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United States Patent '[19] 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.
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