WO1997043768A1

WO1997043768A1 - Coproduction of energy and helium from d¿2?

Info

Publication number: WO1997043768A1
Application number: PCT/US1997/008033
Authority: WO
Inventors: Leslie C. Case
Original assignee: Case Leslie C
Priority date: 1996-05-10
Filing date: 1997-05-12
Publication date: 1997-11-20
Also published as: AU3123097A; JP2001510555A; EP0897580A1

Abstract

It has been discovered that energy can be reliably produced by contacting deuterium, in the gaseous state, with a particularly active metallic catalyst, at an elevated temperature. The product of this process is helium of mass (4). Thus, the reaction appears to be D + D → He-4 + 24 MeV. Only some fraction of metallic 'hydrogenation' catalysts are active in this process, and it has not been possible to predict in advance which candidate catalysts will be active, so a simple screening test has been devised to identify the specifically active catalysts. The most promising catalysts for this process may be certain types of supported platinum-group metals. Palladium appears to be a favored metal, although platinum, and possibly other PGMs are also active. It is envisioned that the procedure can be scaled up to produce commercial-scale energy by running steam tubes through the catalyst bed, and removing the heat produced in the form of steam.

Description

COPRODUCTION OF ENERGY AND HELIUM FROM D₂

BACKGROUND OF THE INVENTION It is now well recognized that various nuclear fusion reactions of D, or D + T, can yield quite large quantities of energy, and that such reactions are very promising for long-term energy production, because of the very substantial D content of natural water, most particularly sea water

Very considerable sums of money have been expended in the study of the possibility of controlled plasma fusion of this type, and lesser sums on laser-initiated fusions The results are positive, but it is clear that we are a long time away from, and vast sums of money short of, practical results here

In the last few years, a number of investigators have looked at the possibility of obtaining such a fusion under relatively mild laboratory conditions, achieving "cold" or "anomalous" fusion Numerous indicative, or possibly positive, results have been obtained, but have not been reproducible, or positive enough, so as to be generally recognized I believe that the most clearly positive prior work is that of Yamaguchi (Jpn. J. Appl Physics, 29 (1666, (1990)), but neither Yamaguchi himself, nor anyone else, has yet reported reproducing this work

It is well known to chemists that metallic catalysts can strongly interact with the electrons ofthe hydrogen molecule, apparently leading in some cases to activated molecules or even atoms adsorbed on, or in, the metallic catalyst For some time, I have focused on the possibility that certain catalysts might so activate deuterium (heavy hydrogen) as to cause the nuclei to self-react, or fuse, once the protecting electron clouds are highly disturbed, or removed And I believe that such an effect might have been the actual cause of Yamaguchi 's fleeting success, and possibly some ofthe other possibly "cold fusion" indicative results

Many months ago, I started obtaining indications that D₂ gas can be caused to produce energy by contacting with various metals known to be active "hydrogenation" catalysts The procedures improved with experimentation, but re¬ mained erratic and unpredictable

I have now determined that energy may be produced on a continuous basis by contacting a specifically active catalyst with a gas comprising D₂, at temperatures at least about 130° C. Because only some proportion of hydrogenation catalysts are active in this process, I have devised a screening process whereby to identify those catalysts which are specifically active. That screening process consists ofthe side-by-side, or se¬ quential, contacting ofthe reduced, and devolatilized, catalyst with H₂ and D₂ gases at about 1 to 3 atm gauge pressure, and about 150 to 200° C Those catalysts which are specifically inactive show no incremental temperature differential between H2 and D₂ The specifically active catalysts show an increased temperature due to the D₂ of at least about 2° C , and preferably greater than 5°C , compared to the H₂

I have found that the only product of this catalytic self-reaction is mass-4 he- Hum. No appreciable quantity of neutrons, or tritium, or mass-3 helium are pro- duced. This is highly unexpected, and contrary to published discussions of possible fusion reactions of H, D , and T

SUMMARY OF THE INVENTION

After much experimentation I have

1) Discovered the general conditions under which energy may be conven- iently obtained by apparent catalytic self-reaction of deuterium;

2) Established a screening procedure by which those catalysts which are specifically active in this procedure are identified,

3) Determined that the (exclusive) product of said catalytic fusion is in fact mass-4 helium

DETAILED DESCRIPTION OF AN ILLUSTRATIVE EMBODIMENT

This application is a continuation-in-part of my prior applications Serial No 07/713,302, filed 6/11/91, Serial No 07/749,149 filed 8/23/91, Serial No 07/830,718, filed 2/04/92; Serial No. 08/135,021, filed 10/13/93; Serial No. 08/188,948, filed 01/27/94, Serial No. 08/262,777, filed 6/20/94; Serial No. 08/459,763, filed 06/02/95, and all applications of which these applications are con- tinuations-in-part, each and all of which applications are incorporated herein by refer¬ ence. My first positive results were obtained by pressuring certain metallic catalysts with D₂ gas, and then devolatilizing, thus following on, and confirming, the results of Yamaguchi. But this is necessarily a batch process, did not yield large amounts of energy, and therefor had little promise for large-scale use.

I have now found that it is possible to produce large amounts of energy (much greater than 1 watt), on a continuous basis, by contacting a gas comprising D₂ with a specifically active hydrogenation catalyst at a temperature of at least about 130° C.

1. General Procedure and Useful Materials

The most important element ofthe instant invention is the discovery and identification of specifically active metallic hydrogenation catalysts. There are innu¬ merable candidate such catalysts, and only some relatively small proportion thereof, is specifically active in the instant process. Central to this invention was the determina¬ tion that such specifically active catalysts do exist, and that identification thereof is an empirical process, wherein many negative results may be traversed before positive results occur. And so far, there is no reliable guide to make an a priori selection among the candidates.

The most easily categorized specifically active catalysts are the supported platinum-group-metal (PGM) hydrogenation catalysts, already well known to be ac¬ tive catalysts, and widely used in the process industries. Those PGM's most widely used are Pt and Pd, of course, although Rh and Ru may be used, and even sometimes Ir. Both Pt and Pd have been found to yield spe¬ cifically active catalysts, with indications that Rh is also useful. Ru, when and as identified as a specifically active metal, may be preferred because of its very low cost, and potential durability in use. The platinum group metals may indeed be specifically active in other forms, such as Pt or Pd black, or as sponge, and so forth.

Supported Ni catalysts are also widely used in the process industries, al¬ though generally not nearly so active as the PGM catalysts. Ni, when and as identi¬ fied as specifically active in the instant invention, would be a preferred embodiment, because ofthe very low cost and wide availability compared to the PGM's. The various supports may be those used for the PGM's. In general, however, the level of Ni loading is higher than for the PGM's, being usually greater than 10%. Raney Ni is also sometimes used in the process industries, and would be similar in utility to the supported Ni catalysts, when and as identified as specifically active. Various other metals are known to be active hydrogenation catalysts, and might be found to be specifically active in some embodiments. Of possible utility are supported Re, Raney Co, and Ti, and the rare earths in various forms.

It is well known that mixtures of various metals are sometimes specially ac¬ tive hydrogenation catalysts, and thus might be promising specifically active catalysts. Of particular interest would be mixtures ofthe PGM's with each other, and with Re.

The supporting material may be any one of those known and commonly used, such as activated carbon, graphite, alumina, silica, kieselguhr, clay, zeolites, and so forth.

It is known that about a 1/2% to 5% loading of metal on the support (preferably about 1%), and that an activated carbon support, is very useful in various hydrogentations, and so it is that both 1% Pd and 1% Pt on activated carbon have been found in some instances to be specifically active. Pd seems more active that Pt.

The specifically active catalyst may either be in powdered or otherwise finely divided form, or may be in the form of porous aggregates, such as pellets or cylin- ders. It is critical that the catalyst must be able to absorb or adsorb a large quantity ofthe fuel gas comprising D₂.

The fuel gas to be contacted with the specifically active catalyst comprises D₂. The actual D₂ content need not approach 100%, however. An atomic proportion of H₂ of a few percent is not especially detrimental. Only at levels of 5% to 10% does the dilution effect of H₂ become large enough to slow down the reaction notably Any content of O₂ in the fuel is detrimental, because it catalytically reacts with D₂ to form D₂O, which may be inactive And H₂O, HDO, and D₂O are undesirable, be¬ cause they may preferentially occupy the specifically active sites, preventing the de¬ sired self-reaction of D₂ N₂ seems to serve merely as a diluent in the fuel gas, and has almost no effect in any reasonable proportion CO may also sometimes be only a diluent CO₂ may preferentially occupy active sites and may be undesirable But both CO and CO₂ are unlikely major constituents of any fuel gas

He, being the product ofthe instantly desired reaction, might seem to be an important, and negative component ofthe fuel gas But it appears that the extreme vigor ofthe desired reaction causes such localized disruption, on an atomic scale, that He is released, rather than being trapped in the catalyst Thus, He seems to serve merely as a diluent, as does N₂ Only when the fuel gas reacts to such a degree that the He content rises to 5%, or 10%, or more, is it desirable to institute some sort of bleeding ofthe contaminated fuel gas, and replenishment by fresh D₂

Most (or all) ofthe commercially available deuterium gas seems quite satis¬ factory as fuel Research and CP grades are perhaps unnecessarily pure, and more costly

The temperature under which the instant self-reaction is conducted is impor- tant. At a temperature level of 150-200°C , the reaction proceeds at a reasonable rate, and the temperature level is high enough so that heat can be transferred to wa¬ ter, creating steam—being that highly desirable vehicle whereby to power turbines, or to carry energy from place to place At temperatures less than about 150° C , the desired reaction is slower, and the temperature difference to create steam impracti- cally low But the operational temperatures may desirably be quite higher than

200°C , if desired Surprisingly, the D₂ fuel may remain in close association with the catalyst at temperatures even well in excess of 200°C , and even at temperatures fa¬ voring devolution ofthe D₂ from the catalyst, increased pressure may be employed to counter the trend. Thus, the upper limit on this reaction may be set by the strength of the materials used, and may extend to 300°C, or 500°C, or even higher.

The pressure used in this process is not so important as the temperature. Es¬ pecially at the lower operating temperatures of 150-200°C, the fuel is highly ab¬ sorbed in, or adsorbed on, the catalyst even at 1 atm. absolute. And some ofthe ac- tive catalysts so strongly attract the fuel that a partial vacuum may appear. Thus it is that a wide range of pressures may be usefully employed. Sometimes a partial vac¬ uum may be present. Generally, 1-10 atm. absolute is easily obtained, easily con¬ tained, and useful. Under special conditions, pressures up to 100 atm. or higher may be desirable, and useful. The apparatus used is generally any leak-tight container capable of tempera¬ ture and pressure regulation, and fitted with tubes through which to circulate water, or other heat-transfer fluid. The specific configuration may vary widely.

There are, however, three factors governing the design of apparatus.

1) As indicated, the catalyst must be in good thermal contact with the tubes carrying heat-transfer fluid ("steam tubes"), so as to facilitate removal ofthe energy generated.

2) The catalyst must be in good contact with the fuel gas, so as to replen¬ ish the fuel converted. This generally may mean that the catalyst lies only in a thin layer, with all same being near to a gas-catalyst interface. A layer about one inch thick is approximately the upper limit in this sense.

3) Insofar as it is difficult to design a reactor having a large, thin surface of catalyst contacting the fuel, it is preferred that the fuel be continuously fed through a bed ofthe catalyst. Thus, the preferred reactor design is either a stationary (or preferably a fluidized) bed of catalyst surrounding and in close contact with the heat- transfer tubes, and through which the fuel gas is circulated under forced draft, to en¬ sure continuous contact between catalyst, and fresh fuel.

Because the instant self-reaction of D₂ produces only He, and no neutrons, tritium, or other radioactivity, the materials of construction can be simple steel, even carbon steel. There is nothing to cause corrosion or embrittlement (save hydrogen embrittlement) At most costly, 302 or 304 stainless steel may be advantageously employed. Exotic materials, such as 316 stainless, or zirconium, are quite unneces¬ sary. And because the product is helium, a most inert and benign gas, the process produces no dangerous effluent, (being even much less damaging to the environment than CO₂). Thus, after processing the bled material to recover useful D₂ fuel, the product He can even be vented to the atmosphere, if desired, as it generally will be

Incidentally, the instant process, apparently by the reaction D + D — > 4-mass helium, evolves almost 24 MeV, which is a huge, and extraordinarily favorable amount of energy Indeed, this reaction appears certain to be the most energetic re¬ action ever conducted by man on a macroscopic scale (There are only few possibly more energetic reactions, such as matter-antimatter extinction, but these can never be run on a macroscopic scale on earth).

2. Screening Procedure for Specifically Active Catalysts

Because there is an infinity of possible catalysts, and only a small proportion ofthe infinity proves specifically active, a simple, easily conducted, screening proce- dure is essential for the practical application ofthe instant invention Even when one starts with those most promising candidates, the supported PGM hydrogenation catalysts, by no means are all specifically active, so the screening procedure is neces¬ sary, to avoid endless experimentation with uniformly negative results Indeed, after 3, or 10, or 100, negative results, and that even after initial encouragement, most re- searchers would give up and try something else And this factor may well already have been "decisive" in many previous attempts at "cold" or "anomalous" fusion

The instant invention relies on such a screening test That test need not be exact in detail, but must involve contacting the reduced, devolatilized candidate catalyst with gases, comprising H₂ and then D₂, at a temperature between about 150°C. and 200°C. (higher temperatures can be used, but are unnecessary), and ini¬ tially at 1-3 atm. absolute (the pressure will generally change as the test proceeds) The catalyst must be in the reduced state, so as not to react with H₂, and give a false reference temperature partially dependent on the reduction reaction And the catalyst must be devolatilized so as to be able to absorb, or adsorb, the fuel gases The experimental device is brought into a stable temperature state using the

H₂ reference gas, said stable temperature being the "reference" temperature Then the H₂ gas is devolved by pulling a good vacuum for some minutes (some catalysts are quite reluctant to devolve adsorbed or absorbed H₂) Then the experiment is re¬ peated, employing the same apparatus, heat input, and configuration, but with D₂ in- stead ofthe H₂.

If the temperature eventually reached with D₂ is about the same as reached with H₂, or less than about 2°C greater, the catalyst candidate is deemed not specifi¬ cally active (it is fairly difficult to be certain that anything much less than 2°C is a genuine result, and not merely some experimental artifact) If the temperature reached with D₂ is at least 5°C. greater than that with H₂, the catalyst is clearly spe¬ cifically active And temperature differences greater than 10°C have been measured in practice.

Although by no means the only suitable screening apparatus, I suggest the following apparatus and procedure which I have successfully used I have modified a 1.7 liter WW II oxygen bottle with an inlet-outlet valve and pressure gauge fitted to the single standard pipe female outlet, a larger pipe female outlet for adding and removing solids, a thermocouple well reaching near the bottom ofthe vessel, and a flask heating mantle which neatly fits the bottom ofthe 300 series stainless gas bottle Enough ofthe candidate catalyst is added so as to cover the end ofthe ther¬ mocouple well, and apparatus is sealed, and then a vacuum pulled with a good me¬ chanical pump H₂ gas is added to about 2 atm pressure, the temperature raised over about onehour to about 125 to 150°C, and the vessel evacuated again H₂ gas is then added again, the temperature raised, and the cycle is repeated if necessary until it appears that the temperature reaches a steady state, indicating that the catalyst has been reduced (if necessary) and all water devolved

Then, the cooled vessel is filled with 2 atm of H₂, and the heating jacket is heated with a specific value of volts and amperes (in my case, about 50 V and 1 5 A.), and the temperature observed until it reaches a level which remains steady for at least about one hour, in the range of about 150-200°C

The vessel is then carefully devolatilized by pumping off the H₂, and cooled Then 2 atm. of D₂ gas is added , and the heating jacket heated with the same value of volts and amperes The temperature is then carefully followed until it reaches a rea- sonably steady level, usually in one or 2 hours If the observed temperature is well in excess of that reached with H₂, then there is apparent reaction with D₂ which does not occur with H₂, and the catalyst is deemed specifically active

This procedure may seem too simple and unrefined, but it is reliable I have sometimes switched back and forth between H₂ and D₂, confirming the initial result And the test may discriminate between different lots ofthe same catalyst

The specifically active catalysts never reach a totally stable temperature with D₂, said temperature always slowly increases over weeks of time

3 The Instant Procedure Makes Only Mass-4 Helium Product

I have made a large-scale test in an important facility well equipped and ex- perienced to determine neutrons When we finally reached a quiet time, with no in¬ terference, there were no neutrons above background for many minutes Thus, the reaction D + D → n + helium - 3 does not occur

And I have analyzed for tritium The tritium content of a product from a weeks-long run was found to be about equivalent to that of distilled water, in fact, with no indication of tritium added in process Thus, the reaction D + D → H + T does not occur to any appreciable extent Theory has it that this reaction should oc¬ cur to an extent equal to that yielding n + heliuιn-3, and the fact that both are zero cause no conflict with theory.

After difficulty, I obtained access to a large magnetic sector mass spectro- graph calibrated to carefully sort out low-mass atoms The sample I sent was diluted with several parts of air to actual sample (during poor handling) so the resulting analysis showed much air But about 100 ppm of mass-4 helium was analytically found The amount corrected for the leak roughly corresponded to the upper limit of helium calculated from a heat balance, based on temperature increase when replacing

Insofar as the amount of helium found, about 100 ppm., is far higher than that found in air, the result seems conclusive, clearly demonstrating that mass-4 helium is produced, in important amounts, apparently being the only elemental product. So it seems.

EXAMPLE 1

Into a 300-series stainless steel bottle of 1700 ml. volume, fitted with pressure gauge, thermowell reaching to near the bottom ofthe bottle, an inlet-outlet valve, and 3/4" plugged opening for addition and removal of solids, and heated on the lower outside and bottom by a hemispherical, electrically-heated heating mantle, was placed 28.0 g. of 1% Pt on activated carbon, of 62% H₂O content, and being very fluffy and light weight.

The vessel was then sealed, and alternatively heated to about 100°C, and evacuated with a good mechanical vacuum pump, until the pressure in the vessel at 100°C. was much less than 1 psia. Then the vessel was filled to 32 psia with high purity (grade 4.7) hydrogen gas.

After heating for several hours, at 60 V. on the heating mantle the vessel stabilized at 156°C. and 18 1/2 psia.

Then the vessel was evacuated well with the mechanical vacuum pump, and filled to 32.5 psia with grade 2.5 deuterium. The vessel was then heated again for several hours, and at 60 V. on the heating mantel, the vessel stabilized at a tempera¬ ture of 166°C.

The current to the heating mantle was 1.79 A for the H₂ run, and 1.78 A for the D₂ run, thought to be indistinguishably different. The temperature difference for D₂ over H₂, at the same power input is 10°C, corresponding to a few watts of power generation.

On maintaining the voltage at 60 V. for many days, the temperature ofthe vessel containing D₂ increased another one or two ° C. EXAMPLE II

Example I was repeated using 21 9 g of 1 % Pd on activated carbon, of 55% H₂O content, and the same procedure to remove the residual water from the catalyst

With hydrogen, the vessel stabilized at a temperature of 152°C , and 31 psia, at 60 V. on the heating mantle

With deuterium, the vessel stabilized at 167 5°C and 39 5 psia, at 60 V on the heating mantle

The incremental temperature difference between H₂ and D₂ was thus 15 5°C

EXAMPLE III

Example I was repeated, using 19 2 g of 5% Pd on activated carbon, of 38% H₂O content, and the same procedure to remove the residual water from the catalyst

With hydrogen, the vessel stabilized at a temperature of 165°C , at 60 V on the heating mantle

With deuterium the vessel stabilized at a temperature of 169 5°C , at 60 V on the heating mantle Thus, the incremental temperature differential between H₂ and D₂ was 4 5°C , just on the borderline of demonstration of specific activity There is some indication that 5% Pd loading is less effective than 1 % Pd

EXAMPLE IV

Example II was repeated using a very similar, but different, 1% Pd catalyst The temperature reached with H₂ and D₂ was almost the same, thus showing no specific activity

Claims

1 1. The process of producing energy which comprises contacting a fuel gas compris-

2 ing D₂, and a specifically active metallic hydrogenation catalyst at a temperature

3 greater than about 130°C.

i 2. The process of Claim 1 wherein the said fuel gas is commercial-grade D₂.

I 3. The process of Claim 1 wherein the said fuel gas is the D₂ produced by electroly-

2 sis of reactor-grade heavy water.

1 4. The process of Claim 1 wherein the temperature is greater than 150°C

I 5. The process of Claim 1 wherein the metal of the said metallic catalyst is selected

2 from the group consisting of Pd, Pt, Rh, Ru, Ir, Re, Ni, Ti, and the rare earths.

I 6. The process of Claim 5 wherein the said metal is selected from the group consist-

2 ing of Pd, Pt, and Ru.

I 7. The process of Claim 5 wherein the said metal is Pd

I 8. The process of Claim 5 wherein the said metal is Ni

I 9. The process of Claim 5 wherein the said metallic catalyst contains a mixture of

2 two or more metals selected from the group consisting of Pd, Pt, Rh, Ru, Ir, and Re

I 10. The process of Claim 5 wherein the said metallic catalyst is on a support selected

2 from the group consisting of activated carbon, graphite, silica, alumina, kieselguhy,

3 zeolite, and clay.

I 11. The process of Claim 1 wherein the operating pressure is less than about 100

2 atm. 1 12. The process of Claim 1 wherein the said metallic catalyst is located in a fixed bed surrounding heat-transfer tubes, with the fuel gas being circulated through said bed.

I 13. The process of Claim 1 wherein the said metallic catalyst is located in a fluidized

2 bed surrounding heat-transfer tubes, with the fuel gas being circulated through said

3 bed.

i 14. The process of Claim 4 wherein helium of mass 4 is coproduced along with the

2 energy.

I 15. The process of Claim 14 wherein the said fuel gas is commercial-grade D₂

I 16. The process of Claim 14 wherein the said fuel gas is D₂ produced by electrolysis

2 of reactor-grade heavy water.

I 17. The process of Claim 14 wherein the metal ofthe said metallic catalyst is se-

2 lected from the group consisting of Pd, Pt, Rh, Ru, Ir, Re, Ni, Ti, and the rare earths

i 18. The process of Claim 14 wherein the metal ofthe said metallic catalyst is se-

2 lected from the group consisting of Pd, Pt, Ru, Rh, Re, and Ni.

I 19. The process of Claim 14 wherein the said metallic catalyst is on a support se-

2 lected from the group consisting of activated carbon, graphite, silica, alumina, kiesel-

3 guhr, zeolite, and clay.

I 20. The process of Claim 14 wherein the said metallic catalyst is located in a flu-

2 idized bed surrounding heat-transfer tubes, with the fuel gas being circulated through

3 the said bed.