DD215587A5 - INTEGRATED METHOD FOR MANUFACTURING LESS ACTIVE METALS AND HYDROCARBONS - Google Patents

Abstract

The invention relates to a chemical process involving the production of elemental potassium and the subsequent reaction of this elemental potassium with other reactants including various metal ores, such as those of magnesium, lead, copper, zinc, arsenic, antimony or silver, to these metals from their naturally occurring forms in the elementary state release. However, the elemental potassium may also be reacted with water to produce potassium hydroxide and hydrogen by reacting further elemental potassium with the potassium hydroxide to produce more hydrogen and a thermally unstable potassium oxide which decomposes to form potassium and potassium peroxide or potassium peroxide. And, if necessary, the aforesaid hydrogen and said potassium may be reacted with each other to produce potassium hydride so as to store the generated hydrogen, or the potassium hydride may be further reacted with carbon to produce potassium acetylide, and optionally hydrogen may be added to the carbon bonds thereof To saturate unsaturated compounds using potassium or potassium hydride obtained from the process for catalyzing the hydrogenation.

Description

Integrated process for producing less active metals and hydrocarbons

Field of application of the invention

The invention relates to a chemical process involving the production of elemental potassium and subsequent reaction of this elemental potassium with other reactants including various metal ores, such as those of magnesium, lead, copper, zinc, arsenic, antimony or silver, to these metals from their naturally occurring forms in the elemental state release. However, the elemental potassium may also be reacted with water to produce potassium hydroxide and hydrogen, by reacting further elemental potassium with the potassium hydroxide to produce more hydrogen and a thermally unstable potassium oxide which decomposes to form potassium and potassium peroxide or potassium peroxide. And, if necessary, the aforesaid hydrogen and said potassium may be reacted together to produce potassium hydride so as to store the generated hydrogen, or the potassium hydride may be further reacted with carbon to produce potassium acetylide, and optionally further hydrogen is used - the carbon bonds saturating these unsaturated compounds using potassium or potassium hydride obtained from the process to catalyze the hydrogenation.

Characteristic of the known technical solutions

There are numerous patents on techniques for producing metals from their salts by obtaining hydrogen as a by-product. In the following, only those pamphlets are considered that are considered to be the most relevant.

Very basic is US-PS 28 52 363, which discloses a method for producing potassium, cesium or rubidium by heating a hydroxide of these metals with zinc in an inert atmosphere to a temperature above the boiling point of the respective alkali metal under the pressure used in the reactor describes the subsequent recovery of the free alkali metal. Although hydrogen is also produced in this process, there is no suggestion regarding its use.

The US-PS 18 72 oil, 10 3k 320, 20 28 390 and 39 38 988 and GB-PS 59 02 7k also describe methods for producing alkali metals or their alloys. However, none of these documents discloses in any way the present method.

Object of the invention

Goal of. The invention is the integration of the production of potassium with its further use for producing less active metals and of hydrocarbons for cost reduction.

-J-

Lament of the essence of the invention

The object of the present invention is to provide a cheap process for producing elemental potassium from potassium oxides or sulfides, which yields high yields, and the potassium obtained in this process for producing carbides, acetylides, hydrogen, hydrides, hydrogen peroxide, oxygen To use potassium hydroxide, less active metals, saturated and unsaturated hydrocarbons to produce the above products and by-products in an integrated process that allows their production at a lower cost than previously possible.

It has been discovered in the present invention, and this finding constitutes the essential conceptual basis of the present invention, that extraordinary process and product advantages can be achieved in the production of potassium and other metals as well as the formation of organic products using the potassium thus obtained. In the method according to the invention, relatively low temperatures can be used and high yields are obtained. Furthermore, the cost-effectiveness of the process is greatly improved «

Basically, the invention resides in an integrated process for producing potassium metal from its non-stoichiometric oxide or sulfide and using this metal to produce less active metals and hydrocarbons through the following steps:

(i) thermally decomposing potassium oxide or sulfide, optionally under reduced pressure, substantially in the absence of water, to potassium metal and potassium peroxide or

Potassium peroxide or potassium disulfide and separating the potassium metal from the other potassium products,

(.2.) Providing a portion of the potassium metal obtained in the previous stage at a temperature above its melting point in the molten or vapor state,

Reacting this potassium with at least one oxide or sulfide of magnesium, copper, calcium, silver, lead, zinc, antimony, cadmium, iron or arsenic or a mixture of the aforementioned metals to liberate the metal from its oxide or sulfide, and

Separating the thus liberated less active metal from the remaining potassium or the potassium compounds,

(3) reacting another portion of the potassium metal obtained in step (i) with water to form hydrogen, potassium oxide and potassium hydroxide,

(4) using a part of the hydrogen obtained in step (3) to produce a hydrocarbon, namely;

(a) by reducing the hydrogen with in step (i) he / she holding potassium metal at a temperature of 250 C to 300 C to form potassium hydride,

reacting the potassium hydride with carbon to form potassium acetylide,

Synthesizing acetylene and KOH by contacting the acetylide with water and

Hydrogenating the acetylene with hydrogen obtained in step (3) to ethene and ethane or

(b) by using said hydrogen to hydrogenate carbon in the presence of a catalyst to produce methane.

Suitably, the hydrogenation catalyst consists of a part of the potassium obtained in step (i) and the hydrogenation temperature is in the range of 180 C to 36O C.

According to an advantageous development, in a further stage, part of the potassium obtained in step (i) is treated with water to form hydrogen.

According to another embodiment, in a further stage, part of the potassium obtained in step (i) is reduced with potassium hydroxide produced in step (3) to produce potassium oxide and hydrogen for reuse in the process.

Advantageously, the potassium oxide in stage, ("l) under a

    %

Pressure of about 133 ° Pa to atmospheric pressure to a temperature of

o '

temperature above 350 C heated.

It is an embodiment of the process of the invention that the sulfide prepared in step (1) is heated under reduced pressure to about 65 ° C. to form potassium sulfide and sulfur.

The potassium suicide formed is suitably recycled to the step (i).

In another embodiment, the potassium sulfide is reacted with water to form potassium hydroxide and potassium hydrosulfide.

It is advantageous that the hydrogen produced in step (3) is dissolved in molten potassium metal obtained in step (i) to be stored in the process for later use.

In a particular embodiment, lead sulfide is reacted with a portion of the potassium metal obtained in step (i), the temperature increased to about 330 ° C. and molten

Remove the lead by removing it from the lighter material floating on the surface.

There is another embodiment in which zinc sulfide is reacted with part of the potassium metal obtained in step (1), then the temperature is raised to about kh0 C and the zinc metal is separated by removal from the material floating on the surface of the system.

According to an advantageous embodiment, iron-copper gravel is reacted with part of the potassium metal obtained in step (1) at about 70 C to produce iron and copper, and then the iron is magnetically separated from the copper.

It is also possible that magnesium oxide is reacted with part of the potassium metal obtained in step (1) at about 36 ° C. and the elemental magnesium is recovered by distilling off the residual potassium.

An expedient embodiment is that the metal to be replaced in step (2) is initially in sulfide form and this metal is separated by dissolving the resulting potassium with or without sulfide in water, sulfur added, the resulting solution filtered under reduced pressure and thereby forming an anhydrous melt, the melt is heated, optionally under reduced pressure, thereby forming sulfur and potassium metal for reuse in the process.

The organic compounds, ethane or methane, can be reacted with a halogen in a manner known per se to form an alkyl halide, which can then be condensed with sodium or potassium obtained by the process of the present invention to form hydrocarbons in the fuel

-7 -

boiling under the conditions of the Wurtz-Fittig reaction. ','

Subordinate reactions produce intermediates and are recycled to the process to produce additional potassium for reuse in the process.

The process according to the invention comprises the following reaction equations:

1. KO - - ^ K ₊ 1/2 KO ₂

350 C - 883 C / i33OPa

2. K + KOH- - »- KO + 1/2 H ₀

36O ° C ^{2 2}

2a. K + 1/2 H ₂ O - »KOH + 1/2 H

3. K + Ι / Ζ H> KH

^ <38O ° C

k. KO ------> 11/2 κ + 1/2

^{2 0} 4 ° '

5. KH + 2 C; > KHC (in molten K)

<38 ° G ^d

6. KHC ₂ + H ₂ O> ^C 2 ^H 2 ^{+ K0H}

7. K ₊ 1/2 H ₂ O> K ₂ 0 + t / 2 H ₂

K ^H ?

8. CH ₉ + H -> C_H. ^ - ^ C ₀ H.

^{22 2} <65 ° C ^{2 4} <65 ° C ^{2 6}

9. KO ₂ - - - ^> K _{2 +} O

²² 653 C - 883 C

9a. 2 KO -V K_0_ + O ₀

2 o _c 2 2 ²

10, K ₂ O ₂ + 2 H ₂ 0 · - 2 KOH + H ₂ O ₃

'11. K + R Y. > KY + R

from xx

This reaction is carried out with molten potassium at temperatures above 65 C or with potassium vapor at temperatures above 78O ⁰ C. Y is either sulfur or 'oxygen and R is magnesium, zinc, cadmium, lead, iron, arsenic, antimony, silver or copper.

12. ^C 2 ^H 5 ^{X + C} 2 ^H 5 ^{X + 2 K = C} 4 ^H 10 ^{+ 2 KX} »

wherein X is chlorine or bromine.

13. c - + Vh ₂ - ^ - ~> CH.

250 c

14. K ₉ S K + 1/2 KS

² ° ²

15. k_s_ Ks

^{2 2} 76O ⁰ C ²

16. K ₂ S

₂ S- ».K ₂ S + K ₂ S

^{2 3} 36O ° C ₅ 65 Pa ^{2 2 2} , 17. K ₂ S + H ₂ O -> KOH + KHS

Further water gives a reversible reaction KHS + H ₂ Q KOH + H ₂ S.

18. Starting at 3V5 ° C: H ₃ S ---> H ₂ + S

19. k K ₂ S ₂ + 8 H ₂ O ^^ - ^ 3 K ₂ S. χ H ₂ O + K ₃ S ₅ '

(in a closed system).

20. k K ₂ S ₄ + χ H ₂ O - ^ 2 K ₂ S ₅ + 2 K ₂ S. χ H ₂ O The minimum amount of water (x), isi ^, which is necessary to form the hydrate of potassium sulfide, which at the temperature

exists at which this hydrolysis takes place.

21. k K ₂ S _4. + Χ H ₂ O - > 3 K ₂ S ₅ + K ₂ S. χ H ₂ O

All of these hydrolysis-decomposition reactions are carried out in a sealed system and at temperatures above 60 ° C

        , -? ,"    .--: , '. *

but below the critical temperature of the water. The minimum amount of water (x) required for these hydrolysis reactions is that which forms the hydrate of the potassium sulfide that exists at the selected temperature or below 206 ° C, the melting point of K_S.

The process of the invention utilizes the lack of thermal stability of the potassium non-stoichiometric sulfide and oxide compounds to produce elemental potassium and a variety of potassium compounds, and this

potassium and some of the potassium compounds are then used to continuously reform these sulfides and oxides of potassium by reaction with water, metal ores, etc.

The above equations 1.4 and 14 are the basic equations of the present invention wherein elemental potassium is formed by thermal decomposition of potassium sulfide to potassium disulfide and said elemental potassium and by the decomposition of the potassium oxide to elemental potassium and potassium peroxide or potassium peroxide Figure 15 illustrates the decomposition of the potassium disulfide to potassium sulfide and sulfur, while equation i6 illustrates the decomposition of potassium trisulfide or a higher polysulfide to potassium sulfide and potassium disulfide. Equations 19f 20 and 21 show the hot water-led hydrolysis of the potassium polysulfide to potassium sulfide hydrate and potassium pentasulfide. The decomposition of the potassium trisulfide according to Equation 16 carried out in the heat and under reduced pressure is equally applicable to potassium tetrasulfide, pentasulfide and hexasulfide. Equations 9 and 9a show the decomposition of potassium peroxide and potassium superoxide. Potassium peroxide is decomposed to elemental potassium and elemental oxygen. Potassium superoxide K0_ is decomposed to potassium peroxide K ₉ O ₉ and oxygen. At temperatures above 780 C, K ₂ X> _ begins to decompose to K and 0.

In the absence of water vapor, potassium does not combine with oxygen or sulfur. Removal of the water vapor from the process system therefore reduces the tendency of the calcium and either sulfur or oxygen to reunite after the reduced pressure thermal expansion.

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see decomposition of potassium oxide or sulfides strong.

Ealium hydroxide, potassium oxides, potassium sulfides and potassium hydrogen sulfides melt and have low water vapor pressures. Quinium sulfides and potassium oxides are non-stoichiometric compounds with defects in the anion sublattice. Water, Hydrogen, and even potassium hydride are incorporated into the anion sublattice. The hydrogen is generated by the reaction of potassium metal with water vapor and in the reaction of elemental potassium to Kaliumhydf oxide. More potassium will react with this potassium hydroxide to form additional hydrogen and potassium oxide. In the case of 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 hydroxide to form additional hydrogen and potassium oxides. At the decomposition temperature of potassium oxide, at 35 ° C, the elemental potassium will combine with some of the hydrogen produced to form potassium hydride. If the temperature is raised above 38O ° C, then the hydride begins to dissociate.

The elemental potassium resulting from the decomposition of potassium sulfide or potassium oxide is soluble in the remaining solids until such conditions of temperature and pressure as are required to vaporize elemental potassium are achieved. As shown by, equations 15-21, it has been found in the present invention that potassium fluoride obtained by reducing the sulfur content of potassium pentasulfide or any other polysulfide having a sulfur content of two or more is found within the present invention.

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    -'; (. '-:, , , ·. '. .:

half of 2k h at a temperature of 78O ° C to elemental potassium and sulfur can be decomposed. Potassium pentasulfide melts at 206 ° C and decomposes to potassium tetrasulfide and sulfur begins at temperatures of 300 ° C. At 2O6 ° C, melts of potassium pentasulfide are essentially anhydrous.

Potassium tetrasulfide melts at 145 ° C, potassium trisulfide melts at 279 ° C xmd Potassium disulfide melts at 47 ° C. Each of _these] compounds produced an anhydrous melt at temperatures above their melting points. It is easier to produce ^{1 of} these water-free melts under reduced pressure. * The reduced pressure permits the easier removal of water of hydration, so that anhydrous melts are formed. The temperature should be at least high enough to reach the melting point of the particular potassium polysulfide and the reduced pressures should be residual pressures in the range of about 130 to about 6550 Pa. Since these potassium polysulfides are decomposed to lower sulfur content polysulfides, the conditions of temperature and reduced pressure should be such as to remove the sulfur by distillation.

Sulfur boils at a pressure of 1 bar at ΊΛ 5 C and at a pressure of about 130 Pa at 185 ⁰ C.

Potassium trisulfide decomposes at 350 C and a pressure of about 7 Pa to a mixture of potassium monosulfide and disulfide. Potassium disulfide decomposes to potassium sulfide and sulfur at 65 ° C. and about 7 Pa, and anhydrous potassium sulfide decomposes at 78 ° C. into elemental potassium and sulfur, while hydrated potassium sulfide requires decomposition to sulfur and potassium 8 ° C. Without reduced pressure, potassium disulfide is the most thermally stable compound of potassium and sulfur.

- 12 -

in the case of anhydrous potassium sulfide at temperatures above 78 ° C and in the case of hydrated potassium sulfide at temperatures of 8 ^ 0 C to elemental potassium and potassium disulfide decomposes, For practical purposes, the decomposition of potassium disulfide takes place at a temperature of 883 C at a pressure of about 133O Pa. Under these conditions, potassium disulfide rapidly decomposes into its elements. The other source of potassium from potassium sulfides is the decomposition of potassium disulfide in potassium sulfide at 78 G and a reduced pressure of about 130 Pa, and the subsequent decomposition of the potassium sulfide into its elements under the same conditions.

If the method according to the invention is based on potassium oxide, then potassium monoxide is decomposed at temperatures above 350 ° C. into pure potassium and potassium peroxide or potassium peroxide, but the potassium from this mixture is not readily extractable at these temperatures. At a pressure of about 7x10 Pa and a temperature of 3 ^ 0 C, something elementary

. '·. ''. ·. · .. '. ^ ' ^: ' -

Res potassium can be separated by distillation. At temperatures above the melting point of potassium peroxide, at 490C, potassium can be separated by distillation at pressures of about 1330 Pa. At temperatures of 7 ^ 0 C almost all of the potassium can be separated by distillation at about 1330 Pa. The potassium monoxide decomposes into potassium peroxide and potassium, and the potassium peroxide is then melted at 490 C to render the mixture anhydrous. The removal of the water retards the formation of hydrides, hydroxides and hydrogen, and this allows the decomposition of the potassium oxides into their constituent elements.

- 13 -

The potassium produced by the present invention is then reacted with less than the stoichiometric amount of water, eg, 15%, less, to produce potassium hydroxide and hydrogen, as shown in Equation 2a. Nucleated potassium and potassium hydroxide give additional hydrogen at temperatures above 360 ° C to form the unstable potassium monoxide (Equation 2). The potassium monoxide K _? 0 then becomes

- '. 'ι'

to potassium and oxygen, or to potassium and potassium peroxide or potassium peroxide, by one of the disclosed methods to produce hydrogen continuously (Equation A). A portion of the potassium peroxide or potassium superoxide may be present in less than the stoichiometric amount of water, e.g. 15% less, to make more potassium hydroxide and hydrogen peroxide (Equation 10 '). The unstable hydrogen peroxide can then be used as an oxygen source. Potassium superoxide and potassium peroxide can also be used as oxygen sources, with superoxide temperatures above 653C and peroxide temperatures above 78O ° C, as shown by Equations 9 and 9a.

At any temperature above its melting point,

x- O "''. '·

65 C, potassium in liquid or vapor form reduces the ores of magnesium, copper, silver, lead, zinc, antimony, arsenic, cadmium and their mixtures to liberate the corresponding metal and form potassium oxide or form the sulfides or oxides of potassium and release of elemental copper, silver, lead, zinc, calcium, antimony, arsenic, cadmium, etc., depending on whether these metals are in oxide or sulphide form in their naturally occurring mixed ores

Ore concentrate present goods.

* '. '· ..' ... · '.. ·

If elemental potassium has been used to produce hydrogen by decomposition of water or potassium hydroxide or by reduction of hydrogen sulfide resulting from the decomposition of the hydrolysis product, potassium hydrogen sulfide or potassium sulfide, then this hydrogen can be stored as potassium hydroxide by adding further elemental potassium at temperatures of 250 C to 36O C. Potassium hydride is miscible with molten potassium.

Potassium hydride dissolved in molten potassium reacts directly with carbon and graphite to produce potassium acetylide. Potassium acetylide reacts with water to form acetylleri. ·. ·. · · .-.; ' ; '·' ''. '' ·

The acetylene thus obtained can be reacted with further hydrogen derived from the process using molten potassium or potassium hydride as the catalyst to form ethene or ethane. The amount of hydrogen present determines whether ethene or ethane is formed. The , .' , ·. , ^ * ''

Temperature for this reaction is any temperature above the melting point of potassium, 65C.

Hydrogen produced by the present invention can be directly reacted with carbon to form methane in the presence of a suitable catalyst, such as nickel, at a temperature of 250G, such as the Raney nickel process. Elemental potassium or potassium hydride dissolved in potassium may be used as the catalyst at temperatures in the range of 180 ° C to 36 ° C.

  - 15 -

/ Ausführunffsbeis Piel ^r '

In the following the invention will be explained in more detail by way of examples

Example I

This example illustrates the preparation of potassium metal from K ^ O present in an ore.

In the practice of this example, an ore containing 10 kg of K "0 was placed in an autoclave below 1 ^! 0 heated to 883 C at a reduced pressure of about 1330 Pa. 4.1 kg of potassium metal were distilled off and 5.9 kg of K ₂ O _{2 remained} behind

Example II

This example illustrates the implementations of equations 2 through 9 and 11 and 12.

Technical grade 90% potassium hydroxide slabs were heated to 380 ° C. A reduced pressure of about 665O Pa was used to dehydrate these platelets to give a substantially anhydrous melt. Then the application of reduced pressure was discontinued and the temperature maintained at 380 ° C and elemental potassium added to the melt. It evolved Vas-

     '. ·, Hydrogen. 1 mole of potassium hydroxide was used, obtained from 62.2 g of the 90 $ pure technical KOH flakes and 1 mole (39 »1 g) of the elemental potassium.

The hydrogen evolved was introduced into molten potassium held at 280 ° C to form potassium hydride. 1 1/2 moles of potassium were used to take up the one mole of hydrogen and form a liquid consisting of

animal solution of potassium hydride in molten potassium.

The potassium hydride solution containing 1 mol of KH in molten potassium would be reacted at 350 C in the absence of air, nitrogen or carbon dioxide with 2 moles of carbon (graphite) to form potassium acetylide.

The mixture was added carefully and slowly to 1 1/2 moles of water to form 1 mole of acetylene and hydrogen as volatiles and a solution of potassium hydroxide. The generated gases, hydrogen and acetylene, under atmospheric pressure at 15 C 3.2 1, indicating the conversion into one mole of acetylene and in 1/2 moles of hydrogen ·. '·' ''.; , '' .. '' ''. , · '·

The potassium oxide formed by the reaction of potassium and potassium hydroxide was heated under a reduced pressure of 1330 Pa at ⁰ C -50P. After 2 l of these conditions, the mixture was heated to 883 C and condensed within 3 b. 20 min 1 1/2 moles of potassium by selective cooling of the discharged gas stream

Example III '. -; ':' . One mole of the potassium prepared according to Example I was treated with water as shown in equation 2a to

 '-.' / ''. · '·.' · '' '.' '

Res hydrogen gas and potassium hydroxide produce *

One mole of the resultant in the following example VI potassium superoxide was at 95 C to 2 moles of water _s added to 1 mole of hydrogen peroxide and 2 moles potassium hydroxide to produce, as illustrated by the equation 10th

This example thus demonstrates the recovery of nearly all of the potassium in the molds that were originally used, i. as elemental potassium and potassium hydroxide.

Example IV

This example shows the thermal decomposition of K «S in Ka

lium, as illustrated in equation Ι ² ». .

About 9-00 gK_S were heated to * 780 C under a reduced pressure of about 655 Pa to remove water. Then the pressure at this temperature was reduced to about 7x10

·. ? * .. '. ·; ';' , , \ '/';'. , ... ' ^: -'. _: '' .. .. '

Sulfur would be distilled off and condensed in a series of liquid nitrogen cooled traps.

,/ . '': '.'. ' . '. ·

After the distillation rate of sulfur had decreased, the temperature was raised to 883C. Potassium sulfate remained in the distillation chamber, which was identified by analytical reaction with barium. Potassium and sulfur were in liquid nitrogen cooled traps

  '·. '.' ·. '' · · ''. ·. ι

condensed. In the absence of water vapor, potassium and sulfur did not combine.

200 g of potassium were obtained

Example V According to Equation 11, the potassium obtained in Example IV was melted under a pressure of approximately 655 Pa and weighed from

  '.' '' '·. 'ν' '.' '

finally decanted.

The potassium was divided into 50 g animal samples and used in molten form.

One of these samples was used to melt 54 g of a lead sulfide concentrate, the? Containing 73 έ lead, "The melting was carried out at 7O ⁰ C. After completion of the reaction (after about 3 min.), Was the temperature to 330 C and the molten lead was separated from the lighter material floating on the lead surface.

- 18 -

Another 5 ° g sample was used to melt 6 g of zinc sulfide concentrate containing 509 c zinc. The temperature for this was 70 ° C. The reaction required about 2 minutes, the temperature was raised to kkO ° C, and the molten zinc was removed under the material floating on the surface of the zinc.

Another. 50 g of sample was used to melt 50 g of a copper sulphide concentrate containing 86% chalcopyrite (CuFeSp). This reaction was carried out at 70 ° C to obtain iron and copper. The iron was magnetically separated from the copper. The copper was melted and separated from the floating material on the copper surface.

The last 50 g of sample was used to melt 25 g of magnesium oxide at 36 ° C. The reaction required 6 minutes, elemental magnesium was obtained.

In all of these samples, the residual potassium was distilled from the generated metals at pressures useful to distill potassium, but which were too low to volatilize the other metal. The 3 sulfide samples were separated from the predominantly inert gangue containing them by dissolving the potassium sulfides in small amounts of Vasser. The solids were then separated from the liquid by filtration.

Sulfur was added to the filtrate and dehydrated by heating to 500 C under a pressure of about 655 Pa. The resulting anhydrous melt was then subjected to a temperature of 883 C under a pressure of 1330 Pa to again form potassium and sulfur vapor, which were then condensed. This reformation of potassium completed

_ 1 Q _ '

the cycle.

The potassium oxide formed in the magnesium melt was directly converted to potassium by heating the gangue and the potassium oxide under a pressure of "1.33-0-Pa 'to 883 ° C .-" Before the distillation of the potassium, some carbon dioxide escaped Carbon dioxide was taken up in potassium hydroxide as it escaped, most of the potassium was recovered after the carbon dioxide was removed from the system, and a second sample showed that the carbon dioxide was recovered.

10, · oxide, by preheating the magnesium oxide under reduced

    * .. ... , '.

Pressure could be removed before reacting the magnesium oxide with potassium. The potassium recovered from the potassium oxides was condensed by cooling and used again to melt other magnesium ores.

..; Example VI .. '.. ./,''V'''' Γ ' ^V - '.' ^: This example illustrates the reactions of equations b * 5 * 9, 10, and 13.

Hydrogen obtained by the process of the present invention was used to hydrogenate carbon (graphite) ^; at 25 ° C. in the presence of molten potassium (potassium hydride dissolved in molten potassium, Raney nickel may also be used). The pressure of the hydrogen resulting from the process system was used. A total of 100 grams of carbon were hydrogenated to methane in half an hour using 1 mole of potassium and 1 mole of potassium hydroxide and continuously recycling these reagents. This recycling consisted of dissolving residual potassium oxides in water and reacting the potassium hydroxide thus obtained with potassium, which was obtained by thermal decomposition of the potassium oxides at 883 C and without

a pressure of 1330 Pa (equations 1 and 2) was obtained. . ' ' ·. ..:. ^_.::: / '. '

A step of reducing the oxygen content of the system, which might have resulted from the decomposition of any potassium peroxide, was carried out by heating the potassium oxides at 653 C at 883 C prior to decomposition. It was carefully forbidden to condense potassium and let the oxygen escape from the Prozeßsysteai. This was done to avoid the production of potassium carbonyl.

The undecomposed residue was used to form potassium hydroxide and hydrogen peroxide by reaction with water (Equation 10). Care was taken to ensure that no hydrogen peroxide or any oxygen, which is formed by decomposition of the hydrogen peroxide, can enter the melt system.

Example VIl . ',''.'

This example demonstrates the preparation of elemental potassium and a mixture of potassium peroxide and potassium superoxide by thermal decomposition of potassium oxide, subsequent reaction of potassium peroxide-superoxide with a stoichiometric amount of water to form potassium hydrogen oxide and oxygen,

-ν '·'. , : L · - '"·; ^..;::':'''-' and the implementation of elemental potassium with potassium hydroxide for the formation of elemental hydrogen and to recover potassium oxide, to recycle it.

This decomposition may be carried out in the temperature range from 36 ° C to 38 ° C, with appropriate addition and removal of product above or below 653 ° C or above 779 ° C.

- 21 -

In the practice of this process, potassium hydroxide was heated to 370 ⁹ C in the absence of air under a reduced pressure of from about 130 Pa to about 10 3 Pa. Elemental molten potassium was added slowly to the anhydrous potassium hydroxide melt at a stoichiometric ratio of 1 MpI to 1 mole. Elemental hydrogen evolved and increased the pressure within the system considerably. Potassium reacts with oxygen, nitrogen, carbon dioxide, etc. Therefore, the application of reduced, Drukkes necessary to push back the reaction between molten potassium and the inert atmosphere. Neon, helium, argon (group 8 gases of the periodic table) can be used instead of reduced pressure.

The system was opened, the hydrogen was allowed to exit the system and collected. After removal of the hydrogen, a reduced pressure was again used. Potassium oxide formed during the evolution of the hydrogen was decomposed, mainly by thermal means. The elemental potassium formed together with potassium peroxide and potassium superoxide (K_O ") was gradually distilled off before the thermal decomposition of the potassium peroxide under reduced pressure. Only the potassium was distilled off. The distilled liquid / gaseous potassium and hydrogen were converted to potassium hydride under atmospheric pressure or higher pressure at temperatures below JBO ⁰ C.

After removal and separation of hydrogen and potassium, less than the stoichiometrically required amount of water, about $ 15 less, was added to form potassium hydroxide and oxygen. This oxygen was

removed separately from the process system, hydrogen and potassium were separated separately from the removed oxygen from the process system »

The excess of elemental potassium removed from the system beyond that which was accounted for by the formation of potassium peroxide, indicated that some potassium peroxide K'0 had formed. "

Potassium and potassium hydride were again reacted with water to form further hydrogen *.

10 '1 mol (56.11 g) Kaiiumhydroxid (85-86 # pure) was heated under a pressure of 1330 Pa ¹ to 380 C. Water was distilled off as the lower hydrates of potassium hydroxide formed. A solid potassium hydroxide melted at 360 ° C .-- 5 ° C. One mole of elemental potassium was melted under an argon atmosphere and added dropwise to the melt of kaolin hydroxide.

After the evolution of hydrogen increased the pressure within the evacuated system to atmospheric or overlying pressure, the system was opened and hydrogen was allowed to escape. After removal of the hydrogen, as shown by a stabilization of the system pressure at a pressure slightly above atmospheric pressure, a reduced pressure of preferably about 130 Pa was again applied. Elemental potassium was distilled from the system and received slightly more than 1 mole of potassium.

The elemental potassium was reacted with the hydrogen at a temperature in the range of 260 ° C to 38 ° C to form solid potassium hydride. The potassium hydride is soluble in excess molten potassium.

A little less than T moles of water were added to the mixture. The amount of water was reduced in the same proportion below one mole in which excess potassium had been removed from the system. Oxygen was developed from the potassium peroxide / superoxide mixture remaining in the reaction vessel and potassium hydroxide was formed. Example VIII '

This example demonstrated the production of hydrogen at high temperature. In carrying out this experiment, 1 mole of commercial potassium hydroxide was heated to 779 ° C under reduced pressure or an inert gas atmosphere (helium, neon, argon, etc.). '^; , ';'·'''''. .:. , . ".

Water was removed as the hydrates of the potassium hydroxide contained therein decomposed to form lower hydrates, with an increase in temperature. At 36O ⁰ G - 5 ° C, potassium hydroxide formed an anhydrous smelting oil. '''. . ',;''';"'... .... ^

Beyond the water of hydration, additional water was released due to the partial thermal decomposition of potassium hydroxide to potassium oxide and water. Above 36O ⁰ C - 5 C there is a progressive decomposition of potassium oxide to potassium peroxide and elemental potassium.

The resulting potassium reacts with the water vapor to form potassium hydroxide and water and with potassium hydroxide to form hydrogen and potassium oxide (equations 20 and 2}).

A balance was achieved after about 13% of the potassium and hydrogen had been distilled off. Thereafter, the decrease in hydrogen content in the process system allows

- 2h -

the further decomposition of potassium hydroxide-potassium oxide-potassium peroxide to potassium, without the potassium recombining with oxygen due to the reduced water content of the system. ,

In 2 1/2 hours 88% of the potassium and 88% of the hydrogen were recovered.

The reaction time was shortened to one hour by adding 1/2 mole of potassium to the anhydrous melt of potassium hydroxide,

Example IX

One mole of hydrogen obtained as indicated above was reacted with the acetylene generated at jGO C to form ethene !, a second mole of hydrogen was added to hydrogenate the ethene to ethane,

1 mole of the ethane was reacted in the gas phase with 1 mole of chlorine to form ethyl chloride. The ethyl chloride was collected and reacted at reflux in absolute ether with potassium under Wurtz-Fittig conditions to give butane. The butane thus prepared was reacted with chlorine gas in the same manner to form butyl chloride, which in turn was reacted with potassium metal obtained above under the conditions of the Wurtz-Fittig reaction to form hydrocarbons.

    .. '' '* ι:'

those who were suitable for use in internal combustion engines because of their performance,

In the following, a suitable device for carrying out the method according to the invention is explained in more detail with reference to the drawing:

The device comprises a melting chamber or retort made of a corrosion resistant metal or

alloy, such as nickel or tungsten, which can be heated under reduced pressure. A molten metal outlet 12 is located at the bottom of the melting chamber 10. A vacuum line Tk connects the melting chamber to a pump, not shown, which can evacuate the melting chamber to a pressure of from about 65 Pa to about 2460 Pa. Between the melting chamber 10 and the vacuum line 1-4, 3 traps A, B, C for condensing and recycling reformed oxides or sulfides and elemental condensed alkali metal are arranged and connected to both the melting chamber and the vacuum line. The return is done by pressing the respective taps 10. It is also a k. Trap 18 is provided, which is located away from the melting chamber 10 to collect sulfur that can be removed through the outlet 20. A suitable means, not shown, is provided on or around the melting chamber 10 to heat it up to 680 C and to heat the areas away from the chamber to gradually decreasing temperatures of 450 ⁰ O to 16O ⁰ C.

A ring 21 fitted within a slot 22 is provided on the melting chamber 10 to receive metal from the condensed vapors flowing through the vacuum line 14.

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Claims (9)

E rf i η d u η g s a η s p r u c hs 1 »An integrated process for Hefstellen less active metals and hydrocarbons by preparing KAII ^s urn from its non-stö'chiometrischen oxide or sulfide and then using potassium generated, the less · '' '. ^. '' '· active metals and the hydrocarbons can be obtained in the following manner Combination of stages is performed? . '.' .. ''''' ι. . '..'. · · (l) thermally decomposing potassium oxide or potassium sulfide, optionally under reduced pressure, substantially in the absence of water to obtain potassium metal and potassium peroxide or potassium superoxide and potassium disulfide, respectively, and separating the potassium metal from the other secondary products, {2) providing a portion of the potassium metal obtained in the previous stage at a temperature above its melting point in the molten or vapor state, reacting this potassium with at least one oxide or sulphide, magnesium, copper, calcium, silver, lead, zinc, antimony, . ''·'.'.'''".''''." . ' .. '\ Cadmium, iron, arsenic or a mixture of the foregoing metals to liberate the metal from the oxide or sulfide and separating the thus liberated less active metal from residual potassium or potassium compounds, (3) reacting another part of the potassium metal obtained in step (1) with water to form hydrogen, potassium oxide and potassium hydroxide; (k) using a part of the hydrogen obtained in step (3) to produce a hydrocarbon, namely: '.-. ·. '. ·. '. ··:.' , -, · (a) by reducing the hydrogen with potassium metal obtained in step (1) at a temperature of from 250 C to 300 ° C to form potassium hydride, reacting the potassium hydride with carbon to form potassium a, cetylide. / to form, '''v'''. · ,. , '. '''. Synthesizing acetylene and KOH by contacting the acetylide with water and Hydrogenating the acetylene with hydrogen obtained in step (3) to ethene and ethane or (b) by using said hydrogen to hydrogenate carbon in the presence of a hydrogenation catalyst to form methane. 2. The method according to item 1, characterized in that the hydrogenation catalyst consists of a part of the potassium obtained in step (i) and the hydrogenation temperature in the range of 18O ° C to 36O ⁰ C. Method according to item 1 or 2, characterized in that, in a further stage, part of the potassium obtained in stage (i) is treated with water in order to add hydrogen k . Process according to item 1, characterized in that in a further stage part of the potassium obtained in step (i) is reduced with potassium hydroxide produced in step (3), '::'. '' I: .-: '..' /. :, '.' ./ ·. · ": '- - ^r 28'- so as to produce potassium oxide and hydrogen for reuse in the process. _a Method according to item 1, characterized in that the potassium oxide in step (1) is heated to a temperature above 350 ° C under a pressure of about 1330 Pa to the atmosphere at the end of the atmosphere. 6. The process of item 1, characterized in that the sulfide prepared in step (i) is heated under reduced pressure to about 65 ° C to form potassium sulfide and sulfur; -the* . '>;; ..-. ' : '.' ^: ' . '. '' 7. The method according to item 1 or 6, characterized in that the potassium sulfide is recycled to the step (1). 8. The method according to item 1, 6 or 7, characterized in that the potassium sulfide is reacted with water to form potassium hydroxide and Kaiiumhydrosulfid. Process according to item 1, characterized in that the water-off-material produced in step (3) is dissolved in molten potassium metal obtained in step (i) for storage in the process for later use. 10. Method according to item 1, characterized in that lead sulphide is reacted with a part of the potassium metal obtained in step (i), the temperature is increased to about 330 ° C and molten lead is removed by removing, from the superficial, lighter material is separated. 11. The method according to item 1, characterized in that reacting zinc sulfide with a portion of the potassium metal obtained in step (i), then raising the temperature to about 4 ^ 0 C and the zinc metal by removing from the floating on the surface of the system Material is separated. 12. A method according to item 1, characterized in that egg shot copper gravel is reacted with a part of the potassium metal obtained in step (1) at about 70 C to produce iron and copper and then the iron is magnetically separated from the copper, 13. The method of item 1, characterized in that magnesium oxide is reacted with a portion of the potassium metal obtained in step (i) at about 36O C and recovered the elemental magnesium by distilling off the remaining potassium ΊΡ 'will. , ., · ·. "" - ^: '" ',. ',''.' -. ''"". , , , '>,. 'ι 14. The method according to item 1, characterized in that the in step (2) to replace metal initially in sulfide form and this metal is separated by dissolving the resulting potassium with or without sulfide in water, sulfur added, the resulting solution under reduced Filtered off pressure and thereby forms an anhydrous melt, one heats the melt, optionally under reduced pressure, and thus forms sulfur and potassium metal for reuse in the process. 1 page drawings