WO1999016082A1

WO1999016082A1 - Catalytic ceramic particles, electrolytic production of heat

Info

Publication number: WO1999016082A1
Application number: PCT/US1997/016720
Authority: WO
Inventors: James A. Patterson
Original assignee: Patterson James A
Priority date: 1997-09-19
Filing date: 1997-09-19
Publication date: 1999-04-01
Also published as: AU4427997A

Abstract

Catalytic particles (36), electrolytic cell (12), system (10) and method for producing excess heat in an electrolyte (59). The catalytic particles (36) are formed of clay loaded with a metallic hydride forming powder and temperature cured into a ceramic. The electrolytic cell (12) includes a non-conductive housing (14) structured for electrolyte (59) flow and a bed (35) of catalytic particles (36) held between spaced conductive grids (38/44). An electric power source provides current to the grids (38/44) so that, when the cell (12) is filled with electrolyte (59) either flowing or not flowing, the particle bed (35) is initially charged and thereafter, the production of excess heat within the liquid electrolyte (59) is supported. An optional external electrolyte heater (21) can be utilized to enhance excess heat output. A metallic hydride forming thin, uniform layer such as nickel may be added atop the loaded ceramic particles (36) to reduce cell resistance and/or to alter excess heat production. Porosity of the ceramic particles (36) may be varied to enhance excess heat production.

Description

CATALYTIC CERAMIC PARTICLES, ELECTROLYTIC PRODUCTION OF HEAT

This invention relates generally to electrolytic cells, and more particularly to an improved electrolytic cell and catalytic particles therefor and system for the electrolysis of a liquid electrolyte to produce excess heat.

The utilization of palladium coated microspheres or beads as a catalytic agent for the absorption of hydrogen is taught in prior U.S. patents 4,943,355 ('355) and 5,036,031 ('031). In these patents, the utilization of cross linked polymer microspheres forming an inner core and having a coating of palladium thereatop exhibit significant improvements in the level of hydrogen absorption and the absorption of isotopes of hydrogen.

Utilizing these catalytic microspheres led to the invention disclosed in U.S. patents 5,318,675 ('675) and 5,372,688 ('688) which teach an electrolytic cell, system and method for, inter alia, producing heat within a liquid electrolyte. More recently, U.S. patent 5,494,559 ('559) discloses an improvement in the layer structure of the catalytic microspheres or beads within the electrolytic cell. The combination of nickel/palladium layers enhance the production of excess heat within the liquid electrolyte.

In each of these prior '675, '688 and '559 U.S. patents, the electrolytic cell described therein included an inlet and an outlet facilitating the flow of the liquid electrolyte therethrough. Thus, as the liquid electrolyte is passed through the electrolytic cell, it is acted upon catalytically by the particular bed of catalytic particles contained within the housing of the electrolytic cell to produce excess heat for use. The present invention improves upon the structure and composition of the catalytic particles which make up the active particle bed within the electrolytic cell through the utilization of clay loaded with palladium or other metallic hydride forming powder to form ceramic particles. Various active metallic hydride forming layers atop the doped ceramic particles are also provided, along with a broad range of powdered palladium or equivalent percentage by volume loading of clay before firing. This invention is directed to catalytic particles, electrolytic cell and system for producing excess heat for separate use in conjunction with a water-based liquid electrolyte. The catalytic particles are formed of clay loaded with a metallic hydride forming powder and temperature cured or "fired" into a ceramic. The powder is taken from the group of metals which are each capable of combining with hydrogen or an isotope of hydrogen to form a metallic hydride or deuteride. The electrolytic cell of the system includes a non-conductive housing structured for electrolyte flow therethrough and includes a bed of the ceramic catalytic particles held within the housing between spaced conductive perforated grids. An electric power source in the system may be operably connected between the grids so that, when the cell is filled with the electrolyte either flowing through the cell or with no external flow of electrolyte, electrical current flows between the grids to initially hydrogen charge the particle bed and to thereafter support the production of excess heat within the electrolyte. An optional external electrolyte heater serves to increase the inlet operating temperature of the electrolyte to substantially enhance heat output. A metallic hydride forming thin, uniform layer such as nickel taken from the group recited in the detailed description herebelow may be added atop the loaded ceramic particles to reduce cell resistance and/or to alter excess heat production.

It is therefore an object of this invention to provide a system, electrolytic cell, method and catalytic particles which utilize a ceramic material which has been doped with a conductive metallic hydride forming powder which is distributed within the ceramic particles before curing.

It is another object of this invention to provide an electrolytic cell and system and method of use for producing excess amounts of heat for separate use in equipment design to operate on, or convert energy from, a heated liquid.

It is still another object of this innovation to utilize conventional clay cured into ceramic particles which is doped or loaded with a metal hydride forming powder before curing as a catalytic agent for use in an electrolytic cell, system and method for producing excess quantities of heat. It is still another object of this invention to provide a ceramic catalytic particle which is doped with a metallic hydride forming powder over a broad range of volume ratios of clay to powder and which may include additional porosity for enhanced performance.

In accordance with these and other objects which will become apparent hereinafter, the instant invention will now be described with reference to the accompanying drawings.

Figure 1 is a schematic view of a system and electrolytic cell embodying the present invention.

Figure 2 is a section view of the electrolytic cell shown in Figure 1. Figure 3 is a graph showing the relationship between curing temperature and percentage weight loss of the clay.

Figure 4 is a graph showing the relationship between curing temperature and percentage weight gain in water uptake of cured ceramic particles soaked in water. Figure 5 is a graph generally showing a typical cell charging curve. Figure 6 is a graph generally showing the relationship between powdered palladium loading of clay and packed particle bed resistance.

Referring now to the drawings, a system embodying concepts of the invention utilized during testing procedures is shown generally at numeral 10. This system 10 includes an electrolytic cell shown generally at numeral 12 interconnected at each end with a closed loop electrolyte circulation system. The circulation system includes a constant volume pump 18 which draws a liquid electrolyte 59 from a reservoir 32 and forces the electrolyte 59 in the direction of the arrow into inlet 54 of electrolytic cell 12. After the electrolytic cell 12 is completely filled with the electrolyte 59, the fluid then exits an outlet 56, thereafter flowing into a gas trap 26 which is provided to separate hydrogen and oxygen gas from the electrolyte 59 when required. A throttle valve 28 downstream of the gas trap 26 regulates the electrolyte flow so as to also regulate the fluid pressure within the electrolytic cell 12 as monitored by pressure gauge 20.

A slide valve 22 provides for the intermittent introduction of ingredients into the liquid electrolyte 59 via syringe 24. A second slide valve 30 provides for the periodic removal of electrolyte 59 into test reservoir 34 for analysis to determine correct electrolyte make-up. In Figure 2, the details of the electrolytic cell 12 utilized during testing procedures is there shown. A cylindrical glass non-conductive housing 14, open at each end, includes a moveable non-conductive end member 46 and 48 at each end thereof. These end members 46 and 48 are sealed within the housing 14 by O-rings 62 and 64. The relative spacing between these end members 46 and 48 is controlled by the movement of end plates 50 and 52 thereagainst.

Also shown in Figure 1 is an in-line heater 21 disposed between the pressure gauge 20 and the slide valve 22. This heater 21 is provided to heat the electrolyte liquid 59 as it flows through the system 10 and the cell 12. Note importantly that the heater 21 may be positioned anywhere in the closed system electrolyte flow path as the heating applied is of a steady state nature rather than only a pre-heating condition of the electrolyte, although positioning of the heater 21 is preferred to be adjacent the inlet 54 of the cell 12 for better liquid electrolyte temperature control. The heating of the electrolyte external to the cell 12 is one means for triggering and enhancing the catalytic reaction within the cell 12 to produce a positive temperature differential (ΔT) of the electrolyte as it flows through the cell 12. Another means preferred for triggering this heat production reaction between the electrolyte 59 and a bed 35 of conductive particles 36 within the cell 12 is by the application of sufficient electric d.c. current across electrodes 15 and 16 as described herebelow. Other forms of electric current such as a.c. and pulsed current sufficient for charging and operating the cell may also be used.

Each of the end members 46 and 48 includes an inlet stopper 54 and an outlet stopper 56, respectively. Each of these stoppers 54 and 56 define an inlet and an outlet passage, respectively into and out of the interior volume, respectively, of the electrolytic cell 12. These end members 46 and 48 also include a fluid chamber 58 and 60, respectively within which are mounted electrodes 15 and 16, respectively, which extend from these chambers 58 and 60 to the exterior of the electrolytic cell 12 for interconnection to a constant current-type d.c. power supply (not shown) having its negative and positive terminals connected as shown. Also positioned within the chambers 58 and 60 are thermocouples 70 and 72 for monitoring the electrolyte temperature at these points of inlet and outlet of the electrolytic cell 12. However, in the experiments reported herebelow, the inlet temperature of the liquid electrolyte was measured just outside of the cell 12 immediately upstream of stopper 54 to more accurately reflect true temperature differential (ΔT) of the liquid electrolyte 59 while passing through the cell 12.

A plurality of separate, packed conductive particles 36 are positioned to define a particle bed 35 within housing 14 immediately adjacent and against a conductive foraminous or porous grid 38 formed of platinum and positioned transversely across the housing 14 as shown. These conductive particles 36 include a conductive metal in powder form uniformly blended within the uncured clay before being temperature cured into a ceramic, the metal powder being readily combinable with hydrogen or an isotope of hydrogen to form a metallic hydride or deuteride. The size and shape of these conductive particles may be varied from the preferred embodiments and still fall within the scope of this invention. The details of these ceramic particles 36 and method of production is described herebelow.

Still referring to Figure 2, a non-conducive foraminous or porous nylon mesh 40 is positioned against the other end of these conductive particles 36 so as to retain them in the position shown. Adjacent the opposite surface of this non-conductive mesh 40 is a plurality of non-conductive spherical microbeads, or more generally particles, 42 formed of cross-linked polystyrene and having a uniform diameter of about 1.0 mm. Against the other surface of this layer of non-conductive microspheres 42 is a conductive foraminous or porous grid 44 positioned transversely across the housing 14 as shown.

Should the system 10 boil off or otherwise inadvertently lose all liquid electrolyte within the cell 12, a means of preventing system shut-down is preferred which replaces the non-conductive microspheres 42 with non-metallic spherical cation ion exchange polymer conductive microbeads preferably made of cross-linked styrene divinyl benzene having fully pre-sulfonated surfaces which have been ion exchanged with a lithium salt. This preferred non-metallic conductive microbead structure will thus form a "salt bridge" between the anode 44 and the conductive particles 36, the non-conductive mesh 40 having apertures sufficiently large to permit contact between the conductive particles 36 and the conductive non-metallic microbeads. The mesh size of mesh 40 is in the range of 200-500 micrometers. This preferred embodiment also prevents melting of the sulfonated non-conductive microbeads 42 while reducing cell resistance during high loading and normal operation.

The end of the electrode 15 is in electrical contact at 66 with conductive grid 38, while electrode 16 is in electrical contact at 68 with conductive grid 44 as shown. By this arrangement, when there is no electrolyte within the electrolytic cell 12, no current will flow between the electrodes 15 and 16.

ELECTROLYTE

When the electrolytic cell 12 is filled with a liquid electrolyte 59, electric current will flow between the electrodes 15 and 16. The preferred formulation for this electrolyte 59 is generally that of a conductive salt in solution with water. The preferred embodiment of water is that of either light water (H₂ ¹0) or heavy water and, preferably deuterium (H₂ ²0). The water (H₂ ¹0) and the deuterium (H₂ ²0) must have a minimum resistance of one megohm with a turbidity of less than 0.2 n.tu. This turbidity is controlled by ultra membrane filtration. The preferred salt solution is lithium sulfate (Li₂S0 ) in a 1 -molar mixture with water and is of chemically pure quality. In general, although a lithium sulfate is preferred, other conductive salts chosen from the group containing boron, aluminum, gallium, and thallium, as well as lithium, may be utilized. The preferred pH or acidity of the electrolyte is 9.0.

CONDUCTIVE CERAMIC PARTICLES

Palladium coated microspheres were originally preferred as disclosed in U.S. Patents '675 and '688 and as taught in U.S. patents '355 and '031. The '599 patent teaches a combination of nickel/palladium layers for enhanced heat output.

Moreover, palladium may be substituted by other transition metals, rare earths and also uranium. In general, any of these metals, whether in element or compound form, which are capable of combining with high volumes of hydrogen to form "metallic hydrides" are acceptable. These metals known to applicant which will serve as a substitute for palladium are lanthanum, praseodymium, cerium, titanium, zirconium, vanadium, tantalum, uranium, hafnium and thorium. Authority for the inclusion of these elements within this group is found in a book entitled "Inorganic Hydrides, by B.L Shaw, published by Pergammon Press, 1967. However, palladium is the best known and most widely studied metallic hydride. Other recent research by R. Mills in an article entitled Excess Heat

Production by the Electrolysis oflnequious Potassium Carbonate Electrolyte and the Implications for "Cold Fusion" published in Fusion Technology 20 dated (1991) 65, suggests that nickel should be added to this category of metallic hydride or deuteride forming metals for production of heat using an H₂O-based electrolyte. In an even more general sense, the broad requirement here is to provide a metallic hydride or deuteride forming particle in the presence of hydrogen, the exact shape and consistency in size being a secondary consideration so long as one of the conductive metals hereinabove described is used as a catalyst.

The primary structural element used to form the present conductive particles 36 are small clay cylinders which have been loaded and uniformly blended with preferably palladium powder (palladium black) in a broad range of volume-to-volume ratios of clay to palladium powder. The uncured clay, which may be conventional red or white clay as available from Poly-Crafts, Inc., Sarasota, Florida, is thoroughly blended with palladium powder such as product number 478 available from Technic, Inc., Engineered Powders Division, Woonsocket, Rhode Island. This palladium powder is an electronic grade typically for use in ceramic capacitor inks and thick film inks and as a catalyst. Particle sizes in the range of 0.1-0.3 mm having a density of 2-6 g/in³ and a specific surface area of 25-35 m²/g are preferred. PREPARATION OF PARTICLES The palladium powder and moist clay (approximately 16.7% moisture) were uniformly blended together. The palladium black was obtained through precipitation of palladium powder in a reduction reaction. The blended clay was then extruded into a mold formed by drilling uniform 1/16" holes through a flat plate having a thickness of approximately 1/16". After the clay is forced into or extruded into the holes, an infrared lamp was applied for approximately twenty minutes to remove pour water obtaining a 5-8% percentage. Thereafter, these dried clay cylinders having a diameter of approximately .061" and a length of approximately 0.64" were removed from the mold and heated at approximately 600°C for approximately 2.5 hours to remove matrix water and to partially cure the clay into a ceramic. The total volume of each particle was approximately 5 ml. The partially cured ceramic cylinders are then placed in a ball mill with a 2X volume of 2.0 mm steel shot and 10X volume of water and ball milled until the desired spherical shape is obtained. The preferred nominal diameter of the spheres obtained and utilized in the testing reported herebelow was approximately 1.0 mm diameter. After ball milling into the desired size and shape, the particles are dried and placed in a 0.1 % Pd Cl₂ aqueous solution and allowed to set for fifteen minutes, after which the particles are drained and placed in a 0.5 hydrogen solution to set the palladium in the ceramic.

After curing, the ceramic particles have essentially no conductivity (greater than 200 mg ohms) so they were soaked in a 3-molar solution of lithium chloride

(LiCI) for approximately 16 hours to increase conductivity. Thereafter, the particles remained above 500 kilo-ohms after soaking, the particles were coated with approximately 1 micron layer of nickel using standard nickel coating solutions EN

PON A and EN PON B from Technic, the previously described supplier of the palladium powder. Although the surface of the particles did not appear to have a metal coating (coarse, non-shiny surface), resistance measurements show that the particles had an average resistance of approximately 2 ohms, sufficient for electrolysis. Specific implementation of, and variation from, the above method of producing the palladium loaded ceramic particles are described herebelow with respect to each specific experimental test result.

POROSITY

Referring to Figure 3, a study of the available porosity within loaded cured clay into ceramic as a function of firing or cure temperature in °C is there depicted.

Generally, with increasing firing temperature, the weight loss steadily increases to indicate greater amounts of porosity as a result of more complete moisture removal and curing. This indication of porosity would appear to reflect the ability of the loaded ceramic particles to increase surface contact with the electrolyte within the cell and to increase excess heat production.

Figure 4 graphically displays the cured ceramic particle water uptake also as a function of curing or firing temperature in °C. Ceramic particles were cured at the data points indicated and then soaked in water and thereafter weighed for percentage of weight gain also as an indication of porosity of the cured ceramic particles. MEASURING POROSITY

A given weight of 1/16" diameter extruded clay particles loaded with an active metallic powder such as palladium, were dried at 180°C and then fired in a furnace at 900°C. The weight of the particles was measured wet, after drying at 180° and after firing at 900°. The cooled, dried ceramics were placed in water at room temperature and then removed and drained free of excess water. The wet weight was then taken, along with the following measurements: W1 = weight wet

W2 = weight after drying at 180° W3 = weight after firing at 900° W4 = weight after loading fired ceramic with water W1 - W2 = weight of free water in clay lost W2 - W3 = weight of matrix water in clay lost

W4 - W3 = weight of water in pores (W4 - W3)/W3 X 100% = % water uptake (W1 - W3)/W1 X 100% = % water loss The percent of water uptake is proportional to the pore volume in the ceramic. The relative pore volume is the free space for the diffusion of the electrolysis induced protons. These protons, it is believed, migrate to any active metal hydride forming surface such as palladium, uranium, nickel, titanium, etc. to produce an excess heat generating reaction. INCREASING POROSITY

There are several techniques to improve the porosity of the ceramic particles loaded before firing with both an active powder and a porosity-increasing material. First, a salt can be desorbed after firing at 900°C. Second, any carbon compound 5 which can oxidize and leave a void in the ceramic can increase the porosity as follows:

C + O₂ => CO₂T Three examples of oxidizable organics which were produced are 20 micron cross-linked Polystyrene Divinyl Benzene spheres, Maresperse N (Lignotech USA) l o which is a soluble lignan, or wood flour and a 20 micron rice power.

Samples of these organics were mixed volume to volume with the loaded clay. The clay was extruded into 1/16" diameter cylinders and treated in the same manner as the above procedure. Below is a table of water loss and water uptake for the different types of loaded ceramic. 15 POROSITY AGENT ADDED

Loaded 1st 2nd Maresperse Rice

Clay PSDVB PSDVB N Power

% Water Loss 12.3 17.0 41 15 37

20 % Water Uptake 16.2 33.0 69 41 68

The table shows the increase in ceramic porosity after firing at 900°C to form the ceramic particles and after each of the organic porosity agents is burned out.

CELL RESISTANCE

In preparing the electrolytic cells for testing, the cell resistance utilizing a

25 Whetstone Bridge or ohm meter was utilized prior to the introduction of the electrolyte into the electrolytic cell. This cell resistance, when dry, should be infinitely high. Otherwise, a short between the anode screen and the cathode beads exists and the unit would have to be repacked. When testing with electrolyte present at 0.02 amps, the resistance should be in the range of 100 to 200 ohms per sq. cm

30 of cross section area as measured transverse to the direction of current flow.

Referring now to Figure 6, the effect of varying the amount of palladium blended in clay before firing is shown as a function of cell resistance. The curve clearly demonstrates the dramatic impact of increasing the palladium loading from 0 to 10%, the impact being substantially reduced with increasing percentage amounts of palladium to clay by volume up to 70% palladium powder.

The data used to produce the graph in Figure 6 was based upon the use of palladium powder from Technic #470. The clay blended uniformly with this powder was fired at 950° after being extruded into cylindrical particles as above described.

In addition to loading the unfired clay with the active palladium powder, nickel powder (mesh size 300), uranium power (mesh size 60), thorium (mesh size 325), and titanium power (mesh size 325) were each also used separately to load the unfired clay with successful results in forming the desired overall structure and consistency of fired ceramic particles, although not otherwise tested in a cell.

RELATIVE SURFACE AREAS The range in diameters of the conductive particles as above described is relatively broad, limited primarily by the ability to plate the cores and the economic factors involved therein. As a guideline however, it has been determined that there exists a preferred range in the ratio between the total surface area of all of the conductive particles collectively within the electrolytic cell and the inner surface area of the non-conductive housing which surrounds the bed of conductive particles.

This ratio is thus affected primarily by the size of the conductive particles, the smaller the diameter, the higher the ratio becomes. Preferably, the ratio of total particle surface area to the inner housing surface area is at least in the range of 5 to

1 (5:1). Improved efficiency was seen with using a ratio of 10 to 1 (10:1) as was typically used in the experiments reported herebelow.

EXPERIMENTAL RESULTS The testing procedures incorporated two stages. The first stage may be viewed as a loading stage during which a relatively low level current (0.05 amps) is introduced across the conductive members, that current facilitated by the presence of the electrolyte as previously described. INITIAL HYDROGEN LOADING During the initial loading, electrolysis of the water within the liquid electrolyte occurs so that the hydrogen active surface of the conductive particles fully absorbs and combines with hydrogen, i.e. becomes "loaded". This loading takes about two hours under a current flow through the cell of about 0.05 amps per two (2) cm³ of particle volume. As the particles load with hydrogen, the resistance of the cell will be seen to increase. The cell's resistance measured at constant temperature should be seen to raise about 10%. It is recommended that the loading should proceed at least until the resistance is no longer increasing. As loading proceeds further, a decrease in resistance will appear. Figure 5 is a general depiction of a typical cell loading curve. Preferably the cell should be run after the loading has proceeded to at least the region beginning at numeral 80. TEST RUNS

After hydrogen and/or hydrogen isotope loading of the hydrogen active material of the conductive particles, the current level between conductive members was then incrementally increased, during which time the electrolyte temperature differential was monitored. The temperature of the electrolyte 59 circulating through the electrolytic cell 12 and system 10 was fully monitored, along with temperature differential between thermocouples 70 and 72 and flow rate of the liquid electrolyte 59. Preferably, and more accurately, in lieu of placing the thermocouple 70 as shown in Figure 2, the electrolyte inlet temperature was monitored immediately upstream of stopper 54 to more accurately reflect temperature differential (ΔT). In general, all tabular results herebelow represent data taken on a steady state basis, input and output temperatures of the liquid electrolyte 59 being taken upstream of stopper 54 and at 72, respectively, voltage (v) and current flow (a) across the electrolytic cell 12 measured between terminals or conductors 15 and 16. The flow rate of the liquid electrolyte 59 (ml/min) and calculated wattage input and wattage output and percent yield are also shown. Percent yield is defined and calculated as the wattage output divided by the wattage input times 100 percent. All percent yield values above 100% indicate production of excess energy in the form of heat added to the electrolyte. With respect to input voltage, a reduction of 1.5 volts was made for loss in electrolyzing H₂O within the liquid electrolyte due to recombination. In the experimental results reported in Table I herebelow, clay extruded particles were prepared mixing 11.8 gms of moist clay (16.7% moisture) and 2.67 gms of palladium black. This produced a blended clay mixture of approximately

19.5% palladium by weight or 4.44% palladium by volume. These clay/palladium powder particles were then cured at approximately 180°C after a 20 minute infrared lamp drying, ball milled as above described, plated with a 1.0 micron thick layer of nickel, and then installed into the electrolytic cell of Figure 2 to produce the test results in Table I herebelow.

Note in these test results that, after 90 minutes of operation of the cell following the charging procedure outlined hereinabove, additional external heat was added from heater 21 in Figure 1 to raise the operating temperature of the electrolyte

59 to an input temperature of approximately 40°C. This electrolyte temperature significantly increased percentage yield of heat output.

TABLE I 4.44% Pd. by Vol.

Nickel Outer Layer

Time ΔT°C T(in)°C Amps Volts V-1.5 Flow Rate Watts Watts % Yield

(min) (To-Tin) (A) (V) ml/min in out

0 .0 22.0 0.02 2.8 1.3 17.0 .026 — —

5 0.10 22.0 0.02 3.0 1.5 17.0 .030 0.12 400.

15 0.15 22.0 0.02 2.9 1.4 17.0 .028 0.18 643.

30 0.20 22.0 0.02 2.9 1.4 17.0 .028 0.24 857.

45 0.30 22.0 0.02 3.1 1.6 17.0 .032 0.36 1125.

60 0.35 22.0 0.02 3.2 1.7 17.0 .034 0.42 1235.

90 0.40 22.0 0.02 3.3 1.8 17.0 .036 0.476 1322.

HEAT ADDED I

18.0 40.0 0.02 3.3 1.8 17.0 .036 21.4 59444. A second test was conducted utilizing a relatively low percentage loading ratio of palladium black to clay of 4.0% (1 :25) by volume. The test results reported herebelow in Table II were taken after a ninety (90) minute period of charging in accordance with the above-described preliminary procedure. Here again, the particles were ball milled into a spherical configuration having a nominal diameter of

1 mm and then having a uniform nickel plate applied thereatop. After twenty eight minutes of operation, external heat was added to elevate the temperature of the liquid electrolyte which significantly increased heat output and percent yield.

TABLE II

4.0% Pd. by Vol.

Nickel Outer Layer

Time ΔT°C T(in)°C Amps Volts V-1.5 Flow Rate Watts Watts % Yielc

(min) (To-Tin) (A) (V) ml/min in out

0 0.2 21.6 .02 4.17 2.67 17.6 .050 .246 492.

4 0.2 21.6 .02 5.50 4.00 17.6 .080 .246 308.

12 0.2 21.8 .02 5.44 3.94 16.7 .070 .235 336.

22 0.2 21.8 .02 5.35 3.85 17.6 .070 .246 352.

28 0.2 22.0 .02 5.20 3.70 17.6 .070 .246 352.

HEAT ADDED

40 7.0 34.8 .02 4.39 2.89 17.6 .057 8.62 15,123.

60 9.0 37.8 .02 4.09 2.59 16.7 .051 10.52 20,627.

80 10.0 41.0 .02 3.88 2.38 17.6 .047 12.32 26,212.

90 10.9 41.9 .02 3.81 2.31 17.6 .046 13.40 29,130.

Two separate batches of particles were prepared having a 20% palladium black by volume to clay. The first batch of particles used in the electrolytic cell 12, the test results of which are reported in Table III herebelow, were coated with nickel only, while the second set of particles used in the electrolytic cell producing the test results reported in Table IV herebelow were coated with a nickel/palladium/nickel (Ni/Pd/Ni) layer arrangement in thicknesses of 2 microns, 1.4 microns and 0.6 microns, respectively.

The particles used to obtain the test results in Table III containing 20% of palladium by volume were not soaked in lithium chloride prior to application of the nickel plating. However, the second set of particles at 20% by volume of palladium reported in Table IV showed a very high electric resistance reading after nickel plating of approximately 65k- ohms. Therefore, a 1 micron thick palladium plating was applied over the nickel coated particles using two coatings under the standard electroless plating procedure which follows the teachings of Rhoda, et al. in U.S.

Patent 2,915,406. After this palladium plating atop the nickel plating, the resistance was decreased to approximately 1.3 ohms, these particles were then coated with a standard 1.5% micron thick nickel plating using the EN PON A and EN PON B solution from Technic.

TABLE III

20% Pd. by Vol.

Nickel Outer Layer

Time ΔT°C T(in)°C Amps Volts V-1.5 Flow Rate Watts Watts % Yield

(min) (To-Tin) (A) (V) ml/min in out

0 .0 22.0 0.02 2.75 1.25 16.7 .025 — —

5 0.10 22.0 0.02 2.80 1.30 16.7 .026 0.17 654.

15 0.20 22.0 0.02 2.85 1.35 16.7 .026 0.23 885.

30 0.25 22.0 0.02 2.90 1.40 16.7 .027 0.29 1074.

45 0.25 22.0 0.02 2.96 1.45 16.7 .027 0.29 1074.

60 0.30 22.0 0.02 3.0 1.50 16.7 .028 0.35 1250.

90 0.35 22.0 0.02 3.0 1.50 16.7 .028 0.41 1464.

HEAT ADDED

24.0 40.0 0.02 3.0 1.50 16.7 .028 28.1 100,357.

TABLE IV 20% Pd. by Vol. Ni-Pd-Ni Outer Layers

Time ΔT°C T(in)°C Amps Volts V-1.5 Flow Rate Watts Watts % Yield

(min) (To-Tin) (A) (V) ml/min in out

0 1.0 24.6 .02 4.80 3.30 17.6 .066 1.23 1863.

4 1.0 24.6 .02 4.79 3.29 17.6 .065 1.23 1892.

14 1.2 24.8 .02 4.90 3.40 17.6 .068 1.47 2161.

26 1.4 24.7 .02 4.78 3.28 17.6 .065 1.72 2646.

32 1.3 24.8 .02 4.74 3.24 17.6 .064 1.6 2469.

38 1.3 24.9 .02 4.43 2.93 17.6 .058 1.60 2759. HEAT ADDED

44 6.0 37.8 .02 3.59 2.09 16.7 .04 7.01 17,525.

60 8.5 41.8 .02 3.30 1.80 16.7 .036 9.93 27,583.

72 9.0 43.9 .02 3.18 1.68 17.6 .03 11.08 36,933.

104 10.0 44.8 .02 3.13 1.63 16.7 .03 11.69 38,967.

130 11.0 45.3 .02 3.06 1.56 17.6 .03 13.55 45,167.

The test results hereinabove again show the application of additional external heat to increase the inlet temperature of the electrolyte to produce significantly increased amounts of heat out and percent yield. A single data point shown herebelow at Table V represents a test run of a cell utilizing ceramic particles loaded with palladium powder at a volume to volume ratio of 75% palladium powder (Technic #470) to 25% clay. These ceramic particles did not have any additional exterior nickel layered coating or any other coating for decreased cell resistance and excess heat production. This data point was taken after initial hydrogen charging as about described and then thirty (30) minutes of continuous operation of the cell as follows. Note that this data point confirms that, as seen at line B of Figure 6, cell resistance becomes sufficiently low for proper cell operation when the percent loading is generally above about 40% to eliminate any need for an additional outer conductive layer. TABLE V

Pd 75% - No Ni Coating

Time ΔT°C T(in)°C Amps Volts V-1.5 Flow Rate Watts Watts % Yield

(min) (To-Tin) (A) (V) ml/min in out

30 0.51 22.0 .02 3.1 1.6 17.0 .028 0.600 2143.

While the instant invention has been shown and described herein in what are conceived to be the most practical and preferred embodiments, it is recognized that departures may be made therefrom within the scope of the invention, which is therefore not to be limited to the details disclosed herein, but is to be afforded the full scope of the claims so as to embrace any and all equivalent apparatus and articles.

Claims

What is claimed is:

1. A system for producing useful excess heat in a liquid electrolyte while within an electrolytic cell comprising: said electrolytic cell including a non-conductive housing and an inlet and an outlet; a first conductive porous grid positioned within said housing adjacent to said inlet; a second conductive porous grid positioned within said housing spaced o from said first conductive grid and adjacent to said outlet; a plurality of conductive ceramic particles each doped with conductive metallic hydride forming powder distributed within each said ceramic particle before curing, said powder combining with hydrogen or an isotope of hydrogen to form a metallic hydride, 5 said conductive ceramic particles in electrical communication with said first conductive grid and electrically isolated from said second conductive grid; means for pumping the liquid electrolyte into said electrolytic cell through said inlet; 0 an electric power source operably connected between said first and second grids. 2. A system as set forth in Claim 1 , wherein: each said conductive ceramic particle is coated with a substantially uniform nickel layer. 5 3. A system as set forth in Claim 2, wherein: each said nickel layer is coated with a substantially uniform palladium layer followed by a substantially uniform second nickel layer. 4. A system as set forth in Claim 1 , wherein: each said conductive ceramic particles is porous. 0 5. An electrolytic cell comprising: a non-conductive housing and an inlet and an outlet; a first conductive porous grid positioned within said housing adjacent to said inlet; a second conductive porous grid positioned within said housing spaced from said first conductive grid and adjacent to said outlet; a plurality of ceramic particles each doped with a conductive metallic hydride forming powder distributed within each said ceramic particle before curing, said powder combining with hydrogen or an isotope of hydrogen to form a metallic hydride, said conductive ceramic particles in electrical communication with said first conductive grid and electrically isolated from said second conductive grid; said active agent becoming a proton carrier when in the presence of hydrogen or an isotope of hydrogen.

6. A system as set forth in Claim 5, wherein: each said conductive ceramic particle is coated with a substantially uniform nickel layer.

7. A system as set forth in Claim 6, wherein: each said nickel layer is coated with a substantially uniform palladium layer followed by a substantially uniform second nickel layer. 8. A system as set forth in Claim 5, wherein: each said conductive ceramic particles is porous.

9. A method of producing excess heat within a liquid electrolyte for use of the heat elsewhere comprising the steps of: A. providing an electrolytic cell including: a non-conductive housing and an inlet and an outlet; a first conductive porous grid positioned within said housing adjacent to said inlet; a second conductive porous grid positioned within said housing spaced from said first conductive grid and adjacent to said outlet; a plurality of conductive ceramic particles each doped with a conductive metallic hydride forming powder distributed within each said conductive ceramic particle before curing, said powder combining with hydrogen or an isotope of hydrogen to form a metallic hydride, said plurality of conductive ceramic particles in electrical communication with said first conductive grid and electrically isolated from said second grid; an electric power source operably connected between said first o and second grids;

B. circulating said electrolyte through said electrolytic cell;

C. passing said electrical current between said first and second grids when said electrolyte is circulating within said electrolytic cell; 5 D. removing excess heat from said electrolyte for separate use after said electrolyte exits said electrolytic cell through said outlet.

10. A system as set forth in Claim 9, wherein: each said conductive ceramic particle is coated with a substantially 0 uniform nickel layer.

11. A system as set forth in Claim 10, wherein: each said nickel layer is coated with a substantially uniform palladium layer followed by a substantially uniform second nickel layer.

12. A system as set forth in Claim 9, wherein: 5 each said conductive ceramic particles is porous.

13. A ceramic catalyst having high hydrogen adsoφtion capabilities comprising: a conductive ceramic particle doped with a conductive metallic hydride forming powder distributed within each said conductive ceramic 0 powder before curing; said powder combining with hydrogen or an isotope of hydrogen to form a metallic hydride.

14. A system as set forth in Claim 13, wherein: each said conductive ceramic particle is coated with a substantially 5 uniform nickel layer.

15. A system as set forth in Claim 14, wherein: each said nickel layer is coated with a substantially uniform palladium layer followed by a substantially uniform second nickel layer.

16. A system as set forth in Claim 13, wherein: l o each said conductive ceramic particles is porous.