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A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.
1. A catalyst combination comprising
(a) an electrocatalyst, and
(b) a homogeneous cocatalyst,
Wherein the catalyst combination is catalytic means for reducing positively-charged ions at a cathode in an electrocatalytic or mediated process of treating organic waste material in an aqueous electrolyte, the positively-charged ions comprising at least one member selected from the group consisting of hydrogen ions and metal ions.
2. A catalyst combination of claim 1 wherein the electrocatalyst is a member selected from the group consisting of cerium (4+) complex, iron (3+) complex, bromine and iodine.
3. A catalyst combination of claim 1 wherein the homogeneous cocatalyst is a member selected from the group consisting of platinum (4+) ion complex, ruthenium (3+) ion complex, rhodium (3+) ion complex, nickel (2+) ion complex, cobalt (2+) ion complex, palladium (2+) ion complex and vanadium (5+) oxide complex.
4. A catalyst combination of claim 3 wherein the electrocatalyst is a member selected from the group consisting of cerium (4+) complex, iron (3+) complex, bromine and iodine.
5. A method for treating organic material comprising combining organic waste material with an electrolyte and a catalyst combination of claim 1, and maintaining an electric potential across an anode and a cathode in an electrochemical cell containing the electrolyte and the catalyst combination, whereby positively charged ions are reduced at the cathode in an electrocatalytic, or mediated process, said positively charged ions comprising at least one member selected from the group consisting of hydrogen ions and metal ions.
6. A method of claim 5 comprising admixing the organic material with an electrolyte and catalyst composition in the electrochemical cell.
7. A method of claim 5 comprising separating the anode from the cathode in the electrochemical cell by interposing an ion-specific membrane therebetween.
8. A method of claim 5 comprising separating the anode from the cathode in the electrochemical cell by interposing a semi-permeable membrane therebetween.
9. A method of claim 5 comprising treating the organic material in a tank, circulating electrolyte solution containing the catalyst combination in reduced form to the electrochemical cell for reoxidation of the electrocatalyst and homogeneous cocatalyst, and recirculating the electrolyte containing electrocatalyst and homogeneous cocatalyst to the tank for treating organic material.
10. A method of claim 9 comprising separating the anode from the cathode in the electrochemical cell by interposing an ion-specific membrane therebetween.
11. A method of claim 9 comprising separating the anode and the cathode in the electrochemical cell by interposing a semipermeable membrane therebetween.
12. A method of claim 9 comprising dissolving the catalyst combination in its reduced form in the electrolyte solution.
13. A method of claim 5 which is carried out at 0� C. to 500� C.
14. A method of claim 5 wherein the anode is constructed of a material selected from the group consisting of platinum, platinum-doped carbon, platinum-clad titanium, niobium, graphite, reticulated vitreous carbon and platinum-plated reticulated vitreous carbon.
15. A method of claim 5 wherein the cathode is constructed of a material selected from the group consisting of platinum, platinum plated reticulated vitreous carbon, platinum-doped carbon, platinum-clad titaniumm, niobium, nickel and nickel-doped carbon.
16. A method of claim 5 wherein the anode is maintained at an operating potential of +0.5 to +1.5 volt, versus that of the normal hydrogen electrode.
17. A method for reducing the energy required for producing hydrogen or electrowinning metals by reacting organic material electrochemically using the catalyst combination of claim 1.
18. An aqueous electrolyte composition comprising a catalyst combination of claim 1.
19. A reaction composition comprising organic material and the aqueous electrolyte composition of claim 18.
This invention was made with the support of the State of New Mexico under Project No. 2-73-4633 awarded by the New Mexico Energy Research and Development Institute. New Mexico has reserved rights in this invention.
This invention relates to a catalyst composition of an electrocatalyst and a homogeneous cocatalyst, and use of the catalyst composition in combination with organic material for the electrochemical production of hydrogen or reduction of metal ions to metal in an aqueous electrolyte.
A related application, Ser. No. 864,410 entitled "A method for treating organic waste material and a catalyst/cocatalyst composition useful therefor" has been filed concurrently herewith, and the specification thereof is incorporated herein by reference.
Carbonaceous materials are oxidized when suspended in an aqueous electrolyte containing a reversible or quasireversible electrocatalyst and a homogeneous cocatalyst. The electrocatalyst is regenerated in an electrochemical cell through which a direct current is passed, the water being reduced to form hydrogen, or the metal ions being reduced to metal, at the cathode. The reduced electrocatalyst is reoxidized at the anode.
U.S. Pat. No. 4,412,893 concerns electrolyzing cations at a cathode of an electrolytic cell, wherein anolyte contains ferrous ion as a reducing agent. The electrolysis is conducted while the anolyte is agitated or while the anode moves with respect to the anolyte, providing relative motion between the anode and the anolyte, promoting contact of the anode with the ferrous ion despite their mutual electrostatic repulsion. A static relationship between the cathode and the catholyte is required. The concentration of the ferrous ion is in the range from 0.5 to 10 grams per liter.
U.S. Pat. No. 4,389,288 relates to electrochemical gasification of carbonaceous material by anodic oxidation in an aqueous acidic electrolyte to produce oxides of carbon at the anode and hydrogen at the cathode of an electrolytic cell using an iron catalyst.
U.S. Pat. No. 4,268,363 provides for electrochemical gasification of carbonaceous materials by anodic oxidation, producing oxides of carbon at the anode and hydrogen or metallic elements at the cathode of an electrolytic cell. Carbonaceous materials may also be hydrogenated at the cathode by electrochemical reactions during which carbonaceous material may also be anodically reacted within the anode compartment of an electrolytic cell. Typical examples of metals produced at the cathode include chromium, manganese, cobalt, nickel, copper, indium, and tellurium.
According to U.S. Pat. No. 4,341,608, hydrogen is produced from an electrolytic cell system by oxidizing a biomass product using a process of depolarizing the anode of an aqueous electrolytic cell. Particular catalyst systems are not disclosed.
U.S. Pat. No. 4,279,710 presents an electrochemical method and associated apparatus for gasification of carbonaceous materials to carbon dioxide with the attendant formation of fuels or high-energy intermediates, such as hydrogen or light hydrocarbons, and production of electric power. No particular catalyst systems are disclosed.
U.S. Pat. No. 4,235,863 considers a method of producing hydrogen in an electrolytic system using a hydride-forming liquid metal, such as liquid lithium or liquid sodium, the resulting hydride being thermally decomposed to produce hydrogen.
U.S. Pat. No. 4,182,662 relates to a method of forming hydrogen by electrolysis in a cell containing an aqueous acid solution. Catalysts used are graphitized carbon, ruthenized titanium or platinized titanium.
U.S. Pat. No. 4,395,316 is an improvement on the process of U.S. Pat. No. 4,341,608, which uses an anode of lead-rich ruthenium polychlore compounds.
In U.S. Pat. No. 4,311,569, an improved catalytic anode of a ternary platinum group reduced metal oxide is used alone or in combination with platinum group metals and/or platinum group metal oxides or mixtures having at least one valve-metal component, such as titanium, hafnium, zirconium, niobium, tantalum, and tungsten, in a process for electrolytically generating oxygen. The invention of U.S. Pat. No. 4,457,824 is an improvement on the same method. In these two patents, the catalysts are in the electrodes, and thus are not available in solution for homogeneous oxidation of any dissolved organics. Oxidation of organic materials using catalytic electrodes is not shown or suggested.
U.S. Pat. No. 2,433,871 provides an electrolytic cell for production of hydrogen and oxygen using alkaline aqueous electrolyte and a vanadium addition agent to reduce the operating voltage.
U.S. Pat. No. 4,105,755 concerns the production of hydrogen by reacting an ash-containing carbonaceous material, optionally on organic waste material, with a halogen to form a halogen acid, and then decomposing the halogen acid to halogen (recycled) and hydrogen. The halogen acid is preferably decomposed electrolytically if this step of the reaction takes place as a separate step from the initial reaction of the ash-containing carbonaceous material and halogen.
An object of the present invention is to provide an electrocatalytic reactor system in which the anode is depolarized by organic material oxidation using a catalyst/cocatalyst combination in an aqueous electrolyte in an electrochemical cell, hydrogen being generated, or metal ions reduced to metal, at the cathode. The over-all reactions in the anode half-cell and in the cathode half-cell are: ##STR1##
The process employs one of several electrocatalysts together with one of several homogeneous cocatalysts to improve the organic oxidation rate and to lower the activation energy for the oxidation of the organic material.
Another object of the invention is to provide a novel catalyst/cocatalyst composition of matter. A further object of the invention is to provide a method of using the catalyst/cocatalyst composition of the invention for the production of hydrogen or for the reduction of metal ions to metal. Yet another object of the invention is to provide an anolyte composition comprising organic material, a conductive electrolyte, catalyst and cocatalyst.
There are several distinct aspects of this invention:
(a) a catalyst/cocatalyst composition,
(b) use of (a) in a method of producing hydrogen electrolytically,
(c) use of (a) in a method of electrowinning metals electrolytically,
(d) use of (a) to reduce potential and thus energy required to produce hydrogen or reduce metal ions to metal,
(e) an aqueous electrolyte composition comprising (a), and
(f) a reaction medium composition comprising organic material in (e).
Component (a) is an indispensable subcombination of each of the other aspects of the invention. The dispersion of (a) throughout the anolyte composition imparts homogeneity to the distribution of the catalyst and of the catalyst.
The benefits derived from use of the catalyst/cocatalyst are several. The production of hydrogen (b) or electrowinning of metals (c) at reduced potentials is an energy-saving, economical process. Likewise, an increase in reaction rates using the catalyst/cocatalyst combination (a) provides energy-saving economy.
FIG. 1 is a vertical sectional view of an electrochemical cell useful for practicing the invention.
FIG. 2 is a cross-sectional view taken on the plane 2--2 of the cell of FIG. 1.
FIG. 3 is a vertical sectional view of apparatus in which the organic reaction area and electrochemical cell are separated.
In the process of the invention hydrogen gas is generated or metal ions reduced to metal in an electrolytic cell. At the cathode of the electrolytic cell, hydronium ion is reduced to hydrogen. The reaction at the anode is a mediated, or electrocatalytic, reaction in which the oxidized form of a reversible redox couple, produced at the anode, subsequently oxidizes the carbon in organic material present in the electrolytic cell. The products of the carbon oxidation are carbon oxides and the reduced form of the redox couple, which is reoxidized at the anode. The process described herein employs one of several electrocatalysts along with one of several homogeneous cocatalysts to improve the organic oxidation rate and to lower the activation energy required for the oxidation of the organic material. Obtained data shown that the mechanism of the organic oxidation is changed by the homogeneous cocatalyst, which apparently forms an electron transfer complex involving the electrocatalyst. This results in improvement in reaction rate and/or lowering of activation energies.
The electron transfer complex must exist at least momentarily to account for increased oxidation rates and lowered activation energies of the reactions taking place. It is postulated that the oxidation mechanism involves a short-lived coordination complex between the organic compound and the homogeneous cocatalyst, such as that of platinum ions or palladium ions and the double bonds of organic compounds, e.g., Ziese's salt anion, the trichloro (ethylene) platinate (II) ion, which is stable in aqueous solution. Similar platinum-organic double-bond complexes are apparently formed in catalyst mixtures of this invention. The standard potential of the iron (II)/iron (III) redox couple in 1.0 M sulfuric acid is +0.69V. The standard potential of platinum (IV)/platinum (II) redox couple in 1.0 M sulfuric acid is also approximately +0.69V. Thus, the platinum (II) species is in equilibrium with the platinum (IV) species, iron (III) and iron (II), and can be considered to be complexed for at least short periods of time to organic double bonds or other appropriate functionality on the organic compounds. The increase in reaction rate produced by platinum, palladium, rhodium and ruthenium is due to the fact that the homogeneous cocatalyst/organic complexes are more long-lived than the electrocatalyst/organic complexes and thus are more efficient at transferring electrons. Lowered activation energies are accounted for by the lower activation energy necessary for formulation of the organic compound-homogeneous cocatalyst complex. The required supply of oxidizing electrons can be derived from direct reduction of the cocatalyst, followed by reoxidation by the electrocatalyst or by formation of a short-lived electrocatalyst/cocatalyst/organic complex in which the cocatalyst compound acts as a bridge to transfer an electron from the organic compound to the electrocatalyst. Thus, the electron transfer complex (ETC) involved in the oxidation forms spontaneously when the homogeneous cocatalyst is added to an electrolyte containing dissolved or suspended organic compounds which have functional groups or bonds capable of interacting with the cocatalyst. The relative weight ratios vary with the type of organic compound, the type of cocatalyst and the electrocatalyst. Preferred ranges of proportions for each component are relatively large amounts of organic material (an activity for the organic of 1 or more), a great concentration of the electrocatalyst (activity of 0.1 to 1.0 or more) and a smaller concentration of the cocatalyst compound (activity of 0.01 to 0.001 or less). The ETC is formed in an electrolyte which solvates the catalysts and at a temperature of 0� C. or higher with an organic material with functionalities which can interact with the cocatalyst, and in the absence of any interfering conditions, such as species which tie up or precipitate the catalysts. The species which precipitate the catalysts are those which form insoluble salts with the catalysts, such as (for the metals), hydroxide, silicate, sulfide, high concentrations of sulfate or high concentrations of phosphate, and (for bromine) silver cation, gold cation or mercury cation. Species or substances which tie up the catalysts include highly absorptive inert materials such as clay or activated carbon, or compounds with which the catalysts react irreversibly, such as the reaction of bromine with some organic compound to form bromoform or tetrabromomethane.
The electrocatalyst is obtained as pure catalyst, from various salts or compounds of the electrocatalyst, or from impurities in the organic material.
The acid solutions usually used in the catalytic system dissolve many metal oxides, sulfides, many metal salts, etc. If any of these compounds exist as impurities in the organic waste used in the reactor, they will be leached out by an acid solution. Iron is one of the most common metals found in sewage sludge, manure and many other biological wastes, and so can supply part or all of the electrocatalyst once leached from the organic material. Bromine or iodine found in sufficient quantity in some waste materials, particularly brominated or iodinated organics, can supply the particularly brominated or iodinated organics, to provide the necessary electrocatalyst concentration. The electrocatalyst is usually added to the electrolyte, as there is not enough normally found in waste materials to develop the desired reaction rate, but some waste materials supply their own electrocatalyst, e.g. when leachable iron, bromine or iodine is present in sufficient quantity in the waste material. It is doubtful that any waste material will contain sufficient quantities of copper, nickel, platinum, vanadium, etc., to supply their own cocatalyst as well, but such is not precluded. Whether the electrocatalyst and cocatalyst are added as metals, metal salts, etc., or leached from the organic waste material does not affect the nature of the process described herein. The catalyst materials are identified by chemical analysis of the waste material to determine catalyst content (if any), and by chemical analysis of the acid electrolyte solution (after it has been thoroughly mixed with the waste and allowed to stand for, e.g., from 24 to 72 hours).
The homogeneous cocatalyst is optionally obtained from pure cocatalyst metal, from various salts or compounds of the cocatalyst, or from impurities in the organic material. The homogeneous cocatalyst is dissolved in or homogeneously distributed throughout the catalyst solution. This is advantageous in that it eliminates one heterogeneous step in the process of transfer of electrons from the electrocatalyst and in that the cocatalyst is available to the entire surface of any solid organic particles immersed in the catalyst solution. The cocatalyst is homogeneous with the electrocatalyst solution, it is a single ion complex (not an admixture), and the homogeneity of the cocatalyst is very critical to the increased reaction rates observed.
The employed electrolyte is any aqueous solution in which the electrocatalyst and cocatalyst are soluble at least in reduced form, but is typically a solution of a strong mineral acid, such as hydrochloric acid, phosphoric acid or sulfuric acid. The acid solution reduces the reduction potential necessary for hydrogen production, while providing a solubilizing medium for the catalyst composition. The system is satisfactorily operated at various temperatures, depending on the catalyst combination and the organic source; temperatures from 70� C. to 200� C. are typical. However, temperatures from 0� C. to 500� C. or more may be used.
The principle advantages of the process are two-fold. Firstly, the process produces electrolytic hydrogen at a potential considerably below that necessary to crack water. The organic/electrocatalyst/homogeneous cocatalyst combination acts as a depolarizing agent to reduce the potential applied at the anode. Using this process, electrolytic hydrogen is produced from inexpensive organic waste material at much lower cost than was formerly possible. Secondly, the process can be used in the electrowinning of metals at potentials lower than those now used, again due to the depolarizing action of the organic/electrocatalyst/homogeneous cocatalyst combination.
Examples of organic material or biomass suitable for practicing the invention are coal, peat, oil shale, woody wastes, cattle manure, garbage, sewage sludge, various industrial chemical wastes, food and fiber processing by-products or waste and grown biomass products, such as bulk grass plants, water plants, etc., or any organic material which can be oxidized by the catalyst solution at a reasonable rate.
Examples of catalyst compositions useful for practicing the invention are various combinations of metal ion complexes and/or oxidizing halogens. The complexes vary and depend upon the composition of the solution and the nature of the organic material. Non-limiting examples of electrocatalysts are cerium (4+) ion complex, iron (3+) ion complex, bromine and iodine. Non-limiting examples of homogeneous cocatalysts are platinum (4+) ion complex, ruthenium (3+) ion complex, rhodium (3+) ion complex, nickel (2+) ion complex, cobalt (2+) ion complex, palladium (2+) ion complex, copper (2+) ion complex and vanadium (5+) oxide complex. The catalyst solutions are made by dissolving the halogen, metal, and/or soluble metal salt in an electrolyte solution. Useful combinations of electrocatalyst and homogeneous cocatalyst include:
bromine with palladium2+ : (fat)
iron3+ with platinum4+ : (urea, wood cellulose, manure and/or fat)
iron3+ with vanadium5+ : (sewage sludge)
bromine with ruthenium3+ : (urea, wood cellulose and/or fat)
bromine with vanadium5+ : (wood cellulose and/or manure)
iron3+ with cobalt2+ : (wood cellulose and/or manure)
iodine with ruthenium3+ : (urea)
iron3+ with palladium2+ : (fat)
iron3+ with nickel+2 : (manure)
The range of electrocatalyst concentration providing a suitable reaction rate is from 0.01 M up to 100 percent. The preferred range is 0.1 M to 1.0 M. The range of cocatalyst providing an appropriate reaction rate is from 0.0001 M to 0.1 M. The preferred range is from 0.001 M to 0.01 M. The preferred ranges provide economy of operation.
In practicing the invention, an aqueous electrolyte, an electrocatalyst and a homogeneous oxidation cocatalyst are combined for producing hydrogen or electrowinning metals (at the cathode of an electrochemical cell).
Anode materials used in the invention are, for example, platinum, platinum-clad titanium, graphite, reticulated vitreous carbon or platinum plated reticulated vitreous carbon. Suitable anode materials are those materials which do not corrode in the electrolyte and at which the electrode-catalyst redox pair is reversible or quasi-reversible.
Suitable cathode materials are, for example, nickel mesh or platinum or platinum plated reticulated vitreous carbon. Other suitable cathode materials are materials which do not corrode in the electrolyte and at which the hydronium-hydrogen redox couple is reversible or quasi-reversible.
The electrolyte is, for example, phosphoric or sulfuric acid in concentrations varying from 1M to 6M, or potassium sulfate at 0.2M. Other useful electrolytes are those which possess the necessary conductivity, dissolve at least the reduced form of the catalyst, and do not interfere with or poison the catalyst. The electrolyte is made by diluting concentrated sulfuric acid, phosphoric acid or potassium sulfate crystals with water of reasonable purity, e.g. distilled water, deionized water or tap water.
The electrolyte solution optionally has many different compositions. Various other acids which are suitable electrolytes are perchloric acid, hydrobromic acid, hydroiodic acid, nitric acid, boric acid, hydrofluoric acid, or any other strong acid which is not irreversibly degraded in the system. There are a variety of salts which are suitable electrolytes, including sodium or potassium choride, bromide or iodide, iron chloride, bromide or iodide, sodium or potassium phosphate, sodium sulfate, any of the alkali-metal fluorides, any of the alkali or alkaline-earth nitrates or perchlorates, iron nitrate, iron perchlorate, any of the soluble borate salts, any of the soluble aluminum or ammonium salts and any other electrolyte salt or salt mixture which is not irreversibly degraded in the system. The important attributes of the electrolyte are that it is able to solvate at least the reduced form of the electrocatalyst, that it provides a low-resistivity medium between the electrodes and that it does not degrade in the oxidation system.
The operating potential of the system is dependent on the electrocatalyst and the electrolyte. The electrolyte, because of its relatively high concentration, generally determines the form of the electrocatalyst complex (if any), and can shift the redox potential of the electrocatalyst by several tenths of volts. For iron (3+) in 1.0 M phosphoric acid, the standard redox potential is +0.49 volt, and the cell anode is operated at any potential from +0.5 to +1.5 volts or more, versus the normal hydrogen electrode (NHE).
The normal hydrogen electrode (NHE) is an imaginary electrode at which the H+ /H2 redox reaction is perfectly reversible, and which is suspended in solution where the activity of the hydrogen cation is 1.0 and where hydrogen gas at 1.0 atmosphere (activity=1.0) is bubbled over the electrode surface. The potential of this electrode is defined to be 0.000 V, and is the standard of reference for redox potentials of other species. In practice, the electrode is approximated by a piece of platinized platinum (platinum covered with platinum black) in an acid solution of H+ activity 1.0, while hydrogen gas at 1.0 atmosphere is bubbled over the surface (H2 activity+1.0).
The preferred operating range for iron (3+) in phosphoric acid is +0.5 to +0.8 volt. For iron (3+) in 1. M sulfuric acid, the standard redox potential is +0.69 volt, and the cell anode is suitably operated at any potential from +0.70 to +1.5 volts or more, versus the NHE. The preferred potential range at the anode for iron (3+) in sulfuric acid solution is +0.7 to +1.0 volt. For bromine, the standard redox potential is +1.087 volts, and the cell anode is effectively operated at any potential from +1.0 to +1.5 volts or more, versus the NHE. Preferred potential range for bromine is from +1.0 to +1.2 volts versus the NHE. For iodine, the standard redox potential is approximately +0.47 volt, and the cell anode is operated at any potential from +0.5 to +1.5 volts or more, versus the NHE. The preferred potential range for iodine is from +0.50 to +0.70 volt.
Referring now to the Figures, FIG. 1 shows an electrochemical cell 2 suitable for practicing the invention. Tank 4 contains electrolyte 5 in which anode 6 and stirrer 10 are immersed. Electrolyte 5 is an electrolyte containing electrocatalyst and homogeneous cocatalyst together with the organic material. Anode 6 and cathode 8 are separated by an ion specific or semi-permeable membrane 12. Anode 6 is connected to lead 14 and cathode 8 is connected to lead 16. Leads 14 and 16 are connected to a source of electric current (not shown). Hydrogen generated in the cathode compartment are removed through conduit 18, and gases generated in the anode compartment are removed through conduit 20. FIG. 2 is a top view of the electrochemical cell 2, showing circular anode 6, circular cathode 8 and anode electrolyte solution 5 containing the electrolyte, electrocatalyst and homogeneous cocatalyst, together with the organic material. Ion specific or semi-permeable membrane 12 is shown as a circular separator between the anode and cathode compartments. FIG. 3 shows tank 30 which contains a mixture 32 of electrolyte, electrocatalyst, homogeneous cocatalyst and organic material resting on optional filter screen 34. Organic material is reacted with electrolyte and catalyst combination in tank 30, and electrolyte solution 35 flows through exit 36 via pump 38 to electrochemical cell 40, which contains electrolyte solution 35 in which anode 42 is immersed. Anode 42 and cathode 43 are separated by ion specific or semi-permeable membrane separator 44. Anode 42 is connected to lead 46, and cathode 43 is connected to lead 48. Leads 46 and 48 are connected to a source of electric current (not shown). Hydrogen generated at the cathode is led off at exit 50. Solution from the anode compartment is returned by conduit 52 to tank 30 for reuse. Gases generated in tank 30 are withdrawn therefrom through conduit 54. Organic material in tank 30 is mixed with catalyst solution by percolation, spraying, stirring, density gradient or other method. Catalyst which is reduced in tank 30 is reoxidized in electrochemical cell 40 before being returned to tank 30.
The electrocatalyst is regenerated from the reduced form by oxidation at the anode. There may be some reoxidation of reduced cocatalyst at the anode, but this is minimal compared with the reoxidation of the electrocatalyst since the cocatalyst is largely not consumed.
The electrochemical cells shown in FIGS. 1 to 3 are non-limiting examples of the invention. The electrochemical cell may be configured as a cylinder, a sphere or other appropriate shape. The anode compartment is alternatively the inner compartment, the outer compartment, or either compartment in a cell in which the electrodes are planar. The separator is, optionally, an ion-specific membrane or any semipermeable barrier.
Suitable ion-specific membranes include cation-specific membranes, for example, Ionics 61 CZL-386 (manufactured by Ionics, Inc.) and Nafion 423 (manufactured by DuPont). The semi-permeable membrane is, e.g., a microporous plastic, sintered (fritted) glass, a gel, such as agar, or any other material which restricts fluid flow and does not allow intimate mixing of the anolyte and catholyte. The Ionics 61 CZL-386 membrane is a modacrylic fiber-backed cation-transfer membrane. Either an ion-specific of a semi-permeable membrane may be used, but the use of ion-specific membranes leads to higher electrochemical cell efficiency since they strongly limit the diffusion of the electrocatalyst between the catholyte and the anolyte. Semipermeable membranes are generally less expensive but do not provide as much of a barrier to electrocatalyst diffusion, thus lowering the efficiency of the electrochemical cell in comparison with a cell using an ion-specific membrane.
Other operating limitations are principally imposed by the materials used in construction of the reactor system. The system may be built of very inert, strong, expensive materials, such as quartz-lined steel, and operated at relatively high temperatures (100� to 500� C. or more) or it may be made from inexpensive materials, such as polypropylene or polyethylene and ordinary glass, and operated at temperatures of 20� C. to 120� C. Electrode materials must not corrode at the operating temperature of the electrochemical cell. Another limitation is the necessity to operate below the critical temperature of the electrolyte solution being used.
Elevated temperatures are used when depolarization is effected with a refractory organic compound, such as lignin, chitin or a saturated aliphatic hydrocarbon; or when excess heat energy is available at low cost and a lower redox potential electrocatalyst (for example, iron in phosphoric acid, or iodine) can be used to reduce electrical costs. When a lower-potential electrocatalyst has an unacceptable reaction rate at, e.g., 70� C., it is not precluded from oxidizing the organic compound at an adequate rate at, e.g. 250� C. The pressure in the system may vary and is dependent on the nature of the electrolyte and the electrocatalyst. A concentrated sulfuric acid solution does not reach one atmosphere (14.7 psia) pressure until 330� C., and concentrated phosphoric acid has a similar low pressure at elevated temperature.
Potential applied to the anode is kept as low as possible to maximize the energy efficiency of the system. An increase in temperature increases the reaction rate and reduces the necessary size of the reactor for producing a given amount of hydrogen or metal. Operating the anode at a higher potential drives the reaction more quickly but is of limited utility beyond about 0.2 to 0.3 volt more (positive) than the electrocatalyst redox potential. The acidity of the electrolyte solution affects the reaction rate by aiding in the decomposition of some organic compounds due to dehydration and other acid catalyzed reactions. With woody organic material greater acid concentrations are particularly effective in increasing the electrocatalytic oxidation reaction rate, due to breakdown of the cellulose chains.
For hydrogen production or metal electrowinning maximum energy efficiency must be achieved with the given organic material used. The reactions at the anode and cathode must be as reversible as possible, so that little overpotential is needed. Preferred materials for the cathode are platinum, platinum-doped carbon, platinum-clad titanium, platinum-clad niobium, nickel or nickel-doped carbon. Platinum, platinum-clad titanium or niobium, platinum-doped carbon or carbon are preferred materials for the anode. The preferred electrolyte solution depends on the electrocatalyst used and the type of organic material. Several satisfactory combinations (useful for hydrogen production) are exemplified below:
0.1 M iron (3+)/0.1 M cobalt (2+)/wood cellulose/6M sulfuric acid;
0.1 M iron (3+)/0.01 M vanadium (V)/sewage sludge/6M sulfuric acid;
0.01 M bromine/0.01 M vanadium (5+)/wood cellulose or manure/6M sulfuric acid;
0.01 M bromine/0.001 M ruthenium (3+)/urea, cellulose or fat/6M sulfuric acid; and
0.1 M iron (3+)/0.001 M platinum (4+)/urea, cellulose or fat/6M sulfuric acid.
The operating potential of the anode is maintained at +0.5 to +1.5 volt versus the NHE, and temperatures of operation are typically from 20� C. to 200� C. With more inert, stronger materials of construction for the apparatus the operating temperature may be 500� C. or more. Lower temperatures require less energy expended in heating the system.
Table I, below, tabulates non-limiting examples of organic material, electrocatalyst, homogeneous cocatalyst, electrolyte, reaction rate, and activation energy, particularly pointing out the advantageous effect when a homogeneous cocatalyst is used in combination with an electrocatalyst contrasted with the use of the electrocatalyst alone. The reaction rate is significantly increased using the combination of electrocatalyst and homogeneous cocatalyst of the invention.
In practicing the invention, the mechanism of organic oxidation is changed by addition of the homogeneous cocatalyst to the electrocatalyst and by formation of an electron transfer complex involving the electrocatalyst, homogeneous cocatalyst and the organic material. The electron transfer complex has not been characterized but its presence is demonstrated by the reduced activation energies and/or increased reaction rates in the presence of homogeneous cocatalyst as opposed to use of the electrocatalyst alone, as shown in Table I. The use of the combination of electrocatalyst and homogeneous cocatalyst of the invention results in an increase in reaction rate and a decrease in activation energies.
TABLE I__________________________________________________________________________ Reaction EAOrganic Electrocatalyst Homogeneous Cocatalyst Electrolyte Rate (sec-1) (kcal/mole)__________________________________________________________________________wood cellulose iron (III) none 6. --M H2 SO4 @ 50� 1.4 � 10-6 12.wood cellulose iron (III) cobalt (II) 6. --M H2 SO4 @ 50� 4.1 � 10-6 11.3wood cellulose iron (III) platinum (IV) 6. --M H2 SO4 @ 50� 3.6 � 10-6 8.1beef fat iron (III) none 1.0 --M H2 SO4 @ 20� <1 � 10-9 --beef fat iron (III) platinum (IV) 1.0 --M H2 SO4 @ 20� 4.7 � 10-7 4.5beef fat iron (III) palladium (II) 1.0 --M HCl @ 20� 2.2 � 10-6 --urea iron (III) none 1.0 --M H2 SO4 @ 20� 4. � 10-9 --urea iron (III) ruthenium (III) 1.0 --M H2 SO4 @ 20� 2.2 � 10-8 --urea iron (III) platinum (IV) 1.0 --M H2 SO4 @ 20� 1.2 � 10-6 4.8urea iodine none 1.0 --M H2 SO4 @ 20� <1 � 10-9 --urea iodine ruthenium (III) 1.0 --M H2 SO4 @ 20� 5. � 10-9 --urea bromine none 1.0 --M H2 SO4 @ 20� 2.0 � 10-5 --urea bromine ruthenium (III) 1.0 --M H2 SO4 @ 20� 2.6 � 10-4 8.6cellulose bromine none 0.2 --M K2 SO4 @ 20� 1.6 � 10-6 --cellulose bromine platinum (IV) 0.2 --M K2 SO4 @ 20� 2.9 � 10-6 --cellulose bromine rhodium (III) 0.2 --M K2 SO4 @ 20� 8.6 � 10-6 --cellulose bromine ruthenium (III) 0.2 --M K2 SO4 @ 20� 1.7 � 10-5 12.cellulose bromine none 6.0 --M H2 SO4 @ 50� 1.6 � 10-5 10.6cellulose bromine vanadium (V) 6.0 --M H2 SO4 @ 20� 4.7 � 10-5 11.4cellulose none vanadium (V) 6.0 --M H2 SO4 @ 20� <1. � 10-6 --fat bromine none 0.2 --M K2 SO4 @ 20� 1.9 � 10-6 --fat bromine palladium (II) 0.2 --M K2 SO4 @ 20� 2.9 � 10-6 --fat bromine ruthenium (III) 0.2 --M K2 SO4 @ 20� 9.3 � 10-6 11.1cattle manure iron (III) none 6.0 --M H2 SO4 @ 50� 4.0 � 10-7 12.3cattle manure iron (III) platinum (IV) 6.0 --M H2 SO4 @ 50� 1.1 � 10-6 --cattle manure iron (III) cobalt (II) 6.0 --M H2 SO4 @ 50� 1.2 � 10-6 8.0cattle manure iron (III) nickel (II) 6.0 --M H2 SO4 @ 50� 8.0 � 10- --cattle manure bromine none 6.0 --M H2 SO4 @ 50� 7.6 � 10-6 10.0cattle manure bromine vanadium (V) 6.0 --M H2 SO4 @ 50� 1.1 � 10-5 5.1sewage sludge iron (III) none 6.0 --M H2 SO4 @ 50� 1.2 � 10-6 18.7sewage sludge iron (III) vanadium (V) 6.0 --M H2 SO4 @ 50� 3.8 � 10-6 13.3__________________________________________________________________________
The invention is further illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated. These non-limiting examples are illustrative of certain embodiments designed to teach those skilled in the art how to practice the invention and represent the best mode contemplated for carrying out the invention.
A catalyst solution of 1.0 M sulfuric acid containing 0.1 M iron (III) and 0.001 M platinum (IV) is prepared by diluting 0.055 liter of concentrated sulfuric acid, 20 grams of iron (III) sulfate, and 0.410 grams of chloroplatinic acid to one liter with water. 70 Grams of urea are then added to the solution. The solution is stirred to dissolve the salts and 600 ml of solution is transferred to the anode half-cell of FIG. 1; a solution of 1.0 M sulfuric acid is added to the cathode half-cell. These two solutions are the anolyte and the catholyte, respectively. The anode is a platinum-clad titanium wire mesh formed into a cylindrical shape, and the cathode is a cylindrical shape formed of fine nickel wire mesh. Both electrodes are totally immersed in solution. A Teflon�-coated stirring bar is used to agitate the solution in the anode half-cell, and an Ionics 61 CZL-386 cation-specific membrane is used to separate the two half-cells. The cell is sealed and maintained at 30� C., and a D.C. potential of approximately 1.0V is applied across the electrodes, resulting in a current of 7 mA. After a 100 hour test period, the hydrogen generated is purged and analyzed by gas chromatography, giving a hydrogen generation efficiency value of 99%, approximately 20% of the urea being consumed. For the anode half-cell solution reaction, the reaction rate constant is 1.2�10-6 sec-1 and the activation energy is 4.8 kcal/mole.
The reactor tank of FIG. 3 is loaded with a supported bed of 500 grams of wood chips over filters of 1.0 mm and 0.25 mm Teflon� screen. A solution of 6.0 M sulfuric acid containing 0.2 M iron (III) and 0.01 M cobalt (II) is prepared by diluting 3.3 liters of concentrated sulfuric acid, 400 grams of iron (III) sulfate and 15.5 grams of cobalt (II) sulfate to 10 liters with water. The solution is agitated to dissolve the salts and then transferred into the reactor tank. The electrodes in the electrochemical cell are a 20 pores/inch reticulated vitreous carbon (RVC) anode and a platinum-plated 20 pores/inch RVC cathode, separated by a Nafion� 423 cation-specific membrane. A potential of 1.0 volt is applied across the electrodes. The reactor tank is sealed, and the catalyst solution is pumped from the tank through the electrochemical cell and back into the tank. The reactor tank is heated to about 80� C. giving a current level of 0.5 to 2.0 amperes. The reaction tank volume is about twice the volume of the solution in liters, the reaction rate is about 1�10-4 sec-1 and the activation energy is 11.3 kcal/mole. The electrochemical cell is operated at more than 95 percent efficiency, and about 13 cubic feet of hydrogen is produced, as determined by gas chromatographic analysis during 100 hours of operation.
A catalyst solution of 1.0 M sulfuric acid containing 0.01 M cobalt and 0.1 M iodine is prepared by diluting 0.055 liter of concentrated sulfuric acid, 1.57 g. cobalt (II) sulfate and 12.7 g. iodine crystals to one liter with water. The reactor cell of FIG. 1 is loaded with 15 g. of potato starch in the inner (anode) chamber. The catalyst solution is added to the outer (cathode) chamber. Each electrode is platinum-clad titanium mesh formed into a cylinder, and the half-cells are separated by a supported Nafion� 423 cation-specific membrane. The reactor cell is sealed and heated to 120� C., and a potential of +0.70 volts is applied to the anode versus the cathode. The resulting reaction rate is approximately 1.7�10-5 sec-1, with the iodine/starch reaction activation energy equal to 13.2 kcal/mole. About 1.7�10-5 moles hydrogen/second are produced at the cathode, at an efficiency of nearly one hundred percent. The starch is consumed in a little over eight hours.
Further examples of systems operated at higher temperatures are shown in Table II.
Variations and modifications may be effected within the scope of the invention as described above, and as defined in the appended claims. Throughout the disclosure and claims all references to "homogeneous cocatalyst" mean that the cocatalyst is substantially uniformly dispensed throughout the electrolyte.
TABLE II__________________________________________________________________________EXAMPLES OF SYSTEMS AT HIGHER TEMPERATURESElectrocatalyst Cocatalyst Electrolyte Medium Temperature Pressure__________________________________________________________________________0.2 --M Iron (III) 0.001 --M Platinum (IV) 6 --M H2 SO4 100.� C. <15 psia0.2 --M Iron (III) 0.01 --M Cobalt (II) H2 SO4 330.� C. ˜15 psia0.2 --M Iron (III) 0.01 --M Vanadium (V) H3 PO4 200.� C. <15 psiaBromine 0.01 --M Vanadium (V) HBr 225.� C. ˜2000 psia0.2 --M Iron (III) 0.001 --M Platinum (IV) AlCl3 200.� C. ˜40 psiaBromine 0.001 --M Ruthenium (III) 6 --M H2 SO4 110.� C. ˜30 psiaIodine 0.01 --M Copper (I) H2 SO4 265.� C. ˜75 psia0.2 --M Cesium (IV) 0.001 --M Palladium (II) 6 --M NaCl 225.� C. ˜300 psia__________________________________________________________________________
Patent Citations
Non-Patent Citations
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text:
Jewish Humor and the Yiddish Joke
Wed, February 27, 2013 • 4:00 PM • CLA 1.302D
A lecture by Dr. Jordan Finkin.
Jews don't have a monopoly on humor, but how does one account for the uncontroversial cultural phenomenon of "Old Jews Telling Jokes"? Humor played an important role in Yiddish-speaking Jewish life, and the joke was a central vehicle of that humor. While liable to be viewed only as entertainment, jokes possessed distinct value beyond the pleasurable, as evidenced by their conspicuous use in the development of modern forms of cultural expression. This talk will address these issues, examining what's so Jewish about Jewish humor through the lens of the joke.

subset: commoncrawl


text:
Unlocking the Key to Deep Sleep
By Sarah Fenske
Making the Ferguson Commission Matter
By Danny Wicentowski
My Fake Boyfriend Became a Real-Life Crush
By Lindsay Toler
Rep. Jeffrey Pogue Bill Would Ban Unisex Bathrooms
By Danny Wicentowski
Darren Wilson Gives Speech to Nonprofit
By Danny Wicentowski
Angel Stewart and Other Victims of Violence Ask for Mercy
By Jessica Lussenhop
Obama Praises St. Louis' LaunchCode
By Lindsay Toler
By Lindsay Toler
But much was shoved aside in the rush to judgment -- including exactly what Kaos and Syllli Asz said, and the context in which their comments were made.
Tensions were already running high at the time of the July 13 broadcast; eight days earlier, nineteen-year-old Kevin Johnson allegedly shot and killed Kirkwood police officer Sergeant William McEntee while the officer was responding to a call in the Meacham Park neighborhood. After an intense three-day manhunt, Johnson's relatives arranged for a peaceful surrender to police in the north-county suburb of Northwoods.
Between July 8 and 10, on an Internet message board popular with St. Louis County cops (http://members5.boardhost.com/COUNTYBROWN), several people -- presumably irked that Johnson was treated humanely upon being taken into custody -- posted missives claiming Northwoods Police Chief Greg Moore "struggled to get a third-grade education" and was "illiterate," among other taunts.
On July 11, Kaos and Syllli Asz, both African-Americans, revealed the postings on their popular show, Kaos in the Morning, which had climbed to second in the ratings since the pair took over KATZ's 5-to-10-a.m. time slot in January.
Two days later, Kaos posed the following scenario to his broadcast partner: If, after being handcuffed by a police officer, that cop willfully took off the handcuffs and challenged Syllli Asz to a fight, would Syllli go for the cop's gun first or his radio? Syllli responded by saying he'd go for the radio first, so that the cop couldn't call for backup.
KATZ owner Clear Channel suspended the DJs indefinitely on July 15. On that same day, the St. Louis Post-Dispatch ran its first account of the imbroglio, which included comments by St. Louis Metropolitan Police Chief Joe Mokwa, who characterized the duo's comments as "taboo and inappropriate." Mokwa also added that he understood "they were trying to be funny, [and that it was] time to let go and move on."
Kaos and Syllli were about to discover another meaning to "let go" and "move on."
In a July 17 "Rimshot" on the Post-Dispatch opinion page, entitled "Wacky Morning Guys," Kevin Horrigan (writing sans byline on behalf of the entire editorial board) chided Kaos and Syllli for engaging in a "public-spirited dialogue with listeners on how best to beat up and otherwise neutralize police officers."
The next day FOX's Hannity & Colmes played host to Mike Guzy, a 21-year veteran of the St. Louis Sheriff's Department and onetime Post-Dispatch editorial columnist. On this broadcast, while acknowledging that he'd "never listened to the program," Guzy opined that Clear Channel should feel "negligent in their obligations to the public to allow these people to use the public airways to air tutorials on how to injure and kill police officers."
KATZ general manager Lee Clear, meanwhile, played a tape of the broadcast for Mokwa, who, according to department public-relations director Richard Wilkes, "didn't provide any insight either way."
"It really is not an issue with the St. Louis Metropolitan Police Department," says Wilkes.
The St. Louis chapter of the Fraternal Order of Police on July 19 called for the immediate firing of the two KATZ DJs, a position the chapter formalized in a July 21 letter to Lee Clear. In the letter, local FOP president Kevin Ahlbrand threatened to "call for an immediate boycott of all advertisers of KATZ and any other Clear Channel media outlet" if the station failed to fulfill their request.
National FOP president Chuck Canterbury echoed Ahlbrand's call for dismissal in a July 26 letter to Clear Channel's board chairman, Lowry Mays. On July 28, Post-Dispatch reporter Emily Dulcan wrote a brief account of police reaction, describing Kaos and Syllli as having "discussed on the air how to injure police officers."
On August 2, Kaos retained the services of Clayton defense attorney Scott Sherman (Syllli has yet to retain counsel but has consulted with Sherman). The next day, Kaos and Syllli were fired, learning of their terminations via a written Clear Channel announcement issued to the news media.
Two days later, Post-Dispatch reporter Todd C. Frankel penned a short recap of the entire affair, describing the jettisoned disc jockeys as "talking with callers about how to injure officers and take away their radios so they couldn't call for help."
When Sherman and Ahlbrand appeared side-by-side on FOX's (Channel 2) Jaco Report two days later, Ahlbrand conceded he'd never heard the broadcast or read its transcript.
(Ahlbrand and Clear did not return multiple phone calls seeking comment for this article.)
On August 8, the Post-Dispatch's opinion page again weighed in, under the headline "Kaotic and Aszinine." Writing for the editorial board, Bob Joiner supported Clear Channel's decision while acknowledging that "some fans of the two hosts stressed that they knew the controversial discussion wasn't meant to be taken seriously."
At this point, no one at the Post-Dispatch had actually heard the broadcast or obtained a transcript. Neither, by their own admission, had any of the FOP officials involved in demanding the DJs' termination.
Sponsor Content


text:
A local bank manager appeared on the popular game show "Wheel of Fortune" on Tuesday, taking home the top prize.
Carol Waddle, a senior vice president for Signature Bank of Arkansas in Fayetteville, identified the Pacific island of BORA BORA in the bonus round to win a MINI Cooper Convertible worth $31,300. She took home a total of $52,980 after beating out two other contestants to appear in the bonus round.
Waddle held a watch party at the Foghorn's sports bar on Green Acres Road in Fayetteville with friends and family who showed support. She said she recorded the show three months in advance of Tuesday's showing.
"It was lots of fun, but it was nerve-racking," she told 5NEWS at the watch party. "It was a great experience."


text:
An illusion apparatus comprises a semi-transparent convex, spherical mirror which makes the image of a primary object, ordinarily a human viewer, appear to interact with a display means such as a television set or a picture or a diorama. The semi-transparent, convex, spherical mirror is located between the viewer and the display means. The viewer is preferably illuminated against a dark backdrop. Because the spherical mirror is semi-transparent, the viewer sees a composite image which includes his own reflection superimposed on a portion of the scene from the television, picture, or diorama behind the mirror. A darkened area is preferably located on the television screen or in the picture or diorama and corresponds to the size and location of the viewer's image. This prevents the scene in the television or diorama from bleeding through the viewer's image. A mirror supporting stand makes it possible to adjust the height of the mirror with respect to the viewer and the display means so as to fine tune the effect. The effect can be modified by using convex, aspherical mirrors for special situations and by adding interactive feedback between the viewer and the television set or diorama so that the viewer can control his environment in the composite image.
1. An illusion apparatus for making an object appear to be inside or on the surface of a display means, said apparatus comprising:
a partially reflective, partially transparent convex mirror located between said primary object and said display means for making an image of said primary object appear to interact with said display means; and,
a vertical mirror height adjustment means attached to said mirror for adjusting the position of said mirror with respect to said display means,
wherein said mirror is convex in the direction of said primary object so as to diminish the size of said image.
2. An illusion apparatus for making a primary object appear to be inside or on the surface of a display means, said apparatus comprising:
a convex mirror located between said primary object and said display means for making an image of said primary object appear to interact with said display means,
wherein said mirror comprises a partially reflective, partially transparent mirror and is convex in the direction of said primary object so as to diminish the size of said image.
3. The apparatus of claim 2 wherein said primary object is adapted to be used by or with a human being.
4. The apparatus of claim 2 wherein said display means comprises a two dimensional display means.
5. The apparatus of claim 4 wherein said two dimensional display means comprises a television.
6. The apparatus of claim 2 wherein display means comprises a three dimensional display means.
7. The apparatus of claim 6 wherein said three dimensional display mean comprises a diorama.
8. The apparatus of claim 7 wherein said diorama is constructed in forced perspective.
9. The apparatus of claim 2 further comprising:
at least one darkened area in said display means corresponding to the location in said display means where said image appears,
wherein the image of said primary object substantially appears in the darkened area of said display means.
10. The apparatus of claim 2 further comprising:
first illuminating means for illuminating said primary object.
11. The apparatus of claim 10 wherein said first illuminating means comprises:
a first light source for lighting said primary object from a location between said primary object and said mirror.
12. The apparatus of claim 2 further comprising:
a backdrop means located on the opposite side of said primary object from said mirror.
13. The apparatus of claim 7 further comprising:
a second illuminating means for illuminating said diorama said second illuminating means located on the opposite side of said mirror from said primary subject.
14. The apparatus of claim 13 wherein said second illuminating means comprises a dimmable illuminating means.
15. The apparatus of claim 2 further comprising:
a stand for supporting said mirror; and,
a mirror height adjustment means attached to said mirror and to said stand for adjusting the position of said mirror with respect to said primary object and said display means.
16. The apparatus of claim 2 wherein said mirror comprises a spherical mirror.
17. The apparatus of claim 2 wherein said mirror comprises an aspherical mirror.
18. The apparatus of claim 2 wherein the distance of the image to said mirror approaches one-half of the radius of said mirror.
19. The apparatus of claim 2 further comprising:
control means controllable by said primary object for controlling the scene displayed by said display means.
20. The apparatus of claim 19 wherein said display means comprises a television.
21. The apparatus of claim 20 wherein said control means comprises:
an electronic control means controllable by said primary object; and,
a video game system connected to said electronic control means and to said television.
22. The apparatus of claim 19 wherein said control means comprises a switch mat.
23. The apparatus of claim 16 wherein:
the radius of said spherical mirror is in the range of 8" to 48" inches.
24. The apparatus of claim 21 wherein:
the radius of said spherical mirror is approximately 8".
1. Field of the Invention
The invention relates to an illusion apparatus including a semi-transparent, convex, spherical mirror for making the image of the viewer appear to be located on the surface of a television screen or picture or in a diorama.
2. Description of Related Prior Art
The use of mirrors and related optics to achieve illusions is known in various parts of the prior art. Two useful background references are "The Technique of Special Effects Cinematography," by Raymond Fielding, Third Edition, Focal Press, 1972 (see, in particular, pages 74-77) and "Magic Stage Illusions, Special Effects and Trick Photography," compiled by Albert Hopkins, reprinted by Dover Press, 1976, (See, specifically, pages 8, 55-60, 86-87 and 520-523).
The following U.S. Patents generally relate to the use of optics to produce theatrical effects: U.S. Pat. Nos. 922,722; 1,775,237; 1,785,347; 2,222,084; 2,232,547 and 4,094,501.
Mirrors and related optical devices have also been employed to superimpose images for advertising purposes. See specifically, U.S. Pat. Nos. 936,344; 2,146,386; 2,165,736; 2,232,110 and 2,273,259.
The optical superposition of images is useful as a teaching aid. See, for example, U.S. Pat. No. 2,875,528 in which a swimmer is superimposed in a swimming environment. Similarly, see U.S. Pat. Nos. 2,494,000 and 3,000,261 in which superimposed images are used to teach an individual how to play golf.
Optically superimposed images are also useful for giving an individual a preview of himself or herself in a particular fashion environment. For example, U.S. Pat. Nos. 2,075,198 and 2,899,860 disclose previewing devices in which a human head is superimposed upon a new hair fashion to give the viewer an idea of what he or she would look like with the new hair style. Similarly, clothing fashions can be previewed by optically superimposing an image of the viewer upon the new fashion wear. In this regard, note U.S. Pat. Nos. 1,236,196 and 3,729,839. U.S. Pat. No. 4,157,633 discloses a fashion preview invention in which the subject is a doll and images of different clothing fashions are superimposed upon the doll's image.
The superposition of faces where a portion of the background is mixed with foreground, are described in the patent literature. See, for example, U.S. Pat. Nos. 4,072,314 and 4,273,418.
Briefly described, the invention comprises an illusion device by which a viewer can superimpose his image on a portion of a television screen or picture or in a diorama. A semi-transparent, convex, spherical mirror is placed between the viewer and a display means such as a television set, picture or diorama. The mirror is half-silvered in such a way that the viewer sees a composite image which includes the reflection of him or herself superimposed on a portion of the television scene or a picture or in a diorama on the other side of the mirror. The television or diorama preferably includes a blacked-out portion roughly corresponding to the image of the viewer so that the viewer does not see the scene behind bleeding through his image but rather sees his image in the context of the scene around it. Lights and a neutral or black backdrop or a backdrop chosen to fit are preferably located near the viewer so as to help define the viewer's image in the scene. If a diorama or picture is used as the display means, a second source of illumination may be provided adjacent to the display means. A height adjustable stand supports the mirror and is employed to change the position of the mirror to improve the illusion. The radius of curvature of the spherical mirror and the distance between the viewer and the mirror and the mirror and display means are such as to improve the illusion in terms of depth stabilization which is balanced against image size and optical aberration considerations.
According to one alternative embodiment the viewer stands on a switch mat which is connected to a video game system which is connected to the television set. In this manner the viewer can interactively control his television environment. According to another alternative embodiment, aspherical mirrors are employed to produce special controlled distortions of the viewers image.
These and other features of the invention will be more fully understood by reference to the following drawings.
FIG. 1 is a side elevational view of the preferred semitransparent, convex, spherical mirror of this invention.
FIG. 2 is a front elevational view of the preferred semi-transparent, convex, spherical mirror illustrated in FIG. 1.
FIG. 3 illustrates an embodiment of the invention where the image of a viewer is superimposed in a diorama.
FIG. 4 illustrates the preferred embodiment of the invention where the image of the viewer is superimposed upon a television screen.
FIG. 5 illustrates an alternative embodiment in which the viewer controls the action on a television screen while his image is superimposed thereon.
FIG. 6A illustrates the surface of a television screen with a portion blackened out to receive the image of the viewer.
FIG. 6B illustrates the television screen of FIG. 6A with the viewer's image superimposed upon the blackened out portion.
FIG. 7A is a side view of an aspherical mirror having a first radius of curvature r1.
FIG. 7B is a top plan view of the aspherical mirror shown in FIG. 7A having a second radius of curvature r2.
FIG. 7C illustrates a distorted image of the viewer produced by the partially silvered, aspherical mirror shown in FIGS. 7A and 7B.
During the course of this description, like numbers will be used to identify like elements according to the different figures which illustrate the invention.
The heart of the invention 10 is the half-silvered mirror 12 illustrated in FIGS. 1 and 2. Mirror 12 is preferably a convex, spherical mirror which is partially silvered so that a viewer standing in front of the mirror 12 sees his or her image superimposed upon objects located behind the mirror 12. Mirror 12 is supported by a circumferential frame 14 which is held by an adjustable stand 16. The height of the mirror 12 above the floor is adjustable by means of wing nuts 18 which travel up and down slots 22. The position or height of the mirror 12 is changeable by setting the wing nuts 18 at various different locations along the slot 22 The wing nuts 18 are on threaded studs attached to the mirror frame 12. Feet 20 support the upright members of the adjustable stand 16. Since convex mirror 12 is a portion of a sphere, it is characterizable by a radius R.
The apparent focus, "prime focus" or "principal focus", is very nearly one-half of the radius of curvature for a convex spherical mirror. Parallel rays of light will reflect from the convex spherical mirror as if emanating from the principal focus. Ordinary means of optical analysis, such as ray tracing, will determine an image position between the mirror and the principal focus.
FIG. 3 illustrates one embodiment of the invention 10 in the context of a diorama 36. A first light source 26 illuminates the viewer 28 who is located a distance C from mirror 12. A second light source 34, in the form of a dimmable bulb, illuminates the diorama 36.
A reduced image 32 of height B of the viewer 28 having a height A is seen by the viewer 28 (or other viewers) at a distance D behind the surface of semi-transparent mirror 12. Viewer image 32 is preferably located at a position where there is a darkened portion 38 suitable to receive viewer's image 32. In this manner, the diorama scene 36 does not bleed through the viewer's image 32.
The preferred embodiment of the invention 10 is illustrated in FIG. 4. The major difference between the embodiments in FIGS. 3 and 4, is that in FIG. 3, the display means comprises a diorama 36 whereas in FIG. 4, the display means comprises the screen of a television set 24. A black, or neutral drape 30 is illustrated behind and beneath the viewer 28. Drape 30 prevents the background behind the viewer 28 from being part of the image 32 seen by the viewer 28 in the mirror 12. Drape 30 could also have been employed behind the viewer 28 illustrated in FIG. 3. The viewer 28 having a height A shown in FIG. 4 is located a distance C from the mirror 12. The screen of the television set 24 is located a distance D on the other side of mirror 12 from the viewer 28. The viewer 28 looking at mirror 12 sees an image 32 of him or herself having a height B, superimposed upon the screen of the television set 24. As with the diorama 36, the image 32 is preferably located over a darkened out section 38, shown in FIGS. 6A and 6B, which prevents the scene on the television screen from bleeding through the image 32.
By placing the semi-transparent, convex mirror 12 between the viewer 28 and the display means (e.g. television 24, diorama 36, or a printed picture, etc.) and illuminating the viewer 28 and the scene, the viewer's image 32 will appear in the scene. Furthermore, the image 32 will appear in the same position for widely spaced viewers.
In order to add interest to the effect, elements of the scene may be animated (as is basically expected for TV use) and may further be controlled by the viewer 28. Creative use of control effectors can give the illusion of the image 32 having physical contact with elements of the scene.
An alternative version 50 of the preferred embodiment illustrated in FIG. 4 is shown in FIG. 5. A switch mat 40 is illustrated under the feet of the viewer 28. Switch mat 40 is connected by wires to a video game system 42 which in turn is connected to the television set 24. The video game system 42 shown in FIG. 5 can be any one of many generally available electronic games or computer systems such as made by Nintendo or Sega. The switch mat 40 is identical or similar to those manufactured by Tapeswitch Corporation of America, 100 Schmitt Blvd., Farmingdale, N.Y. 11735. Several Tapeswitch mats 40 can be joined with appropriate connectors to the video game system 42 or the Tapeswitch Corporation can manufacture a segmented mat 40 for connection to the system 50. The purpose of switch mat 40 and the video game system 42 is to provide interactive control between the viewer 28 and the television 24. Accordingly, the viewer 28 can modify the context in which the image 32 is operating. This allows the viewer 28 to continually change the nature of his image's experience depending upon the position of his feet upon switch mat 40. For example, if the viewer were playing an adventure game a dragon might back away from the approaching image 32 or an "explosion" might occur under his image 32 if the viewer 28 moved to a forbidden position on the mat 40.
Darkened section 38 is shown without a superimposed image in FIG. 6A. A scene 44 on the screen of television 24 includes the darkened section 38 located between two animated figures. The darkened section 38 should correspond roughly to the area of movement of the image 32 or may move with the expected positions of image 32 or may be controlled by the position of viewer 28 to follow the position of image 32. The purpose of darkened section 38 is to make sure that little or none of the animated scene 44 bleeds through the image 32. Image 32 is illustrated superimposed on darkened section 38 in FIG. 6B. A substantially bright image largely overcomes the hands of the figures protruding into darkened area 38. FIGS. 7A and 7B illustrate a use of aspherical half-silvered mirrors to produce special, intended distortions. The half-silvered mirror 46 has a first radius r1 as shown from the side in FIG. 7A and a larger second radius r2 as shown from the top in FIG. 7B. Accordingly mirror 46 has a pair of radiuses r1 and r2 which produce an astigmatic effect shown in FIG. 7C. Image 48 illustrates the effect that a viewer 28 would observe if looking at the front of mirror 46. Image 48 is shortened more from top to bottom then from side to side thereby making the image 48 look fatter than it would if the mirror 46 were spherical. Aspherical mirrors, such as mirror 46, provide the option of producing special, intended distortions, for special purposes. For example, if the image 48 were that of an astronaut on a planet with a very strong gravity field, it would produce the effect that the astronaut's body was being dragged down by the strong effects of the gravitational field. Or, it may be desired to distort the orientation of the image for other special effects such as to enhance the illusion of the image floating in an outer space environment.
The invention 10 has been described in the context of a television set 24 or a diorama 36. It could also be used with a printed picture or for other applications. The invention 10 could be used, for example, for toys (such as a doll house through which a child could appear to walk) or advertising (for example, to introduce the viewer into the world of product "X") or for training (with the participant mimicking tennis strokes alongside of a tennis star on television).
The effect can be varied by changing certain parameters. As previously discussed, areas 38 within the scene (television 24, diorama 36 or picture) are preferably darkened to receive the image 32. Alternatively, where the viewer 28 is lit far more brightly than the scene or where the mirror 12 is of high reflectivity (and therefore low transmissiveness) the image 32 will wash out the scene area in which it appears thus allowing image 32 to be dominant anywhere throughout the scene. For such effects as the subject appearing to be a ghost, a darkened area is not required. Moreover, the adjustability of the relative brightness can be accomplished by changing the brightness control of the television 24 or, in the case of the diorama 36, through the use of an adjustable shutter. Mirror 12 is preferably thin so as to minimize secondary reflections and it should be of uniform thickness unless special effects or corrections are desired.
In the case of a diorama 36, it is possible to use negative lenses or negative Fresnel lenses to introduce objects or people behind the scene into the action. Also, additional semi-transparent or full-silvered mirrors could be used within the scene advantageously. In order to add interest to the effect, the elements of a diorama scene might be animated and further controlled by the viewer 28 electrically as was described with respect to alternative embodiment 50 shown in FIG. 5 or by direct mechanical connections such as levers or cords.
One of the important features of the invention is the effect of depth stabilization. In general, this is taken advantage of where the mirror's radius of curvature R is relatively small and the viewer 28 is located sufficiently distant from the mirror 12.
The mathematical relationship between the distance of the object to the mirror (C), the image to the mirror (D) and the radius of the mirror (R) is expressed as follows: ##EQU1## Note: The negative result indicates that the image 32 is behind the mirror 12.
Also the following mathematical relationship exists between the image height (B), the object height (A), the image distance to the mirror (D) and the object distance to the mirror (C). ##EQU2##
Therefore, looking at expected image position and size for a 5'9" viewer 28 at distances of 4', 8' and 12', respectively, (ignoring aberrations) one can derive the following results where:
Radius of Mirror R=8"
Height of Viewer 28=A=69"
______________________________________Object Distance Image Distanceto Mirror (C) to Mirror (D) Image Heiqht (B)______________________________________48 inches -3.69 inches 5.31 inches96 inches -3.84 inches 2.76 inches144 inches -3.89 inches 1.86 inches______________________________________ (Note: Negative numbers indicate distance behind the mirror 12.)
It has been found that with a convex, spherical mirror 12 having an 8" radius R, a 5'9" (A) viewer 28 standing 8' (C) from the mirror 12 will form an image 32 about 23/4" (B) tall at a distance just under 4" (D) behind the face of the mirror 12. This is of sufficient size for a small television 24 or diorama 36.
Using such a mirror 12, the viewer 28 can back away up to a distance of 12', for example, and cause the image 32 to shrink over 30% while maintaining almost the same distance behind the mirror 12. Basically, the further the viewer 28 is from the mirror 12, in terms of the radius R of the mirror 12, the more stable will be the image's depth position. This depth stabilization is highly advantageous when the concept is applied to a television set 24 and may be exploited in the programming of the television image for greater play value. The use of the concept with respect to printed images also produces the same benefits. The effect of depth stabilization is maximized as the image distance D approaches one-half of the radius of curvature of mirror 12.
The implications of depth stabilization are further described as follows. Basically, the image 32 must remain close to the surface plane of the television 24 in order to appear to be part of the television image 44. Without depth stabilization the viewer 28 would be constrained to a fairly limited distance C from the mirror 12, in order to maintain a constant image distance D. With depth stabilization, attributable to the convex nature of the mirror 12 and the distance C of the viewer, the image 32 remains near the surface plane of the television screen while growing and shrinking to indicate up and down stage motion or to fit into a new scene 44 or to adjust for the size of the viewer 28.
Depth stabilization is not an advantage with regard to dioramas 36. In order to enhance the effect, dioramas, such as diorama 36, can be built in forced perspective, i.e. built with the smaller scale items in the back and larger scale items in the front so as to give the illusion of greater depth. Furthermore, the image forming system for a diorama 36 should be so arranged that the viewer 28 is closer to the mirror 12 in relation to the radius of curvature R of the mirror 12 thus yielding greater depth motion of the image 32. The partial reflectivity (or partial transparency) of the mirror 12 can be created by ordinary means directed either to the density of the reflective coating or to a coating pattern. Alternatively, the reflectivity may be integral to the material rather than applied as a coating. The mirror 12 should preferably be as thin as possible for economy and ease of manufacture but thick enough to ensure integrity of the material so that it does not crack or break. It is generally desired that the mirror 12 be of constant thickness except where special effects are desired. According to the preferred embodiment the mirror 12 is approximately 3/32 of an inch thick for a radius of 8" and formed out of acrylic plastic. It could be somewhat thinner if vacuum formed from blister pack materials. Mirror 12 is preferably 50% reflective but could range from clear glass (or other material) to fully reflective (for the special case where the image is to appear "buried" in a scene). The preferred range of mirror reflectivity is approximately 25% to 75%. The preferred range of mirror size is slightly larger than ordinary television picture tube diagonal measurements. Thus the mirror size would be roughly twelve to thirty inches in diameter or cut to a 4:5 rectangle with those diagonal measurements. The preferred radius R of mirror 12 is 8" and the preferred range of mirror radii of curvature R is approximately 8" to 48".
Convex mirrors are made generally of glass and acrylic by certain American manufacturers. Partially reflective mirrors are also manufactured domestically. A few manufacturers produce convex mirrors that are also partially reflective and those include the Mir-Acryl Company of Belleville, Mich. which makes convex partially reflective mirrors for surveillance purposes.
The vertical position of the image 32 may be adjusted somewhat by translating the mirror 12 upward or downward on the frame 16 by mean of adjustable wing nuts 18. This might be necessary particularly for a television set 24 having a fixed vertical position. If the television set 24 is lower than the standard, then the image 32 may be lowered by lowering the mirror 12 in relationship to the television set 24. This adjustment may increase the spherical aberration due to the increased difference between the subject's head to mirror distance and his/her foot to mirror distance. However, this distortion is usually acceptable within reasonable limits.
Further correction to the aberrations induced by a particular configuration can be achieved by asphericity consistent with the conditions. A small diorama 36 placed on the floor and used by a standing viewer 28 would require its mirror 12 to increase in radius R towards the top to account for the greater distance to the subject's head. The successive centers of curvature could be displaced to create as vertical an image as possible. Alternatively, it might be desired to distort the orientation of image 32 for particular special effects such as to enhance the illusion of the image 32 floating in an outer space scene.
There are potential uses for many different sets of distances, curvature, aberrations etc. The relationships are readily derivable from the equations previously described and provable by conventional ray tracing. Even situations which can lead to fairly serious optical aberrations may be useful. The present invention takes advantage of the convex nature of the half-silvered mirror which presents major advantages over the prior art use of flat mirrors. The advantages, for example, are that it is possible to incorporate an image in a substantially small diorama, picture or scene thus producing economies of scale, portability etc. Also depth stabilization is possible using curved mirrors which is not possible with the flat mirrors due to the flat mirror's one to one (1:1) correspondence between the distance and size of the image and the distance and size of the viewer. The depth stabilization allows the image 32 of viewer 28 to remain at the surface of the printed picture or TV screen while allowing the viewer to move toward and away from the screen. Additional advantages of sufficiently convex mirrors include the ability to tailor image size without requiring the mirror to be repositioned in relationship to the scene or screen.
The preferred embodiment described is reasonable for a twelve inch portable television 24 or a diorama 36 in that size range.
While the invention has been described with reference to a preferred embodiment thereof, it will be appreciated by those of ordinary skill in the art that modifications ca be made to the invention without departing from the spirit and the scope thereof.
Patent Citations
Non-Patent Citations
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text:
Heads Up On A Convention
28th 2010
28th 2010
The 16th Annual International Female Tattoo Art Expo is taking place January 14-16 2011 at the UFC Holiday Inn located in Orlando, FL.
The three-day event is open to all ages and will include Educational Seminars such as A.P.T.'S Preventing Disease Transmission in Tattooing.
The entrance fee is $10– $5 after 8:00pm.
Ufc Holiday Inn
12125 High Tech Avenue
Orlando, FL 32817


text: Prev | Next Jim Adkins of Jimmy Eat World performs at the Austin City Limits music festival on Friday, Oct. 11, 2013 in Austin, Texas. (AP Photo/The Daily Texan, Chelsea Purgahn) Gallery: Austin City Limits Festival Oct. 13, 2013 @ 07:43 AM Some of the nation's top rock and alternative music acts gathered for the Austin City Limits Music Festival held over the past two weekends at Zilker Park in Austin, Texas. (u'nobuy',)


text:
The Albuquerque Police Department are being investigated by the FBI after a YouTube video went up last week, showing APD shooting a homeless man who was camping, after what was reported as a standoff that lasted for hours.
This is the 22nd police shooting since 2010, and outrage has poured out over the incident, sparking the interest of the national media and even Anonymous, which led to protests against police violence all over the city Sunday night.
APD has said that the deadly use of force was warranted in this instance, because the suspect, James Boyd, had a history of mental illness and was armed with multiple knives.
I'd barely noticed the story until the protests started, and didn't really know what to make of it. Maybe APD did have good reason to shoot Boyd. I don't know.
But after witnessing cops in bullet-proof vests and gas masks shooting tear gas into a street filled with peaceful protesters, innocent by-standers, and even children, I've decided to err on the side of the people who weren't being assholes.… Read the rest


text:
Hunter or hunted?Written by Tom Pounds | President / Publisher | email@example.com
Toledo Mayor Carty Finkbeiner is engaged in a tug of war for Toledo-based FedEx Ground, which is reportedly considering a new home that could be in Southeast Michigan or Wood County. At a recent press conference, the mayor accused Wood County of economic "poaching."
"Wood County officials are coming after another major Toledo employer," Finkbeiner said. "Toledo has everything this employer needs to remain economically strong and eventually expand, but Wood County continues to pursue them."
Tom Blaha of Wood County said his group has not poached, but of course pursues any businesses that approach them.
"The United States, the last I checked, was a free-market economy, and people are free to put their sites wherever they want," Blaha told The Blade.
He's right, of course, but it's easy to see how the possibility of losing FedEx Ground, as Owens-Illinois was lost, would greatly upset the mayor (this is a good spot to point out that Toledo did not "lose" Bass Pro to Wood County, as the company reportedly was not seriously considering Toledo, though that's a detail that doesn't console Finkbeiner).
It seems that if Toledo lands a major company, it benefits the entire region, but if a major company chooses the region, it's not necessarily a boon for Toledo, according to mayoral logic. All's fair in love and war, and the fight for business is a battle; Lucas County is going to have to realize that Wood County is a legitimate contender, not a collection of farmland. Between Maumee, Sylvania, Perrysburg, Rossford and Bowling Green, Toledo is in for the fight of its life.
Let's hope the emotional rush of this tug of war lights a long-term fire that leads to a full-time economic development director and an urgency to grow the region while scrapping for every job and dollar Toledo deserves. Companies are not going to stay in Toledo out of any sense of social obligation; we're going to have to earn their business.
Thomas F. Pounds is president and publisher of Toledo Free Press. Contact him at email@example.com.