Apparatus and method for producing hydrogen from hydrogen sulfide
An apparatus is provided for producing hydrogen from hydrogen sulfide. The apparatus includes a container containing a solution that includes hydrogen sulfide. Within the container, and at least partially submerged in the solution, is a photo-anode, formed of an N-type semiconductor, and a photo-cathode, formed of a P-type semiconductor. Each electrode is at least partially covered with a catalyst material. The photo-anode and photo-cathode are electrically coupled to each other and develop charges of opposite polarity when exposed to a light source, which causes the hydrogen to separate from the sulfur in the solution. Also provided is a method for producing hydrogen from hydrogen sulfide.
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This application is related to the inventor's application “APPARATUS AND METHOD FOR PRODUCING SULFUR FROM HYDROGEN SULFIDE,” Ser. No. ______, now ______, which was filed on the same day as the present application and commonly assigned herewith to World Hydrogen, Inc. This related application is incorporated herein by reference.
BACKGROUND OF THE INVENTION1. Field of the Invention
The present invention relates generally to the production of gaseous hydrogen, and more particularly relates to the synthesis of hydrogen atoms from a solution of hydrogen sulfide.
2. Description of the Related Art
The United States and virtually every other country in the world depend almost exclusively on fossil-fuel-powered transportation. Our planes, trains, automobiles, and other engine-powered devices operate by burning petroleum products such as gasoline and diesel fuel. Fossil fuel, however, is a finite resource. According to some projections, its sources will begin to decline in rate of delivery as early as 2010. Currently, the loss of a reliable supply of fossil fuel would have a devastating effect on the whole of western society. For example, people would not be able to travel to work, factories would not be able to transport their products, and emergency services could not be delivered.
In addition to the impending exhaustion of the earth's fossil-fuel resources, fossil fuels suffer from at least four major disadvantages.
1. Air Pollution
When an engine burns gasoline or diesel fuel, carbon dioxide (CO2) and carbon monoxide (CO), a poisonous gas, are emitted as byproducts. In addition to carbon dioxide and carbon monoxide, the process of burning gasoline or diesel fuel further produces nitrogen oxides, the main source of urban smog, and unburned hydrocarbons, the main source of urban ozone. All of these chemicals have been medically proven to be detrimental to human health. In big cities and other largely populated areas, poor air quality can have a profoundly damaging effect on human health.
2. Environmental Pollution
Fossil fuels must be harvested, transported, stored, processed, further transported, and stored at the dispensing stations. These steps, particularly in the case of oil, can cause accidents that almost irreparably damage the earth's environment. Even minor oil spills, which happen rather frequently, are deadly to wildlife, detrimental to human health, costly, and difficult to clean.
3. Global Warming
The process of burning gasoline or diesel fuel in a combustion engine results in the emission of carbon dioxide into the atmosphere. Carbon dioxide is classified as a “greenhouse gas” that is attributed with causing a slow temperature rise on the planet. Global warming is caused by the accretion into the atmosphere of CO2 because CO2 acts as an absorber of the infrared part of the reflected light of the sun, and, as a result, the atmosphere, and the Earth, heat up. If the emission of carbon dioxide is not eliminated or at least reduced, it is projected that the greenhouse effect will be devastating to life on the planet Earth. The increase in temperature will eventually melt the ice caps, causing an increase in sea level that will result in flooding and the destruction of coastal cities in existence today.
4. Dependence
Because the United States is incapable of producing enough oil to meet its own demands, it depends on other oil-producing countries to provide that supply. This dependence leads to economic dependence and unfavorable foreign policies.
The Alternative
A viable alternative to fossil fuel is hydrogen. Hydrogen, unlike petroleum based fuels, does not suffer from any of the above-mentioned disadvantages. Hydrogen is a completely clean fuel, whose only byproduct is water. Thus, hydrogen, when burned, does not produce any of the greenhouse gasses that fossil fuels produce. Additionally, there is never a fear of environmental damage due to a spill, as the hydrogen will simply dissipate into the air, traveling upward into space.
However, most known methods of producing hydrogen do so by using fossil fuels, e.g., methane or “natural gas,” which are converted directly or indirectly to produce hydrogen. Disadvantageously, the fossil fuel conversion also results in a byproduct of CO2. As a result, most of the benefit of using the hydrogen, advertised as a “clean fuel,” is negated.
Electrolysis is a well-known method of producing hydrogen. An electric potential is applied between two leads—an anode having a positive charge and a cathode having a negative charge—which are submersed in a quantity of water. The H2O bonds are strong, however an electric potential of sufficient magnitude to overcome the H2O bond causes each water molecule (H2O) to dissociate into hydrogen (H2) and oxygen (O). The hydrogen evolves on the cathode and the oxygen on the anode. The result is pure hydrogen and pure oxygen, with no environmentally-hazardous byproducts.
On a molecular level, it is the high strength of the H—O bond that must be broken to separate the hydrogen from the oxygen. The generation of an electric potential strong enough to overcome the H—O bond requires the expenditure of energy, the creation of which is expensive, and in most cases, is the product of environmentally hazardous materials, such as fossil or nuclear fuels. Therefore, electrolysis of water does not overcome the above-mentioned disadvantages.
A molecular analog of H2O is hydrogen sulfide (H2S). H2S is readily available in large quantities with minimal cost. H2S, in fact, is considered a pollutant in oil wells and is estimated to have been a major contributing cause of the shut down of over 10,000 wells in the United States alone.
Looking from an atomic level, sulfur and oxygen have the same number of valance electrons, 6, in their outer shell. However, the sulfur atom has more shells than does the oxygen atom. Therefore, the strength of the H—S bond is significantly less than that of the H—O bond. For this reason, the energy necessary to break apart H2S to form hydrogen (H2) and sulfur (S) is less than the corresponding energy necessary to separate hydrogen (H2) from oxygen (O) in H2O.
One previous attempt to use solar energy to disassociate H2S is explained in Kainthla and Bockris, Photoelectrolysis of H2S Using an n-CdSe Photoanode, Int. J. Hydrogen Energy, Vol. 12, No. 1, pp 23-26, 1987, which is herein incorporated by reference. The method relied on solar energy to provide enough power to disassociate the H—S bond. The illuminated electrode was cadmium selenide (N-type) and the counter electrode was platinum. Hydrogen was indeed evolved, but the method and device suffered from the disadvantage of having an efficiency of conversion of light to hydrogen of only 1.5 percent. Because the efficiency was so low, the photo electrolysis process could not be used as the basis of a commercially practical device.
Therefore a need exists to overcome the problems with the prior art as discussed above.
SUMMARY OF THE INVENTIONBriefly, in accordance with one embodiment of the present invention, disclosed is an apparatus for generating hydrogen gas in an environmentally, non-impactful, and energy efficient manner. The apparatus includes a container containing a solution that includes hydrogen sulfide (H2S). At least partially submerged in the solution is a photo-anode formed of an N-type semiconductor material and a photo-cathode formed of a P-type semiconductor material. The photo-anode and photo-cathode are electrically coupled to each other and develop charges of opposite polarity when exposed to a light source. The charges cause the hydrogen to separate from the sulfur in the solution, thus producing pure hydrogen gas.
In one preferred embodiment of the present invention, the photo-anode comprises cadmium selenide over a stainless steel support and further covered by a plurality of ruthenium deposits on a surface of the cadmium selenide.
In some embodiments of the present invention, the photo-cathode comprises gallium phosphide with a plurality of platinum deposits on a surface of the gallium phosphide.
Another embodiment of the present invention provides a method for producing hydrogen from hydrogen sulfide. The method includes providing a solution including hydrogen sulfide within a container. An N-type photo-anode and a P-type photo-anode are provided and at least partially submerged into the solution. The photo-anode and the photo-cathode are exposed to at least one light source. A hydrogen gas byproduct is collected from the container.
BRIEF DESCRIPTION OF THE DRAWINGSThe accompanying figures, where like reference numerals refer to identical or functionally similar elements throughout the separate views and which together with the detailed description below are incorporated in and form part of the specification, serve to further illustrate various embodiments and to explain various principles and advantages all in accordance with the present invention.
While the specification concludes with claims defining the features of the invention that are regarded as novel, it is believed that the invention will be better understood from a consideration of the following description in conjunction with the drawing figures, in which like reference numerals are carried forward. It is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention.
The present invention, according to one embodiment, overcomes problems with the prior art by efficiently producing clean hydrogen without the need for an outside source of electricity and without producing environmentally hazardous gasses. The present invention realizes an efficiency of from 10-100 times great than that of the prior-art devices and methods. Additionally, the present invention produces hydrogen with negative costs.
Described now is an exemplary apparatus according to one embodiment of the present invention. Referring to
Each chamber 104 and 106 is an at least partially closed vessel and contains a quantity of hydrogen sulfide (H2S), into which one of the electrodes 108 or 110 is at least partially submerged. The energy needed to split water at a reasonable rate is about 1.7 V producing a current of 10-100 mA/cm2. However, the energy needed to split H2S into hydrogen and sulfur is only about 1.1 V (excluding IR drop) at about 10 mA/cm2. By utilizing two catalyst-containing electrodes, as described in detail below, each having its own energy gap, enough power is available to increase the efficiency of the conversion to a reasonable value of between 10-20%, with only the input of illuminating light, to separate the hydrogen from the sulfur in each H2S molecule.
In the illustrated embodiment, the chambers are bulbous, but in further embodiments can be any shape that will hold the solution. In other embodiments, the container 102 is a single chamber, which allows the electrodes to be moved closer together thus reducing the IR drop. The single chamber includes the elements shown in
A light source 126 strikes both electrodes and develops charges on the electrodes, with each electrode developing a polarity opposite that of the other. The electrode composition and charge generating mechanics will be described in detail below.
The potential difference between the charges on the two electrodes 108 and 110 is significant enough to disassociate the H2S molecules within the solution 124. As a result, hydrogen gas (H2) 116 is produced at the first electrode 108 in the first chamber 104 and sulfur (S) 118 is produced at the second electrode 110 in the second chamber 106.
The hydrogen gas 116 is collected from an exit port 128 located at an upper portion of the first chamber 104 and the sulfur 118 is removed from a bottom portion of the second chamber 106, where the sulfur 118 collects.
One preferred embodiment of the present invention will now be explained in detail. Referring now to
Doping is a process well known in the semiconductor art that adds impurities to a normally balanced crystalline structure. In N-type doping, the “impurity” atoms have one extra electron in their valance shell than do the atoms making the crystalline structure. The extra electrons are free to move around because there is nothing with which they can bond. Only a small amount of the impurity is needed to create enough free electrons to allow an electric current to flow. N-type doping gets its name because the added electrons have a negative charge.
In P-type doping, the “impurity” atoms have one less electron in their valance shell than do the atoms making the crystalline structure. When mixed into the crystalline lattice, “holes” are formed, where electrons are missing. The absence of an electron creates the effect of a positive charge, hence the name P-type. Holes can conduct current by accepting an electron from a neighbor, as to move the hole over a space.
In one embodiment, the cathode 108 includes a thin layer of gallium phosphide 202, P-doped, over an underlying support of stainless steel 206. In other embodiments, the layer is gallium arsenide (GaAs). In one embodiment, the anode 110 is made of a thin layer of cadmium selenide 208, N-doped, over an underlying support of stainless steel 210. It should be noted that the anode and cathode materials described here are just a single example and that other anode and cathode materials may also be used without departing from the spirit and scope of the present invention. The anode 110 and cathode 108 are coupled to each other through conductive paths 113 and 112.
The maximum energy available in a photo-electrolytic process is the “energy gap,” or difference in energy between the valence band and the conduction band, in the semiconductor material. For an electrode made of cadmium selenide (CdSe), the energy gap is 2.5 eV; cadmium sulfide (CdS) the energy gap is 1.1 eV; and cadmium telluride (CdTe) the energy gap is 1.5 eV. An eV (electron volt) is the amount of energy gained by a single unbound electron when it falls through an electrostatic potential difference of one volt. This is a very small amount of energy: 1 eV=1.60217653×10−19 J. Typical energy gaps needed for photo-electrolysis are between 1.0 and 2.0 eV, depending on the system being used.
Due to the stability of the CdSe in polysulfide solution, various forms of CdSe can be used—single crystal, polycrystal, and thin films, among others—to form the photo-anode 110. In the illustrated embodiment of the present invention, n-CdSe thin films deposited on stainless steel by chemical deposition techniques are used as the photo-anode 110. Similarly, p-gallium phosphide thin films deposited on stainless steel by chemical deposition techniques are used as the photo-cathode 108.
In the illustrated embodiment, deposited on top of the gallium phosphide 202, by pulse electrolysis, is platinum 204, which acts as a catalyst. The platinum 204 is arranged so that “spots” of platinum 204 cover between 10 and 20 percent of the gallium phosphide 202 in this embodiment. The “spots” are actually small mounds, or groups of atoms, deposited on the electrode. The spot diameter is about 0.2 mm.
In the illustrated embodiment, deposited on top of the cadmium selenide 208, by pulse electrolysis, is ruthenium 212, which acts as a catalyst. The ruthenium 212, similar to the platinum 204, is arranged so that “spots” of ruthenium 212 cover between 10 and 20 percent of the cadmium selenide 208 in this embodiment. The “spots” are actually small mounds, or groups of atoms, deposited on the electrode. The spot diameter is about 0.2 mm. In other embodiments of the present invention, other catalyst materials can be used, such as ferrous sulfide (FeS). For example, the ferrous sulfide can be applied by controlled vapor deposition in bursts until 10 to 20 percent coverage has been reached.
As shown in
H2S, when dissolved in NaOH solution, partially dissociates to H+, HS−, and S−−. The latter two ions then deposit on the anode in the chamber. The initial state of the sulfur, after delivery into the anode, and charge transfer (S−−→S+2e), is atomic sulfur, S. Fractions of a second later, the S leaves the anode to form chains of S atoms, mostly S8, i.e., S—S—S—S—S—S—S—S (polysulfide). The lifespan of the polysulfide chains is in the order of minutes and then it gradually decomposes to form crystalline sulfur.
Accordingly, the starting solution is 1M with respect to NaOH. The pH level of the solution is calculated as log (1/H+), i.e., depends on the H+ (or OH−) in the solution 124. If the H is removed, (i.e., in the photo-stimulated evolution of H2), the pH level will change. As the photo-stimulated electrolysis process proceeds (i.e., evolution of H2), pH changes have to be compensated for. Therefore, in one embodiment of the present invention, appropriate amounts of acid, e.g., H2SO4, are added to the solution 124 to increase the H+ level to maintain the pH constant.
In one preferred embodiment of the present invention, cadmium acetate and Na2SeSO3 are provided in the solution. Both substances are found to stabilize the CdSe used as the anode 104 and prevent it from dissolving. In another embodiment, the solution is heated to a temperature of about 80-90° C. The use of higher temperatures in the solution accelerates the synthesis.
Connecting the cathode chamber 104 and anode chamber 106 is a channel 120. The channel 120 allows the solution 124 to flow between the cathode chamber 104 to the anode chamber 106. Because the cathodic reactions is:
H2O+e→½H2↑+OH−
the channel 120 allows hydrogen ions (H+) to flow towards the cathode 102 as the cathode uses up H in the solution.
Although the channel 120 can be any shape and any size that allows fluid to flow between the chambers, in a preferred embodiment, the distance between the electrodes 108 and 110 is made as small as possible to reduce IR losses between the electrodes.
Between the cathode and anode chambers is a membrane 122. The membrane 122 prevents sulfur from drifting over to the cathode 108 and “poisoning” the catalyst on the cathode 108 during operation of the device. In one embodiment, the membrane 122 is a proton passing, cation selective Nafion membrane (such as Dupont #1100).
In the illustrated embodiment, the chambers are bulbous, but in further embodiments of the container can be any shape that will hold the solution. Referring to
Referring again to
When significant photocurrent flows through the container 102, H2 bubbles leave the P-type cathode 108, float to the surface of the solution 124, and exit the chamber 104 through a tube 128 for collection. Under these conditions, photo-generated holes on the surface of the photo-anode 106 oxidize S2−, formed as a result of reaction of H2S with OH−,
H2S+2OH−→S2−+2H2O
to sulfide according to the reactions:
S2−+2h+→S0
S2−+S0→S22−
while the electrons flowing from the anode 110 and then through the external resistor 114 to the cathode 108 reduce H2S to H2, i.e.,
2H2S+2e−→H2+2HS−
The resistor 114 represents normal resistive characteristics of a conductive path or can be an actual load placed between the electrodes. As the distance between the electrodes increases, so do the IR losses in the circuit. As stated above, to reduce IR losses between the anode 110 and cathode 108, the two electrodes should be physically located in as close proximity as possible, while also preventing S−− from reaching the cathode, i.e., separating with a membrane 122.
The current flowing through the external resistor 114 produces a voltage that, although small (about 0.5V), can be harnessed and utilized. An array of such devices can be added together to produce more significant quantities of power.
In one embodiment of the present invention, the light source 126 is a large array of solar collectors or mirrors reflecting the sunlight. However, other light sources can also be used without departing from the spirit and scope of the present invention. For instance, solar simulators are available in many laboratory-type environments. Solar simulators are lamps which have an internal inert atmosphere. The gases which constitute this atmosphere are chosen so that their spectrum is about 95% the same as that of the sun.
In an embodiment of the present invention, the light source used is passed through a beam splitter that separates a single light beam into at least two. One or more mirrors can be used to direct the beams exiting the splitter onto each electrode. In addition, the strength of the light source reaching the electrodes can be controlled to regulate the rate of hydrogen production.
In one embodiment of the present invention, the light source is passed through a filter that removes light in the infrared region. Infrared light, if not filtered, works to heat the electrodes. Infrared light is a relatively low frequency light wave. Conversely, it is the portion of the light spectrum having higher frequency that is desirable for use with the present invention.
It has been shown that in both the cathode 108 and anode 110, the application of the “spots” 204 and 212, which act as catalysts, improves the efficiency of the electrodes by as much as 10-50 times. In the absence of the catalyst spots, H+ ions in the solution are discharged onto the gallium phosphide, a semiconductor. The kinetics of such a reaction are poor and need an electric potential to cause the deposition of H+ and evolution of H2 to function at a practical rate. The presence of a metallic catalyst changes the situation greatly. The H atoms are deposited on the “spots” and no longer deposited on the gallium phosphide, which remains clean and acts as a collector of light and supplier of the photo-generated electrons necessary for transfer to H2O in solution. It should be noted that in an alkaline solution, the photo-electrons emit to H2O according the following equation.
H2O+e→H+OH−
The hydrogen photoevolved during the cell operation is collected. The sulfide formed according to S2−+2h+→S0 dissolves in the anolyte until the solubility limit of the polysulfide is reached. After this point, the excess sulfur precipitates out of the solution and the sulfur can be collected from the bottom of the chamber, where it has formed as a crystalline yellow mass. The net reaction, as shown in the formulas above, is the decomposition of H2S into H2 and S.
Referring to container 302 of
Referring now to
Although H2S is not as readily available as H2O, it is known that H2S is available in abundant quantities throughout the world. For instance, H2S can be found in locations such as under the Gulf of Mexico, in many gas wells, and other places. In fact, H2S is considered a nuisance or pollutant in over 10,000 wells in North America, effectively prohibiting the extraction of natural gas and oil.
The price of hydrogen is often stated in dollars per gigajoule (a joule is 4.18×107 ergs.) The cost of producing hydrogen with prior-art methods is between $10 and $20 per gigajoule. Interestingly, with the present invention, the sulfur produced with a gigajoule of hydrogen would be more than 10 tons. Sulfur, used for many practical applications, such as road making, landfills, and others, is a commercially viable substance, with a value of around $60-$70 per ton. Therefore, each gigajoule of hydrogen produced directly leads to the production of approximately $400-600 worth of sulfur. As a result, the production of hydrogen with the present inventive apparatus and method becomes a cost-free byproduct of the production of sulfur!
Although specific embodiments of the invention have been disclosed, those having ordinary skill in the art will understand that changes can be made to the specific embodiments without departing from the spirit and scope of the invention. The scope of the invention is not to be restricted, therefore, to the specific embodiments, and it is intended that the appended claims cover any and all such applications, modifications, and embodiments within the scope of the present invention.
The terms “a” or “an”, as used herein, are defined as one or more than one. The term plurality, as used herein, is defined as two or more than two. The term another, as used herein, is defined as at least a second or more. The terms including and/or having, as used herein, are defined as comprising (i.e., open language). The term coupled, as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically.
Claims
1. An apparatus for producing hydrogen, the apparatus comprising:
- a container;
- a solution including hydrogen sulfide, the solution provided within the container;
- a photo-anode formed of an N-type semiconductor, being at least partially coated with a catalyst material, and at least partially submerged in the solution; and
- a photo-cathode formed of a P-type semiconductor, being at least partially coated with a catalyst material, and at least partially submerged in the solution, the photo-cathode being electrically coupled to the photo-anode, the photo-cathode and photo-anode developing charges of opposite polarity when exposed to a light source so as to separate hydrogen from sulfur in the hydrogen sulfide of the solution and produce hydrogen gas.
2. The apparatus according to claim 1, wherein the photo-anode comprises one of cadmium selenide, cadmium sulfide, and cadmium telluride.
3. The apparatus according to claim 1, wherein the photo-anode further comprises a stainless steel support.
4. The apparatus according to claim 1, wherein the first catalyst material comprises a plurality of ruthenium deposits on a surface of the photo-anode.
5. The apparatus according to claim 4, wherein the ruthenium deposits cover approximately 10 to 20 percent of the surface of the photo-anode.
6. The apparatus according to claim 4, wherein the ruthenium deposits are each approximately 0.2 mm in diameter.
7. The apparatus according to claim 1, wherein the photo-cathode comprises gallium phosphide.
8. The apparatus according to claim 1, wherein the second catalyst material comprises a plurality of platinum deposits on a surface of the photo-cathode.
9. The apparatus according to claim 8, wherein the platinum deposits cover approximately 10 to 20 percent of the surface of the photo-cathode.
10. The apparatus according to claim 8, wherein the platinum deposits are each approximately 0.2 mm in diameter.
11. The apparatus according to claim 1, further comprising a membrane separating the container into at least two chambers, the photo-anode being disposed in one of the chambers and the photo-cathode being disposed in another of the chambers.
12. The apparatus according to claim 1, wherein the solution further includes NaOH.
13. A method for producing hydrogen, the method comprising the steps of:
- providing a solution including at least hydrogen sulfide within a container;
- providing an N-type photo-anode that is at least partially submerged in the solution;
- providing a P-type photo-cathode that is at least partially submerged in the solution;
- exposing the photo-anode and the photo-cathode to at least one light source; and
- collecting a hydrogen gas from the container, the hydrogen gas being the byproduct of a reaction between the solution and the photo-cathode.
14. The method according to claim 13, further comprising the step of:
- bubbling hydrogen sulfide through the solution before the exposing step.
15. The method according to claim 13, wherein the solution further includes NaOH.
16. The method according to claim 13, further comprising the step of providing a membrane that separates the container into two chambers, one of the chambers including the cathode and one of the chambers including the anode.
17. The method according to claim 13, further comprising the step of:
- adding cadmium acetate and Na2SeSO3 to the solution.
18. The method according to claim 13, further comprising the step of:
- heating the solution to a temperature of between about 80°-90° C.
Type: Application
Filed: Mar 4, 2005
Publication Date: Sep 7, 2006
Applicant: World Hydrogen, Inc. (Gainesville, FL)
Inventor: Burnard Bockris (Gainesville, FL)
Application Number: 11/073,076
International Classification: C25B 11/04 (20060101); C25B 1/02 (20060101);