SE450129B - PROCEDURE FOR THE PREPARATION OF HYDRATED CULVET BASED FROM OIL-BREAKING SHIPS - Google Patents

Description

Journal Chemical Soc, _____________________ 450 129 genter. In addition, valuable by-products such as ammonia are obtained. These by-products are obtained in good yield.

BACKGROUND OF THE INVENTION In previous U.S. Patent Application Serial Nos. 063,824 of August 6, 1979 and 114,207 of January 22, 1980 and 140,604 of April 15, 1980, various methods of treating carbon or heavy hydrocarbon constituents have been presented. the treatment was to obtain lighter constituents of hydrocarbons in the form of gases, light distillates or distillates. In two recently granted U.S. Patent Nos. 4,248,693 and 4,248,659, other processes for treating hydrocarbon constituents have been described.

In these patents and patent applications there are a number of references which state the prior art.

PRIOR ART Regarding the state of the art for the present invention, reference may be made to the following U.S. Patents: 1,300,816, 1,413,005, 1,729,943, 1,904,586, 1,938,672, 1,974,724, 2,145,657, 2,950,245, 3,112. 257, 3 185 641, 3 252 774, 3 368 875, 3 354 081, 3 382 168, 3 483 119, 3 553 279, 3 565 792, 3 617 529, 3 663 431, 3 745 109, 3 787 315, 3,788,978, 3,816,298, 3,926,775, 3,933,475, 3,944,480, 3,960,513, 3,957,503, 4,003,823, 4,007,109, 4,018,572, 4,030,893, 4,057,422, 4,078. 917, 4 119 528, 4 147 611, 4 147 612, 4 155 717, 4 160 721 666 4 210 526.

Further reference may be made to the following technical and chemical-technical literature: Letoffe, et al., Determination des Enthalpies de Formation des Polysulfures de Potassium, pages 427-430, 1974; Journal de Chimie Physique, 71, John S. Thomas and A. Rule (other articles in this series are by Thomas and Riding) The Polysulfides of the Alkali Metals, Part 3 page 1063 et seq., 1973; 450 129 Blitz and Wílke-Dorfurt, Z. Anorg. Chem., Volume 48, pages 297, 1906 (see also §er¿, 53, page 43, 1905); van Krevelen, et al., Euel, 38, 256, 1959, B.K. Mazumdar, et al., Noble, 41, 121, 1962, Hugot, Ann. Chim Phys., 21, 72, 1900; W. Klemm, Z. Anorg. Chem., Pp. 241, 281, 1939; F.W. Bergstrom, J. Amer. Chem. Soc., 147, 1926; F. Feber and H. Berthold, Z. Anorg. Chem., Pp. 247, 1953; Thomas and Rule, J. Chem. Soc., 2819, 1914, R.L. Erbeck, Dissert. Abstract, Ann Arbor, Mich. 3254, 21, 1961; Renegade and Costeanu, Bull. soc. Chim., 15, 721, 1911; Sabbatier, Ann. Chimi Phys. 22, 5, 1881; Marrony, J. Chim. Phys., 56, 214, 221, 1959; MMe Aline Auroux, C.R. Acad. Soc. Paris, 274 pp. 1297-1300, March 1972; Kuster und Herberlein "Beitrage zur Kenntnise der Polysulfide" Z. anorg Chem., Sid 53-84, nov. 1904

In contrast to the foregoing, the process according to the present invention means an improvement in that the extraction of hydrocarbons or carbonaceous constituents or the work-up of products thereof by means of said process can be applied to oil-bearing shale, which is not previously known. Furthermore, the very good yield obtained in the use of the process according to the invention allows for the first time an economical utilization of the large amount of available materials based on both the organic and the inorganic carbon present in said starting material. Furthermore, a combined recycling of hydrocarbons, ammonia and additive metal constituents from the oil-bearing shale results in the conditions being further improved for a more complete utilization of this material source for hydrocarbons. Thus, a large number of countries that are dependent on energy imports can now satisfy their energy needs using the present invention and at the same time, valuable by-products can be obtained from said material sources.

DISCLOSURE OF THE INVENTION The process of the present invention essentially comprises a treatment process for rocks containing carbonaceous constituents. The present method also includes the improvement of the properties of liquid retort-produced products from said rocks. As a preferred embodiment, the treatment of oil-bearing shale in ground or crushed form with an alkali metal hydrogen sulfide, sulfide, plygulfide or hydrated forms thereof, mixtures of these sulfides (including the hydrates) and mixtures of each of the alkali metal sulfide metals with other alkali metal sulfide species are described. , sulphides or polysulphides (including their hydrates) in molten or liquid form in the presence of water or steam and preferably in the presence thereof and also hydrogen sulphide whereby the product obtained is obtained in the form of gas, a light distillate or a distillate.

These hydrocarbon products have an increased hydrogen content when compared to the carbonaceous starting material and as a result of the molecules being smaller, they can be separated relatively easily from the original mineral structure at low temperature and at atmospheric pressure. In addition, the method according to the present invention can also be applied to the low-quality recycled products which today can be obtained from said original material.

Unlike oil sands, oil-bearing shale on average contains about 5 to about 60 weight-Z as well as higher levels of bituminous constituents and kerogens which are associated with a large number of other components such as iron which occurs in the form of various iron salts, calcium salts such as calcium carbonates , magnesium salts such as magnesium sulphates, carbonates, etc. The composition of rocks and their salts is adequately described in books such as OIL SHALE written by TF Yen and published by Elsevier Publ., Co., New York, N.Y. 1976 and by the same author Science and Technology of Oil Shale published by Ann Arbor Science Publishers, Inc., Ann Arbor, Mich. 1976. Regarding the composition of these rocks, reference may be made to the said literature.

The carbonate content of the oil-bearing shale is defined as inorganic co] and may comprise up to 10% by weight of the oil-bearing shale. An unknown amount of this carbon can also be converted to hydrocarbon.

The bitumen content of the oil-curing shale is relatively small.

The yields are based on the total carbon content. This conclusion has been confirmed by the yields obtained when the present invention has been practically applied, since the yields obtained suggest values of 100% plus kerogen conversion to hydrocarbons. Since a strong attack on the oil-bearing shale also causes the reagent to attack oxides and carbonates in the oil-bearing shale, it is important to carry out the initial reaction, i.e. pretreatment and the first step in such a way that the attacks on non-hydrocarbon-producing components in the oil-bearing shale by either potassium or sodium hydroxide, hydrosulfide or sulfide is minimized. At the same time, it is desirable to recover all valuable components of the oil-bearing shale such as heavy metals, for example V, Ni, Mo, U, etc., which are obtained as, for example, water-soluble complexes of molybdenum (in most forms), and vanadium. For the most part, iron, cobalt and nickel will precipitate as hydroxides during flocculation by the reaction with the reagent. While the complex components of the oil-bearing shale are different for each type of oil-bearing shale that can be obtained in different locations around the world, some adjustments are made in connection with the choice of treatment for each type of mineral. These adjustments must be further elucidated.

These and other aspects of the oil-bearing shale have required a number of considerations which have led to the use of the oil-bearing shale as the subject of a successful application of the present invention when applied to a material in which the hydrocarbon constituents are encapsulated or distributed. in a structure of other materials in "low-concentration" form and where the reactions of the structural components must be considered as an important aspect to consider in a successful application of the process.

BRIEF DESCRIPTION OF THE DRAWINGS To illustrate the present invention, reference is made to the accompanying drawing figures, of which Fig. 1 schematically illustrates a reaction sequence for a simple step process for improving the property of retort-treated shale oil; Fig. 2 schematically illustrates the reaction sequence in an Ilersteg process for property improvement of retort-treated shale oil including reagent recovery, Figs. 3 schematically illustrates a reaction chain for the recovery of hydrocarbon constituents from oil-bearing shale comprising the recovery of by-product constituents a reagent recycling carried out in a reaction sequence in a number of different reactors, and Figs. 4 schematically illustrates a reaction chain for the recovery of hydrogen sulfide.

DESCRIPTION OF PREFERRED EMBODIMENTS With reference to the figures which are intended to illustrate the process, Fig. 1 shows the removal of ammonia and sulfur as well as a pretreatment step for working up of retort-treated shale oil. Shale oil may, for example, contain 1.2 to 1.5 weight-Z nitrogen and 5 to 7 weight-Z sulfur. In this pretreatment step, only a mixture of shale oil is added to the reagent, which consists, for example, of KHS, KZSS in alcohol (in the presence of some water). Under ambient conditions, but in a friendly manner. At temperatures below 60 ° C, the reagent and shale oil are mixed by mechanical stirring. If heat is required, this is done by means of heating coils shown in Fig. 1. At this temperature below 600, abundant amounts of ammonia are emitted but only when the temperature is maintained. below about 60 ° C. Ammonia is recycled in a way that is well known to those skilled in the art, for example in water. The removal of ammonia seems to increase the API value (API = American Petroleum Institute), but the said increase can also be attributed to removed sulfur. The sodium reagent emits less ammonia while the potassium reagent reduces the ammonia content from 1.5 to about 0.1 to 0.15 weight-Z. For sodium, the corresponding reduction occurs to 0.6 to 0.7 weight-Z.

Silicon sulfide does not absorb sulfur in aqueous solution. Some elemental sulfur is obtained from the organic sulfur species, apparently as a result of the removal of nitrogen. This sulfur is separated by liquid-solid phase separation under the influence of slow stirring (about 20 rpm) and reaction at this temperature. As a result of this process, elemental sulfur will accumulate on the surface of the stirred liquid. Ammonia production takes place by creating a vacuum in the reaction vessel, for example by suction. The formation of elemental sulfur takes place during ammonia production, but sulfur formation can cease earlier. Mechanical foaming agents can be used to remove the elemental sulfur formed. The reaction for the removal of ammonia is quite slow and can be dispensed with because additional ammonia and sulfur are removed during the hydrotreating reaction. The recovered sulfur can be used to regenerate reagent as further explained. In this step, about 1/6 to 2/3 of the sulfur content is removed from the approximately 5 to 7 Z sulfur contained in retort-treated shale oil.

The reactor 11 is emptied from its bottom and the added shale oil and the reagent are introduced into the reactor 12. In a batch process, the reaction mass can be kept in a single vessel, for example in vessel 11, the stepwise reactions being carried out in one vessel but for the purpose of illustrating the In different aspects of the invention, the various reaction steps have been shown separately. The reactor 12 can be run at a certain set temperature, but the temperature can also be increased step by step.

Addition of reagent can also be introduced, the reagent being, for example, KHS, KS and KZS 2 2 dry state, water being added as steam or sprinkled as XH 2 O, etc., dissolved in water or in 450,129 water in liquid form and H28 being added to the steam. or the water flow.

Normally water or hydrogen sulfide is added at a temperature of about 170 ° C. KZS 'xH2O where x is 5 or 2, i.e. different hydrates constitute a very active reagent and tend to produce mainly gaseous hydrocarbons. At temperatures above 13500 ~ 150 ° C, the reagent consists mainly of a molten K2S or Na2S and its hydrates (in molten form).

Normal temperatures at which reactor 12 can operate are as follows: 220: in z 40 ° C, z 50: in 32 ° C and 360: in 390%. within these temperature ranges, most products are obtained and it is assumed that it is the bitumen fraction that produces the distillate at the higher temperatures. These reaction temperatures can also be reached initially at 100 to 120 ° C and possibly up to 135 ° C. At the lower temperature, an alcoholic solution of the reagent is usually introduced. The light fractions are distilled off from the initial temperature to 135 ° C and these consist of gases and / or light liquid distillates using an azeotropic mixture of water and the alcohol to form the reagent. To keep ammonia in this condensate under reaction, a small amount of KOH or NaOH is added to the solution, i.e. in a quantity sufficient for the evaporation of ammonia. The ammonia is collected in a separate vessel.

These products are collected in vessel 14 in the form of gases and liquid in two layers, the upper layer consisting of light hydrocarbon distillates and, where appropriate, the bottom layer consisting of a water-alcohol mixture. Alcohol-water is used as a starting material for further reagent formation.

The gases and the light distillates are used in a distillation column - the reactor 18 where these are introduced into the bottom of the distillation column part of the reactor column 18.

The distillation reactor column 18 is maintained at a temperature of from 220 to 24000. The reagent is introduced at the bottom of the column 18. However, as is known, the reagent can act as a catalyst in the following distillation and it may occur in various forms for contact with gas and / or liquids. .

For the purpose of supplying hydrogen for the hydrogenation of the shale oil constituents, water and to a much lesser extent hydrogen sulphide are introduced together with the reagent (or separately) at the bottom of reactors 12 and 18.

The shale oil becomes lighter as it becomes hydrogenated, rising in the column and being recovered as the top distillate in single or multiple cooling columns as indicated in Fig. 1 by 19 and 20. As the reagent is formed, provided it is appropriately selected , it is recovered in liquid or solid form at the bottom of column 18 and is recovered for further use as will be explained later.

The gases recovered together with the light distillates from vessel 14 can be recovered after condensation whereby they are introduced into column 18 through a fried disk 17 or a mesh filter. In Fig. 4, which will be described in more detail, the gas separation is illustrated. For reasons of suitability, the separation in Fig. 1 has been shown schematically.

When gases react in the reactor 18, a competing hydrogenation-dehydration reaction also occurs, such as when some KZSS is used at that temperature. By appropriately adjusting the bottom temperatures of column 18 and the water content of column 18 and the H23 content of the same column, the desired end product mixture can be obtained in accordance with what is to be shown below.

In general, it has been found that, for example, a shale oil with 16,200 BTU / lb (2155 wh / kg) can be improved in properties to about 19,000 BTU / lb (2577 wh / kg).

In terms of energy, however, the thermal shale oil retort production process is uneconomical; it may become necessary if the method of oil-bearing shale in accordance with the present invention would not be feasible. Feasibility is affected by the constituents of the oil-bearing clay shale that can consume disproportionate quantities of reagent. However, the main advantages of the present invention lie in the treatment of the oil-bearing shale and accordingly the process according to the invention is focused on a minimization of the reagent consumption and / or an increase in the product yield. Fig. 2 illustrates a process for treating shale oil in several steps, said method including reagent recovery to ensure predetermined product flows starting from shale oil as starting material within the framework of a completely continuous process.

In accordance with the procedure shown in Fig. 2, the same pretreatment is performed in the pretreatment vessel or reactor 110 as the treatment described for the pretreatment reactor 11 in Fig. 1. For that reason, the description in question is not repeated. Similarly, in the reactor 112, the same reactions take place as in the reactor 12 in Fig. 1. However, here the additional reagent (supplementary reagent) from the reagent-recovery chain is supplied as will be described below. From the reactor 112 the bottoms are transferred to a second reactor 116. The upper fraction from the reactor 112 is separated into two layers consisting of light hydrocarbon distillates and a mixture of water and alcohol.

The light distillates and, where appropriate, gases are recovered in the same way as described for the process according to Fig. 1. The bottom content of the reactor 112, i.e. shale oil and reagent, has the composition 3 - 20 grams of reagent per 1000 grams of shale oil. The reagent is substantially free of admixture of alcohol. Hydrogen for hydrogenation in reactor 116 is supplied in the form of water in an amount corresponding to - 100 volume-Z of the amount of hydrocarbon condensate removed and the difference between the hydrogen content of the original and the obtained product (on a 100 gram basis) converted to the amount of water in the reaction, that is, x9 (amount of water required to obtain the reacted hydrogen). These two values are added and give the total amount of water used. The efficiency of water introduction, ie reaction purposes, determines the required percentage of water, with the lower percentage giving an indication of higher efficiency. The primary purpose of the use of hydrogen sulfide is to minimize the amount of reagent used and to keep the reagent in a stable and active state. Since the temperature in reactor 116 is significantly higher than that in vessel 112, heat supply can be provided as needed by means of internal or external heating coils. The reactions in vessel 112 are either endo- or exothermic depending on the catalyst used. Thus, the heat balance can be easily maintained by means of the heating / cooling coils, adjustment of reagent composition or selection of suitable temperature levels.

Bottom products from reactor 116 are introduced into an additional reaction vessel 118 for further hydrogenation and recovery of additional reactants (constituents included in the reaction).

The upper fraction from reactor 116 is returned to a reflux column 117 together with the upper product from reflux column 117 which is taken out at a temperature of, for example, 22500. This fraction with 225 ° C boiling point can also be worked up as shown in Fig. 2. All liquid distillates from reactors 112 , 116 and 118 can be introduced into reactor 121.

In reactor 118, the shale oil product and the reagent are heated to a temperature in the temperature range of 36,000 to 40,000, the reagent being recycled from the reactor bottom to meet upward reaction products. The lighter fractions are usually formed at higher temperatures and include gases, however, the end product depends on the type of reagent and the ratio of alkali metal to sulfur. As the reagent has a higher sulfur content, it tends to dehydrate and reshape the lighter fractions to form heavier fractions. However, this depends on the amount of water added. Thus, the competing hydrogenation reaction will have a more pronounced effect if more water is added. Furthermore, the reagent will be maintained in its more hydratingly active form. As the reagent is formed in reactor 118, it is taken out, for example, by means of a three-way valve 120.

In connection with the work-up of the reflux fraction recovered in column 117, said fraction can be subjected to a further reaction in a further column 121, which is described in more detail below. For the purpose in question, the reagent in column 121 is mainly KZS and KHS in alcohol. It is well known that the alcohol fraction can be easily separated from the upper product, see for example Fig. 4. In the reaction column 450 129 12 121 water with a flow intensity is added in accordance with what has been further described. Thus, sufficient hydration is achieved to obtain through the reflux column 123 a product which is at a boiling point of about 16,000 but also a series of products can be obtained. A stream of spent reagent is combined with the reagent from reactor 118 and recycled to regenerate and recycle the reagent as follows.

In the reactor 123, the hot reagent is cooled to a temperature of, for example, 39006 with cold water. After cooling, water is added to the reagent, the proportions of water in relation to the reagent being between 1 1 and 2: 1. The reaction with water regenerates the reagent EGHOW to form alkali hydroxide and alkali sulphide. When the solution is cooled, a precipitate of other metal constituents is obtained with the exception of vanadium (molybdenum is kept soluble under certain conditions) which is soluble and removed by means of an electrochemical process. If the concentration of the solution is sufficient. As a rule, up to two moles of water are used per mole of alkali (on an elemental basis for alkali). Preferably the smaller amounts are used. The recovery of the heavy metals constitutes one of the advantages of the process according to the present invention and entails that the process becomes economical.

The reagent product stream from reactor 123 is collected and filtered in filter 124 in order to remove impurities and flocculation constituents of heavy metals in suspension or other particles in suspension. In the reagent regeneration vessel 125, the reagent is further cooled in connection with the addition of cold alcohol-water azeotropic solution and hydrogen sulfide. The reagent has a certain solubility in the alkanols (which decreases in connection with an increased number of carbon atoms in the alkanol). Thus, and as previously described, the alkanols methanol and ethanol are preferred. The portion of the reagent taken up by the alkanol is the portion used for the reaction, but the water content (which is required for hydrine and hydrate formation) can also be increased with a mixture of alcohol-reagent-water. A small amount of water is required for the alkali metal sulfides to form the hydrates in the alkanol. As a rule, the alkanol-water composition corresponds to the lower boiling point, the aseptropic composition with a boiling point at about 80 DEG C. (methanol-water).

It will be appreciated that the reagent recovery may be carried out in particular as hydrogen sulphide is present in sufficient quantity both from the reactor 123 on heating and as recovered hydrogen sulphide as shown in Fig. 4.

Hydrogen sulfide introduced into reactor 125 then reacts with the alkali hydroxide to form respective sulfides. This must be done during cooling. Because the sulfide reaction in alkanol is temperature, concentration and solvent dependent, different types of alkali sulfides can be formed. For example, potassium sulfide may be formed if the temperature is not properly maintained. Since the reagents are mixtures in vessel 125, they can be used as such for reactor 110 and thereby dissolved in alcohol. However, individually selected alkali metal sulfide species can also be obtained or regenerated for reactions such as those in reactors 116, 118 or 121, the reagent then being a selection from a narrower mixture. In the use of the process described above, reagents with a certain ratio between alkali metal and sulphide have been used in practice. This will be explained in more detail below.

Figure 3 illustrates a process by which shale oil is obtained directly from a rock either from organic and / or inorganic carbon species by means of the reagent in accordance with the invention.

In accordance with the present invention, oil-bearing shale ground to a particle size of 1/4 inch (about 6 mm) or less is fed into a hopper 210 to be added to the reagent by a feed screw 211. However, the reaction is independent of the size of the mineral. The reagent is liquid and envelops the mineral particles.

For practical reasons, the reagent is supplied through an opening 215 in the feed screw tube in certain measured amounts in such a way that between grams and up to 30 grams of reagent such as KHS (or converted to RHS base) is supplied to 1000 grams of mineral. As a rule, about 8 grams of KHS per 1000 grams of mineral is fully sufficient. 450 129 14 It has also been established that oil-bearing clay shale can be treated equally or more economically efficiently with sodium sulphide varieties. It also appears that the reaction of reagent and water and H 5 with 2 oil-bearing shale is exothermic to some oil shale reagent types as shown by the examples below. Thus, the loops 213 can be used for heating or cooling depending on the requirements of the situation.

As long as the process is carried out batchwise, temperature levels and further temperature increases can be applied to achieve the same effect as with shale oil and as previously described above. In this context, steam and H25 are added in a predetermined sequence (after alcohol distillation) if alcohol is used to dissolve the reagent. If the temperature is kept high in reactor 212, only the products formed, H28 and water can be recovered and only minimal quantities of ammonia are released unless certain measures are taken.

It has been found advantageous to introduce the reagent mixed with oil-bearing shale particles in such a way that the reagent envelops the mineral particles. As shown in Fig. 3, this can be easily realized by dosing the reagent while feeding the mineral particles.

In the reaction vessel 212, which is kept in continuous operation at the selected temperature levels, for example 28000 - 390 ° C, the mineral particles can be stirred by means of pump (s) 217 which causes a circulation of the reactants (reactants) regardless of whether they are liquids. or gases in which these are passed to a lower comic part of the reactor 212 through a large number of openings 218 whereby a part of the mineral is kept in suspension but other stirring means can also be used. Similarly, steam and hydrogen sulphide can also be introduced below the mineral level. Because the mineral is heavier than the reagent and recovered hydrocarbons, the mineral falls to the bottom of the conical reactor. By means of a suitable valve pump 216 the bottom set of the reactor is removed, after which the extracted material is introduced into a washing vessel 219. The washing water is used in sparse amounts because the pre-leached constituents of reagent material or constituents of heavy metals can precipitate from the leaching solution 450 129. The mineral residue is pumped out by means of the valve pump 216 and then filtered, for example, by means of a drum filter 220 which relieves the mineral residue in the form of a filter cake. The material particles are then well powdered.

The upper products from the reactor 212 pass through a sieve, for example a York sieve 212a and consist of ammonia, hydrogen sulphide, gas, distillates depending on the operating temperature and reagent used. Said products are processed as follows. The product gases which can be condensed at cold water temperature are introduced into a second reactor 223 where they are allowed to react with a supported reagent which acts as a catalyst. Two reactors 223 and 230 have been included to illustrate different embodiments.

In connection with conventional operation in which the process consists of a two-stage operation, the process stream 221 is introduced into a reactor 223 illustrated as a plate column where the catalyst is supported on plates located at the bottom of the column. The reactor in question can be placed above the reactor 212. However, for ease of illustration, it has been shown next to the reactor 212. The flow 221 is introduced at the bottom of the column 223, i.e. it is introduced in parallel with a water addition shown in Fig. 3. reflux column 224 can be used. It works in a conventional manner and has the task of removing the desired product mixture. If reactor 212 and column 223 operate in such a way that only one passage occurs, the product flows from the reactor top are utilized, for example by means of a reflux column 224, whereby a gas work-up in particular an H25 work-up can be carried out as shown in Figs. 4. Ammonia is separated, for example, using a vessel 430 with water in the form of a bottom layer with an overlying hydrocarbon layer (no alcohol is used or after expulsion of alcohol). A small amount of KOH or NaOH is added to the condensed water, expelling ammonia which is absorbed in another vessel (not shown and in which water is formed). Hydrogen sulfide is extremely slightly soluble in water and therefore passes. Thereafter, the hydrogen sulphide is worked up as shown in Fig. 4, i.e. starting in 431. 450c 'i29 16 However, if also as shown in the dashed section A-1 in Fig. 3 the reactor is run with a small amount or no liquid distillates and if the reaction is instead carried out at a high temperature with only gaseous upper products and / or volatile distillates being taken out of the reactor 212 via the line 221 then the reaction products from the reactor 212 can be worked up as follows. The reactor contains a reagent in the form of a catalyst (same as in reactor 223). The reagent is of the type described as a supported catalyst catalyst in which the surface support consists of substances with good surface properties such as aluminum hydroxide, silicon aluminosilicate, spinel or similar surface support systems commonly used in the oil industry as catalysts in connection with reforming. The catalyst has previously been described as a reagent in this context, however, it has a characteristic catalyst function based on its surface properties. Thus, the reactions whereby hydrogen is obtained directly take place under the action of catalyst, the reagent acting as catalyst. A commonly used reagent for the first ZS and / wherein the latter two reagents are used in solid form step is KHS (dry) and for the second step K or KZSZ is usually used under the reaction conditions. Other reaction systems consist of NaHS (liquid) under process conditions in reactor 212 preferably NaHS plus 1/10 mol Na2S 'XHZO (in the form of flakes, technical) and in ZS, KZSZ and K2S5 weighted proportion of KZS. A fairly common quantity of reagent catalyst is the second stage K or mixtures thereof with an over-20 gram / 250 ml carrier substance in the form of 3/16 "beads of silicon aluminum silicate. The second reactor catalyst is very long-lived. Hydrogen sulphide and water are also During the treatment in the second step, the products from the reaction in the first step may have a sulfur content which has been reduced to below 3 Z, for example 2 Z, the products being in the 400 range in terms of API values.

Fig. 3 shows that the catalyst is suspended in a basket 232. However, the reaction can just as easily be carried out in any form of column, tower or reactor in which supported catalysts have been distributed. More than one column can be used connected in parallel or in series and alternative columns can be used. As shown in Fig. 3, the basket is movable and rests on a ring 234 on which the upper part 235 of the basket 232 rests, the upper part 235 being formed as a funnel. Water is added to reactor 230. Another reactor, the same as 224, operates at a temperature between 135 ° C and 150 ° C and processes the entire gas flow. However, all condensate is separated in the form of hydrocarbons. The reagent consists of a hydrated melt of KZS - SHZO and the gases are allowed to bubble through the melt.

The liquid hydrocarbons are formed above the melt and are drained at a suitable level. Similarly, two reactors such as the previously described reactor 230 may be used alternatively one at a time as the catalyst or reagent is changed and / or removed and then regenerated for the other. Fig. 4 schematically shows the recovery of hydrogen sulfide gas. A reactor 422 maintained at a temperature of usually 320 ° C to 390 ° C has been charged with oil-bearing shale, a reagent in liquid or solid form, water in the form of steam and hydrogen sulphide gas which charge substances are treated and / or reacted as previously described. Thereafter, these gases are cooled in a condenser, for example 426. A cooling jacket 424 surrounding the condenser 426 facilitates the cooling of the reaction gases. The heavier initial products are recovered from the bottom of the condenser 427. The gaseous products are transferred to a vessel 430 in which water or alkanol (usually methanol or ethanol) is kept in the form of a KOH solution. One mole of KOH to one mole of water at 40 ° C is kept there.

The alcohol solubility corresponds to one mole of KOH / 123 ml of methanol or 190 ml of ethanol. The selected solution in vessel 430 is kept cold and in this way the lighter gases pass through which consist of C to C hydrocarbons including hydrogen sulphide. When alcohol is used, C3 hydrocarbons are absorbed and C4 and C5 hydrocarbons are soluble. Therefore, an aqueous solution is preferred.

In vessel 431, the contents are cooled to about -35 ° C at which temperature liquid G4 and G5 hydrocarbons are removed. While most of the C and C fractions are removed in vessel 431, however, some will be transferred to vessel 432 where these are removed at the temperature of -30 ° C together with the C3 hydrocarbon fraction in ethanol or methanol. A fried glass sheet 433 removes residual traces of these components. At this stage, essentially only H28 and C1 and C2 hydrocarbon fractions remain in the gas stream introduced into vessel 435 containing KOH and alcohol usually ethanol 18 or methanol in aqueous solution. Hydrogen sulphide regenerates therein the reagent which is recovered in the form of a precipitate at the same time as the gases belonging to the light fraction mainly C1 and C2 hydrocarbons pass.

At up to about 97% conversion of KOH to KHS, no H28 passes and is thus recovered in the form of a reagent component and can be reused (or used in the system if RHS is converted to KHSS by dissolving sulfur to form equal molar numbers). If necessary, more than one washing vessel 435 can be used to remove hydrogen sulfide. No H25 is vented into the air. The alcohol-water fraction from vessel 430 obtained during start-up is used to replenish the alcohol extracted from vessel 435. However, this mixture must be cooled in the heat exchanger 436. The recovery of alcohol and water has been shown in accordance with Pig. 4. The recovery schedule does not change if the reagent is used in dry form, ie without alcohol solution. In that case, alcohol is present only in vessel 435, in which the reagent is regenerated and there is only water in vessel 430. Vessel 435 can be run without alcohol below 4000 while cooling the exothermic reaction and while keeping the water content at 2 moles per mole of KOH or just below.

The foregoing hydrogen sulfide recovery process can be applied to the process described with reference to Figs. 1, 2 and 3. It is also for this reason that the reagent is introduced into the reactor vessel 212 by means of a feed screw in the form of a substantially dry reagent, i.e. a product which is in concentrated form and from which alcohol and water have been removed, in connection with the process described in Fig. 3.

The alkali metal hydroxide, for example potassium hydroxide, is obtained from the spent reagent which is regenerated as shown in Fig. 2 or else said hydroxide is obtained by leaching minerals by water addition as shown in Fig. 3, where sodium and potassium are recovered in the form of hydroxide from the spent reagent .

The reagents used in the process according to the invention are empirical hydrates of hydrosullides, monosulphides and polysulphides from the group TA of the elements of the Periodic Table with the exception of hydrogen. For various reasons, compounds with francium and cesium are generally not used. Thus, compounds with sodium, potassium, lithium and rubidium are usually used. Preferably potassium, rubidium and sodium compositions are used. However, rubidium is economically disadvantageous. Sodium in the form of, for example, NaHS is most economical but potassium should Thus, KHS-treated product gives about 3-SO API (API = American Petroleum Institute) easier due to preferably used. more efficient ammonia and sulfur removal. In the case of oil-bearing shale, which is initially treated, sodium hydrosulphide becomes economically advantageous because it forms a melt under process conditions and because under these conditions it is more stable together with water. Thus, in the first reaction 212, better contact between the NaHS species and the kerogen fraction is obtained due to lower melting points at the process temperature. During the reaction in the second reactor, for example 223, the reagent consists of a mixture of the empirical hydrates of the hydrosulphide and sulphides (monosulphides and polysulphides) of each alkali metal used and during the reaction a mutual conversion of these sulfur-containing forms takes place. (As the reaction temperature rises, some of these forms disappear because their decomposition temperature has been exceeded as will be explained below.) The reagent can thus be initially charged to the reaction zone in the form of hydrosulfide, empirical hydrate or in the form of one or more sulfur hydrates or as a mixture of the hydrosulfide and empirical sulfide hydrates. The reagents in the form of empirical hydrates can also be prepared in situ, but are preferably charged in their empirical hydrate form and preferably with the higher hydrogen sulphide content, for example the hydrosulphide because hydrogen sulphide is lost at higher temperatures, for example at 200-22000.

Each of the alkali metal hydrosulfides and mono- and polysulfides may have one or more empirical hydrates, but unless otherwise indicated, the term "hydrate" shall include all hydrates. 4> U'1 CD ... à BJ \ C The amount of reagent used must be sufficient to allow adequate contact with the starting material and to achieve the desired reaction rate. The maximum quantity of oil-bearing shale that can be treated with a given quantity of reagent varies for different types of oil-bearing shale and can be determined in accordance with the rules that will be treated in more detail.

It is understood that if the cost of the reagent, such as the cost of sodium hydrosulfide, is of little importance because its availability is good, then the reagent recovery can be eliminated. The retention or elimination of the said steps then becomes a separate consideration.

It has been established that the reaction gives a better yield if the reaction with oil-bearing shale is carried out with a certain minimum quantity of reagent present. This applies under otherwise unchanged conditions. For this purpose, it is best to carry out the reagent stabilization with hydrogen sulfate based on the highest volume fraction of hydrogen sulfide in the reactor which does not hinder the reaction.

If large quantities of reagent are present, the hydrogen sulfide as part of the total reactor volume in gaseous form cannot stabilize the reagent. On the other hand, the reaction cannot proceed due to the separation between hydrogen and water if a large proportion of the reactor is taken up by hydrogen sulphide. Excess reagent not only attacks the undesired component of the oil-bearing clay shale such as iron in its various forms but also becomes unstable, i.e. the reagent is converted to alkali hydroxides, sulphates and the reagent attacks for example iron components in the structure without attacking carbon components. This applies to alkali hydroxides. By not removing oxygen, sulfur and residues of nitrogen atoms for the kerogen fraction of the oil-bearing clay shale, the misused reagent can transfer the process to an undesirable reaction sequence. These competing considerations are further affected by the different components of different types of oil-bearing shale.

These competing considerations are resolved or partially minimized by the following. If a suitable selection of a reagent is available, for example if a cheap reagent is available as a NaHS (as an industrial commodity), said reagent may preferably be used whereby the recovery of the reagent cannot be considered critical. Hydrogen sulphide should be used in quantities which do not impede the reaction (which is best controlled on the basis of the rate at which the products are recovered). Steam or water can be sprayed into the reactor in the form of a fine mist and when this addition procedure is applied, the following coarse rule of thumb can be applied for the required amount, for example. The amount of water may correspond to 130 wt-z based on the withdrawal of hydrocarbon condensate, but the actual amounts remain as previously described. Hydration water that is present and water in the oil-bearing shale are also taken into account.

In general, the hydrogen sulfide addition is based on a space, time and velocity basis and usually the amount of addition will be 40 - 120 ml / min and gallons (about 10 ml / min and liters to 30 ml / min and liters) reactor space with 20 ml / min and liters can be considered as usual. In other words, half a mole and less H28 is added for 1000 ml of water which is removed by the hydrogenation reaction.

The reason for the addition of hydrogen sulphide is shown in the reactions below. 1. 4KOH + 4H2S --- get 4KHS + 4H2O When carbon-derived sulfur is present, 2. 4S + ÖKOH ----- 9 KZSZO3 + 2K2S + 3H20 in turn follow 3. KZSZO3 + 3H2S ---> KS The decomposition of KZSZ is as follows 4. 4K2S2 + 8H2O '___- fi> 4KOH + ÅKHS + ÅS + ÅHZO 45Ü 129 22 It follows that when H25 is present KOH is converted to KHS and if some KOH forms thiosulfate then the thiosulfate is converted to KZSS.

For example, since KOH attacks iron salts in the gait, the seemingly more advantageous or at least advantageously competing reaction with hydrogen sulfide will minimize the side reactions making the process attractive.

Additional reactions are as follows:. 1 <2s5--> K2s4 + s (over 300%) 6. KS 24 BK S + S 2 3 (over 46000) 7. KHS + KZS + 3H20--9 3KOH + ZHZS 8. KZS + H20 -í-š KOH + Kl-IS 9. KHS + H 2 O 11) H25 + KOH. RHS + KOH-rm K S 2 'xH O 2 (x can be for example 2, 5 etc depending on the temperature).

Thus, sufficient H25 may be present to by mass action keep the reactions in such a state that the reagent is stable, i.e. sulfur is taken up either from shale oil or from oil-curing shale or from the reagent and by the action of the hydrogen sulphide the hydrolysis of the reagent is avoided and further minimized. the formation of free potassium hydroxide. In addition, the thiosulfate generated by the oxygen in the oil-bearing clay shale is regenerated during the reaction to the desired KZSS sulfate. Thus, the reagent is maintained at the desired hydrolysis level by H25. Among the various reagents, the following are preferred because they have the desired stability and ability to attract sulfur, KHS, NaHS, KZS, KZSZ, KZS and then KZS3 KZSB; and among these the order of preference is as follows: KZSZ,. The other sulfides show no stability at _ _. their melting points, for example Na 2 S 2 at 445 ° C, Na 2 S 4 at 275 ° C, or,. o otherwise sulfur is emitted at 760 mm, for example K gives at 300 C K S 2 5 2 4 K254 gives vig 460 ° C KZS3 + S; and K gives at 780 ° C K S + S. 2 2 -i-S; The melting points of the alkali sulfides mentioned above are as follows: for Kzs 948%; Kzsz 470 ° C; Kzs3 279 ° c (sceling point K2s4 145%; KZSS 20600; K2S6 19000. The melting points of the sulphide mixtures are for Ks - Ks 350%; approx. 110 ° C the following (pure or eutectic mixtures): ._ 0 U _ for KZSZ K2S3 225 C, for KZS3 KZS4 On the basis of the above, suitable temperature conditions are selected on the basis of decomposition and / or melting point characteristics in order to allow the use Of course, the different hydrates from the alkali sulphides have different melting and / or decomposition points, which of course also applies to the eutectics of the mixtures. These temperature points can be determined thermographically without difficulty. , which is well known among those skilled in the art.

At the highest operating temperature, for example at AOOOC, KZSS will give sulfur (which can be considered as a useful phenomenon as has been previously stated in connection with the dehydration of additional process flows). Because decomposition temperatures are lowered at lower pressures, shale oil conversion becomes entirely possible at atmospheric pressure despite some advantages being gained from higher pressure operation. For example, it can be said that the additional cost in connection with operation at 5 atö means that operation at said pressure becomes less desirable.

Thus, for practical purposes, the pressure can be varied from about å atö to about 5 atö, whereby, however, the atmospheric pressure of the surroundings is preferable. The various sulfides and their decomposition temperatures, including the reactions, are set forth and described in U.S. Patent 4,210,526, issued July 1, 1980.

It should be noted that there are many competing reactions and that the alkali metal sulfide chemistry is complicated. Efforts have been made to explain the process as it has been perceived, but the basic criterion has nevertheless been the feasibility of the process when applied to shale oil and preferably oil-bearing shale. This has been demonstrated by example.

In the case of potassium reagents, heating to a temperature of 105 DEG-110 DEG C. in a water atmosphere leaves an empirical hydrate melt containing about 35% by weight of Z-bound water. The melt is then dissolved in just a sufficient amount of light boiling alcohol (preferably methanol or ethanol) to form a saturated solution, (heavier solution may be used but they require more energy to evaporate the excess alcohol), In the case of potassium reagents and at ambient temperature, approx. get 150 ml of methanol or a little more ethanol to dissolve one mole of KHS.

Hydrogen sulphide in the form of bubbles may pass through the solution at a temperature which must not exceed 60 ° C, whereby a solution of the reagents in alcohol is obtained.

The embodiments described above have been reported with reference to the drawings. To facilitate understanding and to further illustrate and support various aspects of the described processes, the following examples are presented which are in no way intended to limit the scope of the present invention.

Example I 200 grams of oil shale were obtained by retort treatment of oil-bearing shale which was treated in a first-stage reactor. Hydrogen sulfide was not fed into the reactor containing 50 ml of methanol solution of silicon hydrogen sulfide empirical dihydrate (0.38 grams of KHS / ml solution). 450 129 The first reaction step took place in a vertical, cylindrical vessel with a total volume of about 1 liter which was equipped with a heating jacket. Analyzes of the shale oil, products and residues in the reactor are given below.

Analysis Material Quantity Hydrogen Nitrogen Sulfur Shale oil 200 g 9.90 Z 1.45 Z 6.23 Z Fractions below 2so ° c 22 g 10.33 z 1.16 2 6.85 z Fractional 280 - 300 C 35 g 10.59 Z 0.95 Z 6.80 Z Residual 100 g 8.33 Z 1.47 Z 5.76 Z Non-condensed volatiles total about 43 grams (by diff @ rß fi S) The metal content is given below (unless otherwise stated the figures ppm: "ND" indicates no traces).

Analysis Material Na VK Fe Ni Ca Shale oil 11 124 64 106 86 1223 Fractions below 2so ° c 1.2 5 s N / D 20 - Fractions 280 _ 300 C 0.61 19 4.6 N / DN / D - Residues 21 56 2,892 34 565 - The heavy the metals, for example vanadium, molybdenum and nickel, are recovered as previously explained.

Another batch of the untreated shale oil described in Example I was exposed to fACTiOH. DQSS analysis was as follows: HCSC: H API N Untreated shale oil 10,002 78,652 6,271 lC: l.53H 1.8 1,372 450 129 26 Boiling point range FO (Co) (> 1oz zoz aoz aoz soz eoz voz voz 287 491 547 soo 623 641 665 667 (669 F ° = 21.62 residue) An analysis of the first 122 shale oil distillates with the above analysis treated as above in a simple reactor with KZS 'XHZO formed from KHS charged into the reactor shows a product as follows: API ° at eo ° F (15,6 ° C) 25.4 Density at 6o ° F (1s, 6 ° c) o.9o21 Sulfur Z 6.74 BTU / poxxnd (Hb / kg) BTU / gallon «(Wh / l) NET BTU (Wh ) 17517 (2380) 131553 (146o24 16484 (4830) Ash less than 0.001 Carbon 80.15 Hydrogen 11.32 Sulfur 6.74 Nitrogen 0.68 Oxygen and indeterminate 1.11 Sodium 1.2 PPM Potassium 1.1 PPM Example II Distillation of shale oil from oil-bearing clay shales Two experiments were carried out with oil-bearing In a simple experiment, too little oil was obtained to obtain a distillation zone. The two experiments were combined to obtain provide a sufficient quantity of oil to determine the distillation range. 450 129 27 Experiment no. 1: About 60 ml of the reagent solution described below was reacted with 1900 grams of oil-bearing shale by simply mixing mineral with reagent solution. A two-layer reagent is used which had the following composition. To 6 moles of KOH dissolved in 12 moles of water was added 108 ml of absolute EtOH and 4 moles of moles dissolved therein. In preparing this solution (the exothermic reaction on dissolving KOH in water gave the required heat), an additional 2 moles of S in 108 ml of absolute EtOH were added to obtain an anemic KS 0 2 2 3 third of the solution with the amounts of the solution taken in the proportions - + 2K2S2 + 3H2O. This reagent forms a two-layer solution. A ion in which the two layers relate to each other was added to an equimolar quantity (based on K), of a reagent which was prepared as follows. KOH + 2 H 2 O whereby the solution was saturated in the cold state with H 28. Another mole of KOH is then dissolved in the solution. The solution melts at 60 ° C. The reagent obtained is K 2 S 5H 2 O.

The mineral was mixed in the reactor by mechanical stirring, steam and H23 - 80 ml / minute. The clay oil shale was from Israel.

The reaction continued normally but at 320 ° C (approximate value) the reaction turned into an exothermic reaction at which the temperature rose to 440 ° C. The heat had turned off at 320 ° C but the exotherm had started below 320 ° C. The steam was stopped at 38006 but the exothermic reaction continued to a maximum temperature of 440 ° C. 59 liters of gas were produced. Of the gas, 69 Z consisted of hydrogen, 6 Z of CO 2 (mainly derived from the carbonates of the clay shale) and the remainder were hydrocarbons having a carbon content between 1 and 6. 77 ml of condensate with an API value of 29 and a sulfur content of 7.12 were obtained.

Experiment no. 2: About 60 ml of solution of the following reagent was mixed with 2200 grams of oil-bearing clay shale from Israel. The reagent was consistent with the description from Experiment No. 1 except that the KOH + ZH2O was saturated in the cold state with H28 after which an addition of 1 mole of KHO was made to the resulting solution. The solution was heated to 180 ° C above 180 ° C then reacted with 0.83 moles of sulfur. The second catalyst was the same as in Experiment No. 1 described above except that no additional sulfur was added (vis-a-vi the two previous moles). Equal amounts of K-based solutions were added. The reactor used was the same as in the previous experiment and consisted of a round steel reactor with a capacity of about 1 gallon (3.785 liters) which was heated and stirred mechanically.

The oil is distilled from minerals mainly in the temperature ranges of 220-240 ° C and 280-32000 in the presence of steam and hydrogen sulphide the latter at 80 ml / minute.

The Israeli oil-bearing clay shale contains 5 Z hydrocarbons I 25 Z (of the 5 Z). The sulfur content of the mineral is 2.5 Z.

The hydrocarbon condensate contained 6.25 Z of sulfur and had an API value of 31 and the collecting liquid volume was about 71 ml. The uncondensed distillate consisted of 37 liters of gas containing 66 Z hydrogen, 2 Z carbon dioxide, 1 Z carbon monoxide and 28 Z hydrocarbon having carbon ratios between 1 and 6. Parts of the condensate were lost when excess steam blew some of the mineral into the capacitor vessel.

The distillates from the two experiments were combined and 100 ml were subjected to boiling point determination. The determination of the boiling point range showed an initial boiling point of (160 ° F) equal to 71.1 ° C and a maximum boiling point of 585 ° F (308 ° C) and a residue of 1.7 wt. Z. 1.7 Z contained 3 , 7 Z sulfur. The sulfur content within the 0-50 Z boiling point range was 7.25 Z, the sulfur content in the remaining part of the boiling point range ie from 50 Z to the end point was 4.1 Z. Thus the sulfur content of the oil extracted from Israeli oil-bearing shale in in accordance with the present invention greatest within the fractions having a lower boiling point. The nitrogen content was 0.11 Z. The product was green-brown and clear.

As shown above, a weak reagent is obtained which gives rise to an exothermic reaction at a higher temperature, for example at 360 ° C by combining S '-2H 0 tion of K S2' 2 2 2 xH2O (obtained by heating K 450 129 29 at 100 ° C at 100 ° C. presence of sulfur) and a two-layer reagent which has been prepared as above but which had not been treated by the addition of 2 moles of sulfur. Again, equimolar amounts of the two reagents based on the amount of silicon (on an elemental basis) were used. From the two-layer reagent described above, the solution was taken out in the same proportion as the ratio of the layers.

As is clear from this example, mixtures of sulphides from alkali series can be used, as well as mixtures of the sulphides of the alkali species such as potassium.

Example III 453 grams of the oil-bearing shale was reacted with potassium hydrogen sulfide, KHS, as in Example II, in which KHS appeared in hydrated form and the reaction took place in the presence of water. The amount of reagent used was 60 ml of solution of 0.4 g / ml KHS. The potassium hydrogen sulfide was used in the form of an alkanol solution (methanol and ethanol) of the potassium hydrosulfide and it was removed by raising the temperature to about 135 ° C. At that time, some dcl of the hydrogen sulfide had formed the potassium sulfide hydrate K2S xH2O (x is usually even in these conditions). A portion of the reaction product collected in two series-connected condensers was taken along with the distillate. At about 16,000, the potassium sulfide hydrate decomposed with abundant gas formation as a result.

Significant amounts of liquid hydrocarbon condensate formed from the mineral at between 230 to 25,000 and again at 320 to 35,000 and at 370 ° C and finally at the highest temperature 40,000. However, the amount of condensate at the end of the experiment or at 400 ° C was small.

The gas was not collected. A total of 25 ml of specific product with a specific gravity of 0.89 and API number 26 was collected in the form of condensate.

Since it can be assumed that the hydrocarbon content in this sample of oil-bearing clay shale was 5 Z, the recovery was almost complete, i.e. about 98.2 Z. 450 129 Example IV 453 grams of the same oil-bearing shale were treated with NaHS flakes (technical grade). The amount of reagent was 100 grams. The flakes melted at 112 ° C. The molten state was expanded by the use of an inert atmosphere and the presence of water vapor.

The hydrate melting at 11200 decomposes at a higher temperature with concomitant release of water to a lower hydrate which is solid: Water was introduced into the reactor at a rate corresponding to 6 ml / minute.

During the experiment described in Example III, as well as in this example, no hydrogen sulfide was added. 24.5 ml of the product were obtained in the same manner as in Example III, the condensate also in this case having a specific gravity of 0.89 and an API value (American Petroleum Institute) amounting to 26. A second test also gave a product with API value 26.

When washing the mineral with water, a deep green solution was obtained.

This indicates the presence of alkaline iron and other mineral complexes.

Using hydrogen sulphide, the formation of these complexes (probably ferrite-ferrate complex) was significantly reduced and at the same time the reagent consumption was reduced.

From the above two examples it can be seen that there is no significant difference between the quality and quantity of the hydrocarbon product obtained when sodium hydrogen sulphide (technical grade in the form of flakes) is used in connection with drop supply of water to the reaction vessel and when alkanol solutions of potassium hydrogen sulphide and Steam was used as a reagent in the process.

However, later experiments have found that considerably smaller amounts of reagent can be used when hydrogen sulfide is used in the reaction vessel (thereby improving the economy of the process). 450 129 31 Based on the above representations concerning the practical implementation of a one-step reaction, it can be said that the API value for the condensate can be between 7 and 32, the values 25 to 30 appearing to be quite achievable, the product yield can be around 100 Z and higher based on the amount of organic carbon in the oil-bearing shale. In order to achieve these results, hydrogen sulfide should preferably be present in connection with the reaction.

In a two-step reaction with supported catalysts, the API values can be around 40.

Example V 466 grams of shale oil of the type set forth in Example I was treated with 18.6 grams of reagent in a first reaction vessel and with 12.4 grams of reagent in a second reaction vessel. The reagents were as follows: RHS and K2S 'xH2O in both the first and second reaction vessels.

The reaction in the second reaction vessel took place in the gas phase. The highest temperature in the first reaction vessel was 39,000, in the second reaction vessel the temperature was 22,000.

The analysis of the initial distillate from the second vessel was as follows: API value at eo ° F (1s, e ° c) 22.6 specific fold: at eo ° F (1s, 6 ° c) o.91so Sulfur content in Z 5.94 BTU per pound (Wh / kilogram) BTU per gallon (Wh / liter) 17411 (2315) 133125 (147769> Ash 0.008 KOI _ 80.48 Hydrogen 10.66 Sulfur 5.94 Nitrogen 1.05 Oxygen 1.86 Sodium 0.32 PPM 45Û 129 32 Vanadium N / D (none Traces) Potassium N / D (no traces) Iron N / D (no traces) Analysis for the final distillation fraction: Aer value at eo ° F (1s, e ° c) 19.5 specific fold: at 6o ° F (15.6 ° c) o .9371 Sulfur content Z 6-19 BTU per pound (Wh / kilogram) 17571 (2377) BTU per gallon (Wh / liter) 137124 (152208) Net sin (wh) 164m (4826) viscosity at 100 ° F (37.s ° c) 41.9 ssu Ash 0.007 Carbon 80.51 Hydrogen 12.04 Sulfur 6.19 Nitrogen 0.96 Oxygen 0.29 Sodium 0.42 PPM Vanadium N / D (no traces) Potassium N / D (no traces) Iron N / D (no traces) Nickel N / D (no traces ) It can be noted that while the API value has decreased and (as it should for the later distillates) the hydrogen content has increased, however. ions did not benefit from hydrogen sulfide addition.

Addition of hydrogen sulphide increases product quality.

In later experiments, it has been found that a reduction in the quantity of reagent did not have a negative effect on the yield, provided that hydrogen sulphide was present. As little as 7.5 ml of reagent (KHS base) could be used to treat 500 g of oil. This applies to oil-bearing shale, ie about 7.5 ml (KHS base) of reagent can be used to treat 1,100 g of mineral_ 450 129 33 However, the quantity required to coat the mineral efficiently is, for practical reasons, an essential factor in ensuring an effective reaction with the mineral. The optimum level of efficiency is determined for each type of shale by means of a required series of experiments with progressively decreasing reagent quantities and with the appropriate use of hydrogen sulphide, observing suitable space, time and velocity conditions as previously discussed.

A portion of the potassium hydrosulfide is decomposed during hydrolysis to give potassium hydroxide and hydrogen sulfide. At the higher temperature, hydrogen sulphide is then recovered by appropriate work-up of the gas or by conversion as shown in Fig. 4. Potassium hydroxide is an agent at temperatures of 36006 and higher temperatures by which calcium carbonate in the limestone residues from the oil-bearing clay shale reacts with potassium sulphate from the reagent residues to form calcium sulfate and a mixture of potassium hydroxide and potassium carbonate. Potassium and the sodium content of the residue of the oil-bearing shale are also extracted in hydroxide form at this time, ie by leaching, after which it is worked up for reuse. Young is used as shown above at a temperature at which it is desired to carry out the reaction, i.e. depending on the type of oil-bearing shale and the degree of decomposition of its constituents and with regard to the desired product. For sodium hydrogen sulfide and sulfide series or reactions, water can be sprinkled into the reactors. Similarly, for the exothermic reactions, sprinkling of water can facilitate the control of the reaction process.

Although the reaction mass consisting of oil-bearing clay slides and reagent can be stirred in a suitable manner, it is most advantageous to pre-coat the mineral with a reagent in the absence of oxygen as the oxygen has a tendency to destroy the reagent. 450 129 34 For this reason, it has also been found useful to use a liquid or a loose reagent. Liquid yet stable reagents can be used to coat the oil-bearing shale at or around the appropriate melting point of the selected reagent or liquid eutectic mixture thereof.

As shown above, alkali hydrogen sulfides, alkali sulfides and hydrogen sulfide hydrates can be used as reagent or catalyst in the process. Mixtures of alkali with each other or mixtures of sulfides of each and with each other are included within the scope of the present invention.

Of course, the same approach applies to each alkali metal sulfide hydrate type. From a practical point of view, sodium and potassium sulfides as well as hydrates and mixtures of each of these in their respective series and mixtures with each other in the series may be included (as useful for the process). In addition, as previously shown, a specific sulfide and its hydrates can also be used specifically for the second treatment step and additional treatment steps for the products from the initial reaction, such as in cases where they are exposed to reaction temperatures above 135 ° C. Other alkali compositions in the alkali metal crystals can also be used, but from a cost point of view these are not advantageous. However, rubidium sulphides are highly active and can under special conditions be used as supported catalysts, for example in alumina, etc. Cesium sulphides are another variety in the alkali metal series which are less useful and, moreover, are not preferable from a cost point of view.

In general, the number of water moles in connection with hydration is determined by thermographic recording of temperature and time at which distinct temperature-time levels are observed and at which simultaneous release of water in gaseous form is observed. These temperature levels then indicate the reagent stability.

In addition to the above-mentioned carriers for the above-mentioned "catalysts", the following carriers have also been considered: spinel, potassium, aluminum silicates and especially burnt bentonite clay, etc. 450 129 A reagent attack on the starting material and the product mixture also depend on the chemical composition of the reagent. In particular, the sulfur content of the alkali metal sulphides controls the intensity of the attack, provided that other circumstances remain unchanged.

In particular, it is emphasized that in connection with oil-bearing clay shale, hydrogen sulphides have the ability to extract the oil from the mineral without producing uninhibited gas production. This thus represents a way of extracting corogen-based hydrocarbon constituents from minerals which should be preferred. Thereafter, these constituents can be hydrogenated by means of the sulphide reagents described above supported by a catalyst support and acting as gas phase catalysts.

In addition, different hydrates of the same alkali metal sulphides entail different reagent formations under otherwise equal conditions. If the above is to apply, of course, the hydrates of the above-mentioned sulphides must be stable under the reaction conditions.

The intensity of the reaction can be modified by introducing hydrogen sulfide into the reaction vessel. Hydrogen sulfide modifies the reaction and stabilizes the reagent because it causes additional sulfur to be present when the amount of hydrogen in water or hydrogen sulfide is released for hydrogen substitution or introduction into the hydrocarbon molecule containing nitrogen, sulfur or oxygen. Mixtures of sulphides with different sulfur content can also ensure a predetermined intensity of the attacks. Hydrogen sulphide is also added to substitute for reagent loss.

Addition of water (steam) also ensures in the case of hydrogen substitution or introduction into the hydrocarbon molecule. If a stronger cut of bonds of the starting material molecules is desired, as in the case of heavy fractions of shale oil or more complex molecules of the oil-bearing shale, the catalyst composition, the amount of water and the hydrogen sulphide must be taken into account and all of these must be adjusted accordingly.

It can also be well understood and it has been carefully described that further treatment of the mining products from the initial phase is best treated in connection with the reaction in gas phase i.e. gas phase - solid phase (supported catalysts) reactions intended to in accordance with the above specified instructions produce the desired products.

The above examples and descriptions show the surprising and obvious discovery that the amount of reagent used in the treatment of oil-bearing shale decreases when the reagent is suitably stabilized by means of hydrogen sulphide. Adverse reactions due to the reagent's attack on the mineral structure have obscured the actual reaction conditions, which are far more favorable than could have been foreseen if one takes into account the dissolution factor of the carbon in the mineral and the composition of the mineral material in general.

In addition, the bitumen fraction of shale oil is attacked by the same reagents that attack the kerogens. The co-production of hydrocarbons from these two (production) sources further contributes to the general economic conditions of the process.

In addition, the kerogens contain mineral constituents such as vanadium, nickel, molybdenum, etc., in addition, the presence of inorganic carbon and possibly leachable constituents in the oil-bearing shale such as sodium and potassium, etc. means that the process of the present invention is far superior to prior art thermal processes. say retort processes.

The above description shows that the present invention allows a selective production of saturated and partially unsaturated compounds based on shale oil or oil-bearing shale, which allows highly varying needs in the energy industry and in the chemical industry to be satisfied. As a result, an extensive reserve of raw materials has become easily available and also economically available, which allows a safe and continuous supply of hydrocarbon constituents.

Claims (26)

10 15 20 25 30 35 450 129 37 PATENT REQUIREMENTS A process for the preparation of hydrogenated hydrocarbon constituents starting from starting materials such as shale oil, oil-bearing shale and the like also comprising recovering valuable component constituents from said starting material, characterized in a) that said starting material reacts with an alkali metal metal, alkali metal sulphide, an alkali metal polysulphide or an alkali metal sulphide hydrate of any of the foregoing, mixtures thereof or mixtures of each with the other as a reagent therefor, in the presence of water or alcohol for the purpose of expelling ammonia and elemental sulfur and for the purpose to recycle these; b) that said hydrocarbon constituents are further hydrogenated in the presence of water and hydrogen sulphide and a predetermined reagent at an elevated temperature between 100 ° C and 400 ° C so that all hydrocarbon material with selected properties and additional reaction products is obtained, and c) that said hydrocarbon constituents having selected properties are recovered with by-products from the reaction in step b). Process according to claim 1, characterized in that said further reaction products are subsequently dehydrated with a preselected reagent in the presence of water and hydrogen sulphide to obtain selected hydrocarbon compositions. 3. A method according to claim 2, characterized in that the starting material is shale oil. 4. A method according to claims 1, 2 or 3, characterized in that the starting material is oil-bearing shale. 10 15 20 25 30 35 450 129 38 Process according to Claims 1, 2 or 3, characterized in that the starting material is inorganic betumen carbon containing oil-bearing shale. Process according to Claim 2, characterized in that in step b) the reagent consists of potassium polysulphide and that it is supported. Process according to claim 6, characterized in that the ratio of potassium to sulfur for the supported reagent corresponds to ratio values from KHS to KS 2 4 or mixtures thereof with hydrates thereof, said or mixtures thereof reaction being carried out at a temperature of 180 °. ° C to 400 ° C in the presence of hydrogen sulfide and steam. A process according to claim 1, characterized in that ammonia constituents and elemental sulfur constituents are present during the pretreatment and that the elemental sulfur constituents are converted to hydrogen sulphide used in said process. Process according to claim 2, characterized in that a plurality of steps b) (1) are accompanied by a further series of a plurality of steps b) (2), in which a certain group of hydrocarbons is produced in the presence of a selected reagent wherein said reagent is selected for a specific temperature reaction, the reaction taking place in the presence of water and / or hydrogen sulfide addition. Process according to any one of claims 1 to 9, characterized in that it comprises the following steps: a) Pretreatment of ground oil-bearing shale at a temperature below 72 ° C with a reagent in the form of an alkali metal hydrogen sulphide, an alkali metal sulphide, an alkali metal sulphide hydrate, or mixtures thereof in the presence of an alkali hydroxide and an alkanol, removing ammonia in vacuo while stirring said mixture and removing elemental sulfur formed during stirring and raising the temperature up to about 135 ° C and distilling A mixture of alkanol and water and recovery of light hydrocarbon distillates and hydrogen sulphide further heating said reaction product liberated from alcohol and water in a reaction zone at a temperature above 250 ° C and in the presence of a reagent, hydrogen sulphide and water thereby making the hydrocarbon constituents further hydrogenation which leads to an increase in the volatility of these and further a pre-selective treatment of said hydrocarbon constituents whose volatility has previously been increased which results in selective hydrogenation and / or dehydration in the presence of a preselected reagent, water and / or hydrogen sulphide and also recovery of said reagent for reuse in said process including associated metal parts recovered and in addition said hydrocarbon constituents are recovered. 11. ll. Process according to any one of claims 1-10 for the production of hydrated hydrocarbon constituents starting from oily clay shale as starting material and the like containing kerogens and other organic and inorganic carbon components which can be hydrogenated and other mineral constituents, characterized by a) reacting said starting material in at least one step with a reagent containing sodium hydrogen sulphide, sulphide, polysulphide, mixtures thereof and mixtures of hydrates thereof in the presence of water and / or steam together with hydrogen sulphide, and b) that said hydrocarbon constituents are recovered while at the same time recovering the mineral constituents. A process according to claim 11, characterized in that the reagent further comprises other alkali metal hydrogen sulphides, sulphides, polysulphides, mixtures thereof or mixtures of hydrates thereof. 13. A process according to claim 12, characterized in that the sulfides of said second alkali metals are hydrogen sulfides, sulfides and polysulfides of potassium. 10 15 20 25 30 450 129 40 Process according to claim 11, characterized in that said hydrocarbon constituents are further reacted before being recovered in a further reaction zone in the presence of a supported reagent, steam and / or water and hydrogen sulphide and wherein said reagent is a hydrogen sulphide, sulphide, polysulphide, hydrates thereof and mixtures thereof of an alkali metal. A process according to claim 14, characterized in that said further reaction zone for said hydrocarbon constituents obtains a temperature which is lower than the temperature in the first reaction zone in which said oil-bearing shale during reaction. A process according to claim 14, characterized in that the reaction is exothermic in said first reaction zone. Process according to Claim 14, characterized in that the reaction takes place with oil-bearing shale with at least 5% organic carbon content. 18. A method according to claim 14, characterized in that the metal constituents connected to the oil-bearing shale are recovered by leaching said oil-bearing shale in order to recover at least one reagent precursor and after which said metal constituents are separated from said reagent sheath. 19. A method according to claim 14, characterized in that the recovery of metal constituents is derived from said leached reagent. Process according to any one of claims 1 to 19 for the production of hydrogenated hydrocarbon constituents starting from starting materials such as oil-bearing shale and the like containing kerogens and other organically and inorganic carbon components which can be hydrated and other mineral constituents, characterized by U1 10 15 20 25 30 35 A) that in a first step reaction takes place between said starting material with a reagent comprising an alkali hydrogen sulphide, sulphide, polysulphide mixtures thereof or mixtures of hydrates thereof in the presence of steam and / or water and hydrogen sulphide, and b) further comprising said hydrocarbon constituents at least in a reaction zone in the presence of reagents as defined in a) above; c) the recovery of hydrocarbon constituents; d) to hydrogen sulfide Lillvaratas, and e) to reagent constituents Lillvaratas and associated metal constituents. 21. A process according to claim 20, characterized in that reagents during reaction b) in claim 20 are a supported reagent. 22. A process according to claim 21, characterized in that the reagent is a supported reagent of potassium hydrogen sulphide, sulphide, polysulphide, mixtures thereof or mixtures of hydrates thereof. 23. A process according to claim 20, characterized in that hydrogen sulphide mixed with hydrocarbon constituents is used to regenerate said reagent. A process according to claim 20, characterized in that the process in said first step takes place under exothermic conditions and at a temperature of about 320 ° C. Process according to claim 20, characterized in that the process in said first step takes place under exothermic conditions and at a temperature of about 360 ° C. 10 15 20 25 30 35 450 129 42 26. A method according to claim 20, characterized in that the metal constituents recovered are vanadium, cobalt, molybdenum and nickel metal constituents. p »