TW200915654A - Improved biofuel cell - Google Patents

Abstract

The present invention discloses a new type of biofuel cell, based on the microbial regeneration of the oxidant, ferric ions. The biofuel cell is based on the cathodic reduction of ferric to ferrous ions, coupled with the microbial regeneration of ferric ions by the oxidation of ferrous ions, with fuel (such as hydrogen) oxidation on the anode. The microbial regeneration of ferric ions is achieved by metal oxidizing chemolithotrophic microorganisms from the Leptospirillum genus (excluding Leptospirillum ferrooxidans by itself), members of the Ferroplasma genus, members of the Acidithiobacillus genus(excluding Acidithiobacillus ferroxidans by itself). Electrical generation is coupled with the consumption of carbon dioxide from atmosphere and its transformation into microbial cells, which can be used as a single-cell protein.

Description

200915654 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a fuel cell, and more particularly to a biofuel cell based on oxidant iron ion-based microbial regeneration, which utilizes a chemical microbial The process of aerobic oxidation of iron ions to iron ions to remove carbon dioxide from the atmosphere during power generation. [Prior Art] - Hydrogen is mainly used for fuel cell technology on a large scale in economic development. Although there has been significant progress in the application of fuel cells for daily life, it is not yet widely available due in part to the high cost of generating electricity. See R〇Se, R, . Fuel Cells and Hydrogen: The Path Forward, Report Prepared for the Senate of the USA, http://www.fuelcellpath.org. The slow kinetics of the oxygen transport reaction on the most popular proton exchange membrane (PEM) hydrogen-oxygen fuel cell cathodes is high cost of the fuel cell itself (required, platinum as a catalyst) and low fuel efficiency (about 5%) The main reason for the high cost of both is revealed in Bockris, J. 〇.-M. and L Abdu, J.

Electroanal. Chem., 448, 189 (1997). The use of a redox fuel cell in which oxygen is replaced by another oxidant such as iron ions may cause the cathode reaction rate (or the exchange current density of the electrochemical process) to increase by several times, as disclosed in Bergens, SH, GB Gorman, QTR Palm〇re and GM Whitesides, Science, 265, 1418 (1994); Larsson, R. and B. Folkesson, J. Appl. Electrochem., 20, 907 312XP/invention specification (supplement) 97 -01/96135329 200915654 (1990); and Kummer, J τ and D rn · J* K and 〇ei, J. Appl. hlectrochem., 15, gig (1985). In addition, the rate at which the oxidant mass is transferred to the electrode surface (which is equivalent to the limiting current density in electrochemical terms) is also higher because the solubility in oxygen is compared (depending on the partial pressure and temperature, it is 0.006 g/l to 0.04 g / liter), the solubility of the oxidizing agent in the redox fuel cell is higher than 50 g / liter of OJ. The characteristics of all such redox fuel cells are based on thermodynamic controversy, which theoretically allows the conversion of chemical energy into electrical energy efficiency of up to 8〇% to 9〇% using non-precious gold. However, the main problem in non-redox fuel cells is the oxidizing agent <reduction of the reoxidation efficiency of the formula (emulsifier regeneration), see Urss〇n, R. and B. (10), J. Appl. Electrochem·, 2〇, 9〇 7 (199〇); and ^ ugly ^, j.' T. and D. and D.-G. Oei, J. Appl. Electrochem., 15 619 (1985). For example, 'r-ray irradiation was used for H2_Fe3+/Fe2+ redox batteries for the reoxidation of F2+ to F3+, as revealed by Yearger, j. F, r. j.

Bennett and D. R. Allenson, Proc. Ann. Power Sources c〇nf·, 16’ 39 (1962). Although the efficiency of the fuel cell itself is extremely high, the reported oxidant regeneration efficiency is well below 丨5%. In other cases, the regeneration of the oxidant is carried out using oxygen on an expensive catalyst [Ref. Bergens, SH, GB Gorman, GTR Palmore and GM Whitesides' Science, 265, 1418 (1994)], which has the advantage of eliminating the use of non-turning cathodes. Advantages, but still slow. Therefore, in order to develop a practically feasible oxidation 312XP/invention specification (supplement) 97·〇1/96135329 7 200915654, it is necessary to develop an effective method for oxidant regeneration, as disclosed in Larsson, R. and B. Folkesson, J. Appl.

Electrochem., 20, 907 (1990). The process of aerobic oxidation of ferrous ions to iron ions by a campogenic microorganism such as A. ferrooxidans has been found for more than half a century. Reference A.R. c〇lmer, M E. Hinkle,

Science, 1 06 (1947) 253-256. These microorganisms are widely used in metallurgy for precious metals (An), heavy metals (J), and base metals (Cu, Ni, Zn,

Percolation of Co) and its widespread use in environmental protection. Microbial iron oxidation is based on the following net reactions: (1) 4Fe2++4H++〇2=4Fe3++2H2〇 has not compared the rate of pure chemical reaction using oxygen at pH 1 to pH 2, and the rate of microbial oxidation of ferrous ions is faster. 5〇〇,〇〇〇倍,夂考 DT Lacey,F. Laws〇n,Bi〇techn〇i〇gy _

Bioengineering, 12 (1970) 29-50. When growing on the iron oxide of ferrous ions, Thiobacillus ferrooxidans uses one of the narrowest thermodynamic limitations known to the microbial industry, with reference to W]

Ingledew, Biochimica et Rinnh.rc· » cl〇Physica Acta, 683 (1982) 89-117. The Thunder K electron transport chain of this kind of microbial iron oxidation contains two abundance reactions: (2) 4Fe2+=4Fe3++4e" The reaction is carried out outside the cell membrane and 4e + O2+4H = 2H2 〇 the reaction system Performed inside the cell membrane (3) Reference M. Nemati, STL 312XP / Invention Manual (supplement) 97-01/96135329 8 200915654

Harrison, g.S. Hansford, C. Webb, Biochemical Engineering J〇urnal, i (1998) m-19〇. The electrons are delivered through the cell wall through a chain of three electron carriers, namely rusticyanin, cytochrome c and cytochrome a. The iron oxidizing bacteria Thiobacillus ferrooxidans is a self-sufficient microorganism, that is, carbon dioxide (c〇2) which is usually obtained from the atmosphere as a sole carbon source, and an inorganic reaction such as ferrous ion oxidation (bu 3) supplies energy. The laboratory scale plant oxidation and industrial scale oxidation of iron by ferric acid oxidizing bacteria has been studied in different types of bioreactors. The redox potential can reach a value of 1 000 millivolts under ordinary culture conditions in a growth reactor containing Thiobacillus ferrooxidans grown in ferrous ions, see m. KCAM Luyben, JJ Heijnen, Hyfr〇metaUurgy, 48' (1998) 1-26. Since the potential of the reaction (3) is 1120 mV with respect to the standard hydrogen electrode, up to about 90% of the reaction can be used to produce Fe3+, and the remaining energy (about 10%) can be used by the microorganism for the formation and maintenance of the biomass. The biooxidation of ferrous ions by Thiobacillus ferrooxidans has been used in electrochemical cells for a number of different purposes. In all of these cases, the electrochemical reaction carried out on the cathode surface is: κ

Fe3++e-=Fe2+ (4) Several different counter-electrode (anode) reactions have been described: A) Oxygen formation according to the reaction shown below: (5a) External potential is applied to reduce iron ion iron while the other electrode is applied Oxygen is produced on it. 2H2〇=4e'+〇2+4H+ In this case, such a system to be used on one electrode has been used in the microbial enzyme matrix (ferrous ion) using 312XP/invention specification (supplement) 97-01/96135329 9 200915654 Continuous regeneration of iron) results in extremely high cell yields, see N. Matsumoto, S. Nakasono, N. Ohmura, H. Saiki, Biotechnology and Bioengineering, 64 (1999) 71 6-721; and SB Yunker, JM Radovich, Biotechnology and Bioengineering, 28 (1986) 1867-1875. B) Oxidation of iron ions: _ Fe2+=Fe3++e—(5b) C This type of electro-bioreactor has been used to measure the oxidation rate of microbial ferrous iron by measuring the current value, refer to HP Bennetto, DK Ewart, AM Nobar, I. Sanderson, Charge Field Eff. Biosyst.—2, [Proc. Int. Symp.], (1989) 339-349; and L Kobayashi, K. Ibi, T. Sawada, Bioelectrochemistry and Bioenergetics, 39 ( 1996) 83-88. C) Oxidation of organic compounds such as decyl alcohol: /.... CH3〇H+H2〇=C〇2+6H++6e' (5c) This system is used for the electrochemical decomposition of pollutants (sterols) in water, References A. Lopez-Lopez, E. Exposito, J. Anton, F. Rodriguez-Valera, A. Aldaz, Biotechnology and Bioengineering, 63 (1999) 79-86. U.S. Patent Application Serial No. 10/562,198 (WO 2005/001981), which is incorporated by reference in its entirety, discloses the reduction of ferrous ions based on the reduction of iron ions, and the regeneration of iron ions by the oxidation of ferrous ions. / Invention Manual (Repair) 97-01/96135329 10 200915654 A fuel cell for power generation. The system disclosed in the publication is not disclosed in the disclosure of the microorganisms disclosed in the literature; 2) Fp + 2 / P 4 operating conditions; 3) limited to e - milk 匕The original couple; and 4) reveal a limited number of membranes. Then = iron oxysulfate (4) kinetics of ferrous ion iron oxidation

The Gibbs energy of the μ攸 bio-milk reduction can be used for power generation, while the rest is formed by microbial consumption of cytosol. It has also been found that the growth of Thiobacillus ferrooxidans is oxidatively decomposed by iron under dry conditions, see M. Nemati, STL arnson, QS Hansford, C. Webb, Biochemical: rring Jo110 " 1, 1 (1998) 171, in other words These organisms can oxidize ferrous ions under zero growth conditions. r f Γ Γ Γ is mainly caused by anthropogenic carbon dioxide emissions caused by the major problems faced by the Earth. At present, the most popular way to release emulsified carbon into the atmosphere seems to be the conversion of fossil fuels into hydrogen economy, refer to LQ.M. kkris, Internatlonal

Journal of Hydrogen Energy, 2? (2002) 731-740 〇 ^ M Known oxygen/hydrogen fuel cells do not produce carbon dioxide when hydrogen is used as a fuel. Therefore, biofuel cells based on chemical micro-organisms are extremely excellent, and such biofuel cells are extremely efficient and can consume carbon dioxide from the atmosphere during operation. SUMMARY OF THE INVENTION Shuming provides a redox fuel cell that uses an oxidant regeneration method and consumes carbon dioxide. 312XP/Invention Manual (Repair (1) Ship 35329 11 200915654 The present invention provides a 4 Tan biofuel cell system comprising: &) A fuel cell comprising i) a cathode chamber, a Hegu μ aqueous electrolyte cathode electrode and an oxidation containing The first one of the first one is a oxidized state compared to the one of the redox couples; ii) an anode chamber, each of which has a -% electrode and a pumped The spurs of the stagnation of the stagnation of the scorpion, Wang Chengjing, and the cathode chamber are electrically divided into b) a bioreactor, including a surrounding camping hedge早翁几他碑# μ rT genus oxidized microorganisms are selected from the genus Leptospiri 1 um li (Leptospiri 1 iu ) Li σ " . iUm) genus (Leptospiri 1 lum ferrn ^ m (Ferroplasma) member, acid ', Acidlthlobacillus' oxidized acid sulfur rod ® (except Acidithiobacillus) and its mixture; used to contain oxygen (〇2) and carbon dioxide fluid $ Ah used to pump 3 eyes to the body a pump of the reactor, wherein the bioreactor is in communication with the cathode chamber, wherein the aqueous solution containing the second member of the redox couple is circulated to the biological reaction H, and and

The reaction in the cathode electrode is the reduction of the first member of the redox couple in the A Μ 0 軚 rolling state to the lower f bucket energy 4 Ρ 疋 η η. ^ ^ 乂 乂 low emulsified state redox Even the second scallop, and the reaction of the anode electrode to the fuel for electrochemical oxidation to produce electrons (e-) and protons Γ), wherein the pre-oxidation "T shell (H) system is traversed by the anode chamber In the aqueous electrolyte, and the second member of the oxime and the redox couple in the lower oxidation state is in the presence of the milk of the original sputum in the container, 'aerobic oxidation reaction 312XP/inventive Specification (supplement) 97-01/96135329 12 200915654 I 'Hunting metal ions oxidize microorganisms and are oxidized back to the first member of the reduction couple, and wherein the power system is via: load and money electrode and cathode electrode Obtained by making an electrical connection. Erqi: January - In the specific case, 'biofuel cells are based on iron ions:::: iron ions, plus oxidation by ferrous ions, microbes again" with fuel on the anode (such as but not limited to ions The microbial regeneration can be carried out by chemical microbial agents, such as (4) spirochetes (except for the iron-oxidized fish-tailed spirochetes themselves); = bacillus (except for the genus Thiobacillus ferrooxidans itself) and mixtures thereof And the ferrooxidic acid thiobacillus. The functions and advantages of the present invention will be better understood by reference to the following detailed description. [Embodiment] The system described herein is generally directed to a specific example of a biofuel cell, although specific to the present invention. The embodiments are disclosed herein, but are disclosed herein for purposes of illustration only, and the invention is not intended to be The small details are used to read the details of the structure' and the relevant components are removed to prevent obscuring the novel. Therefore, the specific structure and function disclosed here are not interpreted as restrictive, but instead are only applied for patents. The basis of the scope, as well as the representative basis of the present invention in a variety of ways, are intended to be used by those skilled in the art. For illustrative and non-limiting purposes, specific examples are all specific examples of biofuel cells. "约约"-- when the particle size of the binding range or 312ΧΡ/invention specification (supplement) 97-01/96135329 13 200915654, when used in combination with other physical properties or characteristics, means that there are some slight variations from the upper limit to the lower limit that may exist in the size range. Therefore, the specific example in which the average size is satisfied, but the statistical size may exist outside the range of the region is not excluded. It is not intended to exclude specific examples such as those obtained from the present invention. For example, the specific examples of the present invention are A proton conducting membrane having a pore size of less than about 微米2 μm is used, but a conductive membrane having a pore size slightly larger than this range is not excluded. 'Apparently shown in Fig. 10 of the biofuel electrode. / , 1~山%仰The Wang Haohan system includes a fuel cell section 12 including a cathode chamber 14 and an anode chamber 16 separated by a membrane 18. The anode 2〇 can be carbonized, such as mine carbon. In addition to the uranium carbon: Other compounds used include other metals in the platinum group and mixtures thereof. The anode also includes non-platinum anode catalysts such as tungsten carbide and Other transition metal-containing materials and mixtures thereof. In addition to #" reversed tungsten, iron phosphide and cobalt phosphide are also used as catalysts (only a few examples == making anodes is excellent, because there is no need for two = Heterogeneous;: Zhongguang Electrode will not be formed by the surface of the anode 20 which is formed by the transition metal compound including the transition metal compound, such as carbon monoxide and sulfur-containing compound. Facing the cathode and exposing to the surface of the electrolyte pole to form a hydrophobic; raw. Let two:: all: application of Teflon to the intrusion in the anode chamber. Hydrophobicity prevents the electrolyte permeable membrane from being cationized and decimated (eg, Na fi on proton exchange 312XP / invention specification (supplement) 97-〇1/96i35329 14 200915654 membrane change), anion exchange membrane or Its combination. The membrane may be for protons but less conductive to metal ions. [An example of a bioselective membrane is Japan Asahi Glass. AAhi Glass = Se-. While the membrane 18 is preferably a proton exchange membrane, other types of material are applied to separate the gas (e.g., chlorine fuel) in the impotence in the cathode chamber 14. The membrane may also be a composite membrane Nafion-Selemion membrane. For example, the membrane 18 is not necessarily a proton exchange membrane, and the membrane 18 is substantially qualitative: a typical example of a conductive membrane includes, but is not limited to, a solid electrolyte separated by a cathode electrode and a cathode contained in the cathode chamber (cathode electrolyte) Non-conductive material f. Non-limiting examples include a stone-based cellulose 臈' dialysis membrane having a pore diameter of less than 2 μm; a reverse osmosis membrane. Further, the membrane may be dispensed with, and the anode and cathode may be separated by a liquid electrolyte. The membrane may be an ion exchange membrane, and the membrane may also be a permselective membrane, which is conductive only to certain ions such as protons and to (eg) a heavier ion such as a cymbal. It may also contain any of the foregoing types. A composite material of an ion exchange membrane. The cathode electrode is made of a chemically inert conductive material such as carbon and non-mineral steel. The cathode can also contain a catalyst, and the catalyst can be a plurality of catalysts including bismuth, ruthenium, uranium, and crane carbonization. Catalysts known to those skilled in the art, the cathode electrode may comprise a fibrous layer made of carbon or stainless steel material or in another specific example The cathode can be a solid plate. The catalyst can be pure or catalyst can be combined with stainless steel, titanium, active and 312XP/invention specification (supplement) 97·〇]/96〗 35329 15 200915654 Inactive toner and activated carbon fiber and inactive Any of the carbon fiber mixtures. The bioreactor 26 is in flow communication with the fuel cell section 12. The appropriate biological reaction can be used in the 26 series disclosed in d. G. Karamanev, C. Chavarie, R. Samson, Biotechnology And Bioengineering, 57 (1998) 471-476, which discloses a combination design of a gas-flowing system with a fiber-containing braked microbial cell support. The total volume of the bioreactor is 2 · 2 liters. In several specific examples, Fluidized bed biofilm reactors can also be used, for example, as disclosed in DG Karamanev, LN Nikolov,

Environmental Progress' 15 (1996) 194-196.

Bioreactor 26 is used to highly efficiently convert ferrous ions into iron ions, that is, for oxidant regeneration. By definition, a bioreactor is a container in which a microorganism grows and undergoes a biochemical reaction, such as ferrous ion oxidation in this example. The % bioreactor in the study of the efficiency of the biofuel cell was inoculated with a mixed culture (1% v/v) containing Leptospirillum and Thiobacillus ferrooxidans from copper ore. The medium is an aqueous solution containing a nutrient salt composition of G.4 ruthenium ion as a sulfate and a surfactant of Surman coffee Lundgren (having pJJ ] 8). Air at a rate of 200 liters per hour was sprayed into the bioreactor 26 as a source of oxygen and dioxin. After the autologous brake of the ferrooxidic acid thiobacillus cells on the surface of the fiber-containing support, the oxidation of ferrous ions was sacrificed at a rate of 12 grams per liter of bioreactor per hour. Once the 9 iron ions in the bioreactor medium are oxidized, the latter is circulated through the fuel cell 1 〇 cathode chamber using the screw pump at the flow rate...anode chamber": 312XP/发0纤明书(补件) 97_Q1 Axis 35329 16 200915654 A hydrogen pump was supplied at a rate of 3 ml/sec using a Cole-Parmer. All liquids in contact with the microorganisms (fine or large, in the bioreactor or in the cathode compartment, with or without iron) must contain one or more dissolved nutrient salts to aid in the growth of the microorganisms. Preferred nutrient salts include sulfuric acid, potassium citrate, sulphuric acid, potassium sulphate, indeed (d), and chlorinated. Typical composition of these salts is illustrated by Silverman and Lundgren (j.

Bacteriology, ν.77, ρ·642 (1959)). In one particular embodiment, the liquid in the bioreactor contains any of a variety of inorganic ions, such as Ca'NH/, Κ+, Mg2+, SO, Ν〇" ρ〇43-, and . Chemical metal oxidizing microorganisms include members of the genus Spirulina (except for the iron oxidized fishing end screw itself), members of the genus Trichophyta, members of the genus Thiobacillus (except for the thiobacillus ferricum itself), and mixtures thereof. It may include iron-oxidized Leptospirillum and Thiobacillus ferrooxidans. Members of the genus of the genus Trichothelium include, but are not limited to, the acidophilus ferronidium (10) a acidiPMlum) and the acid weapon ferrogen (ι^Γ〇ρΐ&_ acihrmanus). Members of the genus Leptospira include, but are not limited to, Leptospirillum ferriphilum, Lept〇spirillum thermoferrooxidans, and Leptospiri 1 lum . f errodi azotrophum When the selected redox couple is Fe3+/Fen, the hydrogenation reaction at the anode: &2H2=4H++4e" (6) Reduction of iron ions added to the cathode: 312XP/Invention Manual (Repair ) 97-01/96135329 200915654 4Fe3i+4e~=4Fe2i (7) Protons formed by reaction (6) (η. across the proton conducting solid electrolyte 18 to the cathode to 14). Ferrous ions formed at the cathode (^^2+) is pumped to the bioreactor along with the shellfish, where it is oxidized by the microorganism to iron ions (F,) according to the reaction formula (〗), and then returned to the cathode chamber 14 of the fuel cell for the next power generation cycle. In biofuel cells, she (chemical reaction plus biochemical reaction) can be obtained by the reaction formula: 2H2+〇2 = 2H2〇(8), so the total reaction system of biofuel cell 1与_Oxygen fuel cell total reaction phase Microbial and iron ions are simply used as biocatalysts to promote a large increase in the rate of cathodic reaction. The ratio between the energy used for power generation and the energy used for microbial growth is easily controlled by changing the culture conditions, such as biological The ratio of iron ions to ferrous ions in the reactor effluent. This ratio can be made infinite even by decoupling microbial growth from ferrous ion oxidation. In this case, carbon dioxide is not consumed. Biomass will be produced. Therefore, under ideal conditions (without energy loss in the battery), at most 9% of the Bobs free energy of the reaction equation (8) can be used for power generation, and the remaining m will be used for immobilization by microorganisms. Carbon dioxide results in the formation of biomass and the maintenance of the battery. As explained above, fuel cells that operate on hydrogen and oxygen and use platinum as a catalyst at the two electrodes have a current efficiency of about 5% and the rest are heat-releasing. Difficult to use. Using phase materials and oxidants, novel biofuel cells will generate electricity and produce microbes. 312Xp/Invention Manual (supplement) 97-01/%135329 18 200915654 Quality. The cathode reaction formula (7) on the stone electrode is much faster than the oxygen reduction on the platinum electrode, and the oxygen reduction rate is currently used. Fuel cell limitations, so the fuel cell disclosed here will greatly improve the economic and environmental effects of fuel cell operation, because of the improvement of current efficiency; 2) use of the cathode (4); 3) removal of carbon dioxide from the atmosphere; 4) Manufacture of useful products as well as single cell proteins. Thiobacillus ferrooxidans has been shown to contain 44% protein, 26% lipid, 15% carbohydrate and at least two vitamin B, reference & Nature, 281'555 (1979). It is unknown that this type of biological material has any negative physiological effects, see Tributsch, H, Natui^, 28ι, (1979). A study of the characterization of the biofuel cell 1G was carried out, and all of the listed potentials were white relative to the potential of a standard hydrogen electrode (SHE). The potential was measured using a flip electrode connected to an Or ion pH-mV instrument. A bioreactor containing a brake mixing culture of a camping microorganism is used to oxidize ferrous ions in a batch manner. After the ferrous ion oxidation is about _ converted; the target is sent from the bioreactor 26 to the cathode chamber of the fuel cell. 14 The relationship between the cathode site and the current density is shown in FIG. The total iron concentration is: _ refers to 'PH & 1.8. It can be seen that although the cathode potential is slightly decreased, the cathode potential is 1 millivolt ate at a current density of 35 amps/cm 2 = the decrease in potential is similar to that reported in the reference for the electronization of the oxidized oxygen source. The potential drop 'in some cases is slightly less than the latter potential 312 ΧΡ / invention specification (supplement) 97-01/96135329 19 200915654 The effect of the ascending m fans. The flow rate is from 〇 to u millim. The result of no electric load is dry and negative. The load is also 3, that is, the ride and 5 ohms. Only a small increase, from 610 ang you ^ not to Figure 3 °, the battery potential is less than (10). The elevation fcf of all potentials rises to 661 millivolts, or the rise of the rise is due to the cathode. The emulsifier flow rate is not observed. The anode flow is not observed when the load is zero. ::Two rings: Figure 3). In theory, this is due to the fact that the father is current. Also studied, the effect of oxidant flow rate on fuel power and load is not significantly greater than that of J = 2 (Fig. 4). When the flow rate is from 5 ml, it seems to be 30%. This laugh & s s when a milliliter / sec, the oxidant has; if the amount of fruit flow rate ' below 2 ^ Ddt Α right ten 罝 transfer limit. At a μ speed above this value, no mass shift limit was observed. The stability of the fuel cell during hours of operation. It was found (Fig. 5) that the electric current-current characteristics did not change significantly during the 3.5 hour period. In another experiment, the biofuel cell lasted for more than 6 months without any loss of activity. 0, the car is better than the power generation. The fuel cell shown in the figure is unique: converting the oxidized slave into a battery. Biomass. Therefore, the fuel cell consumes carbon dioxide derived from the atmosphere during operation to produce microbial biomass, which can be used as a single cell protein (SCP). In the current scp technique, toxic chemicals may be found when methanol is used as the enzyme substrate, see Ravindra, A. P., Biotech. Adv, 18, 459 (2000). Inventor's technique 312XP / invention manual (supplement) 97*01 touch 35329 20 200915654 f 1 1 test bio-contamination (occasionally toxic), because I know that any known pathogenic microorganism can be at pH 1 to = Growing on completely inorganic medium. In the method of making SCP from ～, αα, Β 夕 夕 刖 , 从 从 微 微 微 微 微 微 微 微 微 Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra Ra The .Adv' 18' J 1 biofuel cell system requires chlorine, oxygen, and sulphur dioxide. As a result of electrobiochemical reactions, biofuels are heated, water (as water vapor), and microbial cell biomass. The gas is injected; the internal: oxygen and carbon dioxide are consumed in the bioreactor inner garment j and the biomass. In industrial ferrous ion oxidation bioreactors, oxygen and carbon monoxide are supplied from the atmosphere. Biofuel cells have the following characteristics based on #量平衡, stereochemistry and kinetic calculations: during power generation (10) kilowatts of electricity: 4 kilograms: hourly hydrogen and 4 kilograms per hour of carbon dioxide; 9 kilograms per hour of biomass SCP ) 'And a 10 cubic meter bioreactor is preferred. The biofuel cell proposed in this case is superior to the high efficiency (10) side of the currently known type of fuel cell; no need to use a precious metal cathode: and) The unique feature of the fuel cell is that it consumes the anti-oxidation during its operation. This is a useful product, also known as single cell protein (SCP). The energy released by the total chemical reaction 2H2+〇2=2H2〇 is used to form three products: power generation, production of t cell protein (scp) biomass, and heat production. The fuel cell can be operated in the following manner. The ratio of the power generation in the scp manufacturing room is set to any value between 〇 and p infinity, that is, “only raw materials are produced without power generation” and only raw materials are produced and only electricity is generated. any position. §cp Manufacturing M2XP/Invention Manual (Supplement) 97-01/96135329 21 200915654 The required electrons may come from the reaction 2H2+〇2=2H2〇, or directly from the current (microorganisms consume electrons from the cathode). The scp/power ratio can be controlled by changing the cathode potential or 绖 by changing the culture conditions, such as the Fe2VFe3+ concentration ratio. It should be understood that the present invention is not limited to gaseous hydrogen/oxygen fuel cells using only gaseous hydrogen fuel, but other hydrogen-containing fuels that can be electrochemically oxidized, such as methanol, ethanol, methane, may be used, to name a few. For example, in the case of methanol fuel, the anode reaction is: CH3〇H+H2〇=C〇2+6H++6e- Hydrogen ions pass through the separator and the rest of the fuel cell, as well as the biofuel cell system and the gaseous state. Hydrogen fuel biofuel cells are the same. The anode reaction using Methane as a fuel is: CH4+〇2=C〇2+4H++4e- In the case of using ethanol as a fuel, the anode reaction is: C2H5〇H+3H2〇=2C〇2+12H++ 12e- Thus, in another specific example of the biofuel cell, the fuel may be a compound containing a hydrogen component (as a sole component in the case of using hydrogen as a fuel, or as one of several components in the case of a compound) Electrochemical oxidation of fuels produces protons and electrons like helium oxidation, but also includes other products that are pumped into the anode chamber in a fluid in the form of a gas or liquid. Although the present invention has been exemplified by the use of redox oleochonium Fe2+/Fe3+ and iron oxidizing microorganisms, it will be apparent to those skilled in the art that other redox couples can be used in addition to the metal oxidizing microorganisms disclosed herein, 312XP/Invention Manual ( Supplement) 97_qi/96135329 22 200915654 Oxidizing microorganisms are used in the oxidation of a lower oxidation state back to a higher oxidation state. Other redox couples are more than M〇'M◦, which can be borrowed from the same microorganism: oxidized: = two V: '· It is disclosed herein that iron can also be oxidized. 3 cases, as used herein, 'include and 'is open rather than exclusive. In particular, =" must be understood to include and (4) the scope of the patent, "package c is included in this manual for the inclusion of specific features, steps And the second = the change indicates the existence of its features, steps or components. The explanation is to exclude the principle of the invention, but it is not limited to the two examples of the present invention (10). The intention is to be defined by all the specific examples covered in the scope of the following claims. ^〖 and its phase [Simplified description of the drawings] The following description of the use of the group according to the present invention, and with reference to the drawings, the biological Fig. 2 shows a schematic diagram of a biofuel cell composed according to the present invention. Fig. 2 is a diagram showing the flow density of the thunder ice using the material of Fig. 1. The cathode potential obtained is relative to the electrogram 3 The flow rate of the fuel cell of the fuel cell chamber of Figure 1 is relative to the oxidant inflow. The fuel cell potential of the fuel cell of Figure 1 is relative to the flow rate of the oxidant stream 3l2Xmmmmm97-01/96135329 23 200915654 into the cathode chamber. Figure 5 is a graph of the cathode potential of the fuel cell of Figure 1 versus long-term operating time. [Key element symbol description] 10 Biofuel cell - bioreactor system 12 Fuel cell section 14 Cathode chamber 16 Anode Chamber 18 Membrane 20 Anode 22 Cathode 26 Bioreactor

312XP / invention manual (supplement) 97-01/96135329 24

Claims (1)

200915654 X. Patent application scope: 1. A biofuel cell system comprising: a) a fuel cell, including. a cathode chamber comprising a cathode electrode and an aqueous electrolyte containing a redox couple, and the first member of the redox couple has a higher oxidation state than the second member of the oxidation; ', —Π An anode chamber comprising - an anode electrode and - a fuel containing a helium component pumped into the anode chamber, the anode chamber being separated from the cathode; and a knife b) - a bioreactor comprising a surrounding camp A chemolithotrophic metal ion oxidizing microbial organism selected from the group consisting of members of the genus Leptospirillum (except Leptospirillum ferrooxidans), iron ore a member of the genus Ferroplasma, a member of the genus Acidibacterium (Acidi1:hi〇bacillus) (except Acidithi〇baciUus ferroxidans) and mixtures thereof; one for containing oxygen (〇 2) The carbon monoxide fluid is pumped to the pump of the bioreactor, and the delta bioreactor is in fluid communication with the cathode chamber, and the water is dissolved in the second member containing the redox couple. Recycling from the cathode chamber to the bioreactor' and the second member of the redox couple whose reaction at the cathode electrode is reduced to a lower oxidation state by a first member of a redox couple in a higher oxidation state, And wherein the reaction at the anode electrode is electrochemically oxidized to produce electrons (e-) and protons (Η+), wherein the protons (Η+) are from the anode chamber 312ΧΡ/invention specification (supplement) 97-01/96135329 25 200915654 The more the tooth enters the aqueous electrolyte, and the second member of the redox couple in the lower oxidation state is in the presence of oxygen in the vessel, in the aerobic oxidation reaction, by the chemical metal ion oxidizing microorganism And being oxidized back to the first member of the redox couple in the southerly emulsified state, and wherein the power system is electrically connected to the anode electrode and the cathode electrode via a load. 2. The biofuel cell system of claim 2, wherein the member of the iron genus is selected from the group consisting of Ferropl asma aCldlPhllUm and an acid weapon 'Ferroplasma acidarmanus' 3. The biofuel cell system of claim 4, wherein the member of the genus Spirulina is selected from the group consisting of Leptospiri 1 lum fernphi lum, A group consisting of Lepfspiri丨lum therm〇ferr (8) and Leptospiri i lum ferr〇diaz〇tr〇ph(10). a fuel cell bioreactor of 2 or 3, wherein the redox couple is Fe"Fe3+, and the metal oxidizing microorganism is an iron oxidizing microorganism, and the reaction formula represented by 4Fe3++4e-=4Fe2+ in the cathode electrode Reduction of iron ions (FV+); and in the aerobic oxidation reaction indicated by 4Fe, 4m4F, and sputum, ferrous ions (Fe2+) are oxidized to iron ions (Fe3+) by iron oxidizing microorganisms. Patent application scope A fuel cell bioreactor of 2 or 3, wherein the redox couple is one of Cu+/Cu2+& M〇5VM〇6+. 312XP/Invention Manual (supplement) 97·〇1/96135329 26 200915654 6. The biofuel cell system of the invention of claim 4, paragraph 2, 3, 4 or 5, the anode of the crucible is selected from the group consisting of platinized carbon and transition metal compounds. The biofuel cell system of claim 6 wherein the transition metal compound is selected from the group consisting of carbon (4) (10), gas iron and phosphating. 8. If the scope of claims is in items i to 7 Any one of the biofuel cell systems, the 'first/, medium ν» hai anode and the cathode chamber are separated by a chemically inert, porous, non-conductive material contained in the cathode chamber. The biofuel cell system of the scope of the invention is in the scope of the invention, and the biofuel cell system of the invention is separated from the anode chamber and the cathode (four) permeable membrane. 10. The biofuel cell system according to claim 9 of the patent scope, wherein The proton-permeable lanthanide is selected from the group consisting of a cation exchange membrane and an anion Membrane, composite anion/cation exchange membrane, group which has conductivity to f and conductivity selectivity to metal ions. 11. Biofuel cell system as claimed in claim 8 Wherein the proton permeable membrane is made of a Sterile inert material having a diameter extending less than about 100 microns through which the pores are filled, the pores being filled with electrolyte contained within the cathode chamber. 12. The biofuel cell system of claim 8, wherein the proton permeable membrane is made of a substantially inert woven fibrous material or a non-woven fibrous material having pores for the cathode The electrolyte contained in the chamber is filled, wherein the electrolyte is a proton conductor. 13. The biofuel 312XP/invention specification (supplement) 97_01/96135329 27 200915654, as claimed in any one of claims 1 to 2, wherein the anode electrode has a porous electrode structure. Wherein the yang: electric circumference a V: electricity:: biofuel cell system, τ* the cathode electric core table::: water: and the porous electric raft: / gold please / two range item 7 A fuel cell system in which a powder is formed into a porous anode::. Electricity (4)^, Γ Γ: Shen / Erli range of items 1 to 15 - Life: The reactor and the cathode chamber contain dissolved nutrients that promote the growth of vegetative micro-organisms. 2-7. The biofuel cell system according to Table 16 of the application, wherein the locus nutrient is selected from the group consisting of -, ρη 3- r ΝΗ4 Κ, Ca2+, S〇42_, 3 4 , C and The group consisting of the combinations. Pool system:, Shen:: A wide range of items 1 to 17 of the biofuels of the ... - Xuan 3 fuel with hydrogen components selected from helium, sterol, ethanol, ammonia, and cesium The group consisting of. Hey? Shen: Fen patent range of items 1 to 17 of the biofuel electric 兮..., the medium slanting hydrogen component fuel is hydrogen (5), and the electrochemical oxidation reaction is 2H2=4H++4e Representation of the oxidation of hydrogen in the Yangsheng electrode, and thus the total biofuel cell reaction is represented by 2H2+〇2=2H2〇. The biofuel cell system according to any one of the preceding claims, wherein the cathode electrode comprises a porous material layer selected from the group consisting of carbon and stainless steel. 312XP/Invention Manual (Repair) 97_G 1/96135329 200915654 2 1 · In the scope of the patent scopes 1 to 1 g - the pool system, wherein the cathode electrode comprises a group of sinister fuel and stainless steel; The material of the board is selected from the group consisting of the biofuel cell system of the carbon source, for example, in the scope of the invention, wherein the cathode electrode comprises a catalyst. a battery system, wherein the catalyst is one of gold, platinum, palladium, tungsten carbide, and lead. The biofuel cell system of the 21st or 22nd item is clean, and the catalyst is pure' or It is a mixture with stainless and inactive carbon powder, activated carbon fiber and inactive carbon fiber. Also, season: Shen: Erli range, items 1 to 24, biofuels, electrotechnical to bioreactor (〇2) The fluid includes carbon dioxide (c〇2) for making & biomass 26. The biofuel Z control means of claim 25 for applying voltage to the cathode electrode and controlling electricity 2: : Changing microbial culture parameters while controlling electricity Compared with the biomass system, such as the bio-fuel electrical material method of claim 25 or 26, the method for controlling the ratio of the two electric power production to the biomass in the redox couple. Item 27 of the biofuel cell system, wherein 4 reagent control means are used to control the dissolved nutrient concentration to control the power generation by changing the microbial culture parameters by 312 ΧΡ / _ ^ _ (repair) 97-01/96135329 29 200915654 The biofuel cell system according to any one of claims 1 to 28, wherein the mixture of the chemical metal oxidizing microorganisms comprises L. iron oxide and iron oxysulfate A biofuel cell system according to claim 6, wherein the transition metal compound is selected from the group consisting of tungsten carbide (wc), iron phosphide, and phosphating. a group; wherein the oxidized microorganism of the metal ion is a Helicobacter pylori; and wherein the anode chamber and the cathode chamber are chemically inert by one of the electrolytes contained in the cathode chamber 31. The biofuel cell system of claim 6, wherein the transition metal compound is selected from the group consisting of carbonized crane (wc), lithilated iron, and a group consisting of: the chemical metal ion oxidizing microorganism is a oxidized Leptospirillum; and the anode proton permeable membrane is separated. 碏i ί, such as the biofuel cell system of claim 31 Wherein: the permeable membrane is selected from the group consisting of a cation exchange membrane, an anion-crossing metal ion, and a osmotic selective membrane having a conductivity of π 质. • The biofuels (4) system of the scope of the patent, the tenth proton permeable membrane system is made of solid centroids with a hole of about 100 microns, at ^ ^ _ month; The electrolyte contained in the cathode chamber is filled. A. 34. The patent application scope 筮 312XP / invention manual (supplement) 97·_6ΐ3 help solid brother 31 biofuel cell system, wherein 30 200915654 the proton permeable membrane is made of a substantially inert woven fiber material with pores or The non-woven fibrous material is formed by filling an electrolyte contained in the cathode chamber, wherein the electrolyte is a proton conductor. 312XP/Invention Manual (supplement) 97-01/96135329 31