JPS60163827A - Continuous method for use of non-stoichiometric sulfide or oxide of pottasium to manufacture of lower activity metal and hydrocarbon - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION A branch of the invention The present invention relates to the production of potassium from its non-stoichiometric oxides or sulfides, and then use of the produced potassium to obtain less active metals and hydrocarbons. Concerning the continuous method for. More particularly, the present invention involves producing elemental potassium and then reacting the elemental potassium with various metal ores (e.g., magnesium, lead, zinc, copper, arsenic, antimony or silver ores) to form these metals. is released in elemental form from its naturally occurring form or reacted with water to produce potassium hydroxide and hydrogen, and an additional amount of elemental potassium is reacted with potassium hydroxide to produce larger amounts of hydrogen and hydrogen. Potassium oxide, which is unstable to heat (
This decomposes to produce potassium and potassium peroxide or potassium superoxide), optionally reacts this hydrogen with potassium to produce potassium hydride, and stores the produced water (6); or This potassium hydride is then reacted with carbon to produce potassium acetylide, optionally with additional amounts of hydrogen to saturate the carbon bonds of these unsaturated compounds, and hydrogenated with process potassium or potassium hydride. catalytic method.

It is an object of the present invention to provide a low cost and high yield process for producing elemental potassium from potassium oxide or potassium sulfide.

Another object of the invention is to process potassium into carbide,
Aceti IJ 1.゛Used in the production of hydrogen, hydrides, hydrogen peroxide, oxygen, potassium hydroxide, low activity metals, saturated and unsaturated hydrocarbons to reduce the production of these products and by-products to lower levels than previously achieved. The goal is to provide it using a continuous method that allows production at cost.

PRIOR ART There are numerous patents relating to the production of metals from their metal salts and to the production of hydrogen as a by-product. Therefore, the description of this technical background will be limited to what is considered to be most relevant to the problem (7) at hand.

The very basic one is US Pat. No. 2,852,363. This contains potassium, cesium or rubidium,
A process for producing hydroxides of these metals together with zinc in an inert atmosphere under pressure employed in a reactor to a temperature above the boiling point of the alkali metal in question and recovering the free alkali metal. Says. Hydrogen can also be obtained by this method, but there is no suggestion of its use.

U.S. Patent Nos. 1,872,611 and 1,064,32
No. 0, No. 2,028,390, No. 3.9.38,98
No. 5 and British Patent No. 590,274 are also concerned with the description of a method for producing alkali metals or their alloys.

As discussed below, none of these statements are intended to describe, imply, or suggest in any manner our unique, novel, or nonobvious methods.

Disclosure of invention The drawings attached hereto illustrate the method of thermal reduction (8). 1 is a schematic diagram illustrating one form of an apparatus for carrying out.

It has been found that surprising process and product advantages with respect to obtaining potassium and other metals and using the potassium thus obtained to produce organic products are achieved by the practice of the present invention, This is the basis for forming the concept of the present invention. Relatively low temperatures are employed in this process, thereby achieving high yields. Furthermore, the economics of the method is greatly improved.

Basically, the invention consists in a continuous process for producing metallic potassium from its non-stoichiometric oxide or sulfide by the following steps and using this metal for the production of less active metals and hydrocarbons. .

1. Thermal decomposition of potassium oxide or potassium sulfide to metallic potassium in the substantial absence of water to produce potassium peroxide or potassium superoxide and potassium disulfide, respectively; and collecting metallic potassium; 2. Part of the potassium thus produced is made into a molten state (9) or vapor, and it is mixed with magnesium, copper, calcium, silver, lead, zinc, antimony, cadmium, iron, arsenic and mixtures thereof. After the metal has been removed from this oxide or sulfide by reaction, the metal is collected; another part of the potassium previously obtained is reacted with water to form hydrogen and potassium oxide. ;
4. Using the hydrogen generated earlier, (a) Combine this hydrogen with the potassium obtained in step 1 above and 250
React at temperatures of ~300°C to produce potassium hydride, react the potassium hydride with carbon to produce potassium acetylide, and react the acetylide with water to produce acetylene and KOH; Organic compounds are produced by hydrogenating acetylene to produce ethane and edene; or (b) hydrogenating carbon in the presence of a catalyst using hydrogen as described above to produce methane.

The organic compound ethane or methane can be reacted with a halogen in a manner known per se to form an alkyl halide, which can then be reacted with sodium or process potassium under Wurz-Witeizg reaction conditions. Hydrocarbons boiling in the lower fuel range can be produced.

In the accompanying reactions intermediate compounds are produced which are recycled to produce additional potassium for reuse in the process.

The method of the present invention uses the following reaction formula.

2a, to +I/2H20→KOH+]/2H,.

6, K HC2+H20-→C2H,,+KOH7K+
1/2H20→KO+1/2H2(11) 10, K2O2+ 2H20→2KOH+H2O211
, K+Ra Y →K x Y x+R, This reaction is carried out with molten potassium at a temperature above 65°C or with potassium vapor at a temperature above 780°C. Y is sulfur or oxygen and R is magnesium, zinc, cadmium, lead, iron, arsenic, antimony, calcium, silver or copper.

12, C2H, X 0 C2H, X+2 = C, H, +2K
X where X is chlorine or bromine.

i 16, K2S, - to 2S+ to 2S2 (172mmHg
At a pressure of (12) at 360°C) 17, K2S+H,,0-→KOH+KH8Addition of water causes a reversible reaction KH8-1-H2O-+KOH+H,,S18, reaction starting temperature 615°C H2S→H2+S19.4 to 2S2+
8H20→3,,S,+X,H,O+,,S.

(In a closed system) 20.4, , S4 + XH2O → 2 to 2 S5 + 2 to 2
The minimum amount of S,

21, 2S on 4, 2S on +XH2O-+3, 2S on +
, XH2O These hydrolysis reactions are all closed systems, and 6
It is carried out at a temperature above 0° C. and below the critical temperature of water. The minimum amount of water required for these hydrolysis reactions is determined by the selected temperature i.e. 206°C (melting point of K2S5) J-J
This is the amount that constitutes the potassium sulfide hydrate present below.

The process of the present invention takes advantage of the lack of thermal stability of non-stoichiometric potassium sulfide and potassium oxide (13) to produce elemental potassium and various potassium compounds, and then Potassium or a certain type of potassium compound is used to continuously regenerate potassium sulfide and potassium oxide by reaction with water, metal ores, etc.

Regarding the above reaction formulas, reaction formulas 1.4 and 1
4 is the basic reaction formula of the present invention. Elemental potassium is thereby produced by thermal decomposition of potassium sulfide to potassium disulfide and elemental potassium, and by decomposition of potassium oxide to elemental potassium and potassium peroxide or superoxide.

Reaction equation 1615 shows the decomposition of potassium disulfide to potassium sulfide and sulfur, while reaction equation 16 shows the decomposition of potassium trisulfide or higher polysulfides to potassium sulfide and potassium disulfide. Reaction formula A19.20
and 21 show hydrothermal hydrolysis of potassium polysulfide to potassium sulfide hydrate and potassium trisulfide. The heat-vacuum decomposition of potassium trisulfide shown in Reaction Formula 16 (14) can also be applied to potassium tetrasulfide, potassium trisulfide, and potassium hydrosulfide. Equations 9 and 9a show the decomposition of potassium superoxide and potassium peroxide. Potassium peroxide decomposes into elemental potassium and oxygen. Potassium superoxide (KO2)
decomposes into potassium peroxide 202 and oxygen. 7
At temperatures above 80°C, 202 begins to decompose into K and 02.

Potassium does not combine with oxygen or sulfur in the absence of water vapor. Removal of water vapor from the system of this process greatly reduces the tendency of potassium to recombine with sulfur or oxygen after thermo-vacuum decomposition of potassium oxide or potassium sulfide.1° Potassium Hydroxide, Potassium Oxides, Potassium Sulfide and potassium hydrosulfides are deliquescent and have aqueous tension (aqu
eous tension) is low. Potassium sulfides and potassium oxides have anion sublattice
It is a non-stoichiometric compound with a deficiency in ice). water,
Hydrogen and even potassium hydride will substitute into the anion sublattice. Hydrogen is produced by (15) the reaction of metallic potassium with water vapor and the reaction of elemental potassium with water to produce potassium hydroxide and hydrogen. Additional amounts of potassium will react with the potassium hydroxide to produce additional amounts of hydrogen and potassium oxide. In the case of potassium oxides, water will also react directly with potassium oxide to form potassium hydroxide. Early in the thermal decomposition of potassium sulfides or potassium oxides, elemental potassium will react with the potassium hydroxide to produce additional amounts of hydrogen and potassium oxide. At the decomposition temperature of potassium oxide, 650° C., elemental potassium will react with a portion of the hydrogen produced to form potassium hydride. As the temperature rises above 380°C, potassium hydride begins to dissociate.

Elemental potassium produced by decomposition of potassium sulfide or potassium oxide is soluble in the remaining solids until temperature-pressure conditions are higher than those required for boiling of the elemental potassium. As shown by Reaction Equations 15.16.19 to 21, the present inventor (16) has prepared potassium sulfide by reducing the sulfur content of sulfur trisulfide or a polysulfide having a sulfur content above 2U. It has been found that it can be decomposed into elemental potassium and sulfur in less than 24 hours at 780°C. Potassium trisulfide melts at 206°C and decomposes above 300°C to potassium tetrasulfide and sulfur. 206°C
The potassium trisulfide melt is essentially anhydrous. Potassium tetrasulfide melts at 145°C, and potassium trisulfide melts at 27°C.
It melts at 9°C, and potassium disulfide melts at 470°C.

All of these compounds form anhydrous melts at temperatures above their melting points. These anhydrous melts are easier to produce under reduced pressure. Reduced pressure removes the water of hydration more easily, producing an anhydrous melt. The temperature must be at least as high as the melting point of the polysulfide and the vacuum must be at a residual pressure of 1 to 50 mm H&. Since these potassium polysulfides decompose to polysulfides with lower sulfur content, the temperature-vacuum conditions must be suitable for distillation of the sulfur. Sulfur (17) boils at a temperature of 45°C at a pressure of 760 mmHg and lm
At mHg it boils at 185°C.

Potassium trisulfide decomposes at 350° C. and 0.05 mmHg to a mixture of potassium sulfide and potassium disulfide. Potassium disulfide decomposes into potassium sulfide and sulfur at 650°C and 0.05 mmHf1, anhydrous potassium sulfide decomposes into elemental potassium and sulfur at 780"C, but hydrated potassium sulfide decomposes into elemental potassium and sulfur. Potassium disulfide is the most thermally stable combination of potassium and sulfur in the absence of reduced pressure; Hydrated potassium sulfide decomposes to elemental potassium and potassium disulfide at temperatures above 840 DEG C. DJ.

In practical terms, potassium disulfide decomposes at 886°C and at a pressure of 1
Performed at 0 mmHg. At this temperature and pressure, potassium disulfide rapidly decomposes into its elements. Another source for obtaining potassium from potassium sulfide (18) is the decomposition of potassium disulfide to potassium sulfide at 780 °C under a reduced pressure of 1 mmHg, and then the fractionation of potassium sulfide into its element under the same conditions. .

If the process starts from potassium oxide, the potassium oxide decomposes at temperatures above 650°C to a mixture of elemental potassium and potassium peroxide or potassium superoxide;
Elemental potassium cannot be easily removed from this mixture at this temperature. 5 x 10-4 mm and a pressure of Hg at 360 DEG C. some elemental potassium can be distilled off. . At temperatures above the melting point of potassium peroxide, 490"C, potassium is heated at 10 mmH.
，! It can be removed by distillation at a pressure of 9. At a temperature of 780°C, almost all potassium 'Y
It can be removed by distillation at 10 mmHg. This elemental potassium becomes a mixture of potassium peroxide and potassium, which then melts at 490'C to form a mixed anhydride. Removal of water inhibits the formation of hydrides, hydroxides and hydrogen, thereby decomposing potassium oxides into their constituent elements.

The potassium produced according to the invention is then reacted with a less than stoichiometric amount of water, for example 15% less than the stoichiometric amount, to produce potassium hydroxide and Generate hydrogen. Additional amounts of potassium and potassium hydroxide will produce more hydrogen at temperatures above 660°C and produce unstable potassium oxide (Equation 2). The potassium oxide 20 is then decomposed by one of the steps described above to potassium and oxygen, or potassium and potassium peroxide or potassium superoxide;
Potassium is continuously produced (reaction formula 4).

Potassium peroxide or a portion of potassium superoxide can be dissolved in a less than stoichiometric amount (e.g. -15%) of water to produce additional amounts of potassium hydroxide and hydrogen peroxide ( Reaction formula 10).

The unstable hydrogen peroxide then serves as the source of oxygen.

It can be used as Potassium superoxide and potassium peroxide can also be used as a source of oxygen at temperatures above 65 °C for superoxide and 780 °C for peroxide, as shown in equations 9 and 9a (20) I can do it.

Potassium in liquid or vapor form reduces ores of magnesium, copper, silver, m, zinc, calcium, iron, antimony, arsenic, cadmium and mixtures thereof to free metals at any temperature above its melting point of 65°C. None, producing potassium oxide, or elemental magnesium, depending on whether these elements are in the form of oxides or sulfides in their natural mixed ores or ore concentrates, Generates potassium sulfide or oxide by releasing copper, silver, lead, zinc, calcium, iron, antimony, arsenic, cadmium, etc.

When hydrogen is produced by the decomposition of water or potassium hydroxide using elemental potassium, or by the reduction of hydrogen sulfide derived from the decomposition of the hydrolysis product potassium bisulfide (from potassium sulfide), this hydrogen and This hydrogen can be stored as potassium hydride by reacting additional amounts of elemental trigium(21) at temperatures between 250 and 360°C. Potassium hydride is miscible with molten potassium.

Potassium hydride dissolved in molten potassium reacts directly with carbon and graphite to form potassium acetylide. Potassium acetyl reacts with white water to produce acetylene.

The acetylene produced can be reacted with an additional amount of process hydrogen using molten potassium or potassium hydride as a catalyst to produce etheno or ethane. The amount of hydrogen present determines the production of etheno or ethane. 3. The temperature of this reaction is the melting point of potassium, 65°C.
Any of the above temperatures may be used.

The hydrogen produced in the present invention combines directly with carbon to form methane by the Raney nickel process at a temperature of 250° C. in the presence of a suitable catalyst (eg nickel). Potassium or potassium hydride dissolved in potassium is 18
It is used as a catalyst at temperatures between 0 and 660°C (22).

Example 1 This example demonstrates the production of metallic potassium from potassium oxide present in ore.

According to this example, 10 kg of ore containing 20 was placed in an autoclave and 88
By heating to 6℃, 4.1 kg of metallic potassium
was distilled out, and 5.9 kg of 202 remained.

Example 2 This example shows the reaction of reaction formula 2-9.11-12.

90% purity industrial potassium hydroxide flakes at 380℃
heated to. In preparing an essentially anhydrous melt, a vacuum of 50 mm Hg was employed to dehydrate the flakes.

Hydrogen was generated. The stoichiometric amounts are 1 mole of potassium hydroxide (obtained from 62.2 g of industrial grade 90% KOH flakes (23)) and 1 mole of elemental potassium (391
g).

The generated hydrogen was passed through molten potassium held at 280"C to produce potassium hydride. 11/2 mole of potassium was used to incorporate 1/2 mole of hydrogen, resulting in hydrogenation in the molten potassium. A liquid consisting of potassium solution was formed.

A potassium hydride solution containing 1 mole of KH in molten potassium was treated with 2 moles of carbon (graphite) at 650° C. in the absence of air, nitrogen or carbon dioxide to produce potassium acetylide.

This mixture was carefully and gradually added to 11/2 moles of water, producing 1 mole of acetylene and hydrogen as volatile components and a potassium hydroxide solution. The gases produced (hydrogen and acetylene) account for 3.21 at atmospheric pressure at 15 °C, and 1 mole of acetylene and 1/2 mole of hydrogen
It was shown that the amount was converted to 2 moles.

Potassium oxide produced by the reaction of potassium and potassium hydroxide was heated to Vc500 (24
) After holding at 10 mm at °C and Hg for 2 hours, the mixed T
11/2 moles of potassium were condensed by heating to 88° C. and selectively cooling the gas stream released in 6 hours 20 minutes.

Example 6 Potassium 1 mol'k produced in Example 1 Anti-G formula 2 a
Additional amounts of hydrogen gas and potassium hydroxide were produced by treatment with water as shown in .

1 mole of potassium peroxide produced in Example 6 was added to 2 moles of water at 95°C to produce 1 mole of hydrogen monoxide and 2 moles of potassium hydroxide as shown in Reaction Scheme 10.

This example therefore shows that almost all of the potassium in the originally used form was recovered (ie, elemental potassium and potassium hydroxide).

Example 4 This example demonstrates the thermal decomposition of K2S to potassium, as shown in Equation 14.

Two pounds of K2S (approximately 0.9 kg) were heated to 780"C under a pressure of 50 mmHg to remove water. The pressure was then reduced to 5 x 10-4 mmHg at this temperature.

Sulfur was distilled and condensed into a series of liquid nitrogen traps.1 Once the rate of sulfur distillation had decreased, the temperature was increased to 883°C. The distillation chamber was left with potassium sulfide (identified by barium analysis reaction), and the potassium and sulfur were condensed in a new trap cooled with liquid nitrogen. Potassium and sulfur did not recombine in the presence of water vapor.

200g of potassium was collected.

Example 5 Regarding Reaction Formula 11, the potassium produced in Example 4 was heated to 50 mmH,! It was melted under a pressure of i' and decanted from the sulfur.

This potassium was divided into four 50 g samples and used in its molten form.

A lead sulfide concentrate containing 73% lead, 54!9, was smelted using one sample f4 of 50.9. Smelting was carried out at 70'C. After the reaction has stopped (about 3 minutes), reduce the temperature to O'
The molten lead was extracted from the lighter material floating on the surface of the lead by tapping.

One 50 g sample was used to smelt 41.6 g of zinc sulfide concentrate containing 50% zinc at a temperature of 70°C. The reaction required approximately 2 minutes. The temperature was raised to 440° C., and liquid molten zinc was taken out from below the material floating on the surface of the zinc by tapping.

Using one 50g sample, chalcopyrite (CuFeS2)8
50 g of copper sulfide concentrate containing 6% was smelted.

The reaction was carried out at 70°C. Iron and copper were manufactured.

Iron was separated from copper by magnetism. The copper was melted and separated from the material floating on the surface of the copper.

One 50 g sample was used to smelt 25 g of magnesium oxide at 60°C. The reaction requires 6 minutes■.

Ta. Magnesium element was produced.

The residual potassium in all of these samples was distilled off from the formed metal at a pressure suitable for distilling potassium but too low to volatilize other metals. Three sulfide samples were separated from the largely inert gangue containing them by dissolving the (27) hypotassium sulfates produced in this smelting operation in a small amount of water. Next, the solid was separated from the liquid by filtration. 1. Sulfur was added to the R solution, and the P solution was heated at 500°C for 50 mH.
Dehydration was carried out at a pressure of g. The resulting anhydrous melt was then brought to 883° C. under a pressure of 10 mm Hg to regenerate potassium and sulfur vapors, which were then condensed. This potassium condensation ended the cycle.

Potassium oxide produced during magnesium smelting is
Gangue and potassium oxide were directly recycled to potassium by heating to 883°C at 10 mmHg. Some carbon dioxide was distilled off before the potassium was distilled off. The carbon dioxide was incorporated into the potassium hydroxide as it was released from the system. Potassium was mostly recovered after carbon dioxide was removed from the system. A second sample showed that carbon dioxide could be removed by preheating the magnesium oxide under reduced pressure before reacting with potassium (28). The potassium produced by recycling potassium oxide was condensed by cooling and used to further smelt magnesium ore.

Examples in Examples show the reactions of Reaction Schemes 4.5.9-10 and 13.

Hydrogen produced according to the invention is used to prepare carbon (graphite) 'f;r hydrogen in the presence of molten potassium (potassium hydride (or Raney nickel) molten in molten potassium can also be used) at 250 °C. added 7
, no pressure other than that of the hydrogen released from the system for this process was employed. A total of 100 g of carbon was hydrogenated to methane in 1/2 hour by using 1 mole of potassium and 1 mole of potassium hydroxide and continuously recycling these reagents. Dissolve potassium oxides in water, then dissolve this potassium hydroxide in 8
By reacting with potassium produced by thermal decomposition of potassium oxides at 10 m, m, Hg at 83 °C (2
9) (Reaction formulas 1 and 2).

The process of reducing the oxygen content of the system by removing any potassium superoxide that may have formed is a process described in 886
This was done by heating the potassium oxides to 656°C before decomposition at °C. Care was taken to condense the potassium and allow oxygen to escape from the operating system. This was done to avoid potassium hydroxide formation.

Potassium hydroxide was produced by reaction with water using the undecomposed residue, and hydrogen peroxide was produced (reaction formula 10). Care was taken to prevent hydrogen peroxide or oxygen generated from decomposition of hydrogen peroxide from entering the smelting system.

Example 7 This example involves pyrolyzing potassium oxide to create a mixture of elemental potassium and potassium peroxide and potassium superoxide; then reacting the potassium peroxide and potassium superoxide with a stoichiometric amount of water. to form potassium hydroxide and oxygen; the elemental potassium is then reacted with potassium hydroxide to form elemental hydrogen and reform potassium oxide for recycling.

This decomposition is carried out at a temperature range of 360-380 °C and the product is removed at a temperature range of up to 656 °C or at 779 °C.
It was added as appropriate at the above temperature and then taken out.

In carrying out this operation, potassium hydroxide was heated to 70°C under a vacuum of 1-10 mm Hg in the absence of air. Molten elemental potassium was gradually added to the anhydrous solution of potassium hydroxide in a stoichiometric ratio of 1 mole to 1 mole. Elemental hydrogen was generated and the pressure in the system increased substantially.
Since potassium is likely to react with oxygen, nitrogen, carbon dioxide, etc., it is necessary to employ reduced pressure to reduce the reaction between the molten potassium and the inert atmosphere. Neon, helium, or argon (Group 8 gases) can also be used instead of reduced pressure.

The system was opened and hydrogen was vented from the operating system and collected. After removing the hydrogen, vacuum was applied again. The potassium oxide formed during hydrogen evolution was in principle decomposed only by thermal means. The elemental potassium formed together with potassium peroxide (31) and potassium superoxide (KO2) was generally distilled off slowly before the thermo-vacuum decomposition of potassium peroxide. Only potassium was distilled out. Distilled liquid/gas potassium and hydrogen into 6
It was converted to potassium hydride at temperatures below 80° C. and under atmospheric pressure or superpressure.

After removal and separation of hydrogen and potassium, a less than stoichiometric amount, e.g.
5% less water was added to generate potassium hydroxide and oxygen. The oxygen was separated off from the operating system. Hydrogen and potassium were separated from the operating system separately from the removed oxygen.

More elemental potassium was removed from the system above than would be expected from the formation of potassium peroxide 202, indicating that some potassium superoxide KO2 was formed.

Potassium and potassium hydride were again reacted with water to produce more hydrogen.

1 mole (32) (56,11,9) of potassium hydroxide (purity 85-86%) under a pressure of 10 m, m, Hg 6
80"C. Water distilled out as lower potassium hydroxide hydrate was formed. Solid potassium hydroxide then melted at 360±5°C. Elemental potassium, l-
One mole was melted under an atmosphere of alcohol and added dropwise to the potassium hydroxide melt.

When the pressure of the evacuated system increased to atmospheric pressure or overpressure due to the generated hydrogen, the system was opened and hydrogen was discharged from the system. Once the hydrogen was removed (as indicated by the system pressure stabilizing at slightly above atmospheric pressure), vacuum was again employed, preferably about 1 m, mHg. Elemental potassium was distilled from the system. Slightly more than 1 mole of potassium was distilled out.

Elemental potassium was reacted with hydrogen at a temperature of 260-680°C to produce solid potassium hydride. Potassium hydride was soluble in excess molten potassium.

Slightly less than 1 mole of water was added to the system9, the amount of water being the same ratio (potassium peroxide remaining in the reactor - potassium superoxide) as the excess potassium was removed from the system (33). ), it decreased by less than 1 mol.

Oxygen evolved and potassium hydroxide was formed.

Example 8 This example demonstrates high temperature production of hydrogen. In carrying out this operation, commercially available potassium hydroxide was heated to 779° C. under reduced pressure or under an inert gas atmosphere (helium, neon, argon, etc.).

Water was removed as the series of potassium hydroxide hydrates decomposed into lower hydrates with increasing temperature. Potassium hydroxide at 660±5°C produced an anhydrous melt.

Partial thermal decomposition of potassium hydroxide to potassium oxide and water resulted in the release of more water than hydrate water. Potassium oxide gradually decomposed into potassium peroxide and elemental potassium at temperatures above 60±5°C.

The potassium thus produced reacted with steam to produce potassium hydroxide and hydrogen, which reacted with potassium hydroxide to produce hydrogen and potassium oxide (34) (reaction formulas 2a and 2).

Equilibrium was reached when approximately 16% of potassium and hydrogen had been distilled off. Then, as the hydrogen content of the operating system decreased, potassium hydroxide-potassium oxide-potassium peroxide further decomposed to become potassium. Potassium and oxygen did not recombine because the water content of the system was reduced.

88% potassium recovered in 21/2 hours, approx.
of hydrogen was also recovered.

The reaction time was accelerated to 1 hour by adding 1/2 mole of potassium to the anhydrous melt of potassium hydroxide.

Example 9 One mole of hydrogen produced above was reacted with acetylene produced at 360°C to produce etheno. A second 1 mole of hydrogen was supplied to hydrogenate the etheno to ethane.

One mole of ethane was reacted with one mole of chlorine in the gas phase to produce ethyl chloride. Ethyl chloride was collected and reacted with potassium by refluxing in anhydrous ether under Urzufiteitz reaction conditions (35) to produce butane. The butane thus obtained is similarly reacted with chlorine gas to produce butyl chloride, which is then reacted with the metallic potassium produced above under the same Ultuhuiteitsch reaction conditions to produce an internal combustion engine. Hydrocarbons of a grade suitable for use were produced.

As shown in the drawings, apparatus suitable for practicing the invention includes a melting chamber or retort 10 made of a corrosion-resistant metal or alloy (eg, metallic nickel or tungsten) that can be heated under reduced pressure. A tap 12 for molten metal is formed or fixed at the bottom of the melting chamber. A vacuum line 14 is connected to a pump (not shown) capable of evacuating the melting chamber to a pressure of 1/2 to 26 mmHg. Between the melting chamber and the vacuum line 14, three traps A, B, B are provided for condensing the regenerated oxide or sulfide and condensed elemental alkali metals and returning them to the melting chamber 10 via a stopcock 16. C is connected. A fourth trap 18 is provided for the collection of sulfur (36) at a location remote from the melting chamber, which can be removed via an outlet 20. Means for heating the melting chamber 10 or its surroundings by 68[1" cVC and suitable means (not shown) for gradually reducing the area remote from the melting chamber to a temperature of A50 to 160° C. are provided. It is being

A ring 21 (liquid metal overflow) fitted within the slot 22 is provided in the metal chamber 10 and connected to the vacuum line 17i.
captures metals from condensed vapors passing through it.

It is to be understood that the above detailed examples are presented for purposes of illustration and explanation only, and the invention is not limited to the details of these examples.

The foregoing description has been presented to enable those skilled in the art to readily modify it for various uses by applying current knowledge to the description. Therefore, this type of modification shall be included within the scope equivalent to the scope of the claims.

[Brief explanation of the drawing]

The drawing is a schematic diagram showing one form of the apparatus for carrying out thermal reduction of the present invention (37), and each symbol represents the following. 10: Melting chamber; 12: Tap 14: Vacuum line; 16: Stopcock A, B,
C:) Rap; 18: Trap (sulfur) 20:
Outlet; 22 Nislot 21: Ring (liquid metal overflow) Patent applicant
Laurent Swanson (38) Drafter of the drawings (no changes to the same) Procedural amendment (method) 1. Indication of the case 1939 ``Ifu Permit No. /2-FaY No. ψtsukt
If) 2 1L sinkage amount correction tsu 474 Isu L dimension (
I Ln Tomi 7-J Soibeni Beggar-1v no 1〉Reminds me of =
;;Bii6in1c Rabbit σfuhesha d+-iJK゛di°cor [Junnimo 3, Relationship with the person making the amendment case Applicant Address: Hisashi Laurent Soufunn 4, Agent

Claims (1)

[Claims] (1) A continuous process for producing potassium from its non-stoichiometric oxide or sulfide and then using the unproduced potassium to obtain less active metals and hydrocarbons. 1) pyrolyzing potassium oxide or potassium sulfide in the substantial absence of water, with or without employing reduced pressure, thereby producing potassium metal and potassium peroxide, respectively;
or producing potassium superoxide and potassium disulfide; extracting metallic potassium from other potassium products: 2) Part of the metallic potassium obtained above is heated to a molten state at a temperature of "2" with its melting point "earth or steam" This potassium is mixed with at least one oxide or sulfide of a mixture of magnesium, copper, calcium, silver, lead, zinc, antimony, cadmium, iron, arsenic, etc. Reacting to expel the metal from its oxide or sulfide and removing the less active metal thus expelled from the remaining potassium or potassium compound; 3) combining another part of the metallic potassium obtained in step 1 with water; React to produce hydrogen, potassium oxygen and potassium hydroxide: 4) Using a portion of the hydrogen obtained in step 3, (a) combine this hydrogen with the metallic potassium obtained in step 1 above at 250-300°;
Acetylene and KOH are synthesized by reacting at a humidity of C to produce potassium hydride, then reacting this potassium hydride with carbon to produce potassium acetylide, and contacting this acetylide with water; using the hydrogen obtained in step 3 above to form eggs and ethane; or (b) - using the above hydrogen to hydrogenate carbon in the presence of a hydrogenation catalyst to form methane. Generate. (2) A method characterized by a combination of steps. -(2) The method according to claim 1, wherein the hydrogenation catalyst consists of a part of the potassium obtained in step 1, and the hydrogenation temperature is in the range of 180 to 360°C. (3) The method according to claim 1 or 2, characterized by one or more additional steps of treating a portion of the potassium obtained in step 1 with water to generate hydrogen. (4) characterized by one or more additional steps in which a portion of the potassium obtained in step 1 is reduced with potassium hydroxide produced in the process filter, thereby producing potassium oxide and hydrogen to be reused in the process; A method according to claim 1. (5) A method according to claim 1, characterized in that the potassium oxide of step 1 is heated to 350° C. or less under a pressure ranging from 10 mH to atmospheric pressure. (6) The method according to claim 1, characterized in that the sulfide produced in step 1 is heated to about 650° C. under reduced pressure to generate potassium sulfide and sulfur. (7) A method according to claim 1 or 6, characterized in that potassium sulfide is recycled to step 1. (8) The method according to claim 1, 6 or 7, characterized in that potassium sulfide is reacted with water to produce potassium hydroxide and potassium bisulfide. (9) A process characterized in that the hydrogen produced in step 6 is dissolved in the molten metallic potassium obtained in step 6 for storage and for later use in the process. 00) It is characterized by reacting lead sulfide with a part of the metallic potassium obtained in step 1, increasing the temperature to about 630°C, and extracting the molten lead from lighter substances floating on the surface of this system by tapping. A method according to claim 1. (11) The zinc sulfide is reacted with a part of the metallic potassium obtained in step 1, and the temperature is then raised to about 440°C. (4) The metallic zinc is then extracted from the substance floating on the surface of the system by tapping. The method according to claim 1. (12) Claims characterized in that chalcopyrite is reacted with a portion of the metallic potassium obtained in step 1 at about 70°C to produce iron and copper, and then iron is separated from the copper by magnetic means. The method described in paragraph 1. (13) Magnesium oxide is reacted with a portion of the metallic potassium obtained in step 1 at about 360'C, and elemental magnesium is collected by distilling off the remaining potassium. the method of. 04) In step 2, the metal to be expelled is initially in the form of sulfides, the remaining potassium, l- (with or without sulfides) is dissolved in water, sulfur is added and the resulting solution is P is separated under reduced pressure, thereby producing an anhydrous melt, and this melt is heated with or without employing reduced pressure, thereby freeing sulfur and metallic potassium for reuse in the process. 2. A method according to claim 1, characterized in that the metal is harvested by forming (5).