may be directly inoculated with Kleibsiella oxyfoca .
  • the inoculum for the bioreactor is a 48 h culture in nutrient broth added to diluted grape juice and the bioreactor was operated in batch mode until gas production commenced.
  • the heating source preferably is heat exchanger 14 that uses heat or heat waste from dual hydrogen producing apparatus 16 to heat the organic feed material, wherein passage 44 is a bridge between the primary and secondary hydrogen production apparatus.
  • Any heat exchanger known in the art designed for efficient heat transfer can be used in the apparatus including but not limited to parallel flow, counter flow, cross flow, shell and tube, plate, regenerative, adiabatic wheel, boiler and steam generator heat exchangers. Heat exchangers that heat a fluid separated from the heat source by a solid wall are preferred.
  • the method preferably includes at least one temperature sensor for sensing a temperature indicative of the organic feed material temperature.
  • an electronic controller is provided having at least one microprocessor adapted to process signals from one or a plurality of devices providing organic feed material parameter information, wherein the electronic controller is connected to the at least one actuatable terminal and is arranged to control the operation of and to controllably heat the heat exchanger 12 and/or any contents therein.
  • the electronic controller operable related to heat exchanger 14 or heat exchanger 12 and may be located or coupled to those locations or be at a third or remote location.
  • a heating source for system 100 preferably is heat exchanger 12 that uses heat or heat waste from industrial facility 50 to heat the organic feed material, wherein the heat exchanger is a heat exchanger known in the art.
  • the heat exchanger can be a liquid phase-liquid phase or gas-phase/liquid phase as dictated by the phase of the heat waste.
  • a typical heat exchanger for example, is a shell and tube heat exchanger which consists of a series of finned tubes, through which a first fluid runs. A second fluid runs over the finned tubes to be heated or cooled.
  • Another type of heat exchanger is a plate heat exhanger, which directs flow through baffles so that fluids to be ehated and cooled are separated by plates with very large surface area.
  • the secondary hydrogen production apparatus can include any hydrogen producing apparatus wherein that includes heat.
  • the secondary hydrogen production apparatus is an apparatus that produces hydrogen with by separating H 2 O into hydrogen or water in one or a series of reactions.
  • the secondary hydrogen production apparatus is an electrolyzer or a sulfur-iodine system.
  • a steam based high temperature electrolyzer is combined with the primary hydrogen production apparatus 96 of the invention as shown in FIG. 4 .
  • Electrolyzer 114 includes cell 102 having a cathode 104 and an anode 106 , wherein applied electrical current 112 is applied to the cell.
  • the cell may further include a membrane 108 as needed.
  • Steam and hydrogen stream 110 is conveyed into cell 102 , wherein the steam is heated at a temperature from about 100-1000° C.
  • the amount of energy needed as a function of temperature is generally known in the art, as shown in Table 4.
  • the thermal and electro forces will cause a portion of the water or steam to split, wherein oxygen will pass through ion conducting membrane 108 to the anode side and is removed on that side.
  • the condenser can function as heat exchanger 12 or can be a separate condenser that functions in tandem with heat exchanger 12 . Either way, the heat exchanger 12 obtains heat from the steam that exits cell 102 and uses the heat to dually produce hydrogen in the primary hydrogen production apparatus by elevate the temperature of organic feed material to about 60 to 100° C.
  • secondary hydrogen production apparatus is a high temperature electrolyzer that uses heated water, as in FIG. 5 .
  • an electrical current is applied to cathode 116 and anode 118 under heated temperatures of about 100-1000° C., separating a portion of the heated water into oxygen and hydrogen.
  • the oxygen migrates to the anode side across diaphragm 120 , while hydrogen migrates to the cathode side.
  • Heat exchanger 12 can obtain heat from the heated water remaining the electrolyzer or by the released, heated oxygen.
  • the secondary hydrogen production apparatus is a sulfur-iodide system.
  • sulfuric acid is heated under high temperatures of about 750-1000° C. and low pressure under the reaction H 2 SO 4 ⁇ H 2 O+SO 2 +1/2O 2 .
  • iodine can combine with the resultant sulfur dioxide and water under conditions known in the art under the reaction I 2 +SO 2 +2H 2 O ⁇ 2HI+H 2 SO 4 .
  • the 2HI reacts with water and sulfur dioxide to under temperatures of about 350° C. to produce hydrogen and sulfur dioxide under the reaction 2HI ⁇ H 2 +I 2 .
  • the net result of the process is the same as electrolysis: 2H 2 O ⁇ 2H 2 +O 2 .
  • Heat exchanger 14 can use heat from any heat source from this process, for example, the heated H 2 SO 4 , heated H 2 O or oxygen. Regardless of where heat exchanger 44 acquires heat, the dual method enables two separate methods of hydrogen production, wherein the primary system uses heat energy from the secondary system in order to treat organic feed material for use in bioreactor 10 .
  • the apparatus combines a bioreactor with a high temperature electrolyzer.
  • the organic feed material is a grape juice waste product diluted in tap water at approximately 32 mL of juice per liter.
  • the solution uses chlorine-free tap water or is aerated previously for 24 hours to substantially remove chlorine.
  • the dilution and aeration occur in a treatment container.
  • the organic feed material is then conveyed into the heat exchanger 12 through a passage.
  • the organic feed material is heated in the heat exchanger 12 to about 65° C. for about 10 minutes to substantially deactivate methanogens.
  • the organic feed material is heated with excess heat from the high temperature electrolyzer with a heat exchanger.
  • the organic feed material is conveyed through a passage to the bioreactor wherein it is further inoculated with Kleibsiella oxytoca .
  • the resultant biogases produced by the microorganisms metabolizing the organic feed material include hydrogen without any substantial methane.
  • a multiplicity of reactors were initially operated at pH 4.0 and a flow rate of 2.5 mL min ⁇ 1 , resulting in a hydraulic retention time (HRT) of about 13 h (0.55 d). This is equivalent to a dilution rate of 1.8 d ⁇ 1 .
  • the ORP ranged from ⁇ 300 to ⁇ 450 mV, total gas production averaged 1.6 L d ⁇ 1 and hydrogen production averaged 0.8 L d ⁇ 1 .
  • the mean COD of the organic feed material during this period was 4,000 mg L ⁇ 1 and the mean effluent COD was 2,800 mg L ⁇ 1 , for a reduction of 30%.
  • the molar H 2 production rate as a function of pH ranged from 0.32 to 2.05 moles of H 2 per mole of glucose consumed.
  • the pathway appropriate to these organisms results in two moles of H 2 per mole of glucose, which was achieved at pH 5.0.
  • the complete data set is provided in Tables 3a and 3b.
  • hydrogen gas is generated using a microbial culture over a sustained period of time.
  • the optimal pH for this culture consuming simple sugars from a simulated fruit juice bottling wastewater was found to be 5.0.
  • a hydraulic residence time of about 0.5 days resulted in the generation of about 0.75 volumetric units of hydrogen gas per unit volume of reactor per day.

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