SU1297734A3 - Method for producing hydrocarbons from hydrogen-containing materials - Google Patents

Abstract

Conversion of shale oil, shale oil rock, sandstone or limestone with encapsulated kerogens or other precursors of like kind, as source materials thereof, yield low viscosity, hydrogenated products, and allow ammonia, sulfur, and metal value recovery from these source materials; these source materials are reacted in the presence of an alkali metal hydrosulfide or alkali metal sulfide or polysulfide reagent and steam, water or an alkanol, optionally with hydrogen sulfide.

Description

The invention relates to methods for processing kerogen-containing shales or resins derived from shale, and can be used in the oil shale industry.

The aim of the invention is to expand the base by processing sour shale or their products.

Fig. 1 schematically shows an installation for carrying out a one-step process of improving the quality of shale oil; Fig. 2 shows an installation for carrying out a multistage process for improving the quality of shale oil, including the regeneration of re-ReHTaJ in Fig. 3 — a facility for the regeneration of hydrocarbons from shale, including regeneration of by-products, as well as recycling of reagents, which in practice is implemented by carrying out a sequence of reactions in a number of different reactors i in Fig. 4 — installation for regeneration of a hydrogen sulfide Yes.

The method is carried out as follows.

According to the flowchart shown in Fig. 1, shale oil or shale is fed to line 1 via line 2, and line 3, a reagent consisting of a mixture of KHS, in an alcohol medium containing some water.

If the temperature is below 60 ° C, the mixed reagent and the hot slate are mechanically mixed. If heat is required, it is supplied with the help of a heated coil 4. While maintaining the temperature at a value below, 5 remove ammonia in a known manner,. for example by treatment with water.

Line 6 removes the liberated elemental sulfur which is formed during the removal of ammonia.

From the bottom of the reactor 1, through line 7, a mixture of the treated slate and the reactant is fed to the reactor 8. The heater 9 is intended to maintain the required reaction temperature in the reactor 8.

Line 10 may introduce additional reagents, such as KHS, KjSj, dissolved in alcohol or in water. In addition, water, steam, or hydrogen sulfide is supplied through line 10.

Temperature ranges at which the reactor 8 can operate, after

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the following: 220-240, 280-320 and. ZBO-ZDO C. In such temperature ranges the bulk of the products are formed. Typically, water and hydrogen sulfide are added at 170 ° C with KjS-x H O, where X is 5 or 2, i.e. various hydrates are very active reagents and contribute to the formation of gaseous hydrocarbons. At temperatures of about 135-150 ° C, such a reagent is a K 8 melt.

The light hydrocarbons formed through line 11 together with gases and water flow into the separator 12, where separation occurs. The gases are discharged through line 13. The liquid phase is exfoliated into two layers. The top layer, if present, is the light hydrocarbon fraction, and the bottom is. SRI - water-alcohol mixture. A mixture of water and alcohol is used as a starting material for the subsequent formation of a reactant.

Part of the gases and light distillates are fed through line 14 to the distillation column — reactor 15, where they are introduced from the bottom of the distillation column (reactor) 15.

In the distillation reactor 15, the temperature is maintained at 220-240 ° C. The mixture of shale and reagent is also introduced from the bottom of the column 15 through line 16.

In order to ensure the supply of hydrogen to hydrogenate the components of the oil shale, water and, to a much lesser extent, hydrogen sulfide are introduced further along lines 17 and 18 from the bottom of the reactor. As the oil shale is hydrogenated, the hydrocarbons rise through the column and are discharged as vapor through line 19, cooled in refrigerators 20 and 21, and through line 22 are fed for further processing. After testing the reagent, if it is properly selected, it is regenerated in liquid or solid form at the bottom of the column 15 and withdrawn via line 23 for further use.

FIG. 2 shows an installation for a multi-stage process for treating oil shale, including the regeneration of a reagent, so that in the case of a completely continuous process, to ensure pre-established product flows from the original shale material. In accordance with the process depicted in FIG. 2, in the reactor

24, the pretreatment process is carried out in the same manner as in the pretreatment reactor 1, shown in FIG. In the reactor 25, the same reactions take place as in the reactor 8 in FIG. From the reactor 25, the bottom products are fed via line 26 to the second reactor 27.

The top fraction from the reactor 27 is withdrawn via line 28 and refluxed in a reflux condenser 29, the top product from the reflux condenser 29 being withdrawn via line 30 at a temperature of, for example, 225 ° C and processed as shown in FIG.

The aqueous-alcoholic mixture is recycled via line 31 to reactor 27. Hydrogen required for hydrogenation is fed to reactor 27 via line 32.

Since the reaction temperature in the reactor 27 is significantly higher than in the reactor 25, it is necessary to heat through the internal and external coils 33.

Bottom products from reactor 27 are introduced via line 34 to reactor 35 for additional hydrogenation and regeneration of the reactants.

In the reactor 35, the oil shale and the reagent are heated in the range of 360-400 C, and the reagent is recycled from the bottom of the reactor towards the downstream reaction product. As the reactant accumulates in the reactor 35, it is discharged using a three-way valve 36.

The refluxed fraction recovered from column 29 is fed through line 30 to additional column 37. The reagent used in column 37 is mainly Kj S and KHS in an alcohol medium. Water is added to column 37 along the line t7. The reagent waste stream from the column 37. through line 38 is combined with the reagent discharged through line 39 from reactor 35 and returned to regenerate and recycle the reagent to the process.

In the reactor 40, to which hot reagent, for example, is fed via line 41, for example, the latter is cooled with cold water. After cooling, water is added in an amount of 1-2: 1 with respect to the reagent. The reaction with water leads to the re-formation of the reagent and the formation of an alkali metal hydroxide and an alkali metal sulfide.

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The reagent and product stream from reactor 40 is withdrawn and filtered on filter 42 to remove impurities and suspended heavy metal flakes or other suspended particles. In the vessel 43 for reforming the reagent, the latter is subjected to additional cooling when mixed with a cold azeotropic alcohol-water solution and hydrogen sulfide. The hydrogen sulfide introduced into the reactor 43 through line 18 reacts with an alkali metal hydroxide to form the corresponding sulfides. This reaction should be carried out with cooling. Since the reaction of sulfide in alcohol depends on temperature, concentration, and solvent, various kinds of alkali metal sulfides can form, for example, potassium sulfides, if the temperature is not maintained at an appropriate level.

Since reactant mixtures are present in reactor 43, they can be used as such in reactor 24 and diluted with alcohol. However, individually obtained alkali metal sulfides can also be obtained or reformed for further reactions carried out in reactors 27, 35 or 37, and then mixtures with a narrower number of reactant forms are obtained.

FIG. 3 shows a plant for carrying out a process in which a shale resin is obtained directly from the rock, both from organic and / or from inorganic carbon formations using the described reagent. Accordingly, the rock containing shale resin is crushed to particles with a size of 6 mm or less and fed to the hopper 44 and mixed through a screw feeder 45 with the reagent supplied through line 46. However, the reaction does not depend on the size of the rock particles. The regentant is in liquid form and covers a particle of rock. The mixture then enters the reactor 47. Since the reaction of the reagent and water and HjS with rock shale is exothermic for some systems, the oil shale is a reagent, the coils 48 can be used for heating as well as cooling depending on the situation.

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In the reactor 47, in which the temperature is maintained during the continuous process, for example, 280-390 C5 rock can be mixed by means of pumps 49 supplying part of the reactants both in the liquid and gaseous state to the lower conical part of the reactor 47 through a plurality of holes 50 resulting in part by

childbirth is maintained in suspension, or

other mixing agents are used. Similarly, steam and hydrogen sulfide can also be introduced below the level of the rock through line 51. If the rock is heavier reagent and regenerated hydrocarbons, it falls to the bottom of the conical reactor.

Through the appropriate valve pump 52. the components deposited in the reactor are removed from it and discarded or introduced into the scrubber 53. Scrubber water is used in limited quantities as it provides leaching of the precursors of the reagent or heavy metals that can precipitate from leach solution with water. The remainder of the rock is pumped through the valve pump 54 and then filtered on a drum filter 55, on which the remainder of the rock remains as a residue on the filter. The spent rock is diverted via line 56.

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The reactor 61 contains a catalyst reagent. The same applies to reactor 59. The reagent is deposited on alumina with a large surface area of aluminum-potassium silicate, spinel or similar carriers, which are commonly used in the petroleum industry to form a catalyst.

Although the catalyst is suspended on a grid 62, the reaction can equally be carried out in any column (or reactor) in which supported catalysts are used. The grid 62 can be removed and rested on the rim 63, with the edge 64 of the grid 62 being used as a funnel. Water is added to reactor 61. The dephlegmator 65 is similar to the dephlegmator 60, it operates at 135-150 ° C and it processes the whole ha30

zov stream.

4 shows an installation for carrying out the process of regenerating hydrogen sulfide gas. The reactor 66, usually operating at 320-390 ° C, is loaded with rock shale rock, with a reagent in hid or solid form. Products emerging from the top of the reaction with water in the form of steam and hydrogen sulfide, torus 47 pass through a sieve 57 and are treated in the same way. described consist of ammonia, hydrogen sulfide, ga- above. Then, the resulting gases, cooling, distillates, depending on the operating temperature and reagent used. Gaseous products, which can condense at cooling water temperature, are introduced via line 58 to the second reactor 59 and react there with applied reactant acting as a catalyst. A stream of reaction products through line 58 is introduced into the reactor 59, made in the form of a plate column, in which the catalyst is deposited on the bottoms of the plates. This reactor can be placed on top of the reactor 47. The stream 58 is introduced from the bottom of the column 59. The upper stream of the reaction product is separated by means of a reflux column 60.

In case the reactor is operated with the formation of a small amount of liquid distillates, if any, and the reaction is carried out at high

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temperature so that only gaseous overhead products and / or high-boiling distillates are removed from reactor 47 via line 58, the reaction products from reactor 47 can be processed as follows, represented from the dotted part A-1.

The reactor 61 contains a catalyst reagent. The same applies to reactor 59. The reagent is deposited on alumina with a large surface area of aluminum-potassium silicate, spinel or similar carriers, which are commonly used in the petroleum industry to form a catalyst.

Although the catalyst is suspended on a grid 62, the reaction can equally be carried out in any column (or reactor) in which supported catalysts are used. The grid 62 can be removed and rested on the rim 63, with the edge 64 of the grid 62 being used as a funnel. Water is added to reactor 61. The dephlegmator 65 is similar to the dephlegmator 60, operates at 135-150 ° C and it processes the whole g45

give, for example, in the condenser 67. The cooling jacket surrounding the cooler 67 contributes to the cooling of the reaction gas. The initial and heavier products regenerate from the bottom of condenser 68. Gaseous products are fed to vessel 69, in which water or alcohol (usually methanol or ethanol) is found in KOH solution. The solution in vessel 69 is kept cool so that light gases, such as hydrogen sulfide, pass through the vessel. If alcohol is used, the gases C are absorbed, and C and Cg dissolve, therefore an aqueous solution is more preferable.

In vessel 70, the contents are cooled to approximately and at this temperature the gases C and C are removed. Although most of the fractions C and GS

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removed in vessel 70; some of them are fed to vessel 71, where they are removed at -30 ° C together with fraction C in ethanol or methanol. The porous glass disk 72 removes the remaining mist from these components. At this point, mainly H jS and fractions C and C are present in the gas stream and this stream is then introduced into a vessel 73 containing KOH and alcohol, usually ethanol or methanol in the form of an aqueous solution. Hydrogen sulfide re-forms the reagent, which is regenerated as a precipitate, while the light gaseous fractions, mainly C and C, pass this vessel. Several scrubbers can be used to remove hydrogen sulfide, similar to scrubber 73. Hydrogen sulfide is not released into the atmosphere. The water-alcohol fraction from vessel 70 is first used to compensate for the alcohol removed from vessel 73. This mixture should be cooled in a heat exchanger 74.

In addition to the regeneration of alcohol and water, shown in Fig. 4, the scheme in which the reagent is used in a dry form, i.e., is equally applicable. without diluting with alcohol. In this case, the alcohol is present in the vessel 73, in which the reagent is reformed, and the water is present in the vessel 69. The vessel 73 can work without alcohol at a temperature difference of uncondensed volatile substances of 43 g.

The temperature is lower, but it should be cooled due to the exothermicity of the reaction and the water content should be kept just below 2 mol per mole of KOH.

The hydrogen sulfide regeneration described is applicable to the processes described in Figures 1, 2 and 3.

Example t. 200 g of shale resin is obtained by heating in the retort of combustible shale and treated in the reactor of the first stage (figure 1) when heated from 20 to.

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Characteristics of shale resin: density 1,0136 g / cm; C: H ratio: 1.53, elemental composition, wt.%: C 78.65, H 10.0, - S 6.27; N 1.37. Fractional composition, C: NC - 192; 10% - 255; 20% - 286, 30% - 316, 40% - 328 50% - 338, 60% - 352, 70% - 353; the remainder is 21.6% - 354. Processing time is 2 hours. Hydrogen sulfide is not fed into the reactor, the solution contains 50 ml of methanol solution of empirical potassium hydrosulfide dihydrate (0.38 g of KHS / ml of solution). The first reaction stage is carried out in a vertical cylindrical vessel with a total volume of approximately 1 liter, equipped with a heating jacket. The analysis of shale tar, products and residue in the reactor is given in Tavl.

Table 1

The metal content is given in table 2.

Shale resin

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25.4

0.902 6.74

Another portion of untreated shale tar is reacted, the characteristic given above at final temperatures of 230-250 ° C in one reactor with .xEyO obtained from KHS loaded into the reactor. The amount of reagent is 8.5 g per 1000 g of resin.

The reaction starts at 20 ° C and leads to it. The characteristics of the first portion of distillate (12% of resin) are given below:

Density API Density Sulfur, May. Higher heat of combustion, kcal / l 9715 Nissha tesh1o, that combustion, kcal / l 8759 Ash, wt.%, Not

more than 0.001

Carbon, wt.% 80.15 Hydrogen, may.% 11.32

Nitrogen, wt.% 0,68

Oxygen + indefinable substances, wt.% 1.11 Sodium, ppm 1.2 Potassium, ppm 1.1 Example 2. Test 1. 60 ml of the reagent solution are reacted with 1900 g of oil shale by simply mixing the shale and reagent solution. Use two layers of reagent of the following composition. 108 ml of absolute ethanol and 4 mol of sulfur are added to 6 mol of KOH dissolved in 12 mol of water. After getting it

table 2

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The second solution (the exothermic dissolution of KOH in water implies a heat sink) is additionally introduced with 2 mol of sulfur in 108 ml of absolute ethanol to obtain an empirical composition of + 2K.2S +. This reagent forms a two-layer solution. 1/3 of the solution, taken in ratios in which the two layers are equal to each other, is added to the equimolar amount (based on K) of the reagent obtained as follows: KOH + in solution saturated under conditions cooling with hydrogen sulfide; the other mol KOH is then dissolved in the solution. The solution melts at 60 C. The reagent has a composition K S.

Oil shale is treated in a 3.8 l reactor with mechanical stirring with steam and a stream of hydrogen sulfide supplied at a rate of 80 ml / min. Oil shale was obtained from Israel. Before introducing the reagent to the crushed material, the reactor is thoroughly purged from oxygen from air. The temperature rise begins by slowly heating the reaction vessel in which the reactant and hydrogen sulfide are present. In addition, the reagent can be introduced into the reactor in the form of a solution in alkanol.

Ammonia is released at about 50 ° C. With increasing temperature, a small amount of additional products is released from the rock, and

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products obtained by this heating and slow reaction are collected (for example, ammonia in water) by condensation.

When the reaction mass is slowly heated to 70 ° C, hydration water is removed from the reagent. Water should then be introduced into the reaction zone in order to maintain the reagent in an active state. О With a further rise in temperature, different amounts of reagents are obtained, which are collected and condensed. At 320 ° C, the reaction becomes exothermic and the temperature rises to 440 ° C. The temperature is again reduced to 320 ° E, but the exothermic reaction starts already below 320 ° C. At 380 ° C, the steam supply is stopped, but the exothermic reaction occurs until the maximum temperature of 440 ° C is observed. The reaction takes two hours, get 59 L ha Hydrocarbon condensate contains 6.25 wt.% sulfur, has an API 31 and the collected liquid volume is 71 ml. In addition, a gas is obtained which contains 66% by volume of hydrogen, 2% by volume of carbon dioxide; 1% by volume of carbon oxide and 28% by volume of hydrocarbons containing 1-6 carbon atoms. A part of the condensate was lost when an excess of steam carried part of the shale into the condensation vessel.

The distillates from the two experiments were combined and 100 ml were subjected to boiling point determination. The initial boiling point is 71 ° C and the final temperature is 307 ° C with a residue of 1.7% by weight, which contains 3.7% by weight of sulfur. The sulfur content in the boiling product (0-50%) is 7.25% by weight, the sulfur content in the second half of the fraction (above 50%) is 4.1% by weight. The nitrogen content is reduced to 0.11% by weight. The product has

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COjj is 6% by volume (C02 is obtained from the car: in. In the gas, hydrogen is 69% by volume, the greenish-brown color is transparent to j.-4 f or -1)

Example 3. 453 g of combustible shale were reacted, as in Example 2, with potassium hydrogen sulfide, KHS in hydrated form, in the presence of species. thirty

oil shale bonates), the rest is hydrocarbons with a carbon content from 1 to 6. Obtain 77 ml of condensate with an API number of 29 and containing 7.1 wt.% sulfur.

The amount of reagent used is 60 ml of solution from 4 g / ml KHS. The potassium hydrosulfide used is taken as an alcoholic solution (methanol and ethanol) of potassium hydroxide, and the alcohol is removed to increase the temperature to 175 ° C. At the same time, a certain amount of hydrosulfide is converted to potassium sulfide HjO hydrate (under these conditions, k is usually 5). Some products of the reaction, which are taken on two condensers, are further subjected to distillation. At 160 ° C, the potassium sulfide hydrate decomposes to produce an abundant amount of gas.

Experience 2. 60 ml of the solution of the following reagents are mixed with 2200 g of combustible shale Israel. The reagent is used as in Phase 1, except that the COY + 2H20 is saturated under conditions of cooling with hydrogen sulfide, and 1 mol of KOH and the resulting solution are added. The solution is heated to a temperature above, then 8.3 mol of sulfur reacts with this solution. The other catalyst is the same as in Experiment 1, except that no additional amount of sulfur is added (compared to 2 mol, as it was before).

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Equivalent amounts of solutions added based on potassium. A round steel reactor with a capacity of 3.8 liters with heating and mechanical stirring is used. The resin is distilled from combustible shale, usually at 220-240 and 280-320 ° C in the presence of steam and hydrogen sulfide at a flow of 80 ml / min.

The shale oil Izrail contain 5 wt.% Hydrocarbons ± 25% (from 5%). The sulfur content in the shale is 2.5 wt.%.

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29773412

The hydrocarbon condensate contains 6.25 wt.% Sulfur, has an API 31, and the collected liquid volume is 71 ml. In addition, a gas is obtained which contains 66% by volume of hydrogen, 2% by volume of carbon dioxide; 1% by volume of carbon monoxide and 28% by volume of hydrocarbons containing 1-6 carbon atoms. A part of the condensate was lost when an excess of steam carried part of the shale into the condensation vessel.

The distillates from the two experiments were combined and 100 ml were subjected to boiling point determination. The initial boiling point is 71 ° C and the final temperature is 307 ° C with a residue of 1.7% by weight, which contains 3.7% by weight of sulfur. The sulfur content in the boiling product (0-50%) is 7.25% by weight, the sulfur content in the second half of the fraction (above 50%) is 4.1% by weight. The nitrogen content is reduced to 0.11% by weight. The product has

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Example 3. 453 g of combustible shale were reacted, as in Example 2, with potassium hydrogen sulfide, KHS in hydrated form, in the presence of species. 0

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The amount of reagent used is 60 ml of solution from 4 g / ml KHS. The potassium hydrogen sulfide used is taken as an alcohol solution (methanol and ethanol) of potassium hydroxide 5 and the alcohol is removed when the temperature is increased to 175 ° C. At the same time, a certain amount of hydrosulfide is converted to potassium sulfide HjO hydrate (under these conditions, k is usually 5). Some reaction products, which are taken on two condensers, are further subjected to distillation. At 160 ° C, the potassium sulfide hydrate decomposes to produce an abundant amount of gas.

Significant amounts of liquid hydrocarbon condensate from shale are obtained at a temperature of 230-250 ° C, 320-350 and at maximum temperature. However, at the end of the experiment at 400 ° C some condensate is released. Gas collection was not provided. 25 ml of oil with a density of 0.89 g / cm and an API number of 26 are collected in the form of condensate. Since this sample of oil shale contains 5% by weight of hydrocarbons, their extraction is 98.2% by weight.

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Example 4. The experiment was carried out with 453 grams of the same oil shale as in Example 3, with NaHS flakes. The amount of the reagent is 100 g. This float melts at 112 C. The melt state is maintained by using an inert atmosphere and in the presence of water vapor.

The hydrate, melting at 112 ° C, decomposes at a higher temperature, which is accompanied by the release of water and its conversion into a lower hydrate, which is a solid. Water was introduced into the reactor at a rate of 6 ml / min. During the experiment, no hydrogen sulfide is added. In the same manner as in Example 3, 24.5 ml of product is obtained, and this condensate also has a specific gravity of 0.89 g / cm and an API number of 26. A second experiment under the same conditions also results in an API 26 .

By washing the shale with water after treatment with the reagent, a green color solution is obtained which has a very deep green color. This means the presence in the sample of alkaline iron, including other mineral complexes.

When hydrogen sulfide is used, the formation of these complexes (predominantly ferrite-ferrite) is significantly reduced and the reagent consumption is also reduced.

From examples 3 and 4 it follows that there are no C5 differences between the quantity and quality of the hydrocarbon product obtained using sodium hydrosulfide (technical grade in the form of flakes) wetted with water in a reaction vessel and obtained using alkaline solutions of potassium hydrosulfide and steam. as reagents in the way.

From the latter experiment, it follows that a noticeably smaller amount of reagents can be used when hydrogen sulfide is used in the reaction vessel.

When the reaction is performed in one stage, the API number for the condensate can be in the range of 20-32 with a fairly easily reachable range of 25-30, with product yields of 100% by weight or more, based on the amount of organic carbon in the oil shale. For these purposes, it is preferable to use hydrogen sulfide.

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In a two-stage reaction carried out in the presence of catalysts, the API numbers can be about 40.

Example 5. 466 g of shale resin, as in example 1, is treated with 18.6 g of reagent in the first reaction reactor and 12.4 g of reagent in the second reaction reactor.

Take the following reagents: KHS and KjS xHjO in the reactor of the first reaction, S also in the second. The reaction in the second reaction reactor is carried out in the gas phase. In the reactor of the first reaction, the maximum temperature is 390 ° C, in the reactor of the second reaction - 220 ° C. The processing time is about one and a half hours.

The analysis of the initial distillate from the second reactor is as follows; API number 16 ° C 22.6 Specific weight

16 ° С, g / cm 0.9180

Sulfur, wt.% 5,94

The heat of combustion is higher,

kcal / kg 9665

The heat of combustion is lower, kcal / l 8863 Ash content, wt.% 0.006 Carbon, wt.gr 80.48 Hydrogen, wt.% 10.66 Nitrogen, wt.% 1.05

Oxygen, wt.% 1.86 Sodium, ppm: 0.32 Vanadium Undeterminable

Potassium Undefinable

Iron Undeterminable

Analysis of the final distillation fraction;

AP1 number 160С19,5 Specific weight

16 C, g / cm3.9371

Sulfur, wt.% 6,19 Higher heat

combustion, kcal / kg9752 Low heat

combustion, kcal / l9130

Viscosity, 38 ° C41.9

Ash content, wt.% 0,007

Carbon, wt.% 80,51

Hydrogen, wt.% 12,04

Nitrogen, wt.% 0,96

Oxygen, wt.% 0,29

Sodium, M.PN share 0,42

Vanadium Undefinable

Potassium Undefinable

Iron Undeterminable

Nickel Undefinable

151297734

It should be noted that although the number of APIs is decreasing (as follows from recent distillations), the hydrogen content increases. The above reactions are carried out without the use of hydrogen sulfide. Adding hydrogen sulfide improves product quality.

Reducing the amount of reagent does not impair the yield, since hydrogen sulfide is present, 7.5 ml of reagent (based on KHS) can be used to process 500 g of resin. The same is true for oil shale, i.e. about 7.5 ml (based on KHS) of the reagent will need to process 1100 g of shale, although there are 16

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The quantity required for an efficient mixing is best to precoat the shale with reagents in the absence of oxygen, since oxygen tends to degrade the reagent.

It is preferable to use a liquid or dissolved reagent. Liquid stable reagents can be used to coat combustible shale, at the appropriate melting point of the selected reagent or their eutectic liquid mixture.

Usually, the number of moles of hydration water is determined thermographically by the dependence of temperature on time and the observation of various levels of temperature — time, also by the release of water in the form of gas.

For shale coating, for practical reasons, it is important to guarantee a thorough reaction with shale. The optimal level of efficiency is established for each type of shale using the necessary series of experiments with a sequential decrease in the amounts of the reagent and the appropriate use of hydrogen sulfide at the required place, time, and speed.

Some of the hydrosulfide of the carbon dioxide, as carbonaceous malium, are decomposed by hydrolysis into materials using shale kerosene hydroxide and hydrogen sulfide. The hydrogen-containing rocks or shale to those at a higher temperature of the resin, contacting them is carried out with hydrogen at a temperature of 100-400 ° C in the presence or in the treatment of gas.35 hydrosulfide, sulphide, polysulfurium potassium oxide provides for Potassium sulphide hydrate, taken at and above, whereby the calcium carbonate from the lime residue of the combustible shale reacts with the potassium sulfate from the residue of the reagent to form calcium sulfate and a mixture of potassium hydroxide and potassium carbonate. At this time, the content of potassium and sodium in the remainder of combustible shale. also extracted in hydroxide form, i.e. by leaching, and recycled.

The steam is applied at a temperature depending on the type of shale and the levels of decomposition of the constituents, as well as the target product. For sodium hydrosulfide and a range of sulphides or reactions, water may be barrated in the reaction formula of the invention.

Claims (4)

1. A method of producing hydrocarbons from carbon-containing materials by mixing them with sulfur compounds - 25 alkali metals and contacting at elevated temperature with the release of hydrocarbons, ammonia and sulfur, characterized in that, in order to expand the raw material Z40 individually, or in combination, in the form of alcoholic solutions or their hydrates, or sodium hydrosulfide, taken as a hydrate. 45 2. Method POP1, characterized in that the process is carried out in the presence of water vapor and / or water and hydrogen sulfide. 3. Method pop. 1, which differs from the fact that the process is carried out either in one step or in two, and the processing in the second stage is performed with hydrosulfide or potassium sulfide hydrate at temperatures lower than the treatment in the first stage. . torus. Similarly, for exothermic reactions, bubbling of water allows control of the reaction. Although the reaction masses of combustible shale and reagent may be Invention Formula 20 1. A method of producing hydrocarbons from carbon-containing materials by mixing them with sulfur compounds - 25 alkali metals and contacting at elevated temperature to release hydrocarbons, ammonia and sulfur, characterized in that, in order to expand the raw material, potassium sulphide hydrate, taken individually, or in combination, in the form of alcoholic solutions or their hydrates, or sodium hydrosulfide, taken as a hydrate. yes, potassium sulphide hydrate, taken five 2. Method POP1, characterized in that the process is carried out in the presence of water vapor and / or water and hydrogen sulfide. 3. Method pop. 1, which differs from the fact that the process is carried out either in one step or in two, and the processing in the second stage is carried out with hydrosulfide or potassium sulfide hydrate at temperatures lower than the processing in the first stage. . 4. Method pop. 3, characterized in that the processing of the carbon-containing material is carried out in the first stage under exothermic conditions at 320-360 ° C. five  7 Priority points: 15.04.80 under section 1.3; 1297734 8 01/05/81 according to claim 2; 03.20.81 under Clause 1. H, s  Ya8GG- - MMMv4AI are i .: -§  Kom l R one I I I I I I -GI I o "in tS R 1st Editor A. Lezhnin Companion E. Gorlov Tehred N.Glushenko Proofreader E. Roshko 801/65 Circulation 464 Subscription VNIIPI USSR State Committee for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5 Production and printing company, Uzhgorod, st. Project, 4