United States Patent ‘[19] [11] 4,441,923 Swanson [45] Apr. 10, 1984

{54] INTEGRATED PROCESS USING 3,938,988 2/1976 Othmer ...... 75/10R NON-STOICHIOMETRIC SULFIDES OR OXIDES OF POTASSIUM FOR MAKING FOREIGN PATENT DOCUMENTS LESS ACTIVE METALS AND 590274 7/ 1947 United Kingdom ...... 75/66 HYDROCARBONS OTHER PUBLICATIONS [76] Inventor: Rollan Swanson, 220 California St., Mellor, “A Comprehensive Treatise on Inorganic and Santa Monica, Calif. 90403 Theoretical Chemistry”, 1922, pp. 445-451. [21] Appl. No.: 343,977 “Comprehensive Inorganic Chemistry”, Pergamon Press, 1973, pp. 371-373. [22] Filed: Jan. 29, 1982 Primary Examiner—Edward J. Meros Related US. Application Data Attorney, Agent, or Firm—-Albert F. Kronman [63] Continuation of Ser. No. 169,281, Jul. 16, 1980, aban [57] ABSTRACT doned, which is a continuation-in-part of Ser. No. Disclosed is a combinative integrated chemical process 706,795, Jul. 19, 1976, abandoned, and Ser. No. 3,590, Jan. 15, 1979, abandoned. using inorganic reactants and yielding, if desired, or ganic products. The process involves ?rst the produc [51] Int. Cl.3 ...... C21B 15/00; C22B 5/02; tion of elemental potassium by the thermal or thermal C22B 26/10 reduced pressure decomposition of potassium oxide or [52] US. Cl...... 75/28; 75/20 R; potassium sul?de and distillation of the potassium. This 75/66; 75/67 R; 75/69; 75/71; 75/72; 75/77; elemental potassium is then used to reduce ores or ore 75/86; 423/414; 423/560; 423/561 A; 423/567 concentrates of copper, zinc, lead, magnesium, cad A; 423/641; 423/657; 585/500; 585/534; mium, iron, arsenic, antimony or silver to yield one or 585/638; 585/700; 585/733 more of these less active metals in elemental form. Pro [58] Field of Search ...... 423/414, 560, 561 A, cess potassium can also be used to produce hydrogen by 423/567 A, 641, 657, 179, 200, 203, 414; 75/28, reaction with water or potassium hydroxide. This hy 71, 72, 77, 86, 20 R, 66, 67 R, 69, 21, 62, 65 R; drogen is reacted with potassium to produce potassium 585/500, 534, 638, 700, 733 hydride. Heating the latter with carbon produces potas [56] References Cited sium acetylide which forms acetylene when treated with water. Acetylene is hydrogenated to ethene or U.S. PATENT DOCUMENTS ethane with process hydrogen. Using Wurtz-Fittig re 1,034,320 7/ 1928 Specketer ...... 75/66 action conditions, the ethane can be upgraded to a mix 1,872,611 8/1932 Thurm 75/66 ture of hydrocarbons boiling in the fuel range. 2,028,390 1/1936 Hanson 75/66 2,852,363 9/1958 Adams ...... 75/66 13 Claims, 1 Drawing Figure

4,441,923 1 2 nent for disclosing processes for the production of alkali INTEGRATED PROCESS USING metals or alloys thereof. NON-STOICHIOMETRIC SULFIDES OR OXIDES As will be seen hereinafter, none of these disclose, OF POTASSIUM FOR MAKING LESS ACI‘IV E hint, or suggest in any manner whatsoever applicant’s METALS AND HYDROCARBONS unique, novel and unobvious process. REFERENCE TO CO-PENDING APPLICATION BRIEF DESCRIPTION OF THE DRAWING This application is a continuation of application Ser. The single FIGURE accompanying this speci?cation is a diagrammatic representation of one type of appara No. 169,281 ?led July 16, 1980, now abandoned, which l0 is a continuation-in-part of co-pending applications Ser. tus for carrying out the thermal reduction of the present No. 706,795, ?led July 19, 1976, now abandoned, and of process. Ser. No. 003,590, ?led Jan. 15, 1979, and now aban SUMMARY OF THE INVENTION doned. , It has been discovered and forms the substantial con BACKGROUND OF THE INVENTION 15 ceptual basis of this invention that extraordinary pro This invention relates to a chemical process which cess and product bene?ts relating to the winning of comprises the production of elemental potassium and potassium and other metals and to the formation of the subsequent reaction of said elemental potassium organic products with potassium thus obtained can be with other reactants, including various metallic ores, achieved by the practice of this invention. Relatively such as those of magnesium, lead, zinc, copper, arsenic, low temperatures can be used in the process and high antimony or silver to release said metals from their yields achieved therewith. Furthermore, the economics naturally occuring forms, in elemental state, or with of the process are much improved. water to produce potassium hydroxide and hydrogen Fundamentally, the invention resides in an integrated and further reacting additional elemental potassium 25 progress for producing potassium metal from its non with said potassium hydroxide to produce more hydro stoichiometric oxide or sul?de and using this metal to gen and a thermally unstable potassium oxide which produce less active metals and hydrocarbons by the decomposes into potassium and potassium peroxide or steps of: potassium superoxide, optionally reacting said hydro l. thermally decomposing potassium oxide or sul?de gen and potassium to produce potassium hydride to 30 substantially in the absence of water into potassium store the produced hydrogen or to further react said metal and to form, respectively, potassium peroxide or potassium hydride with carbon to produce potassium potassium superoxide, and potassium disul?de; and re acetylide and optionally using additional hydrogen to covering the potassium metal; saturate the carbon bonds of these unsaturated com 2. providing a portion of the thus formed potassium in pounds, utilizing process potassium or potassium hy 35 the molten or vapor state and reacting same with at least dride to catalyze the hydrogenation. one oxide or sul?de of magnesium, copper, calcium, silver, lead, zinc, antimony, cadmium, iron, arsenic and OBJECTIONS AND FEATURES OF THE mixtures thereof to displace the metal from said oxide or INVENTION sul?de followed by recovery of said metal; An object of this invention is to provide a low-cost, 3. reacting another portion of the previously obtained high-yield process for producing elemental potassium potassium with water to form hydrogen and potassium from potassium oxides, or sul?des. oxide; Another object of the invention, is the utilization of 4. utilizing the previously formed hydrogen to pre process potassium in the manufacture of carbides, ace pare an organic compound by either: tylides, hydrogen, hydrides, hydrogen peroxide, oxy 45 (a) reacting said hydrogen with potassium obtained gen, potassium hydroxide, less active metals, saturated by step 1, above, at a temperature of between 250° and and unsaturated hydrocarbons so as to provide the 300° C. to form potassium hydride, reacting said potas aforementioned products and by-products in one inte sium hydride with carbon to form potassium acetylide and reacting said acetylide with water to produce acet grated process leading to their manufacture at lower 50 costs than heretofore attainable. ylene and KOH; then hydrogenating said acetylene to form ethane and ethene; or, DESCRIPTION OF PRIOR ART DISCLOSURES (b) using said hydrogen to hydrogenate carbon in the There are numerous patents on techniques for pro presence of a catalyst to form methane. ducing metals from their salts and for obtaining hydro 55 The organic compounds, ethane or methane, can be gen as a by-product. Accordingly, this background reacted with a halogen in manner known per se to form disclosure is restricted to those which are believed most an alkyl halide which can then be condensed with so relevant. dium or process potassium to form hydrocarbons boil Very basic is US. Pat. No. 2,852,363, which describes ing in the fuel range under Wurtz-Fitig reaction condi a method for preparing potassium, cesium or rubidium tions. by heating a hydroxide of these metals with zinc in an In subsidiary reactions, intermediate compounds are inert atmosphere at a temperature above the boiling formed and recycled to produce additional potassium point of the particular alkali metal under the pressure for reuse in the process. used in the reactor and recovering the free alkali metal. DESCRIPTION OF PREFERRED While hydrogen also is produced in that process, no 65 suggestion is made about using it. EMBODIMENTS US. Pat. Nos. 1,872,611; 1,034,320; 2,028,390; The process of the invention comprises the following 3,938,985; and British Pat. No. 590,274 also are perti equations: 4,441,923 '3 4 temperature or below 206° C., the melting point of

K255. v v‘ = 1" .' 1' K10 ssotssr c./10 mm .19..1? + 5 K202 The process of this invention utilizes the lack of ther mal stability of the non-stoichiometric sul?de and oxide \ compounds of potassium, to produce elemental potas sium and a variety of potassium compounds, thereafter utilizing this elemental potassium or some of the potas sium compounds to continually reform these sul?des and oxides of potassium by reaction with water, metal 10 lic ores, etc. 3' K l'iHz <3s0°c. KH Referring to the above equations: Equations 1, 4 and 14, are the basic equations of this invention, whereby elemental potassium is formed by thermal decomposi 4‘ K20 7 380° 0.420" c.‘ 15 K + 4 K02 tion of potassium sul?de into potassium disul?de and said elemental potassium and the decomposition of po " 5.: Kn + 2c <38“, C KHC2 (in molten K) tassium oxide into elemental potassium and potassium peroxide or potassium superoxide. Equation'No. 15 illustrates the decomposition of po 6. =KHC2 + H20 ---9 021-12 + KOH tassium disul?de into potassium sul?de and sulfur, while 20 equation No. 16 illustrates the decomposition of potas 7.: "K + lino-9x20 + 5H; sium trisul?de, Qrhigher polysul?de, into potassium sul?de and potassium disul?de. Equations-No. 19, 20 and 21, illustrates the hot water hydrolysis of potassium 8- C2112 + H2 W CzH4 w CZHG polysul?de into potassium sul?de hydrate and potas-' 25 sium pentasul?de. The heat-reduced pressure decompo; sition of potassium trisul?de as illustrated in equation No. 16 are equally applicable to potassium tetrasul?de, potassium pentasul?de and potassium hexasul?de. 9a. Equation No. 6, 9 and 9a illustrate the decomposition of 30 potassium peroxide and potassium superoxide.- Potas sium peroxide is decomposed into elemental potassium .10. K102 + 2Hzo KOH + H202 and elemental oxygen. Potassium superoxide(KO2) is decomposed into potassium peroxide K202 and oxygen. 11. K+R,,Y[r->KxYx+R.'This reaction is carried out At temperatures above 780° C., K202 begins to decom with molten potassium, at temperatures above 65° C. or 35 pose to K and O2. , ' ‘ with potassium vapor at temperatures above 780° C. Y Potassium does not unite with oxygen or sulfur in the is either sulfur'or'oxygen and R is magnesium, zinc, absence of water vapor. Removal of water vapor from cadmium, lead, iron, arsenic, antimony or silver or cop the process system will greatly reduce the tendency of per. " - potassium and either sulfur or oxygen to reunite follow 12. C2H5X+C2H5X+2 K=C4H10+2 KX, wherein ing the thermal reduced pressure decomposition of X is chlorine‘ or bromine. I potassium oxide or potassium sul?de. Potassium hydroxide, potassium oxides, potassium sul?des and potassium hydrosul?des are deliquescent 13. c + 2 H2 zsgi'c CH4 and have low aqueous tensions. Potassium sul?des and 45 potassium oxides are non-stoichiometric compounds with de?ciencies in the anion sub-lattice. Water, hydro l4." K25 K + t K2S2 gen, 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 7 1s. KZSZW K25 + s reaction with elemental potassium to produce potas sium hydroxide and hydrogen. Additional potassium 16. K2S3—->K2S+k2S2 at 21, mm Hg pressure at 360° C. will react with this potassium hydroxide to form addi 17. K2S+H2O->KOH+KHS Additional water tional hydrogen and potassium oxide. In the case of the gives a reversible reactions KHS-l-H2O—>KOH+H2S potassium oxides, water will also react directly with 18. Beginning 315° C. HzS—>H2+S 55 potassium oxide to form potassium hydroxide. At the l9. 4 KgSg-l-B H20—>3K2S+X.H20+K2S5 (in a beginning of the thermal decomposition of the potas closed system). - sium sulfidesor oxides, the elemental potassium will 20. 4 K2S3+X H2O—>2 K2S5+2K2S.X.H20. The react with this potassium hydroxide to form additional minimum amount of water (X) is that required to form hydrogen and potassium oxides. At the 350° C. decom the hydrate of potassium sul?de which exists at the 60 position temperature of potassium oxide, the elemental temperature at which this hydrolysis occurs. potassium will unite with some of the hydrogen pro duced and form potassium hydride. As the temperature‘ All of these hydrolysis decomposition reactions are is elevated to above 380° C., potassium hydride begins carried out in a closed system and at temperatures to dissociate. ' Y ' above 60° C. and below the critical temperature of 65 The elemental potassium, produced from the decom- ’ . water. The minimum amount of water (x) required for position of potassium sul?de or potassium oxide, is solu these hydrolysis reactions is that which constitutes the ble inthe solids remaining until'temperature-pressure hydrate of potassium sul?de which exists at the selected conditions above those necessai'yttov boil'elernental po 4,441,923. 5 6 tassium are reached. As shown byvEquations 15-21, I metric, to produce potassium hydroxide and hydrogen, have observed that potassium sul?de, prepared by the as shown in equation 2a. Additional potassium and the reduction of the sulfur content'of potassium pentasul potassium hydroxide at temperatures above 360° C. will ?de or any polysul?de with a sulfur content of two or produce additional hydrogen and form the unstable greater, can be decomposed to elemental potassium and potassium ‘monoxide (equation 2). The potassium mon sulfur at 780° C. in a twenty-four hour period. Potas oxide KZO is then decomposed to potassium and oxygen sium pentasul?de melts at 206° C. and decomposes to or potassium and potassium peroxide or potassium su potassium tetrasul?de and sulfur at temperatures begin ning at 300° C. At 206° C., potassium pentasul?de melts peroxide by one of the processes disclosed, to continu are essentially anhydrous. Potassium tetrasul?de melts ously produced hydrogen (Equation 4). A part of the at 145° C., Potassium trisul?de melts at 279° C. and potassium peroxide or potassium superoxide can be potassium disul?de melts at 470° C. Any of these com dissolved in an amount of water less than the stoichio pounds produce an anhydrous melt at temperatures metric amount, such as 15% less than stoichiometric to above their melting points. It is easier to form these produce additional potassium hydroxide and hydrogen anhydrous melts under reduced pressure. The reduced peroxide (Equation 10). The unstable hydrogen perox pressures allow the water of hydration to be removed ide can then be used as a source of oxygen. Potassium more easily to form anhydrous melts. The temperature superoxide and potassium peroxide can also be used as should be at least as high as the melting point of the sources of oxygen at temperatures above 653° C. for the particular potassium polysul?de and the reduced pres superoxide or above 780° C. for the peroxide, as shown sures should be residual pressures of from 1 mm Hg to 20 by Equation 9 and 9A. 50 mm Hg. As these potassium polysul?des are decom At any temperature above its melting point, 65° C., posed into lower sulfur content polysul?des, the tem potassium in liquid or vapor form will reduce the ores perature-reduced pressure conditions should be ade of magnesium, copper, silver, lead, zinc, antimony, ar quate to distill the sulfur. Sulfur boils at 445° C. at 760 senic, cadmium, and mixtures thereof to the free metal mm Hg pressure, at 185° C. at 1 mm Hg pressure. 25 and form potassium oxide or form either the sul?des or Potassium trisul?de decomposes to a mixture of po oxides of potassium by the liberation of elemental cop tassium monosul?de and disul?de at 350° C. at 0.05 per, silver, lead, zinc, calcium, antimony, arsenic, cad Torr. Potassium disul?de decomposes to potassium mium, etc. depending upon whether these metals were sul?de and sulfur at 650° C. at 0.05 Torr and anhydrous in oxide or sul?de form in their naturally occurring potassium sul?de decomposes to elemental potassium 30 and sulfur at 780° C. while hydrated potassium sul?de mixed ores or ore concentrate. requires 840° C. to decompose to sulfur and potassium. When elemental potassium has been used to form Without reduced pressures, potassium disul?de is the hydrogen by the decomposition of water or potassium most stable union of potassium and sulfur thermally, hydroxide or by the reduction of hydrogen sul?de, with potassium sul?de decomposing to elemental potas 35 derived from the decomposition of the hydrolysis prod sium and potassium disul?de at temperatures above 780° uct, potassium hydrosul?de, from potassium sul?de, this C. for anhydrous potassium sul?de or 840° C. for hy hydrogen may be stored as potassium hydride by reac drated potassium sul?de. tion of said hydrogen with additional elemental potas For practical purposes, the decomposition of potas sium at temperatures between 250° C. and 360° C. Po sium disul?de occurs at 883° C. at 10 mm Hg pressure. tassium hydride is miscible in molten‘ potassium. At this temperature pressure, potassium disul?de is Potassium hydride dissolved in molten potassium rapidly decomposed into its elements. The alternate reacts directly with carbon and graphite to produce source of potassium from potassium sul?des is the de potassium acetylide. Potassium acetylide reacts with composition of potassium disul?de into potassium sul water to produce acetylene. ?de at reduced pressures of 1 mm Hg at 78° C. and the The acetylene produced can be reacted with addi subsequent decomposition of potassium sul?de into its tional process hydrogen, utilizing molten potassium or elements under the same conditions. potassium hydride as the catalyst to form ethene or Where the present process starts with potassium ox ethane. The amount of hydrogen present will determine ide, potassium monoxide is decomposed into elemental the formation of ethene or ethane. The temperature of potassium and potassium peroxide or potassium super 50 this reaction is any temperature above the melting point oxide at temperatures above 350° C., however, the po of potassium, 65° C. tassium is not readily available for extraction from this Hydrogen produced in the present invention can be mixture, at these temperature. At pressures of 5 ><10—4 at 360° C. some elemental potassium can be extracted by directly combined with carbon to form methane in the distillation. At temperatures above the melting point of 55 presence of a suitable catalyst such as nickel at tempera potassium peroxide, 490° C., potassium can be extracted tures of 250° C. by the Raney-Nickel method. Elemen by distillation at pressures 10 mm Hg. At temperatures tal potassium or potassium hydride dissolved in potas of 780° C., almost all of the potassium can be extracted sium may be used as the catalyst at temperatures be by distillation at 10 mm Hg. The elemental potassium tween l80° C. and 360° C. decomposes into potassium peroxide and potassium and EXAMPLE I the potassium peroxide is then melted at 490° C. to make the mix anhydrous. By the removal of the water the This example illustrates the preparation of potassium formation of hydrides, hydroxides and hydrogen is metal from K20 present in an ore. retarded and this allows the decomposition of the potas In conducting this example, an ore containing 10 kg sium oxides into their elements of formation. 65 of K20 was placed in an autoclave and heated to 883° The potassium, produced by the present invention, is under a reduced pressure of 10 mm of Hg. 4.1 kg of then reacted with an amount of water less than the, potassiummetal was distilled, leaving behind 5.9 kg of stoichiometric amount, such as 15% less than stoichio¢ 4,441,923 7 8 200 grams of potassium were collected. , EXAMPLE II ~EXAMPLE V This example illustrates the reactions of Equations 29, 11-12. As per Equation 11, the potassium produced in Ex Technical grade ?akes of potassium hydroxide of ample IV was melted under 50 mm of Hg pressure and 90% purity were heated to 380° C. A reduced pressure decanted from the sulfur. of 50 mm Hg was used to dehydrate said flakes during The potassium was divided into four ?fty gram sam the making of an essentially anhydrous melt. ples and was used in its molten form. Thereafter, the use of reduced pressures was discon One ?fty gram sample was used to smelt 54 grams of tinued and with the temperature maintained at 380° C., - 0 a lead sul?de concentrate containing 73% lead. The elemental potassium was added to the melt. Hydrogen smelting was done at 70° C. After the reaction had was evolved. The stoichiometry was one mole of potas~ ceased (in approximately three minutes) the tempera sium hydroxide, derived from 62.2 grams of 90% tech ture was elevated to 330° C. and the molten lead was nical ?akes of KOH, and one mole (39.1 g) of elemental tapped from the lighter material ?oating on the lead potassium. 15 surface. The hydrogen evolved was passed into molten potas One ?fty gram sample was used to smelt 41.6 grams sium maintained at 280° C. to form potassium hydride. of zinc sul?de concentrate, containing 50% zinc. The One and one-half moles of potassium were used to take temperature was 70° C. The reaction required approxi up the one mole of hydrogen and to form a liquid con mately two minutes. The temperature was elevated to sisting of a solution of potassium hydride in molten 20 440° C. and the liquid'molten zinc was tapped from potassium. below the material floating on the surface of the zinc. The potassium hydride solution containing one mole One ?fty gram sample was used to smelt 50 grams of of KH in molten potassium was treated at 350° C. in the a copper sul?de concentrate containing 86% chalcopy absence of air, nitrogen, or carbon dioxide with two rite (CuFeSg). The reaction was carried out at 70° C. moles of carbon (graphite) to form potassium acetylide. 25 Iron and copper were produced. The iron was magneti The mixture was carefully and slowly added to one cally separated from the copper. The copper was and a half mole of water to form one mole of acetylene melted and separated from the material ?oating on the and hydrogen as volatiles and form a solution of potas copper surface. sium hydroxide. The gases produced, hydrogen and One ?fty gram sample was used to smelt 25 grams of acetylene, occupied 3.2 liters at 15° C. at atmospheric magnesium oxide at 360° C. The reaction required six pressure, indicating conversion to one mole of acety minutes. Elemental magnesium was produced. ' lene and one-half mole of hydrogen. In all of these samples, the residual potassium was The potassium oxide, formed by the reaction of potas distilled from the metals produced at pressures adequate sium and potassium hydroxide, was heated to 500° C. to distill potassium but too low to volatilize the other under a reduced pressure of 10 mm Hg. After two hours metal. The three sul?de samples were separated from of being maintained at 500° C. under 10 mm Hg., the their carrying and largely inert gangue by dissolving mixture was heated to 883° C. and one and one half the potassium sul?des produced in this smelting opera moles of potassium were condensed by selectively cool tion in small quantities of water. The solids were then ing the emitting gas stream in three hours and twenty separated from the liquid by ?ltration. minutes. Sulfur was added to the ?ltrate and the ?ltrate were dehydrated at 500° C. under 50 mm Hg. pressure. The EXAMPLE III resulting anhydrous melt was then subjected to temper One mole of potassium produced in Example I was atures of 883° C. under 10 mm pressure to reform potas treated with water as shown in Equation 2A to provide sium vapor and sulfur vapor which were then con additional hydrogen gas and potassium hydroxide. 45 densed. This reformation of the potassium completed One mole of potassium superoxide produced in Ex the cycle. ample VI was added to two moles of water at 95° C. to The potassium oxide produced in the magnesium produce one mole of hydrogen peroxide and two moles smelting was directly recycled to potassium by heating of potassium hydroxide, as illustrated by Equation 10. the gangue and the potassium oxide to 883° C. under 10 This example thus shows the recovery of nearly all mm Hg. Some carbon dioxide was distilled prior to the the potassium in the forms originally used; i.e. elemental distillation of the potassium. The carbon dioxide was potassium and potassium hydroxide. taken up in potassium hydroxide as it emitted the sys tem. The potassium was largely recovered after the EXAMPLE IV carbon dioxide had been removed from the system. A This example shows the thermal decomposition of 55 second sample showed that the carbon dioxide could be KZS into potassium, as shown by Equation 14. removed by pre-heating the magnesium oxide under Two pounds of K28 were heated to 780° C. under a reduced pressures prior to reacting same with potas pressure of 50 mm to remove water. The pressure was sium. The potassium produced by the recycling of the then reduced to 5 X 10-4 at that temperature. potassium oxides was condensed by cooling and used to Sulphur was distilled and condensed in a liquid nitro 60 smelt additional magnesium ore. gen series of traps. . _ EXAMPLE VI When the distillation rate of sulfur decreased, the temperature was elevated to 883° C. The distillation This example illustrates the reactions of Equation 4,5, chamber was left with potassium sulfate, identi?ed by 9-10 and 13. the barium analytical reaction, with the potassium and 65 Hydrogen, produced by this invention, was used to sulfur condensed in fresh traps cooled by liquid nitro hydrogenate carbon, (graphite) at 250° C. in the pres gen. The potassium and the sulfur did not reunite inthe ence of molten potassium (potassium hydride dissolved absence of water vapor. in molten potassium (Raney-Nickel, also can be used). 4,441,923 10 No pressures were used other than the pressure of the the process system. The hydrogen, potassium are sepa hydrogen issuing from the process system. A total of rated from the process system separately from the oxy 100 grams of carbon was hydrogenated to methane in gen removed. one-half hour by the use of one mole of potassium and The surplus of elemental potassium removed from the one mole of potassium hydroxide by continually recy system above that predicted from the formation of po cling these reagents. This recycling consisted of dis tassium peroxide K02 indicates' that some potassium solving residual potassium oxides in water and then superoxide K202 has been formed. reacting this potassium hydroxide with potassium pro The potassium and the potassium hydride are again duced by the thermal decomposition of potassium ox reacted with water to form additional hydrogen. ides at ‘883° C. under 10 mm Hg (Equation 1 and 2). 1 M (56.11 Grams) of potassium hydroxide (85-86% A step to reduce the oxygen content of the system by purity) was brought to 380° C. under 10 MM pressure. decomposing any potassium superoxide that might be Water was distilled as progressively lower potassium produced was carried out by heating the potassium hydroxide hydrates were formed. A solid potassium oxides to 653° C. prior to decomposition at 883° C. Care hydroxide then melts at 360° C.i5° C. One mole ele was taken to condense potassium and allow the oxygen mental potassium was melted under an argon atmo to escape the process system. This was done to avoid sphere and added drop by drop to the melt of potassium the production of potassium carbonyl. hydroxide. The undecomposed residue was used to form potas When the evolution of hydrogen increased the pres sium hydroxide and to form hydrogen peroxide by sure of the evacuated system to atmospheric or super reaction with water (Equation 10). Care was taken not 20 atmospheric pressure, the system is opened and hydro to allow hydrogen peroxide or any oxygen arising from gen is exited from the system. When the hydrogen has the decomposition of hydrogen peroxide to enter the been removed, as evidenced by the stabilizing of system smelting system. pressure at slightly above atmospheric reduced pressure is again used preferably at approximately 1 MM Hg. EXAMPLE VII 25 This example shows the production of elemental Elemental potassium is distilled from the system. potassium and a mixture of potassium peroxide and Slightly over one mole of potassium is distilled. potassium superoxide by thermal decomposition of po The elemental potassium is reacted with the hydro tassium oxide; next reacting potassium peroxide and gen at temperatures between 260° C.—380° C. to form superoxide with a stoichiometric quantity of water to 30 solid potassium hydride. Potassium hydride is soluble is form potassium hydroxide and oxygen; then reacting excess molten potassium. elemental potassium with potassium hydroxide to form Slightly less than 1 M of water is added to the mix. elemental hydrogen and to reconstitute potassium oxide The amount of water is reduced below 1M by the same for recycling. ratio that excess potassium had been removed from the This decomposition can be practiced in the 360'‘ 35 system, to the potassium peroxide-superoxide remaining C.—380° C. temperature range with appropriate addition in the reaction vessel. Oxygen is evolved and potassium and withdrawal of product, over or at a temperature hydroxide is formed. . range below 653° C. or at a temperature of over 779° C. EXAMPLE VIII’ In conducting this run, potassium hydroxide is heated to 370° C. in the absence of air under a reduced pressure 40 This example shows the high temperature production of 1-10 MM Hg. Elemental molten potassium is slowly of hydrogen. In conducting this run, one mole of com added to a potassium hydroxide anhydrous melt, in a 1 mercial potassium hydroxide is heated to 779°C. under mole to 1 mole stoichiometric ratio. Elemental hydro reduced pressure or under an inert gas atmosphere (he gen is evolved and substantially increases the pressure lium, neon, argon, etc.). within the system. Potassium will react with oxygen, 45 Water is removed as the series of potassium hydrox nitrogen, carbon dioxide, etc. Therefore, the use of ide hydrates contained therein is decomposed to lower reduced pressure is necessary to reduce the reaction hydrates with the rise in temperature. At 360° C.i5° between molten potassium and the inert atmosphere. C., potassium hydroxide forms an anhydrous melt. Neon, helium, argon, (group 8 gases) can be used in lieu Additional water, above that of the hydrates, is given of reduced pressure. 50 off by the partial thermal decomposition of potassium The system is opened, hydrogen is allowed to exit the hydroxide to potassium oxide and water. Above 360° process system and collected. Following the removal of C.i5° C., there is a progressive decomposition of po the hydrogen, the reduced pressure is again employed. tassium oxide'to potassium peroxide and elemental po The potassium oxide formed during the evolution of tassium; hydrogen, is decomposed, principally by thermal means 55 The potassium thus produced reacts with the water alone. The elemental potassium formed along with po vapor to form potassium hydroxide and water and with tassium peroxide and potassium superoxide (K202) is potassium hydroxide to form hydrogen and potassium gradually distilled prior to the thermal-reduced pres oxide (Equations 20 and 21). sure decomposition of potassium peroxide. Only the An equilibrium is reached when approximately 13% potassium is distilled. The distilled liquid/ gas potassium 60 of the potassium and hydrogen have been distilled. and the hydrogen are converted into potassium hydride Thereafter the decrease of the hydrogen content of the at temperatures below 380° C. under atmospheric pres process system allows further decomposition of the sure or super-atmospheric pressure. . potassium hydroxide-potassium oxide-potassium perox Following removal and separation of hydrogen an ide to potassium without recombining of potassium with potassium, an amount of water less than the stoichio 65 oxygen due to the diminished water content of the sys metric amount, such as 15% less than stoichiometric tem. potassium peroxide (K02) to form potassium hydroxide 88% of the potassium is recovered in 2,‘. hours and and oxygen. This oxygen is separately removed from about 88% of the hydrogen is also recovered. 4,441,923. 11 t 12 The reaction time is’ accelerated to 1 hour by the nesium,.-,copper, calcium, silver, lead, zinc, anti addition of % Mole of potassium to the anhydrous melt mony, cadmium, iron, arsenic and mixtures thereof of potassium hydroxide. . to displace the metal from said oxide or sul?de and recovering the thus displaced less active metal ' EXAMPLEVIX 5 from residual potassium or potassium compounds; One mole'of hydrogen produced as above indicated 3. reacting another portion of the previously obtained was reacted’ with the acetylene- produced at 360° C. to potassium with water to form hydrogen, potassium form ethene. A second mole of hydrogen was supplied oxide and potassium hydroxide; to hydrogenate the ethene to ethane. ' 4. utilizing a portion of said hydrogen obtained in One mole of ethane was reacted in the gaseous phase 10 Step 3 to prepare a hydrocarbon by either: with one mole of chlorine to form ethyl chloride. The (a) reducing said hydrogen with potassium metal ethyl chloride was collected and reacted with potas-1 obtained in step 1, above, at a temperature of sium by re?uxing in absolute ether under Wurtz-Fittig between 250° C. and 300° C. to form potassium Reaction ‘conditions to form butane. The butane thus hydride, next reacting said potassium hydride produced was reacted in the same manner with chlorine I with carbon to form potassium acetylide, synthe gas to form butyl chloride which in turn was reacted sizing acetylene and KOH by contacting said withpotassium metal produced as above indicated also acetylide with water; hydrogenating said acety under Wurtz-Fitting Reaction conditions to form hy lene to ethene and ethane with hydrogen ob drocarbons having octane ratings suitable for use in tained in step 3, above, or . internal combustion engines. (b) using said hydrogen to hydrogenate carbon in Suitable’ apparatus for carrying out the present pro the presence of a hydrogenation catalyst to form cess as shown in the drawing comprises a melting cham methane. - > . beror retort 10 made of corrosion resistant metal or 2. The process of claim 1 in which the hydrogenation alloy such as nickel or tungsten metal which can be catalyst consists of a portion of the potassium obtained heated iinder reduced pressure. A tap 12 for molten 25 in step 1 and the hydrogenation temperature ranges meta‘l'is' formed or secured at the bottom of the cham from 180° to 360° C. . - r ber. A vacuum line 14 connects the chamber to a pump 3. The process of claim 1, comprising the further (not shown) capable of exhausting the chamber to a step(s) of treating a portion of the potassium obtained in pressure of 5 to 26 mm Hg. pressure. Connected be step 1 with water to form hydrogen. , , _. tween the chamber and the vacuum line 14 are three 4. The process of claim 1, comprisedby the further traps A,B,C, for condensing and returning reformed steps of reducing a portion of potassium obtained in step oxides or sul?des and elemental condensed alkali metal 1 with potassium hydroxide produced in step .3, thereby to chamber 10 through stopcocks 16. A fourth trap 18 is forming potassium oxide and hydrogen for reuse in the provided remote from melting chamber 10 for collec process. tion of sulfur which can be removed through outlet 20. 35 5. The . process of claim 1, wherein I the potassium Suitable means (not shown) are provided on or around oxide in step 1 is heated to above 350° C.Yunder a pres the melting chamber 10 to heat it up to 680° C. and the sure from 10 mm Hg to atmospheric. ' areas remote from the chamber to gradually decreasing 6. The process of claim 1, wherein the sul?de pro temperatures of 450° C. to 160° C. duced in step 1 is heated to about 650° C. under reduced ‘.A‘ring'ZI-?tted within slot 22 is provided on the pressure to form potassium sul?de and sulfur. metal chamber .10 to pick up metal from condensed 7. The process of claim 1 wherein the potassium sul vapors passing‘thr'ough the vacuum line 14. ?de is recycled to step 1. . e _ ltéisio beunderstood that the foregoing speci?c ex '8. The process of claim 1, wherein the potassium amples are presented by way of illustration and explana sul?de is reacted with water to form potassium hydrox tion only and that the invention is not limited by the 45 ide and potassium hydrosul?de. , , . i. . details of such- examples. 9. The process of claim 1, wherein the hydrogen The foregoing is believed to so disclose the present produced in step, 3 is dissolved in molten potassium invention that those skilled in the art to which it apper metal obtained in step 1 for storage and later utilization tains can, by applying thereto current knowledge, in said process. readily modify it for various application. Therefore, 50 10. The process of claim 1, wherein lead sul?de is such modi?cations are intended to fall within the range reacted with a portion of potassium metal obtained in of equivalence of the appended claims. step 1, the temperature is increased to about 330° C. and What I claim is: molten lead is recovered by tapping from lighter mate 1. An integrated process for producing potassium rial ?oating on the surface of the system. from its non-stoichiometric oxide or sul?de and subse 55 11. The process of claim 1, wherein zinc sul?de is quently using the potassium produced to obtain less reacted with a portion of the potassium metal obtained active metals and hydrocarbons, comprising the combi in step 1 and that thereafter the temperature is increased nation of steps of: to about 440° C. and that zinc metal is tapped from l. thermally decomposing potassium oxide or potas material ?oating on the surface of the system. I sium sul?de substantially in the absence of water l2...The process of claim ‘1, wherein chalcopyrite is thereby obtaining potassium metal, and, respec reacted with a portion of the potassium metal obtained tively potassium peroxide or potassium super ox in step 1 atabout 70° C. to produce iron and copper and ide, and potassium disul?de; recovering said potas then magnetically separating the iron from said copper. sium metal from the aforesaid other products; ‘ .13. The processwof claim 1, wherein the magnesium 2. providing a portion of the previously obtainedv 65 oxide is reacted with a portion of the potassium metal potassium metal at a temperature above its melting obtained in step 1 at about 360° C. .and elemental magne point in the molten or vapor state; reacting said sium is recovered by distilling residual-potassium. potassium with at least one oxide or sul?de-of mag - * * * * *