Integrated process using non-stoichiometric sulfides or oxides of potassium for making less active metals and hydrocarbons

Disclosed is a combinative integrated chemical process using inorganic reactants and yielding, if desired, organic products. The process involves first the production of elemental potassium by the thermal or thermal-reduced pressure decomposition of potassium oxide or potassium sulfide and distillation of the potassium. This elemental potassium is then used to reduce ores or ore concentrates of copper, zinc, lead, magnesium, cadmium, iron, arsenic, antimony or silver to yield one or more of these less active metals in elemental form. Process potassium can also be used to produce hydrogen by reaction with water or potassium hydroxide. This hydrogen is reacted with potassium to produce potassium hydride. Heating the latter with carbon produces potassium acetylide which forms acetylene when treated with water. Acetylene is hydrogenated to ethene or ethane with process hydrogen. Using Wurtz-Fittig reaction conditions, the ethane can be upgraded to a mixture of hydrocarbons boiling in the fuel range.

BACKGROUND OF THE INVENTION 
This invention relates to a chemical process which comprises the production 
of elemental potassium and the subsequent reaction of said elemental 
potassium with other reactants, including various metallic ores, such as 
those of magnesium, lead, zinc, copper, arsenic, antimony or silver to 
release said metals from their naturally occuring forms, in elemental 
state, or with water to produce potassium hydroxide and hydrogen and 
further reacting additional elemental potassium with said potassium 
hydroxide to produce more hydrogen and a thermally unstable potassium 
oxide which decomposes into potassium and potassium peroxide or potassium 
superoxide, optionally reacting said hydrogen and potassium to produce 
potassium hydride to store the produced hydrogen or to further react said 
potassium hydride with carbon to produce potassium acetylide and 
optionally using additional hydrogen to saturate the carbon bonds of these 
unsaturated compounds, utilizing process potassium or potassium hydride to 
catalyze the hydrogenation. 
OBJECTIONS AND FEATURES OF THE INVENTION 
An object of this invention is to provide a low-cost, high-yield process 
for producing elemental potassium from potassium oxides, or sulfides. 
Another object of the invention, is the utilization of process potassium in 
the manufacture of carbides, acetylides, hydrogen, hydrides, hydrogen 
peroxide, oxygen, potassium hydroxide, less active metals, saturated and 
unsaturated hydrocarbons so as to provide the aforementioned products and 
by-products in one integrated process leading to their manufacture at 
lower costs than heretofore attainable. 
DESCRIPTION OF PRIOR ART DISCLOSURES 
There are numerous patents on techniques for producing metals from their 
salts and for obtaining hydrogen as a by-product. Accordingly, this 
background disclosure is restricted to those which are believed most 
relevant. 
Very basic is U.S. Pat. No. 2,852,363, which describes a method for 
preparing potassium, cesium or rubidium by heating a hydroxide of these 
metals with zinc in an inert atmosphere at a temperature above the boiling 
point of the particular alkali metal under the pressure used in the 
reactor and recovering the free alkali metal. While hydrogen also is 
produced in that process, no suggestion is made about using it. 
U.S. Pat. Nos. 1,872,611; 1,034,320; 2,028,390; 3,938,985; and British Pat. 
No. 590,274 also are pertinent for disclosing processes for the production 
of alkali metals or alloys thereof. 
As will be seen hereinafter, none of these disclose, hint, or suggest in 
any manner whatsoever applicant's unique, novel and unobvious process.

SUMMARY OF THE INVENTION 
It has been discovered and forms the substantial conceptual basis of this 
invention that extraordinary process and product benefits relating to the 
winning of potassium and other metals and to the formation of organic 
products with potassium thus obtained can be achieved by the practice of 
this invention. Relatively low temperatures can be used in the process and 
high yields achieved therewith. Furthermore, the economics of the process 
are much improved. 
Fundamentally, the invention resides in an integrated progress for 
producing potassium metal from its non-stoichiometric oxide or sulfide and 
using this metal to produce less active metals and hydrocarbons by the 
steps of: 
1. thermally decomposing potassium oxide or sulfide substantially in the 
absence of water into potassium metal and to form, respectively, potassium 
peroxide or potassium superoxide, and potassium disulfide; and recovering 
the potassium metal; 
2. providing a portion of the thus formed potassium in the molten or vapor 
state and reacting same with at least one oxide or sulfide of magnesium, 
copper, calcium, silver, lead, zinc, antimony, cadmium, iron, arsenic and 
mixtures thereof to displace the metal from said oxide or sulfide followed 
by recovery of said metal; 
3. reacting another portion of the previously obtained potassium with water 
to form hydrogen and potassium oxide; 
4. utilizing the previously formed hydrogen to prepare an organic compound 
by either: 
(a) reacting said hydrogen with potassium obtained by step 1, above, at a 
temperature of between 250.degree. and 300.degree. C. to form potassium 
hydride, reacting said potassium hydride with carbon to form potassium 
acetylide and reacting said acetylide with water to produce acetylene and 
KOH; then hydrogenating said acetylene to form ethane and ethene; or, 
(b) using said hydrogen to hydrogenate carbon in the presence of a catalyst 
to form methane. 
The organic compounds, ethane or methane, can be reacted with a halogen in 
manner known per se to form an alkyl halide which can then be condensed 
with sodium or process potassium to form hydrocarbons boiling in the fuel 
range under Wurtz-Fitig reaction conditions. 
In subsidiary reactions, intermediate compounds are formed and recycled to 
produce additional potassium for reuse in the process. 
DESCRIPTION OF PREFERRED EMBODIMENTS 
The process of the invention comprises the following equations: 
##EQU1## 
11. K+R.sub.a Y.sub.b .fwdarw.K.sub.x Y.sub.x +R. This reaction is carried 
out with molten potassium, at temperatures above 65.degree. C. or with 
potassium vapor at temperatures above 780.degree. C. Y is either sulfur or 
oxygen and R is magnesium, zinc, cadmium, lead, iron, arsenic, antimony or 
silver or copper. 
12. C.sub.2 H.sub.5 X+C.sub.2 H.sub.5 X+2 K=C.sub.4 H.sub.10 +2 KX, wherein 
X is chlorine or bromine. 
##EQU2## 
16. K.sub.2 S.sub.3 .fwdarw.K.sub.2 S+k.sub.2 S.sub.2 at 1/2 mm Hg pressure 
at 360.degree. C. 
17. K.sub.2 S+H.sub.2 O.fwdarw.KOH+KHS Additional water gives a reversible 
reactions KHS+H.sub.2 O.fwdarw.KOH+H.sub.2 S 
18. Beginning 315.degree. C. H.sub.2 S.fwdarw.H.sub.2 +S 
19. 4 K.sub.2 S.sub.2 +8 H.sub.2 O.fwdarw.3K.sub.2 S+X.H.sub.2 O+K.sub.2 
S.sub.5 (in a closed system). 
20. 4 K.sub.2 S.sub.3 +X H.sub.2 O.fwdarw.2 K.sub.2 S.sub.5 +2K.sub.2 
S.X.H.sub.2 O. The minimum amount of water (X) is that required to form 
the hydrate of potassium sulfide which exists at the temperature at which 
this hydrolysis occurs. 
21. 4 K.sub.2 S.sub.4 +X H.sub.2 O.fwdarw.3 K.sub.2 S.sub.5 +K.sub.2 S.X 
H.sub.2 O. 
All of these hydrolysis decomposition reactions are carried out in a closed 
system and at temperatures above 60.degree. C. and below the critical 
temperature of water. The minimum amount of water (x) required for these 
hydrolysis reactions is that which constitutes the hydrate of potassium 
sulfide which exists at the selected temperature or below 206.degree. C., 
the melting point of K.sub.2 S.sub.5. 
The process of this invention utilizes the lack of thermal stability of the 
non-stoichiometric sulfide and oxide compounds of potassium, to produce 
elemental potassium and a variety of potassium compounds, thereafter 
utilizing this elemental potassium or some of the potassium compounds to 
continually reform these sulfides and oxides of potassium by reaction with 
water, metallic ores, etc. 
Referring to the above equations: Equations 1, 4 and 14, are the basic 
equations of this invention, whereby elemental potassium is formed by 
thermal decomposition of potassium sulfide into potassium disulfide and 
said elemental potassium and the decomposition of potassium oxide into 
elemental potassium and potassium peroxide or potassium superoxide. 
Equation No. 15 illustrates the decomposition of potassium disulfide into 
potassium sulfide and sulfur, while equation No. 16 illustrates the 
decomposition of potassium trisulfide, or higher polysulfide, into 
potassium sulfide and potassium disulfide. Equations No. 19, 20 and 21, 
illustrates the hot water hydrolysis of potassium polysulfide into 
potassium sulfide hydrate and potassium pentasulfide. The heat-reduced 
pressure decomposition of potassium trisulfide as illustrated in equation 
No. 16 are equally applicable to potassium tetrasulfide, potassium 
pentasulfide and potassium hexasulfide. Equation No. 6, 9 and 9a 
illustrate the decomposition of potassium peroxide and potassium 
superoxide. Potassium peroxide is decomposed into elemental potassium and 
elemental oxygen. Potassium superoxide (KO.sub.2) is decomposed into 
potassium peroxide K.sub.2 O.sub.2 and oxygen. At temperatures above 
780.degree. C., K.sub.2 O.sub.2 begins to decompose to K and O.sub.2. 
Potassium does not unite with oxygen or sulfur in the absence of water 
vapor. Removal of water vapor from the process system will greatly reduce 
the tendency of potassium and either sulfur or oxygen to reunite following 
the thermal reduced pressure decomposition of potassium oxide or potassium 
sulfide. 
Potassium hydroxide, potassium oxides, potassium sulfides and potassium 
hydrosulfides are deliquescent and have low aqueous tensions. Potassium 
sulfides and potassium oxides are non-stoichiometric compounds with 
deficiencies in the anion sub-lattice. Water, hydrogen, and even potassium 
hydride will substitute in the anion sub-lattice. The hydrogen is produced 
by the reaction of potassium metal with water vapor and the reaction with 
elemental potassium to produce potassium hydroxide and hydrogen. 
Additional potassium will react with this potassium hydroxide to form 
additional hydrogen and potassium oxide. In the case of the potassium 
oxides, water will also react directly with potassium oxide to form 
potassium hydroxide. At the beginning of the thermal decomposition of the 
potassium sulfides or oxides, the elemental potassium will react with this 
potassium hydroxide to form additional hydrogen and potassium oxides. At 
the 350.degree. C. decomposition temperature of potassium oxide, the 
elemental potassium will unite with some of the hydrogen produced and form 
potassium hydride. As the temperature is elevated to above 380.degree. C., 
potassium hydride begins to dissociate. 
The elemental potassium, produced from the decomposition of potassium 
sulfide or potassium oxide, is soluble in the solids remaining until 
temperature-pressure conditions above those necessary to boil elemental 
potassium are reached. As shown by Equations 15-21, I have observed that 
potassium sulfide, prepared by the reduction of the sulfur content of 
potassium pentasulfide or any polysulfide with a sulfur content of two or 
greater, can be decomposed to elemental potassium and sulfur at 
780.degree. C. in a twenty-four hour period. Potassium pentasulfide melts 
at 206.degree. C. and decomposes to potassium tetrasulfide and sulfur at 
temperatures beginning at 300.degree. C. At 206.degree. C., potassium 
pentasulfide melts are essentially anhydrous. Potassium tetrasulfide melts 
at 145.degree. C., Potassium trisulfide melts at 279.degree. C. and 
potassium disulfide melts at 470.degree. C. Any of these compounds produce 
an anhydrous melt at temperatures above their melting points. It is easier 
to form these anhydrous melts under reduced pressure. The reduced 
pressures allow the water of hydration to be removed more easily to form 
anhydrous melts. The temperature should be at least as high as the melting 
point of the particular potassium polysulfide and the reduced pressures 
should be residual pressures of from 1 mm Hg to 50 mm Hg. As these 
potassium polysulfides are decomposed into lower sulfur content 
polysulfides, the temperature-reduced pressure conditions should be 
adequate to distill the sulfur. Sulfur boils at 445.degree. C. at 760 mm 
Hg pressure, at 185.degree. C. at 1 mm Hg pressure. 
Potassium trisulfide decomposes to a mixture of potassium monosulfide and 
disulfide at 350.degree. C. at 0.05 Torr. Potassium disulfide decomposes 
to potassium sulfide and sulfur at 650.degree. C. at 0.05 Torr and 
anhydrous potassium sulfide decomposes to elemental potassium and sulfur 
at 780.degree. C. while hydrated potassium sulfide requires 840.degree. C. 
to decompose to sulfur and potassium. Without reduced pressures, potassium 
disulfide is the most stable union of potassium and sulfur thermally, with 
potassium sulfide decomposing to elemental potassium and potassium 
disulfide at temperatures above 780.degree. C. for anhydrous potassium 
sulfide or 840.degree. C. for hydrated potassium sulfide. 
For practical purposes, the decomposition of potassium disulfide occurs at 
883.degree. C. at 10 mm Hg pressure. At this temperature pressure, 
potassium disulfide is rapidly decomposed into its elements. The alternate 
source of potassium from potassium sulfides is the decomposition of 
potassium disulfide into potassium sulfide at reduced pressures of 1 mm Hg 
at 78.degree. C. and the subsequent decomposition of potassium sulfide 
into its elements under the same conditions. 
Where the present process starts with potassium oxide, potassium monoxide 
is decomposed into elemental potassium and potassium peroxide or potassium 
super oxide at temperatures above 350.degree. C., however, the potassium 
is not readily available for extraction from this mixture, at these 
temperature. At pressures of 5.times.10.sup.-4 at 360.degree. C. some 
elemental potassium can be extracted by distillation. At temperatures 
above the melting point of potassium peroxide, 490.degree. C., potassium 
can be extracted by distillation at pressures 10 mm Hg. At temperatures of 
780.degree. C., almost all of the potassium can be extracted by 
distillation at 10 mm Hg. The elemental potassium decomposes into 
potassium peroxide and potassium and the potassium peroxide is then melted 
at 490.degree. C. to make the mix anhydrous. By the removal of the water 
the formation of hydrides, hydroxides and hydrogen is retarded and this 
allows the decomposition of the potassium oxides into their elements of 
formation. 
The potassium, produced by the present invention, is then reacted with an 
amount of water less than the stoichiometric amount, such as 15% less than 
stoichiometric, to produce potassium hydroxide and hydrogen, as shown in 
equation 2a. Additional potassium and the potassium hydroxide at 
temperatures above 360.degree. C. will produce additional hydrogen and 
form the unstable potassium monoxide (equation 2). The potassium monoxide 
K.sub.2 O is then decomposed to potassium and oxygen or potassium and 
potassium peroxide or potassium superoxide by one of the processes 
disclosed, to continuously produced hydrogen (Equation 4). A part of the 
potassium peroxide or potassium superoxide can be dissolved in an amount 
of water less than the stoichiometric amount, such as 15% less than 
stoichiometric to produce additional potassium hydroxide and hydrogen 
peroxide (Equation 10). The unstable hydrogen peroxide can then be used as 
a source of oxygen. Potassium superoxide and potassium peroxide can also 
be used as sources of oxygen at temperatures above 653.degree. C. for the 
superoxide or above 780.degree. C. for the peroxide, as shown by Equation 
9 and 9A. 
At any temperature above its melting point, 65.degree. C., potassium in 
liquid or vapor form will reduce the ores of magnesium, copper, silver, 
lead, zinc, antimony, arsenic, cadmium, and mixtures thereof to the free 
metal and form potassium oxide or form either the sulfides or oxides of 
potassium by the liberation of elemental copper, silver, lead, zinc, 
calcium, antimony, arsenic, cadmium, etc. depending upon whether these 
metals were in oxide or sulfide form in their naturally occurring mixed 
ores or ore concentrate. 
When elemental potassium has been used to form hydrogen by the 
decomposition of water or potassium hydroxide or by the reduction of 
hydrogen sulfide, derived from the decomposition of the hydrolysis 
product, potassium hydrosulfide, from potassium sulfide, this hydrogen may 
be stored as potassium hydride by reaction of said hydrogen with 
additional elemental potassium at temperatures between 250.degree. C. and 
360.degree. C. Potassium hydride is miscible in molten potassium. 
Potassium hydride dissolved in molten potassium reacts directly with carbon 
and graphite to produce potassium acetylide. Potassium acetylide reacts 
with water to produce acetylene. 
The acetylene produced can be reacted with additional process hydrogen, 
utilizing molten potassium or potassium hydride as the catalyst to form 
ethene or ethane. The amount of hydrogen present will determine the 
formation of ethene or ethane. The temperature of this reaction is any 
temperature above the melting point of potassium, 65.degree. C. 
Hydrogen produced in the present invention can be directly combined with 
carbon to form methane in the presence of a suitable catalyst such as 
nickel at temperatures of 250.degree. C. by the Raney-Nickel method. 
Elemental potassium or potassium hydride dissolved in potassium may be 
used as the catalyst at temperatures between 180.degree. C. and 
360.degree. C. 
EXAMPLE I 
This example illustrates the preparation of potassium metal from K.sub.2 O 
present in an ore. 
In conducting this example, an ore containing 10 kg of K.sub.2 O was placed 
in an autoclave and heated to 883.degree. C. under a reduced pressure of 
10 mm of Hg. 4.1 kg of potassium metal was distilled, leaving behind 5.9 
kg of K.sub.2 O.sub.2. 
EXAMPLE II 
This example illustrates the reactions of Equations 2-9, 11-12. 
Technical grade flakes of potassium hydroxide of 90% purity were heated to 
380.degree. C. A reduced pressure of 50 mm Hg was used to dehydrate said 
flakes during the making of an essentially anhydrous melt. 
Thereafter, the use of reduced pressures was discontinued and with the 
temperature maintained at 380.degree. C., elemental potassium was added to 
the melt. Hydrogen was evolved. The stoichiometry was one mole of 
potassium hydroxide, derived from 62.2 grams of 90% technical flakes of 
KOH, and one mole (39.1 g) of elemental potassium. 
The hydrogen evolved was passed into molten potassium maintained at 
280.degree. C. to form potassium hydride. One and one-half moles of 
potassium were used to take up the one mole of hydrogen and to form a 
liquid consisting of a solution of potassium hydride in molten potassium. 
The potassium hydride solution containing one mole of KH in molten 
potassium was treated at 350.degree. C. in the absence of air, nitrogen, 
or carbon dioxide with two moles of carbon (graphite) to form potassium 
acetylide. 
The mixture was carefully and slowly added to one and a half mole of water 
to form one mole of acetylene and hydrogen as volatiles and form a 
solution of potassium hydroxide. The gases produced, hydrogen and 
acetylene, occupied 3.2 liters at 15.degree. C. at atmospheric pressure, 
indicating conversion to one mole of acetylene and one-half mole of 
hydrogen. 
The potassium oxide, formed by the reaction of potassium and potassium 
hydroxide, was heated to 500.degree. C. under a reduced pressure of 10 mm 
Hg. After two hours of being maintained at 500.degree. C. under 10 mm Hg., 
the mixture was heated to 883.degree. C. and one and one half moles of 
potassium were condensed by selectively cooling the emitting gas stream in 
three hours and twenty minutes. 
EXAMPLE III 
One mole of potassium produced in Example I was treated with water as shown 
in Equation 2A to provide additional hydrogen gas and potassium hydroxide. 
One mole of potassium superoxide produced in Example VI was added to two 
moles of water at 95.degree. C. to produce one mole of hydrogen peroxide 
and two moles of potassium hydroxide, as illustrated by Equation 10. 
This example thus shows the recovery of nearly all the potassium in the 
forms originally used; i.e. elemental potassium and potassium hydroxide. 
EXAMPLE IV 
This example shows the thermal decomposition of K.sub.2 S into potassium, 
as shown by Equation 14. 
Two pounds of K.sub.2 S were heated to 780.degree. C. under a pressure of 
50 mm to remove water. The pressure was then reduced to 5.times.10.sup.-4 
at that temperature. 
Sulphur was distilled and condensed in a liquid nitrogen series of traps. 
When the distillation rate of sulfur decreased, the temperature was 
elevated to 883.degree. C. The distillation chamber was left with 
potassium sulfate, identified by the barium analytical reaction, with the 
potassium and sulfur condensed in fresh traps cooled by liquid nitrogen. 
The potassium and the sulfur did not reunite in the absence of water 
vapor. 
200 grams of potassium were collected. 
EXAMPLE V 
As per Equation 11, the potassium produced in Example IV was melted under 
50 mm of Hg pressure and decanted from the sulfur. 
The potassium was divided into four fifty gram samples and was used in its 
molten form. 
One fifty gram sample was used to smelt 54 grams of a lead sulfide 
concentrate containing 73% lead. The smelting was done at 70.degree. C. 
After the reaction had ceased (in approximately three minutes) the 
temperature was elevated to 330.degree. C. and the molten lead was tapped 
from the lighter material floating on the lead surface. 
One fifty gram sample was used to smelt 41.6 grams of zinc sulfide 
concentrate, containing 50% zinc. The temperature was 70.degree. C. The 
reaction required approximately two minutes. The temperature was elevated 
to 440.degree. C. and the liquid molten zinc was tapped from below the 
material floating on the surface of the zinc. 
One fifty gram sample was used to smelt 50 grams of a copper sulfide 
concentrate containing 86% chalcopyrite (CuFeS.sub.2). The reaction was 
carried out at 70.degree. C. Iron and copper were produced. The iron was 
magnetically separated from the copper. The copper was melted and 
separated from the material floating on the copper surface. 
One fifty gram sample was used to smelt 25 grams of magnesium oxide at 
360.degree. C. The reaction required six minutes. Elemental magnesium was 
produced. 
In all of these samples, the residual potassium was distilled from the 
metals produced at pressures adequate to distill potassium but too low to 
volatilize the other metal. The three sulfide samples were separated from 
their carrying and largely inert gangue by dissolving the potassium 
sulfides produced in this smelting operation in small quantities of water. 
The solids were then separated from the liquid by filtration. 
Sulfur was added to the filtrate and the filtrate were dehydrated at 
500.degree. C. under 50 mm Hg. pressure. The resulting anhydrous melt was 
then subjected to temperatures of 883.degree. C. under 10 mm pressure to 
reform potassium vapor and sulfur vapor which were then condensed. This 
reformation of the potassium completed the cycle. 
The potassium oxide produced in the magnesium smelting was directly 
recycled to potassium by heating the gangue and the potassium oxide to 
883.degree. C. under 10 mm Hg. Some carbon dioxide was distilled prior to 
the distillation of the potassium. The carbon dioxide was taken up in 
potassium hydroxide as it emitted the system. The potassium was largely 
recovered after the carbon dioxide had been removed from the system. A 
second sample showed that the carbon dioxide could be removed by 
pre-heating the magnesium oxide under reduced pressures prior to reacting 
same with potassium. The potassium produced by the recycling of the 
potassium oxides was condensed by cooling and used to smelt additional 
magnesium ore. 
EXAMPLE VI 
This example illustrates the reactions of Equation 4,5, 9-10 and 13. 
Hydrogen, produced by this invention, was used to hydrogenate carbon, 
(graphite) at 250.degree. C. in the presence of molten potassium 
(potassium hydride dissolved in molten potassium (Raney-Nickel, also can 
be used). No pressures were used other than the pressure of the hydrogen 
issuing from the process system. A total of 100 grams of carbon was 
hydrogenated to methane in one-half hour by the use of one mole of 
potassium and one mole of potassium hydroxide by continually recycling 
these reagents. This recycling consisted of dissolving residual potassium 
oxides in water and then reacting this potassium hydroxide with potassium 
produced by the thermal decomposition of potassium oxides at 883.degree. 
C. under 10 mm Hg (Equation 1 and 2). 
A step to reduce the oxygen content of the system by decomposing any 
potassium superoxide that might be produced was carried out by heating the 
potassium oxides to 653.degree. C. prior to decomposition at 883.degree. 
C. Care was taken to condense potassium and allow the oxygen to escape the 
process system. This was done to avoid the production of potassium 
carbonyl. 
The undecomposed residue was used to form potassium hydroxide and to form 
hydrogen peroxide by reaction with water (Equation 10). Care was taken not 
to allow hydrogen peroxide or any oxygen arising from the decomposition of 
hydrogen peroxide to enter the smelting system. 
EXAMPLE VII 
This example shows the production of elemental potassium and a mixture of 
potassium peroxide and potassium superoxide by thermal decomposition of 
potassium oxide; next reacting potassium peroxide and superoxide with a 
stoichiometric quantity of water to form potassium hydroxide and oxygen; 
then reacting elemental potassium with potassium hydroxide to form 
elemental hydrogen and to reconstitute potassium oxide for recycling. 
This decomposition can be practiced in the 360.degree. C.-380.degree. C. 
temperature range with appropriate addition and withdrawal of product, 
over or at a temperature range below 653.degree. C. or at a temperature of 
over 779.degree. C. 
In conducting this run, potassium hydroxide is heated to 370.degree. C. in 
the absence of air under a reduced pressure of 1-10 MM Hg. Elemental 
molten potassium is slowly added to a potassium hydroxide anhydrous melt, 
in a 1 mole to 1 mole stoichiometric ratio. Elemental hydrogen is evolved 
and substantially increases the pressure within the system. Potassium will 
react with oxygen, nitrogen, carbon dioxide, etc. Therefore, the use of 
reduced pressure is necessary to reduce the reaction between molten 
potassium and the inert atmosphere. Neon, helium, argon, (group 8 gases) 
can be used in lieu of reduced pressure. 
The system is opened, hydrogen is allowed to exit the process system and 
collected. Following the removal of the hydrogen, the reduced pressure is 
again employed. The potassium oxide formed during the evolution of 
hydrogen, is decomposed, principally by thermal means alone. The elemental 
potassium formed along with potassium peroxide and potassium superoxide 
(K.sub.2 O.sub.2) is gradually distilled prior to the thermal-reduced 
pressure decomposition of potassium peroxide. Only the potassium is 
distilled. The distilled liquid/gas potassium and the hydrogen are 
converted into potassium hydride at temperatures below 380.degree. C. 
under atmospheric pressure or super-atmospheric pressure. 
Following removal and separation of hydrogen and potassium, an amount of 
water less than the stoichiometric amount, such as 15% less than 
stoichiometric potassium peroxide (KO.sub.2) to form potassium hydroxide 
and oxygen. This oxygen is separately removed from the process system. The 
hydrogen, potassium are separated from the process system separately from 
the oxygen removed. 
The surplus of elemental potassium removed from the system above that 
predicted from the formation of potassium peroxide KO.sub.2 indicates that 
some potassium superoxide K.sub.2 O.sub.2 has been formed. 
The potassium and the potassium hydride are again reacted with water to 
form additional hydrogen. 
1 M (56.11 Grams) of potassium hydroxide (85-86% purity) was brought to 
380.degree. C. under 10 MM pressure. Water was distilled as progressively 
lower potassium hydroxide hydrates were formed. A solid potassium 
hydroxide then melts at 360.degree. C..+-.5.degree. C. One mole elemental 
potassium was melted under an argon atmosphere and added drop by drop to 
the melt of potassium hydroxide. 
When the evolution of hydrogen increased the pressure of the evacuated 
system to atmospheric or super-atmospheric pressure, the system is opened 
and hydrogen is exited from the system. When the hydrogen has been 
removed, as evidenced by the stabilizing of system pressure at slightly 
above atmospheric reduced pressure is again used preferably at 
approximately 1 MM Hg. Elemental potassium is distilled from the system. 
Slightly over one mole of potassium is distilled. 
The elemental potassium is reacted with the hydrogen at temperatures 
between 260.degree. C.-380.degree. C. to form solid potassium hydride. 
Potassium hydride is soluble is excess molten potassium. 
Slightly less than 1 M of water is added to the mix. The amount of water is 
reduced below 1 M by the same ratio that excess potassium had been removed 
from the system, to the potassium peroxide-superoxide remaining in the 
reaction vessel. Oxygen is evolved and potassium hydroxide is formed. 
EXAMPLE VIII 
This example shows the high temperature production of hydrogen. In 
conducting this run, one mole of commercial potassium hydroxide is heated 
to 779.degree. C. under reduced pressure or under an inert gas atmosphere 
(helium, neon, argon, etc.). 
Water is removed as the series of potassium hydroxide hydrates contained 
therein is decomposed to lower hydrates with the rise in temperature. At 
360.degree. C..+-.5.degree. C., potassium hydroxide forms an anhydrous 
melt. 
Additional water, above that of the hydrates, is given off by the partial 
thermal decomposition of potassium hydroxide to potassium oxide and water. 
Above 360.degree. C..+-.5.degree. C., there is a progressive decomposition 
of potassium oxide to potassium peroxide and elemental potassium. 
The potassium thus produced reacts with the water vapor to form potassium 
hydroxide and water and with potassium hydroxide to form hydrogen and 
potassium oxide (Equations 20 and 21). 
An equilibrium is reached when approximately 13% of the potassium and 
hydrogen have been distilled. Thereafter the decrease of the hydrogen 
content of the process system allows further decomposition of the 
potassium hydroxide-potassium oxide-potassium peroxide to potassium 
without recombining of potassium with oxygen due to the diminished water 
content of the system. 
88% of the potassium is recovered in 21/2 hours and about 88% of the 
hydrogen is also recovered. 
The reaction time is accelerated to 1 hour by the addition of 1/2 Mole of 
potassium to the anhydrous melt of potassium hydroxide. 
EXAMPLE IX 
One mole of hydrogen produced as above indicated was reacted with the 
acetylene produced at 360.degree. C. to form ethene. A second mole of 
hydrogen was supplied to hydrogenate the ethene to ethane. 
One mole of ethane was reacted in the gaseous phase with one mole of 
chlorine to form ethyl chloride. The ethyl chloride was collected and 
reacted with potassium by refluxing in absolute ether under Wurtz-Fittig 
Reaction conditions to form butane. The butane thus produced was reacted 
in the same manner with chlorine gas to form butyl chloride which in turn 
was reacted with potassium metal produced as above indicated also under 
Wurtz-Fitting Reaction conditions to form hydrocarbons having octane 
ratings suitable for use in internal combustion engines. 
Suitable apparatus for carrying out the present process as shown in the 
drawing comprises a melting chamber or retort 10 made of corrosion 
resistant metal or alloy such as nickel or tungsten metal which can be 
heated under reduced pressure. A tap 12 for molten metal is formed or 
secured at the bottom of the chamber. A vacuum line 14 connects the 
chamber to a pump (not shown) capable of exhausting the chamber to a 
pressure of 1/2 to 26 mm Hg. pressure. Connected between the chamber and 
the vacuum line 14 are three traps A,B,C, for condensing and returning 
reformed oxides or sulfides and elemental condensed alkali metal to 
chamber 10 through stopcocks 16. A fourth trap 18 is provided remote from 
melting chamber 10 for collection of sulfur which can be removed through 
outlet 20. Suitable means (not shown) are provided on or around the 
melting chamber 10 to heat it up to 680.degree. C. and the areas remote 
from the chamber to gradually decreasing temperatures of 450.degree. C. to 
160.degree. C. 
A ring 21 fitted within slot 22 is provided on the metal chamber 10 to pick 
up metal from condensed vapors passing through the vacuum line 14. 
It is to be understood that the foregoing specific examples are presented 
by way of illustration and explanation only and that the invention is not 
limited by the details of such examples. 
The foregoing is believed to so disclose the present invention that those 
skilled in the art to which it appertains can, by applying thereto current 
knowledge, readily modify it for various application. Therefore, such 
modifications are intended to fall within the range of equivalence of the 
appended claims.