WO2006130677A2 - Method of hydrogen production combining a bioreactor with a power plant and associated apparatus - Google Patents

Abstract

The present invention provides a method of hydrogen production, wherein organic feed material is heated with excess or diverted heat from a power plant, thereby substantially deactivating or killing methanogens within the organic feed material. Hydrogen producing microorganisms contained or added to the organic feed material metabolize the organic feed material in a bioreactor to produce hydrogen. As the methanogens are no longer substantially present to convert produced hydrogen to methane, a biogas that contains hydrogen without substantial methane can be produced.

Description

METHOD OF HYDROGEN PRODUCTION COMBINING A BIOREACTOR WITH A POWER PLANT AND ASSOCIATED APPARATUS

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority under 35 U.S.C. § 119(e) to U.S.

Provisional Patent Application Serial No. 60/685,822, filed May 31, 2005, entitled "METHOD OF HYDROGEN PRODUCTION UTILIZING EXCESS HEAT FROM A REFINERY PLANT."

FIELD OF THE INVENTION

[0002] The present invention relates generally to a method for concentrated production of hydrogen from hydrogen producing microorganism cultures. More particularly, the invention relates to a method that synergistically combines a hydrogen production method with an electricity generating power plant. The hydrogen production method uses or uses heat waste that is produced during typical usage of the power plant, thereby reducing energy costs of the hydrogen production method and conserving energy from the power plant.

BACKGROUND OF THE INVENTION

[0003] The production of hydrogen is an increasingly common and important procedure in the world today. Production of hydrogen in the U.S. alone currently amounts to about 3 billion cubic feet per year, with output likely to increase. Uses for the produced hydrogen are varied, ranging from uses in welding to production of hydrochloric acid. An increasingly important use of hydrogen relates to the production of alternative fuels for machinery such as motor vehicles. Successful use of hydrogen as an alternative fuel can provide substantial benefits to the world at large. This is important not only in that the hydrogen can be formed without dependence on the location of specific oils or other ground resources, but in that burning of hydrogen for fuel is atmospherically clean. Essentially, no carbon dioxide or greenhouse gasses are produced during the burning. Thus, production of hydrogen is an environmentally desirable goal. [0004] Creation of hydrogen from certain methods and systems are generally known. For example, electrolysis, which generally involves the use of electricity to decompose water into hydrogen and oxygen, is a commonly used process. Significant energy, however, is required to produce the needed electricity to perform the process. Similarly, steam reforming is another expensive method requiring fossil fuels as an energy source. As could be readily understood, the environmental benefits of producing hydrogen are at least partially offset when using a process that uses pollution-causing fuels as an energy source for the production of hydrogen.

[0005] New methods of hydrogen generation are therefore needed. One possible method is to create hydrogen in a biological method 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 micro-organisms, however, is problematic. The primary obstacle to sustained production of useful quantities of hydrogen by microorganisms 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. As the appearance of methanogens in a biological method has previously been largely inevitable, continuous production of hydrogen from hydrogen producing micro-organisms has been unsuccessful in the past.

[0006] 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). Among the various organisms mentioned, 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. While fermenting glucose, these micro-organisms split the glucose molecule forming two moles of pyruvate (Equation 1); an acetyl group is stripped from each pyruvate fragment leaving formic acid (Equation 2), which is then cleaved into equal amounts of carbon dioxide and hydrogen as shown in simplified form below (Equation 3). Glucose → 2 Pyruvate (1)

2 Pyruvate + 2 Coenzyme A → 2 Acetyl-CoA + 2 HCOOH (2)

2 HCOOH → 2 H₂ + 2 CO₂ (3)

[0007] Thus, during this process, one mole of glucose produces two moles of hydrogen gas. Also produced during the process are acetic and lactic acids, and minor amounts of succinic acid and ethanol. Other enteric microorganisms (the 2, 3 butanediol fermenters) use a different enzyme pathway which causes additional CO2 generation resulting in a 6:1 ratio of carbon dioxide to hydrogen production (Madigan et al., 1997). After this process, the hydrogen is typically converted into methane by methanogens. [0008] There are many sources of waste organic matter that 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 wastes such as sewage and manures.

[0009] A power station or power plant is a facility known in the art for the generation of electric power. Electric power in substantially all power plants is created from a generator, which is typically a device that converts rotational mechanical energy into electrical energy by creating relative motion between a magnetic field and a conductor. Thermal power plants, as opposed to non-heat based power plants such as solar or water power plants, create mechanical energy with heat, wherein thermal energy, often from combustion of a fuel such as coal, into converted into rotational energy. As thermal power plants typically produce steam, these are sometimes called steam power plants. Generally, in a thermal power plant, coal or other energy source is used to heat water into steam, wherein the produced steam is conveyed under high pressure to a turbine, thereby rotating the turbine and creating mechanical energy. The turbine spins a generator, which in turn to produces electrical power. The turbines in a power plant can be any of a wide variety of turbines that extract thermal energy from steam and convert it into mechanical energy.

[0010] Not all thermal energy is transformed to mechanical energy, however, and power plants also produce large amounts of heat waste. If no use is found for the heat, it is lost to the environment as heat waste. The heat may be released into the surrounding environment directly as an exhaust stream or indirectly through a cooling method, wherein the heat waste is cooled by water and the resultant vapor is released to the atmosphere. This understandable is deterimental to the surrounding environement. The cooling water may alternatively be released into a nearby water body, such as a river, ocean or lake. This, however, can deterimentally raise the temperature of the body of water. It is therefor desireable to reduce the amount of heat waste. [0011] New types of hydrogen generation are therefore needed that produce substantial and useful levels of hydrogen in an inexpensive, environmentally sound method that additionally reduces the amount of heat waste produced in a typical power plant.

SUMMARY OF THE INVENTION

[0012] Therefore, it is an object of the present invention to create a method of hydrogen production wherein hydrogen is produced in a bioreactor by hydrogen producing microorganisms by utilizing heat or heat waste from a power plant to deactivate or kill methanogens that would otherwise metabolize the produced hydrogen. [0013] It is a further object of the invention to provide a method for producing hydrogen from an organic feed material including producing electricity by a rotating turbines and converting mechanical energy into electricity, the rotation of the turbines producing heat waste, transporting the heat to a hydrogen producing system, heating the organic feed material with the obtained heat, wherein the organic feed material is conducive to the growth of hydrogen producing microorganisms, conveying the organic feed material into a bioreactor, wherein the bioreactor is an anaerobic environment, and removing hydrogen from the bioreactor.

[0014] It is a further object of the invention to provide a method wherein a bioreactor is readily combinable and proximate with a power plant, the bioreactor utilizing heat and optionally organic waste from the power plant to create hydrogen, wherein the hydrogen is not substantially converted to methane subsequent to production. [0015] It is a further object of the invention to heat the organic feed material prior to entry into the bioreactor, wherein heating is achieved in any one or a multiplicity of upstream containers or passages, such that heating the organic feed material at temperatures of about 60 to 100⁰C kills or deactivates methanogens while substantially leaving hydrogen producing microorganisms intact. [0016] These and other objects of the present invention will become more readily apparent from the following detailed description and appended claims.

BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a plan view of the method showing a bioreactor combined with a power plant.

[0018] Figure 2 is a plan view of a power plant combined with the bioreactor.

[0019] Figure 3 is a side view of one embodiment of the bioreactor.

[0020] Figure 4 is a plan view the bioreactor.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0021] As used herein, the term "microorganisms" include microorganisms and substantially microscopic cellular organisms.

[0022] 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.

[0023] As used herein, the term "methanogens" refers to microorganisms that metabolize hydrogen in one or a series of reactions that produce methane as one of the end products.

[0024] As used herein, the term "power plant" refers to a thermally based processing facility that uses turbines and generators to produce electricity from the conversion of mechanical energy into electrical energy.

[0025] As used herein, the term "heat waste" refers to heat that is produced by a power plant that is otherwise not recycled into the power plant, such as excess heat or heat produced by a power plant that is being used in an industrial process, wherein some of the heat is diverted into the method of the present invention.

[0026] One embodiment of a method for sustained production of hydrogen in accordance with the present invention is shown in Figure 1, wherein the method uses a method 100 having power plant 50, heat exchanger 12, and a multiplicity of containers, wherein the containers include bioreactor 10, heat exchanger 12, equalization tank 14 and reservoir 16. The method enables the production of sustained hydrogen containing gas in bioreactor 10, wherein the produced gas substantially produces a 1 : 1 ratio of hydrogen to carbon dioxide gas 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.

[0027] In preferred embodiments, organic feed material is a sugar containing organic feed material. In further preferred embodiments, 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. In additional embodiments, 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 and animal manures. However, any feed containing organic material is usable.

[0028] Hydrogen producing microorganisms 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 → 2 H₂ + 2 CO₂ (3)

[0029] During this process, one mole of glucose produces two moles of hydrogen gas and carbon dioxide. In alternate embodiments, 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. For example, the electrolyte contents (Na, K, Cl, Mg, Ca, etc.) of the organic feed material can be adjusted. Further, the solution may be supplemented with phosphorus (NaH₂PO₄) or yeast extract. [0030] 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. In further preferred embodiments, the inoculation is an initial, one-time addition to bioreactor 10 at the beginning of the hydrogen production process. The initial inoculation provides enough hydrogen producing microorganisms to create sustained colonies of hydrogen producing microorganisms within the bioreactor. The sustained colonies allow the sustained production of hydrogen. Further inoculations of hydrogen producing microorganisms, 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. In preferred embodiments, the hydrogen producing microorganisms, whether occurring naturally or added in an inoculation step, are preferably microorganisms that thrive in pH levels of about 3.5 to 6.0 and can survive in temperature of 60-100⁰F 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. [0031] In one embodiment embodiments of the invention, organic feed material is first contained in reservoir 16. 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. In one embodiment, 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. In preferred embodiments, reservoir 16 is a wastewater well that is adaptable to receive and contain wastewater and/or effluent from a power plant. In further preferred embodiments, reservoir 16 is adaptable to receive and contain wastewater that is effluent from a juice manufacturing power plant, such that the effluent held in the reservoir is a sugar rich juice sludge.

[0032] The organic feed material in reservoir 16 is thereafter conveyed throughout the system, such that the system is preferably a closed system of continuous movement. Conveyance of organic feed material can be achieved by any conveying means known in the art, for example, one or a multiplicity of pumps. The method uses a closed system, such that a few well placed conveying means can convey the organic feed material throughout the system, from reservoir 16 to optional equalization tank 14 to heat exchanger 12 to bioreactor 10 to outside of bioreactor 10. In preferred embodiments, organic feed material contained in reservoir 16 is conveyed into 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. In a preferred embodiment, pump 28 is a submersible sump pump.

[0033] The method may further include temporary deactivation of conveyance from reservoir 16 to equalization tank 14 or heat exchanger 12 if the pH levels of organic feed material in reservoir 16 exceeds a predetermined level. In this embodiment, reservoir 16 furthers include a low pH cutoff device 52, such that exiting movement into passage 22 of the organic feed material is ceased if the pH level 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. If the monitor detects a pH level of a solution in reservoir 16 out of range, the device ceases operation of pump 28. The pH cut off level in reservoir 16 is typically greater than the preferred pH of bioreactor 10. In preferred embodiments, the pH cutoff level is set between about 7 and 8 pH. The conveyance with pump 28 may resume when the pH level naturally adjusts through the addition of new organic feed material into reservoir 16 or by adjusting the pH through artificial means, such as those of pH controller 34. In alternate embodiments, particularly when reservoir 16 is not adapted to receive effluent from a power plant, the pH cutoff device is not used.

[0034] Passage 22 provides further entry access into equalization tank 14 or heat exchanger 12. 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. An equalization tank is most useful when reservoir 16 received effluent from a power plant 50 such that it is difficult to control flow into reservoir 16. The equalization tank can be formed of any material suitable for holding and treating the organic feed material. In the present invention, 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. [0035] The method preferably further includes discontinuance of conveyance from equalization tank into heat exchanger 12 if the level of organic feed material in equalization tank 14 falls below a predetermined level. Low-level cut-off point device 56 ceases operation of pump 26 if organic feed material contained in equalization tank 14 falls below a predetermined level. This prevents air from being sucked by pump 26 into passage 20, thereby maintaining an anaerobic environment in bioreactor 10. 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, thereby preventing excessive levels of organic feed material from filling equalization tank 14. 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. In alternate embodiments, equalization tank 14 is not used and organic feed material moves directly from reservoir 16 to heat exchanger 12. This is a preferred embodiment when the method is not used in conjunction with power plant 50 such that effluent from the power plant is directly captured in reservoir 16. If reservoir 16 is one or a multiplicity of storage tanks holding an organic feed material, equalization tank 14 may not be necessary. In these embodiments, passages connecting reservoir 16 and heat exchanger 12 are arranged accordingly.

[0036] The organic feed material is heated prior to conveyance into the bioreactor to deactivate or kill undesirable microorganisms, i.e., methanogens and non-hydrogen producers. The heating can occur anywhere upstream. In one embodiment, 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. Organic feed solution can be additionally heated at additional or alternate locations in the hydrogen production system. 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 W

embodiments, pump 26 is an air driven pump for ideal safety reasons, specifically the interest of avoiding creating sparks that could possible ignite hydrogen. However, motorized pumps are also found to be safe and are likewise usable. [0037] To allow hydrogen producing microorganisms within the bioreactor 10 to metabolize the organic feed material and produce hydrogen without subsequent conversion of the hydrogen to methane by methanogens, methanogens contained within the organic feed material are substantially killed or deactivated. In preferred embodiments, the methanogens are substantially killed or deactivated prior to entry into the bioreactor. In further preferred embodiments, 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 60-75⁰C for a period of at least 15 minutes. Additionally, methanogens are generally damaged or killed when heated to temperatures above about 90⁰C for a period of at least 15 minutes. Heat exchanger 12 enables heating of the organic feed material to temperature of about 60-100⁰C 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. In preferred embodiments, 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.

[0038] A heating source for method 100 preferably is heat exchanger 12 that uses heat or heat waste from power plant 50 to heat the organic feed material, wherein the heat exchanger is a heat exchanger known in the art. The heat waste may be transferred through passage 44. Passage 44 may further be associated with a pump device to control flow rates. After exiting heat exchanger 12, heat waste originally conveyed through passage 44 may be discarded through an effluent pipe (not pictured) or recycled back into the power plant. 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 liquid-liquid 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.

[0039] Heat is captured from power plant 50 and used to partially or fully heat the organic feed material, wherein power plant 50 includes a heat waste source. There is great diversity among these types of power plants in terms of power plant layout. One embodiment of power plant 50 is depicted in Figure 2. Coal 102 is fed into boiler 104 and heated to temperatures sufficient to heat water into steam. Produced steam enters steam line 106 which, under high pressures, is conveyed to a unit housing one or a multiplicity of turbines 108. The steam rotates turbines 108, creating mechanical energy, and generator 110 converts the mechanical energy into electricity. After turning turbines 108, the remaining steam is heat waste. Some of the steam may be condensed in condenser 112 back into water and fed back into boiler 104. Other steam becomes is cooled with cooling water and is released into the atmosphere as vapor or into a nearby body of water as water that is elevated to temperatures above room temperature, often high above room temperature.

[0040] Heat exchanger 12 captures a portion of heat waste created by power plant

50 to heat the organic feed material. As stated above, heat exchangers are known in the art. Heat exchanger 12 may be a gas-liquid heat exchanger, wherein heat waste is captured from steam prior to entry into condenser 112 or from water vapors, for example, a cooling tower. Alternatively, as shown in Figure 2, a liquid-liquid heat exchanger can receive cooling water at elevated temperatures to heat organic feed material prior to entry into bioreactor 10.

[0041] Turning back to Figure 1, in one embodiment, to maintain the temperatures at desired levels as known in the art, at least one temperature sensor 48 monitors a temperature indicative of the organic feed material temperature, preferably the temperature levels of equalization tank 14, heat exchanger 12 and/or a passage such as passage 20. In preferred embodiments, 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, and temperatures can be adjusted manually in response to temperature readings taken from temperature sensor 48.

[0042] Organic feed material is then conveyed from heat exchanger 12 to bioreactor 10. 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. When pumps are operating and not shut down by, for example, low pH cut off device 52, the system 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 in the system 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. In preferred embodiments, pump 26 also enables conveyance from heat exchanger 12 to bioreactor 10 through passage 18. In alternate embodiments, an additional conveying device can be specifically operably related to passage 18. [0043] The organic feed material is conveyed through 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.

[0044] 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 microorganisms will subsequently be converted to methane, reducing the percentage of hydrogen in the produced gas. Sustained production of hydrogen containing gas is achieved in bioreactor 10 by a number of method steps, including but not limited to providing a supply of organic feed material as a substrate for hydrogen producing microorganisms, controlling the pH of the organic feed material, enabling biofilm growth of hydrogen producing microorganisms, and creating directional current in the bioreactor.

[0045] Bioreactor 10 can be any receptacle known in the art for holding an organic feed material. Bioreactor 10 is anaerobic and therefore substantially airtight. 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. Generally, the receptacle will be a limiting factor for material that can be produced. The larger the receptacle, the more hydrogen producing microorganisms 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.

[0046] A preferred embodiment of a bioreactor is shown in Figure 3. Bioreactor

80 can be formed of any material suitable for holding an organic feed material and that can further create an airtight, anaerobic environment. In the present invention, 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. The openings may further contain coverings known in the art that cover and uncover the openings as desired. For example, bioreactor 80 preferably includes a central opening covered by lid 86. In alternate embodiments of the invention, the capacity of bioreactor 80 can be readily scaled upward or downward depending on needs or space limitations. [0047] Fresh organic feed material is frequently conveyed into bioreactor 10 to provide new substrate material for the hydrogen producing microorganisms in bioreactor 10. To account for the additional organic feed material and to maintain the solution volume level at a generally constant level, the bioreactor preferably provides a system to remove excess solution, as shown in Figures 1 and 4. In the present embodiment, 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. When bioreactor 10 is filled with organic feed material, the open first end of the effluent passage allows an excess organic feed material to be received by effluent passage 36. 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.

[0048] Bioreactor 10 preferably contains one or a multiplicity of substrates 90 for providing surface area for attachment and growth of microorganism 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.

[0049] Substrates 90 preferably are substantially free of interior spaces that potentially fill with gas. In the present embodiment, the bioreactor comprises about 100- 300 pieces of 1" plastic media to provide surface area for attachment of the microorganism biofilm. In one embodiment, substrates 90 are Flexiring™ 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. When a recirculation system is operably, 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.

[0050] In preferred embodiments, a directional flow is achieved in bioreactor 10.

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 organic 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. As could be readily understood, 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.

[0051] In preferred embodiments, as shown in Figure 1, 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. In preferred embodiments, pump 30 is an air driven centrifugal pump. Other arrangements can be used, however, while maintaining the spirit of the invention. For example, a pump could be operably related to a single passage that extends from one located of the bioreactor to another.

[0052] One or a multiplicity of additional treatment steps can be performed on the organic feed material, either in bioreactor 10 or elsewhere in the system, for the purpose of making the organic feed material more conducive to proliferation of hydrogen producing microorganisms. The one or a multiplicity of treatment steps include, but are 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, adjusting electrolyte contents (Na, K, Cl, Mg, Ca, etc.) and adding additional chemical compounds to the W

organic feed material. Additional chemical compounds added by treatment methods include anti-fungal agents, phosphorous supplements, yeast extract or hydrogen producing microorganism inoculation. The apparatus performing these treatment steps can be any apparatuses known in the art for incorporating these treatments. For example, in one embodiment, a dilution apparatus is a tank having a passage providing controllable entry access of a dilutant, such as water, into bioreactor 10. In some preferred embodiments, the treatment steps are performed in recirculation system 58. In other embodiments, treatment steps of the same type may be located at various points in the bioreactor system to provide treatments at desired locations.

[0053] Certain hydrogen producing microorganisms proliferate in pH conditions that are not favorable to methanogens, for example, Kleibsiella oxytoca. Keeping organic feed material contained within bioreactor 10 within this favorable pH range is conducive to hydrogen production. In preferred embodiments, pH controller 34 monitors the pH level of contents contained within bioreactor 10. In preferred embodiments, 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. In further preferred embodiments, 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 Figure 1, pH controller 34 monitors the pH level of contents contained in passage 62, such as organic feed material, with pH sensor 64. As could readily be understood, 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 Figure 5.

[0054] If 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 microorganisms to function while similarly providing an environment unfavorable to methanogens. This enables 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. In one embodiment, 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. In a preferred embodiment, the pH monitor controls the bioreactor solution's pH through automated addition of a sodium or potassium hydroxide solution. One such apparatus for achieving this 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. [0055] The hydrogen producing reactions of hydrogen producing microorganisms 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. [0056] In one embodiment, the wastewater is a grape juice solution prepared using Welch's Concord Grape Juice ™ 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.

Constituent Concentration (unit indicated)

Mean Range

Carbohvdrates¹ 15-18 % glucose 6.2 % 5-8 % fructose 5.5 % 5-8 % sucrose 1.8 % 0.2-2.3 % maltose 1.9 % 0-2.2 % sorbitol 0.1 % 0-0.2 %

Organic Acids¹ 0.5-1.7 %

Tartaric acid 0.84 % 0.4-1.35 %

Malic acid 0.86 % 0.17-1.54 %

Citric acid 0.044 % 0.03-0.12 %

Minerals¹

Calcium 17-34 mg/L

Iron 0.4-0.8 mg/L

Magnesium 6.3-11.2 mg/L

Phosphorous 21-28 mg/L

Potassium 175-260 mg/L

Sodium 1-5 mg/L

Copper 0.10-0.15 mg/L

Manganese 0.04-0.12 mg/L

Vitamins¹

Vitamin C 4 mg/L

Thiamine 0.06 mg/L Riboflavin 0.04 mg/L

Niacin 0.2 mg/L

Vitamin A 80 LU. pH 3.0-3.5 Total solids 18.5% additional trace constituents in these categories may be present.

[0057] 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. [0058] The method further includes capturing hydrogen containing gas produced by the hydrogen producing microorganisms. Capture and cleaning methods can vary widely within the spirit of the invention. In the present embodiment, as shown in Figure 1, 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. In preferred embodiments, 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).

[0059] Exhaust system 70 exhausts gas. Any exhaust system known in the art can be used. In a preferred embodiment, as shown in Figure 1, exhaust system includes exhaust passage 72, backflow preventing device 74, gas flow measurement and totalizer 16, and air blower 46.

[0060] The organic feed material may be further inoculated in an initial inoculation step with one or a multiplicity of hydrogen producing microorganisms, such as Clostridium sporogenes, Bacillus licheniformis and Kleibsiella oxytoca, while contained in bioreactor 10. These hydrogen producing microorganisms are obtained from a bacterial culture lab or like source. Alternatively, the hydrogen producing microorganisms that occur naturally in the waste solution can be used without inoculating the solution. In further alternative embodiments, additional inoculations can occur in bioreactor 10 or other locations of the apparatus, for example, heat exchanger 12, equalization tank 14 and reservoir 16.

[0061] In the present embodiment, the preferred hydrogen producing microorganisms 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 1:1 ratio often contains enough hydrogen such that additional cleaning of the produced gas is not necessary. The source of both the Kleibsiella oxytoca may be obtained from a source such yeast extract. In one embodiment, 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. Alternatively, the bioreactor may be directly inoculated with Kleibsiella oxytoca. In one embodiment, 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.

Example 1

[0062] The apparatus combines a bioreactor with a coal burning power plant.

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 heating tank through a passage.

[0063] The organic feed material is heated in the heating tank to about 65⁰C for about 10 minutes to substantially deactivate methanogens. The organic feed material is heated with excess heat from the turbine-generator of the coal burning power plant 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.

Example 2 [0064] A multiplicity of bioreactors were initially operated at pH 4.0 and a flow rate of 2.5 niL 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. After one week all six bioreactors were at pH 4.0, 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%. After one week, the pHs of certain bioreactors was increased by one half unit per day until the six bioreactors were established at different pH levels ranging from 4.0 to 6.5. Over the next three weeks at the new pH settings, samples were collected and analyzed each weekday. It was found that the optimum for gas production in this embodiment was pH 5.0 at 1.48 L hydrogen d^"1. This was equivalent to about 0.75 volumetric units of hydrogen per unit of bioreactor volume per day.

Table 2. Production of hydrogen in 2-L anaerobic bioreactors as a function of pH.

H2

Total H2 H2 per Sugar

PH gas L/day L/day L/g COD moles/mole

4.0^a 1.61 0.82 0.23 1.81

4.5^b 2.58 1.34 0.23 1.81

5.0^c 2.74 1.48 0.26 2.05

5.5^d 1.66 0.92 0.24 1.89

6.0^d 2.23 1.43 0.19 1.50

6.5^e 0.52 0.31 0.04 0.32 ^a mean of 20 data points ^b mean of 14 data points ^c mean' of 11 data points ^d mean of 7 data points ^e mean of 6 data points

[0065] Also shown in Table 2 is the hydrogen production rate per g of COD, which also peaked at pH 5.0 at a value of 0.26 L g^"1 COD consumed. To determine the molar production rate, it was assumed that each liter of hydrogen gas contained 0.041 moles, based on the ideal gas law and a temperature of 25° C. Since most of the nutrient value in the grape juice was simple sugars, predominantly glucose and fructose (Table 1 above), it was assumed that the decrease in COD was due to the metabolism of glucose. Based on the theoretical oxygen demand of glucose (1 mole glucose to 6 moles oxygen), one gram of COD is equivalent to 0.9375 g of glucose. Therefore, using those conversions, the molar H₂ production rate as a function of pH ranged from 0.32 to 2.05 moles of H₂ per mole of glucose consumed. As described above, the pathway appropriate to these organisms results in two moles of H₂ per mole of glucose, which was achieved at pH 5.0. The complete data set is provided in Tables 3a and 3b. [0066] Samples of biogas were analyzed several times per week from the beginning of the study, initially using a Perkin Elmer Autosystem GC with TCD, and then later with a Perkin Elmer Clarus 500 GC with TCD in series with an FID. Methane was never detected with the TCD, but trace amounts were detected with the FID (as much as about 0.05 %).

[0067] Over a ten-day period, the waste solution was mixed with sludge obtained from a methane-producing anaerobic digester at a nearby wastewater treatment plant at a rate of 30 mL of sludge per 20 L of diluted grape juice. There was no observed increase in the concentration of methane during this period. Therefore, it was concluded that the preheating of the feed to 65° C as described previously was effective in deactivating the organisms contained in the sludge. Hydrogen gas production rate was not affected (data not shown).

[0068] Using this example, 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. Under these conditions, using plastic packing material to retain microbial biomass, 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 bioreactor per day.

[0069] Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims. Table 3a. Bioreactor Operating Data

GHS Liquid Readings COD Performance

Total Efler collection volume scrubbing Effluent NaOH Net Feed Feed Effluent Removal Loading Consumed Total gas H2 H2

Date Reactor hours (frt-J (mLJ ImL) (ITL) (mLJ QRP PH imgfL) (mflJL) øπglL) (a! tø} LJday L/day LtøCOD

14-Nov A 5 540 220 780 0 780 408 40 4,480 2,293 2,187 3494 1706 259 106 013

14-Nov B 5 330 220 840 0 840 -413 41 4,480 2,453 2,027 3763 1702 182 106 013

14-Nov C 5 350 170 870 0 870 -318 41 4,480 2,293 2,187 3898 1902 168 082 0fl9

14-Nov D 5 320 130 920 0 920 -372 41 4,480 1,920 2,560 4122 2355 154 062 ODS

14-Nov E 5 240 100 920 0 920 324 43 4,480 2,773 1,707 4122 1570 115 048 0J06

14-Nov F 5 90 25 810 0 810 -329 40 3,307 2,080 1,227 2679 0994 024 012 0J03

15-Nov A 55 450 230 1120 25 1095 400 40 3,307 3,787 (480) 3621 -0525 196 100 -044

15-Nov B 55 450 235 1180 35 1145 -384 40 3,307 3,253 54 3787 0061 196 103 3B2

15-Nov C 55 250 130 640 0 640 -278 40 3,307 3,520 (213) 2116 -0136 109 057 -095

15-Nov E 55 455 225 1160 0 1160 435 40 3,307 3,467 (160) 3836 -0185 199 098 -121

15-Nov F 55 430 235 1160 0 1160 -312 40 3,307 3,413 (106) 3836 -0123 188 1 CB -191

16-Nov A 5 330 190 1020 27 993 414 40 4,693 3,627 1,066 4660 1059 182 091 018

S-D EC A 45 200 110 500 35 465 439 40 4,267 4,160 107 1984 0050 107 059 221 to 18-Nov A 5 360 190 200 0 200 423 40 3,680 5,227 (1547) 0736 0.309 1.73 091 -061

¹⁰ 21-Nov A 4 320 170 800 40 760 429 40 3,493 3,680 (187) 2655 -0142 192 1 CG -120

22Nov A 375 235 190 725 21 704 432 40 4,107 2,293 1,813 2891 1277 182 122 015

23-Nov A 425 310 155 750 24 726 439 40 5,013 3,520 1,493 3640 10S4 175 088 014

2-Dec A 375 250 120 660 26 634 438 40 4,587 3,893 694 2908 0440 160 077 027

6-Dec A 3 150 75 540 0 540 441 40 4,853 3,093 1,760 2621 0950 1.20 060 OJ08

17-Noυ A 55 300 160 1010 30 980 414 40 4,907 3,520 1,387 4809 1359 131 070 012 swerage^ 481 324 164 830 13 817 -392 40 4,092 3,213 879 3344 0718 161 082 023

16-Nov B S 400 200 1125 45 1080 397 45 4,693 3,520 1,173 5068 1257 192 096 016

16-Nov D 5 400 165 960 eo 900 -360 45 4,693 3,573 1,120 4224 1008 192 079 016

16-Nov E 5 490 240 1100 72 1028 -324 45 4,693 3,413 1,280 4824 1315 235 115 018

1-Dec B 35 500 260 570 45 525 415 45 5,173 3,680 1,493 2716 0784 343 178 033

6-Dec B 3 470 240 650 40 610 411 45 4,853 3,360 1,493 2960 0911 376 192 026

21-Nov B 4 5S0 300 930 SQ 880 -397 45 3,493 3,147 346 3074 0305 a36 180 0S8

2-Dec B 375 640 320 830 50 780 407 45 4,587 3,413 1,174 3578 0915 410 205 025

17-Noυ B 55 450 220 1165 50 1115 406 45 4,907 2,933 1,974 5471 2201 156 096 010

18-Nov B 5 330 220 880 42 818 406 45 3,680 2,980 720 3010 0589 187 106 037

22-Nov B 375 535 395 835 50 785 397 45 4,107 2,720 1,387 3224 1089 374 253 036

23-Nov B 425 620 320 920 42 878 410 45 5,013 3,307 1,707 4402 1433 350 181 021

5-DEC B 45 390 190 750 37 713 417 45 4,267 3,840 427 3042 0304 208 101 OJ62

16-Nov F 5 400 200 1082 33 989 324 45 4,693 3,093 1,600 4641 1582 192 096 013

16-Nov C 5 400 203 930 74 876 325 46 4.693 2.933 1.760 4111 1541 192 096 013 a/εrages 445 478 243 909 54 856 385 45 4,539 3,278 1 ,261 38B3 1079 258 134 023

Table 3b. Bioreactor Operating Data Continued.

GAS Ligud COQ PUΓUΠUΠGB

Tot .titer collection volume scrubbing Effluent NaOH Net Feed Feed EfTiLWt Removal Loving Consumed Total gas H2 H2

Die Reactor hours (mLJ JmLj ImL) (nlj ORP PH tmtfLJ (mgU (0 (B) I/day L/dJ/ UgCOD

17-Nw C 5.5 360 200 840 120 720 -344 4.9 4,907 2,080 2,027 3.533 1.459 1.57 0.87 0.14

IB-NOY C 5 370 200 1120 70 1050 -328 4.9 3,680 2,480 1,200 3.864 1.260 1.78 0.95 0.16 U _L

2S-Nw C 4.25 415 200 920 SO 870 -403 4.9 5,013 3,093 1,920 4.362 1.670 234 1.13 0.12

17-Nbv E 5.5 430 270 1210 115 1095 -352 5.0 4,907 4,747 160 5.373 0.175 214 1.18 1.54

1-Dec D 3.5 540 250 710 85 625 -395 5.0 5,173 3,573 1,600 3.233 1.000 370 1.71 0.25

17-Nw F 5.5 475 225 1120 130 930 -367 5.0 4,907 3,760 1,147 4.853 1135 207 0.98 0.20

5-Deε D 4.5 530 310 710 77 B33 -423 5.0 4,267 3,573 694 2701 0.439 309 1.65 0.71

6-Dec D 3 450 240 490 43 447 -420 5.0 4,853 3,253 1,600 2163 Q715 360 1.32 0.34

17-Nw D 3.5 680 415 580 83 497 -326 5.0 4,907 4,213 694 2439 Q345 4.66 2.85 1.20

2-Dec D 375 640 340 830 66 764 -412 5.0 4,587 3,787 800 3.504 Q 611 4.10 2.18 0.56

22Nw C 375 450 295 8CO 50 760 -349 5.0 4,107 1,280 2,827 3.080 2120 294 1.89 0.14

3/erages 4.34 436 268 848 81 767 -374.5 5.0 4,664 3,331 1,333 3.579 1.023 274 1.48 026

5-Dec C 4.5 470 250 SOO 103 797 -429 5.4 4,267 3,413 854 3.401 0.680 251 1.33 0.37

1B-Mw F 5 sα 45 600 55 545 -451 5.5 3,680 3,440 240 2006 0.131 043 0.22 0.34 to 21-Nw D 4 130 70 830 80 750 -454 5.5 3,493 3,360 133 2620 0.100 Q78 0.42 0.70

22Mw D 375 360 250 766 Θ9 696 -461 5.5 4,107 2,880 1,227 2853 0.854 230 1.60 0.29

2S-Nw D 4.25 100 50 S40 100 B40 -456 5.5 5,013 3,307 1,707 4.211 1.434 056 0.2a 0.03

2-Dec C 375 550 280 810 93 717 -430 5.5 4,587 3,573 1,014 3.289 Q727 352 1.86 0.40

6-Dec C 3 250 130 570 45 525 -428 5.5 4,853 3,627 1,226 2548 Q644 20D 1.04 0.20 averages 4.04 279 155 774 78 696 -444.1 5.5 4,286 3,371 914 2982 0.636 1.66 0.92 024

21-Mw 4 350 250 930 130 800 -400 6.0 3,493 2,987 506 2794 Q4O5 210 1.50 0.62

22-Nw E 375 330 280 820 127 693 -411 6.0 4,107 2,453 1,653 2846 1.146 243 1.79 024

2a Nw E 4.25 330 230 670 71 799 -467 6.0 5,013 1,973 3,040 4.006 2429 203 1.30 0.09

1-Dec E 3.5 420 250 770 127 643 -471 6.0 5,173 2933 2240 3.326 1.440 288 1.71 0.17

2-Dec E 375 230 170 540 85 455 -443 6.0 4,587 3,360 1,227 2087 Q553 1.79 1.09 0.30

5-Dec E 4.5 410 240 330 153 774 -487 6.0 4,267 3,253 1,014 3303 0.785 219 1.28 031

6-Dec E 3 230 170 660 105 555 -490 6.0 4,853 2293 2,550 2693 1.421 224 1.36 0.12 a'erages 382 354 227 789 114 674 -453 6.0 4,499 2750 1,749 3.033 1.179 223 1.43 0.19

29-htav F 4.25 SO 45 B70 150 720 -501 6.5 5013 1,707 3,307 3.610 23m Q51 0.25 0.02

2-Dec F 3.75 20 0 810 133 674 -497 6.5 4,587 3,573 1,014 3.092 0.683 Q13 0.00 0.00

22-Nw F 375 120 105 790 123 662 -477 6.5 4,107 2,240 1,837 2719 1.236 077 0.67 0.08

5-Dα 4.5 10 0 670 121 543 -532 6.5 4,267 2,827 1,440 2343 0,791 005 0.00 0.00

6-Dec F 3 a> 50 4B0 90 390 -515 6.5 4,853 2240 2,613 1.833 1.019 0.48 0.40 0.05

21-Nw F 4 200 100 910 150 760 -472 6.5 3,493 2613 880 2655 Q669 1.20 0.60 0.15 werages 388 83 50 755 129 626 -499 6.5 4,387 2,533 1,853 2745 1.160 0.52 0.31 0.04

Selected Citations and Bibliography

Brosseau, J.D. and J.E. Zajic. 1982a. Continuous Microbial Production of Hydrogen Gas. Int. J. Hydrogen Energy 7(8): 623-628.

Brosseau, J.D. and J.E. Zajic. 1982ba. Hydrogen-gas Production with Citrobacter intermedins and Clostridium pasteurianum. J. Chem. Tech. Biotechnol. 32:496-502.

Cheresources Online Chemical Engineering Information, http://www.cheresources.com/heat_transfer_basics.shtml.

Iyer, P., M.A. Bruns, H. Zhang, S. Van Ginkel, and B.E. Logan. 2004. Hydrogen gas production in a continuous flow bioreactor using heat-treated soil inocula. Appl. Microbiol. Biotechnol. 89(1):119-127.

Kalia, V.C., et al. 1994. Fermentation of biowaste to H2 by Bacillus licheniformis. World Journal of Microbiol & Biotechnol. 10:224-227.

Kosaric, N. and R. P. Lyng. 1988. Chapter 5: Microbial Production of Hydrogen. In Biotechnology, Vol. 6B. editors Rehm & Reed, pp 101-137. Weinheim: Vett.

Logan, B.E., S.-E. Oh, LS. Kim, and S. Van Ginkel. 2002. Biological hydrogen production measured in batch anaerobic respirometers. Environ. Sci. Technol. 36(ll):2530-2535.

Logan, B.E. 2004. Biologically extracting energy from wastewater: biohydrogen production and microbial fuel cells. Environ. Sci. Technol., 38(9):160A-167A

Madigan, MX, J. M. Martinko, and J. Parker. 1997. Brock Biology of Microorganisms. Eighth Edition. Prentice Hall, New Jersey. Nandi, R. and S. Sengupta. 1998. Microbial Production of Hydrogen: An Overview. Critical Reviews in Microbiology, 24(l):61-84.

Noike et al. 2002. Inhibition of hydrogen fermentation of organic wastes by lactic acid bacteria. International Journal of Hydrogen Energy. 27:1367- 1372

Oh, S.-E., S. Van Ginkel, and B.E. Logan. 2003. The relative effectiveness of pH control and heat treatment for enhancing biohydrogen gas production. Environ. Sci. Technol., 37(22):5186-5190.

Prabha et al. 2003. H₂-Producing bacterial communities from a heat- treated soil

Inoculum. Appl. Microbiol. Biotechnol. 66:166-173

Wang et al. 2003. Hydrogen Production from Wastewater Sludge Using a Clostridium Strain. J.Env. Sci. Health. Vol. A38(9): 1867- 1875

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Claims

We Claim:

1. A method for producing hydrogen from an organic feed material comprising the steps of:

obtaining heat waste produced by an electrical power plant,

heating the organic feed material with the heat waste, wherein the organic feed material is conducive to the growth of hydrogen producing microorganisms,

conveying the organic feed material into a bioreactor, wherein the bioreactor is an anaerobic environment, and

removing hydrogen from the bioreactor.

2. The method of claim 1 , further comprising the step of inoculating the organic feed material with additional hydrogen producing microorganisms.

3. The method of claim 2, wherein the organic feed material is inoculated within the bioreactor.

4. The method of claim 1, wherein the organic feed solution is heated by the heat waste in a heat exchanger.

5. The method of claim 1, wherein the heat waste is steam heat.

6. The method of claim 1, wherein the organic feed material is heated in one or a multiplicity of containers or passages prior to conveyance into the bioreactor.

7. The method of claim 1, wherein the organic feed material is heated to a temperature of about 60 to 100⁰C.

8. The method of claim 1, wherein the organic feed material in the bioreactor has a controlled pH.

9. The method of claim 8, wherein the controlled pH is between about 3.5 and 6.0 pH.

10. The method of claim 1, wherein the power plant is a coal fired power plant.

11. The method of claim 1, wherein the organic feed material is conveyed into the bioreactor with the aid of a pump.

12. The method of claim 1, wherein a temperature of the organic feed material is controlled with an electronic controller.

13. The method of claim 1, wherein hydrogen is produced in the bioreactor by the hydrogen producing microorganisms metabolizing the organic feed material.

14. A combined bioreactor and electrical power plant, wherein the electrical power plant produces heat waste, comprising the bioreactor adapted to receive an organic feed material to produce hydrogen from microorganisms metabolizing the organic feed material, means for heating the organic feed material with the heat waste before it is introduced into the bioreactor, wherein methanogens in the organic feed material are substantially killed or deactivated, and means for removing the hydrogen from the bioreactor.

15. The method of claim 14, wherein the means for heating the organic feed material before it is introduced into the bioreactor with the heat waste is a heat exchanger associated with the heat waste.

16. The apparatus of claim 14, wherein the organic feed material is heated in one or a multiplicity of containers or passages prior to conveyance into the bioreactor.

17. The apparatus of claim 14, wherein the power plant is a coal fired power plant.

18. The apparatus of claim 14, wherein the organic feed material is heated to a temperature of about 60 to 100⁰C.

19. The apparatus of claim 14, wherein the organic feed material in the bioreactor has a controlled pH.

20. The apparatus of claim 19, wherein the controlled pH is between about 3.5 and 6.0 pH.