Aluminosilicate Zeolite-A Reaction Matrices for Ni:H and Co:H Exothermic Processes:
The Zeocat Reactor Concept
N.A. Reiter and Dr. S.P. Faile
18 September 2012
Aluminosilicate zeolite lattices have been used widely for geometric sequestering and isolation of metallic species, primarily for catalytic purposes. The family of Zeolite-A forms commonly used as molecular sieve media is especially useful for engineered containment of Ni, Pd, Ag, Au, Cu, Co, Mn, and Fe atoms. We considered that in light of recent developments in Ni:H exothermic reaction technology, where Ni and other transition metals are exposed to hydrogen in a nano-structured form, zeolite constrained atomic or ionic species might exhibit vigorous reactions similarly.
In this document, we outline and disclose our observations to date, related to novel exothermic reactions by zeolite constrained species, both in a pressurized environment of H2 gas blends as well as a physical proximity to a decomposing metal hydride performing the role of a hydrogen generator.
Technical discussion is provided, as well as experimental details for replication efforts.
In late 2011, we observed and confirmed that 3A, 4A, 5A, and 13X zeolite molecular sieve beads were capable of adsorbing / exchanging, and holding ionic species of Ni, Ag, Au, Pd, Pt, Co, Cu, Pb, Fe, and Mn. Furthermore, we found that when exposed to a reducing gas mixture – either H2 or N2:H2 5% at temperatures above 350C, several of these species were reduced to atomic form. Ni, Pd, Ag, Cu, and Co in particular were quite reliable in this process. Our general procedure for loading zeolite beads consisted of the following steps:
An aqueous solution of the metal salt was prepared, generally 1M or greater in concentration. Chlorides, acetates, or citrates were used, depending on the metal.
A quantity of the selected zeolite molecular sieve beads (purchased in bulk commercially) were desiccated at between 200C and 250C for one hour, cooled, and weighed.
The beads were poured into a container of the aqueous metal salt solution, and allowed to soak with occasional stirring for between 24 and 96 hours at room temperature.
Following soaking, the beads are drained, rinsed, dried, and re-desiccated at 200C. We then re-weigh them.
From multiple trials, we determined that at least for Ni, Pd, and Co, the absolute amount of ionic metal adsorbed by 10 grams of beads was usually between 300 and 700 milligrams. Experimentally, it was also determined that 3A mol sieve beads (Zeolite A – K) were most robust against fracturing and spalling, either during soak or desiccation phases.
Some metal species appear to have an ionic radius that is either too large for the 3 angstrom “holes” of the zeolite, or otherwise react in such a way with some component of either the zeolite OR the attapulgite clay binder of the beads, and do not infiltrate very far into the bulk structure of the individual bead. Cu and Pb were notorious for only infiltrating a fraction of a millimeter into the bead bulk. Ni and Co are good infiltrators, and generally are adsorbed to a maximum extent possible within 48 hours.
The following photos illustrate the appearance of selected loaded bead species and conditions:
Incorporation of Loaded Zeolites in a Novel Reactor Geometry:
Advocates of Ni:H and Pd:D systems of LENR (Low Energy Nuclear Reactions) have become rightfully focused on nano-geometry and topology of reaction surfaces, particularly since early 2011. Speculation abounds regarding preferential geometry and dimensions, as well as catalysts in Ni powder systems. However, in principle, 1-dimensional arrays of metal ions or atoms in a zeolite cage represent the ultimate venue of atomic scale access of H or D. How best to utilize Ni (or other metal) loaded zeolites in a simple reactor form, in order to search for signs of exothermic properties that would be suggestive of non-chemical origins?
In order to test loaded zeolites in the presence of H2, we built a very simple “screening” reactor. The body of the reactor is a commercial 316 stainless steel ½”NPT “Tee” fitting, with a single thermocouple extending into the interior, a gas inlet fitting, and a bleed and purge valve. Loading of the vessel is conducted through the bleed valve pipe fitting. The assembly is placed on a hot plate with simple rheostat control, and covered with kaowool ceramic fiber insulation. All “hot zone” components are made of 316 stainless, as is the .0625” diameter sheath of the K-type thermocouple used to take the internal “fuel” temperature.
See the photos below:
Our initial procedure was quite simple. We would load a charge of about 20 to 25ml of the zeolite beads (metal salt loaded and desiccated) into the vessel, replace the vent valve port, and then turn the hotplate on to a roughly calibrated setting denoted by a null run (reactor loaded with non-infused zeolite beads only) and marks on the rheostat. No PLC or feedback power control was used with the initial screening reactor design. By using simple dial settings, we were able to establish reliable and reproducible temperature settings for a given reactor run.
With the reactor at a desired temperature, as read by the internal thermocouple buried in the bead bed, we would then pressurize the vessel to 30 to 60psig of a desired gas. For most experiments in this configuration, we used N2:H2 5%, primarily for safety sake. Comparison runs were also made with pure N2 and argon in some cases.
Using this mode, referred to as “purge-heat-pressurize-vent” or PHPV, we were able to see the first indications of mild exothermic reactions. Essentially, upon pressurizing, we would look for a rise in the temperature of the bead bed. Despite the admittedly simple design and crude operating protocol, first indications of viable reaction were observed with Ni loaded 3A zeolite beads.
The below plot shows a typical early run, conducted in the PHPV mode.
We thus entered a period of intense experimentation, using the little screening reactor that we nicknamed “Zeocat01”. A large number of recipes were derived and tried, including blends of Ni with Cu, Ni with Co, and the use of speculative additives such as Mg, Li, Be, La, Gd, Ag.
During this time, we observed an unexpected phenomenon. While some recipes, such as Ni, or Ni doped with small amounts of Gd, etc. consistently produced minor but viable temperature rises of 5 to 20 C degrees over ambient, especially in the range of 300 to 450C for starting temperature, we also observed dramatic drops in temperature upon pressurizing! Recipes that tended to produce an endothermic effect upon pressurizing included those containing Cu, Fe, Co, Mn, or blends of these. In some cases, cooling was found to be due to minor leaks at the stainless fittings, however even under leak free operation, the phenomenon was quite apparent. We also discovered that Cu tended to transport out of the zeolite beads wildly, and would plate up the inside of the reactor vessel.
In the PHPV mode, we observed that the longevity of any deviation from a null ambient temperature, for many recipes, was typically on the order of 20 to 30 minutes, out to about 4 hours. Recipes that resulted in dramatic and rapid temperature drops (in the case of one Cu:Ni variant, over 100C degrees in 5 minutes!) generally lost any noticeable temperature deviation from ambient in fractions of an hour.
This tended to make characterization and any modeling extremely difficult. What was happening inside the Zeocat? The recipes that appeared most reproducible, such as Ni:Gd 1% soaked 3A beads also tended to give only very modest exothermic performance. Use of pure H2 as a pressurizing gas was discouraged by those sharing the experiment facility, and so we continued to make comparisons using N2:H2, N2, and Ar. Endothermic or invert effects actually became more prevalent than exothermic, outside of primarily Ni recipes. Some of these arrangements were found to be very reproducible, such as Fe or Fe:Co, and thus we began to consider what practical applications might be found for this “cool burst” effect.
During most of these experiments, we used an older Baird Atomic 914 Geiger counter to monitor the reactor location for any indication of radioactivity. To date, no significant rises over natural background (between 30 and 80CPM) have been observed.
The performance of metal loaded zeolite beads, as a whole, though, was somewhat bewildering and unpredictable. This situation was overcome in August of 2012.
Enhancement of Performance by use of a Thermally Decomposed Hydrogen Source:
In the course of discussions held online, a new approach to hydrogenation of the metal loaded zeolites was derived. It had been claimed as well that other researchers in the field have been moving toward an engineered hydrogen source apart from pressurized gas.
Our new concept included the use of commercially available potassium hydride (KH) as a coarse powder in oil or paraffin. At temperatures above 300C, the mineral oil encapsulation medium would in principle decompose, allowing the reactive KH to contribute hydrogen into the reactor volume.
In order to test this mode of operation, which we have called “activation by metal hydride decomposition” (AMHD mode) we loaded typical volumes of different recipe metal loaded zeolite beads into our reactor, along with a small volume of KH in oil slurry. The reactor is then purged for five minutes at 5 to 10 slpm of N2, before closing off supply and vent valves. The reactor is then heated up on the hotplate to a standardized temperature determined by a null run (reactor with non-loaded beads). Over a number of trials, we were able to establish this pre-set to 345C +/- 10C degrees. From available literature, we were able to establish that the mineral oil vehicle used for the KH would begin to decompose significantly at this temperature.
Our experimental pursuit then was to see if any evidence could be found for the development of an exothermic condition that would take the reactor vessel to a temperature significantly above the null setting.
Repeating the general steps of the investigation of the PHPV mode of activation, we began to try various recipes of metal loaded zeolite beads with KH slurry added. Ni, Ni with 1% Gd, Cu:Ni, Cu:Ni:Co, Co, Co with 1%Gd, and Fe were tried.
Shown here are some typical early results:
The AMHD mode of operation appears to produce very significant and reproducible results. Using .5 to 1.0ml of KH slurry, with Ni or Ni:Gd, we have seen temperature rises sustained for multiple hours of between 5 and 20C degrees over null. Best results to date have been found with Co and Co:Gd 1% loaded beads, with sustained exothermic periods of up to one week being demonstrated, at 30 to 50 C degrees over null. In a very recent run, increasing the mass of KH slurry and providing a more uniform distribution of the slurry in the bead bed, with Co loaded beads, resulted in a week duration run at 425C average – a 70 to 90 degree rise over null.
This has been surprising. An exothermic condition lasting for a few hours could be easily attributed to chemical reaction. However, one lasting for multiple days would seem more indicative of an unusual process, some component of which at least exists outside of known chemistry.
As with the PHPV mode runs of the Zeocat01 reactor, we have monitored the reactor location with our Geiger counter, and have seen no indication at all of over-ambient rates.
Overview and Summary of Results to Date:
The primary purpose of this paper is to provide adequate technical information and a modest amount of historical background for the interested experimentalist, in order to successfully replicate the effects we have observed. This is not intended to stand alone as a project summary or thesis.
Commercially available molecular sieve beads made with zeolite-A may be loaded with either metallic or ionic forms of transition and platinum group metals, by soaking these beads in aqueous solutions of the metal salts.
Some metal loaded beads appear to display unusual exothermic and endothermic properties, when either loaded with H2 under pressure, or when exposed to hydrogen from a decomposing metal hydride.
As such, these properties are in concurrence with claims of LENR activity by other current researchers.
The species found to produce the most reliable and dramatic exothermic (or in the case of PHPV operation, endothermic) properties are: Co, Ni, Cu+Ni, Fe, or various combinations of these. Co and Ni stand out as best single component metals.
The addition of a small amount of gadolinium (Gd) to the Ni or Co infusion appears to provide a slight to modest enhancement of performance. This is done by adding .5% to 1% by weight GdCl2 to the NiCl2 or CoCl2 aqueous solution before soaking the zeolite beads.
Using 3A zeolite-A beads, loaded with ionic cobalt, and blended with a decomposition hydrogen source of potassium hydride in mineral oil, we have sustained significant exothermic operation of a small reactor vessel for periods greater than seven days.
Topics for Technical Discussion:
The Zeocat01 reactor concept was not intended to be definitive in engineering terms, only to explore the possibility that metals used in other LENR embodiments could be loaded into aluminosilicate zeolite lattices, and therein find a novel and effective matrix for reaction with H or H2. As such, thermometry on the device is minimalist, as is mode of heating. We were looking for an effect, and seem to have found a recipe that produces one – one that exceeded our expectations in various ways. Now it needs to be examined more carefully and optimized to practice.
As far as practical utilization of this technique, our preference at this time is the AMHD mode, where an easily available and moderately safe to handle metal hydride is added to the “fuel” bead bed. Once taken to a temperature where the organic vehicle of the hydride decomposes, useful exothermic operation appears to simply take off.
Because we have not operated any AMHD mode Zeocat reactor for a period of time long enough to observe a natural end to the reaction or effect, we cannot address such issues as mass consumption or final reaction products. Mass balance performed after a one week run with Co:Gd, along with visual inspection of beads did not provide any reasonable clues to project a lifetime. It is certainly recognized that the mass of an infused metal atom or ionic species in a zeolite bead of the sort we use does not exceed 10%. Thus the Zeocat concept appears to rely more on thoroughness of the unknown reaction, and the availability of sites per unit volume where the reaction can occur.
The possibility that the Pd:D system of LENR is approachable with a zeolite concept would be a reasonable presumption, however, in order to work within an economically viable realm for experimental replication AND eventual engineering scale-up, we have not yet explored that.
True thermometry and calorimetry is essential, and this is the focus of our own next-phase efforts. We have begun construction of the Zeocat02, which will have multiple thermocouples, power and current monitoring for the system heater, more homogeneous insulation, and an overall greater volume for bead fuel (approximately 150ml).
Thus far, we have ranked the following variables from most important to least, in their relative degree of influence on the unusual effects seen:
Species or recipe of metal infused into the zeolite beads.
For AMHD operation, the amount and uniformity of the added KH metal hydride slurry.
The “kindling” temperature, for AMHD operation, or starting temperature regime for PHPV mode.
The presence of minor amounts (<1%?) of water remaining after 200C desiccation may play a significant role in the reaction process (es). We have often found droplets of water condensed in the plastic polyflow tubing, to the cold end of the gas inlet.
Pre-treatment of zeolite beads before loading into the reactor. We discovered that if the metal infused zeolite beads are baked at high temperatures in air, the metal atomic or ionic species oxidize, and thus all effect appears to be lost in following operation.
Experimental Details – Best Recipe to Date:
An aqueous solution of cobalt (II) chloride hexahydrate was prepared. 8 grams of the CoCl2:H2O was mixed into 60ml of DI water. ~100mg of GdCl2 was also added and dissolved along with the CoCl2.
40ml of 3A zeolite-A beads were added to the solution, and stirred occasionally over 48 hours of soaking time. The solution and beads were in a Nalgene beaker, kept in a dark warm room at about 30C.
At 48 hours, we decanted the remaining solution off of the beads, and rinsed for 30 seconds with DI water. The beads were dried for three hours in the beaker, at 80C in a small drying oven.
Following this, the beads were placed in a glass beaker, and desiccated in air at 200C, for 1 hour.
The beads were allowed to cool to room temperature.
About 5 grams of beads were added to the Zeocat01 vessel.
About 1ml of KH slurry in oil (we strive to use the KH rich “mud” from the bottom of the bottle) was taken up with a plastic pipette, and squirted over the beads in the vessel.
Another ~5 grams of beads were loaded into the vessel, and these were again soaked or topped with KH slurry. A final ~2 grams of beads were added to top off the vessel, and the vent valve port fitting was screwed on (Teflon thread sealant is used).
The reactor was placed on the hotplate, and covered with the kaowool blanket.
A flow of 5 slpm of N2 was purged through the Zeocat01 for 5 minutes, to remove as much air as possible. Valves were shut off in sequence to let the vessel sit at ~1 atm of N2.
The hotplate was plugged in, with its rheostat already set to the standard “null” setting (345C +/- 10C for a dry-run reactor mass and insulation.
Upon plugging the hotplate in, we start a timer, and record temperatures at five minute intervals, or whenever possible.
The run was sustained and monitored for slightly over one week. During this time, occasional slow drifts (on order of 2 to 3 hours) in temperature were noted, ranging from 421C to 429C. These fluctuations did not appear to correlate with ambient lab temperature.
At 15:20EST on 20 September, 2012, the hotplate was unplugged, and a five minute vent at 5slpm of N2 was performed. The reactor was cooled and opened, and the contents examined.
The initial (first 5 hours) performance and operation of this particular run is shown thus:
Molecular Sieve Beads:
3A, 4A, 5A, and 13X “mSorb” beads (4x8 size) were obtained from Delta Adsorbents www.deltaadsorbents.com
Metal Salts and KH in Oil:
Primarily obtained from Alfa Aesar div. Johnson Matthey – typical purity used was ACS Grade.
316 Stainless Steel Tee fittings, reducers, and adapters from McMaster Carr Co.
1/16” 316 SS sheath K type thermocouples obtained from Omega.
Fisher Scientific manual controlled 6” x 6” heated surface, with stirrer.
For the experimentalist with access to a hotplate, fume hood, and thermocouple meter, the balance of chemicals, stainless steel fittings, and simple lab-ware should not exceed a budget of $600US to make a good quality effort of replication work.
We would like to extend a special round of gratitude toward Mr. Keith Nagel, administrator and owner of the Newcandle experimentalists discussion group, and Mr. Jones Beene, for their ongoing inspiration and intellectual contribution.
“Isotope Effect for Heat Generation upon Pressurizing Nano-Pd/Silica Systems with Hydrogen Isotope Gases”, Tatsumi Hioki, Noriaki Sugimoto, Teppei Nishi, Akio Itoh and Tomoyoshi Motohir, Toyota Central R & D Laboratories, Inc., Japan, firstname.lastname@example.org (presented at ICCF-17, 2012)
“Does Gas Loading Produce Anomalous Heat? (PowerPoint slides).” Kidwell, D., et al. 15th International Conference on CondensedMatter Nuclear Science. 2009. Rome, Italy: ENEA.