CH637688A5 - METHOD FOR OBTAINING HYDROGENED HYDROCARBONS FROM STONES. - Google Patents

Description

The invention relates to a process for the production of hydrogenated hydrocarbons from rock containing organic and inorganic hydrogenatable carbon components and minerals as the starting material, including the production of further components of this starting material. The invention provides an economically attractive process for recovering various hydrocarbon materials, such as gases and distillates, to obtain valuable fuel, feedstock, or feedstock from sources previously thought to be too expensive and unattractive for various economic and environmental reasons. These carbonaceous materials are often classified under different names, but are generally intended to include those materials that have carbon in one form or another, i.e. dispersed or distributed as mixtures of inorganic carbon and organic carbon with various hydrocarbon forms including nitrogen, oxygen, sulfur, etc. in an inorganic rock base material. Typically these are shale oil rock, gilsonite, kukersite, sandstone or limestone, which contain encapsulated kerogens of various forms or any other derivative thereof, including the distilled or extracted products of such rock formations (hereinafter "shale oil rock") and "shale oil".

As a result of the new process, it is now possible to remove these hydrocarbon materials from the rock formation in excellent yields with low energy expenditure without subjecting the rock to distillation (and thereby losing a large proportion of the total calorific value from the hydrocarbon materials in the rock). In addition, according to the present process, it is easily possible to convert this source of carbonaceous material into a series of products by combining process steps and appropriately using selectively selected reagents. In addition, valuable by-products such as ammonia are obtained in good yields.

In U.S. Patent Applications Serial No. 063,824, filed August 6, 1979, and No. 114,207, filed January 22, 1980, and No. 140,604, filed April 15, 1980, various methods for the treatment of Coal or io heavy hydrocarbon materials to obtain lighter materials, such as gases, light distillates or distillates. Other methods of treating hydrocarbon materials have been described in U.S. Patents 4,248,693 and 4,248,659.

15 There are a number of citations in these patents, and these patents and the citations therein are listed below for completeness.

The following patents are to be considered when considering the present invention: US Pat. Nos. 1,300,816,

20 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, 25 4 030 893.4 057 422.4 078 917.4 119 528.4147 611.4 147 612,

4 155 717.4 160 721 and 4 210 526.

In addition, the following references must be taken into account: Letoffe et al., Determination of the enthalpies de formation of the polysulfures de potassium, Journal de Chimie Physique, 71, 30 pp. 427-430, 1974; John S. Thomas and A. Rule (other articles in this series were written by Thomas and Riding), The Polysulfides of the Alkali Metals, Journal Chemical Soc., Part 3, pp. 1063 ff., 1973; Blitz and Wilke-Dorfurt, Z. Anorg. Chem., Vol. 48, pp. 297, 1906 (see also Ber., 53, pp. 43, 1905); van Kre-35 velen et al., Fuel, 38, pp. 256, 1959; B.K. Mazumdar et al., Fuel, 41, pp. 121, 1962; Hugot, Ann. Chim. Phys., 21, pp. 72, 1900; W. Klemm, Z. Anorg. Chem., P. 241, p. 281, 1939; F.W. Bergstrom, J. Amer. Chem. Soc., Pp. 147, 1926; F. Feher and H. Berthold, Z. Anorg. Chem., Pp. 247, 1953; Thomas and Rule, J. Chem. Soc., P. 40 2819, 1914; R.L. Erbeck, dissertation. Abstract, Ann Arbor, Mich., Pp. 3254, 21, 1961; Renegade and Costeanu, Bull. Soc. Chim., 15, pp. 721, 1911; Sabbatier, Ann. Chim. Phys., 22, pp. 5,1881; Mar-rony, J. Chim. Phys., 56, pp. 214 and 221, 1959; Mme Aline Auroux, C.R. Acad. Soc. Paris, 274, pp. 1297 to 1300, March 45, 1972; Küster and Herberlein «Contributions to the knowledge of poly-sulfides», Z. Anorg. Chem., Pp. 53 to 84, November 1904.

In contrast to the above, the present process represents a further advance in that the extraction of hydrocarbons or carbon-containing materials or the processing of their products by the process described here is not known with regard to shale oil rock. In addition, the extraordinary yields first of all make it possible to economically exploit the abundant materials with regard to both organic and inorganic carbon in these materials. In addition, the possibility of the combined extraction of hydrocarbon, ammonia and additional metal from the shale oil rock makes this process more attractive for a more complete exploitation of this type of hydrocarbon sources. This means that a number of countries that are dependent on energy imports can now be enabled to meet their energy needs, while at the same time being able to extract valuable by-products from these material sources.

65 The present method involves the treatment of a rock that contains hydrogenatable carbonaceous substances. Furthermore, the present method enables the refinement or concentration of heavy distillation or retort

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Products from these rocks. As one of the preferred auschants due to the reaction with the reagent, the shale oil rock is being crushed in or out. Insofar as the complex components of the shot-crushed form with an alkali metal hydrogen sulfide, sulfate oil rock are different for each shale oil rock depending on the under-fid or polysulfide or hydrated forms of the same, different location in the world

Mixtures of these sulfides (including the hydrates) and 5 generally some mixes of each of the alkali metal sulfide types with one or more genes for each rock treatment, and these are discussed in more detail below.

several other alkali metal hydrogen sulfides, sulfides. The invention is further explained or polysulfides (including the hydrates thereof) in the accompanying drawing in. In this means:

molten or liquid form in the presence of water FIG. 1 shows a reaction scheme for a one-step process or water vapor and most advantageously in the presence of - for refining distilled shale oil,

water and also treated with hydrogen sulfide, wherein FIG. 2 shows a reaction scheme for a multi-stage process product obtained in a product form, such as a gas, light for refining distilled shale oil including the distillate or distillate. This coal reagent extraction,

Hydrogen products have an increased hydrogen content. FIG. 3 shows a reaction scheme for the production of carbon

compared to the carbonaceous feedstock and 15 shale oil hydrocarbon materials included, as a result of the smaller molecular size, by-product extraction and reagent recycling, such as the rock base material at low temperatures, can easily be driven off in a series of reactions in a number of different ways at atmospheric pressure. Reactors are also practiced, and the advantages of the present invention are also shown in the same way. FIG. 4 shows a reaction scheme for the extraction of welding

applicable to the 20 hydrogen sulfide distilled from these raw materials.

Low quality products. In the drawing, which corresponds to the description of an execution

The process according to the invention is used to obtain the form of the process, FIG. 1 shows a removal of hydrogenated hydrocarbons from rocks containing ammonia and sulfur and a pretreatment stage for organic and inorganic hydrogenatable carbon - the processing of the distilled shale oil. For example, components and minerals as the starting material is 25 shale oil contains about 1.2 to 1.5 wt .-% nitrogen and 5 to 7 finally the extraction of further components of this wt .-% sulfur. In this pretreatment stage, the starting material is characterized in that it is merely mixed with the reagent in a little oil, such as with at least one stage the starting material with a reagent that contains KHS or K2S5 in alcohol (with some water being present) from alkali metal hydrogen sulfide , Alkali metal sulfide, alkali metals- At ambient conditions, but typically below tall polysulfide or mixtures thereof or mixtures thereof, the added reagent and the shale oil consisting of their hydrates are mechanically stirred in the presence of water. If heat supply is required and / or water vapor and hydrogen sulfide converts and this takes place with the aid of heating coils, as shown in FIG. 1 the hydrocarbons including the further compos. At this temperature below 60 ° C nenten are won. released large amounts of ammonia, but only as long as

In contrast to tar sands, shale oil rock at 35 temperature is kept below about 60 ° C. Ammonia agent about 5 to 60 wt .-% and more of bitumen and keroge is collected in a known manner, such as in water. Those with a number of other components, such as iron in ammonia removal, also appear to increase the API number, various forms of iron salts, calcium salts, but how the increase can also be based on sulfur removal, calcium carbonates, magnesium salts, such as magnesium sulfate. Sodium reagents drive out less ammonia, carbonates, etc., are linked. Compositions 40 while potassium reagents reduce the ammonia from about 1.5% of rock and these salts are found in books as described 0.1 to 0.15% by weight, for sodium reagent ben is as described by T.F. Yen et al., Oil Shale, Elsevier Pubi. Co., New this 0.6-0.7 wt%.

York, N.Y. 1976 and by T.F. Yen, Science and Technology of Potassium Hydrogen Sulphide does not give sulfur in aqueous

Oil Shale, Ann. Arbor Science Publishers, Inc., Ann. Arbor, solution. Some elemental sulfur can be extracted from the organi-Mich. 1976, to which reference is made here. The carbonate- 45 see sulfur can be obtained, apparently as a result of the shale oil rock's proportion as inorganic carbon. a nitrogen removal. This sulfur can be defined by rivers and can make up to 10% by weight of shale oil rock solids separation as a result of slow stirring. An unknown proportion of this carbon can (about 20 rpm) and the reaction at this temperature

can also be converted into hydrocarbons. The Bititu be separated. As a result, the sulfur content of the shale rocks is quite small. Yields 50 in elemental form on top of the stirred liquid. They are related to the total carbon available. Ammonia production is generally carried out with application. This conclusion is justified because of the yields that can be obtained from a vacuum to the reaction vessel, such as by suction, in the practice of the invention, since the formation of elemental sulfur occurs during the

Yields a kerogen conversion to hydrocarbon ammonia production, but can stop earlier, show 100%. In so far as a serious attack on the mechanical skimmers, shale oil rock can also be used to attack the reagent to remove the elemental sulfur formed. Oxides and carbonates caused in the shale oil rock. The ammonia removal reaction is generally quite advantageous, the initial reaction, i.e. the pretreatment was slow and can be omitted if not desired, and the first stage could be carried out in such a way that the additional ammonia and sulfur during the wash

Attack on non-hydrocarbon producing composite treatment reaction is removed. So recovered in the shale rock by the potassium or sodium sulfur can be used to rebuild the reagent back to umhydroxide, hydrogen sulfide or sulfide to a minimum, as further explained herein. About a sixth until held. At the same time, it is desirable to extract any valuable two-thirds of the sulfur content from the approximately 5 to 7% heavy components in the shale oil rock, which may be contained in a distilled shale oil, such as heavy metals, e.g. V, Ni, Mo, U, etc., which are removed, for example, at this stage. The reactor 11 is obtained from as water-soluble complexes of molybdenum (emptied in most of its bottom, and the mixture of shale oil forms) and vanadium. Most of the reagent is introduced into reactor 12. Of course, iron, cobalt and nickel can be used as hydroxides as a floc - the reaction mass in one batch process

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only container, such as container 11, are held so that the reactions are then carried out gradually in one container. However, to explain the different aspects of the invention, the different reaction stages are shown separately. The reactor 12 can be operated at a fixed temperature or the temperature can be increased in stages.

Supplementary reagent, which consists for example of KHS, K2S2 or K2S • XH2O etc., can also be dissolved in alcohol or water or introduced dry, water being added as water vapor or being bubbled in as liquid water and H2S being added to the water vapor or water streams. Typically, water or hydrogen sulfide is added at about 170 ° C. K2S • H2O, where x is 5 or 2, i.e. various hydrates, is a very active reagent and tends to produce mainly gaseous hydrocarbons. At temperatures above 135 to 150 ° C, the reagent is essentially a melt of K2S or Na2S and their hydrates (in molten form).

Typical temperatures at which the reactor 12 can be operated are as follows: 220 to 240 ° C, 280 to 320 ° C and 360 to 390 ° C. Most of the products are preserved at these temperature ranges. At the higher temperature, it is believed that the bitumen fraction is the one that gives the distillate. These reaction temperatures can also be reached when starting at 100 to 120 ° C and can be raised to 135 ° C. An alcohol solution of the reagent is generally introduced at the lower temperature. The light end fractions are distilled off from the initial temperature to 135 ° C and consist of gases and / or light liquid distillates and an azeotrope of water and the alcohol used to form the reagent. To keep the reacting ammonia in this condensate, a small amount of KOH or NaOH is added to the solution, i.e. in an effective amount to drive off ammonia. Ammonia is collected in an additional container. These products are collected in container 14 as gases and a two-layer liquid, the top layer consisting of the light hydrocarbon distillates, if any, and the bottom layer being a mixture of water and alcohol. The alcohol-water mixture is used as a starting material for the subsequent formation of the reagent.

The gases and light distillates are used in a distillation column reactor 18 where they are introduced at the bottom of the distillation column part of the reactor column 18. The distillation reactor column 18 is kept at a temperature of 220 to 240 ° C. The reagent is introduced at the bottom of column 18. However, the reagent, which can act as a catalyst in the subsequent distillation, can be in many forms for contact with gases and / or liquids.

To provide hydrogen for the hydrogenation of the shale oil components, water and, to a much lesser extent, hydrogen sulfide are introduced with the reagent (or separately) at the bottom of reactors 12 and 18. If the shale oil is hydrogenated, it becomes lighter and rises in the column and is obtained as overhead distillates in a single or in multiple cooling columns, as shown in FIG. 1 with 19 and 20. Because the reagent, when properly selected, will accumulate, it will be recovered at the bottom of column 18 in liquid or solid form and used as explained herein. The gases obtained from the container 14 with light distillates can be recovered after the condensation and introduced into the column 18 through a frit disk 17 or a sieve. The gas separation is illustrated in FIG. 4, which is discussed further herein, and the separation is shown schematically in FIG. 1 for convenience.

When gases are reacted in the reactor 18, a hydrogenation-dehydrogenation competition also occurs, for example when some K2S5 is used at that temperature. By appropriately adjusting the temperature at which the bottoms of column 18 are maintained, the water content in column 18 and the H2S content in column 18, the desired final product cuts are obtained as shown below. In general, it has been found that, for example, 16,200 BTU / lb of shale oil can be improved to approximately 19,000 BTU / lb.

In terms of energy, however, the thermal shale oil distillation process is wasteful. It may be necessary if the shale oil rock process as described here cannot be carried out. Feasibility is affected by the components of the shale oil rock, which can consume undue amounts of reagent. However, the main merit of the invention lies in the treatment of shale oil rock, and for this purpose the various findings described here are used to minimize reagent consumption and / or to increase product yield.

2 illustrates a multi-stage embodiment of the shale oil treatment process including reagent recovery so as to obtain predetermined product streams from the shale oil source material for a fully continuous process.

According to the method shown in FIG. 2, the same process is carried out in the pretreatment tank or reactor 110 as described with reference to the pretreatment reactor 11 of FIG. 1, so that this description need not be repeated. Similarly, the same reactions take place in reactor 112 as in reactor 12 in FIG. 1, but the replenisher is supplied from the reagent recovery section of the process scheme, as further described herein. The soil products are sent from the reactor 112 to a second reactor 116. The overhead fraction from reactor 112 is separated into two layers, namely the light hydrocarbon distillates and a mixture of water and alcohol, the light distillates and gases, if any, being recovered in the same manner as with reference to the process 1 is described. The bottom products of reactor 112, i.e. Shale oil and reagent are present in a ratio of about 3 g reagent to 1000 g distilled shale oil to 20 g reagent to 1000 g shale oil. The reagent is essentially free of mixed alcohol. Hydrogen for hydrogenation in the reactor 116 is replaced by water in an appropriate ratio of 15 to 100% by volume (as a liquid) of the volume of the hydrocarbon condensate removed as a liquid and in the amount of the difference between the hydrogen content of the initial product and the product obtained ( with a 100 g base), calculated back to the amount of water converted, ie times 9 (amount of water required to obtain the hydrogen that was reacted). These two values are added together and give the total amount of water used. The efficiency of water introduction, i.e. for implementation purposes, determines the percentage of water required, with a lower percentage indicating higher efficiency. The main purpose of using hydrogen sulfide is to keep the amount of reagent used to a minimum and to keep the reagent in a stable and active state.

If the temperature in the reactor 116 is significantly higher than in the vessel 112, heat may be applied through internal or external heating coils if necessary. The reactions in container 112 are either endothermic or exothermic, depending on the reagent used. So can

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the heat balance easily through heating / cooling coils, so the preferred alkanols are methanol and ethanol. Position of the reagent composition or selection suitable- That part of the reagent which is held by the alkanol-recorded temperature levels. is the part used for the implementation, but

Bottom products from the reactor 116 can also be introduced in one of the water content (required in the hydrogenation and for the hydrate-further reaction tank 118 for additional hydrogenation 5) with a mixture of alcohol and recovery of the reactants. Reagent water can be enlarged. A small proportion of the

The top fraction of the reactor 116 is required in the reflux water, so that the alkali sulfides in the alkali column 117 are heated under reflux, the top product noi forming the hydrates. In general, the ratio of that withdrawn from the reflux column 117 is approximately at 225 ° C. Alkanols to water the azeotropic mixture with lower This fraction with a boiling point of 225 ° C can also, io boiling point, which boils at about 88 ° C (methanol-water).

as shown in Fig. 2 can be worked up. All liquid It is easy to see that the reagent recovery

Distillates from reactors 112, 116 and 118 can be easily carried out, particularly since hydrogen sulfide is introduced from reactor 121. Reactor 123 when heated or recovered as in

In the reactor 118, the shale oil product and rea- Fig. 4 is shown, is available in quantities. In the reactor 125 gens heated in the range of 360 to 400 ° C, the reagent 15 introduced hydrogen sulfide then reacts with the alkali from the bottom of the reactor is returned to with the hydroxide to form the sulfides in question. This should coincide with upcoming reaction product, taking place under cooling conditions. Since the sulfide reaction in typically the higher temperatures produces lighter fractions of alkanol, depending on temperature, concentration and solvent including gases, but the end product is gigantic, many types of alkali sulfides, such as potassium sulphide, can depend on the type of reagent and the ratio of alkali metal to 20 , form when the temperature does not depend on suitable sulfur. At a higher ratio the sulfur content is maintained.

The reagent tends to reform the lighter final fraction. As the reagents represent mixtures in the container 125 to dehydrate and animal to form heavy fractions, they can be reformed as such for the reactor 110. However, this depends on the added water and diluted with alcohol. But it can also be a lot off. Thus, when more water is added, the 25 alkali metal sulfide types produced or reactivated more intensively in reactors 116, 118 or 121 for reactions such as competing hydrogenation reactions. In addition, the reagent will be prepared in its more hydrogenation active, in which case the reagent will be kept in a selection of a form. When the reagent in the reactor 118 is a narrower mixture. It has been the practice for the above-described accumulation, for example with a three-way valve method, to withdraw reagents of a certain ratio 120. 30 to use from alkali metal to sulfide. This will be in this

Turning now to a revision of the description from the column described later.

117 recovered reflux fraction, it can be said that FIG. 3 explains a method in which shale oil can be converted directly from this in a further column 121, rock, either from organic and / or anorga-as described further here . The reagent in the column of niche carbon materials, with the help of the 121 described here for this purpose, is predominantly K2S and KHS in alcohols 35 is obtained. According to this embodiment, hol. As is known, the alcohol of the overhead product of the invention can be separated into particles of a size of about 6 mm ('fraction fraction, see for example inch) and less crushed shale oil rock in one

Fig. 4. In the reaction column 121, water is fed in with the funnel 210 above and added at a speed explained by a screw conveyor 211. This allows a mixed out with reagent. The implementation, however, is independently reaching hydrogenation to a product via the reflux 40 of the rock size. The reagent is in liquid form to obtain lonne 123, which has a boiling point of about and coats the rock particles. It is conveniently located at 160 ° C, but a product area can be obtained through an opening 215 in the screw conveyor trays. A spent reagent stream is introduced with the reagent from in measured amounts such that about 5.0 is combined into the reactor 118 and recycled for reprocessing and up to 30.0 g of reagent such as KHS (or converted to KHS-based) recycling of the reagent as follows . 45 per 1000 g of rock are added. Generally up to

In the reactor 123, the hot reagent becomes plentiful to about 8 gKHS per 1000 g rock. It was also found

Chilled at 390 ° C with cold water. After cooling, that shale oil rock may be equally economical, water in an amount of about 1 to 2: 1 water is added to the reagent if not more economically with types of sodium sulfide. Reaction with water represents the reagent can be treated again. It also appears to be the case that an alkali hydroxide and alkali sulfide are formed 50 Reaction of reagent and water and H2S with shale oil. When the solution is cooled, other metal rocks fail for some of the shale oil reagent types exothermic bonds, except that vanadium (is molybdenum, as shown by the examples here. It can remain soluble under the same conditions) is soluble and winding (s) 213 can be used to heat or to be removed electrolytically if it cools sufficiently in the solution, depending on the situation.

is concentrated. In general, up to 2 moles of water can each 1 55 As long as the process is carried out batchwise, moles of alkali (based on elements of the alkali) can be used to increase the temperature levels and further temperature increases. The smaller amounts are preferred. The threads used to achieve the same effect as shale oiling of the heavy metals provides one of the advantages of the process as described above. In that case, it will and will be allowed to be cost effective. the water vapor and H2S in a predetermined order

The reagent product stream from reactor 123 is withdrawn (after alcohol distillation) 60 when alcohol is distilled and filtered in filter 124 to remove contaminants and used to dissolve the reagent. However, if the temperature-suspended flocculant or flakes of heavy metal temperature in the reactor 212 are kept high, then oils or any suspended particles will be removed. Recovered in only the products formed, H2S and water, and the reagent recovery tank 125, the reagent minimal amounts of ammonia are expelled, except cooled, when used with a cold alkanol-water azeo if certain steps are followed.

Tropl solution and hydrogen sulfide is mixed. The rea- It proved to be advantageous that the with the shale oil

gens has a certain solubility in the alkanols (to introduce the reagent mixed with stone particles in such a way that the increasing carbon atom content in the alkanol decreases). stone particles are covered. As shown in Fig. 3,

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this can be easily achieved by metering the reagent during and instead of reacting at such a high temperature with the rock particle feed. In which it is carried out that only gaseous top products and /

Reaction kettle 212, which is withdrawn from the reak-selected temperature level, such as 280 to gate 212, via line 221 during continuous operation on the or highly volatile distillates.

390 ° C, the rock can be held by a pump or 5 The reactor 230 has therein a reagent in the form of a plurality of pumps 217, which are part of the reactant, catalyst. The same is found in the reactor 223. Be these liquids or gases, to a lower cone-forming reagent of the type described here as the catalyst part of the reactor 212 is present through a plurality of openings 218 and is a supported catalyst in which the Allow the carrier to be cultured, stirred, whereby a part of the rock, for example an alumina or a potassium aluminum silicate, is kept in suspension, or any io a spinel or similar carrier system with large stirrers can be used. Similarly, area that is typically used in the petroleum industry for reforming steam and hydrogen sulfide also below the catalytic converter. Although the catalyst

Rock are introduced. In this case, since the rock is heavier than that described with reference to the «reagent», reagent and the hydrocarbons recovered, it functions as a typical rock rock to the bottom of the cone-shaped reactor. 15 because of the large surface. Thus the reaction takes place at

The settled hydrogen is easily supplied by a suitable valve pump 216, withdrawn with the support of the contents of the reactor and thrown away or in a reagent which acts as a catalyst instead. A typical wash bowl 219 is introduced. The wash water is used in a few- reagent for the first stage, KHS (dry), and for the second gene quantities, since it is depleted reagent precursor stage, it is K2S and / or K2S2, which supplies the latter two reagent or heavy metal compounds with water from the 20 parts are in solid form under the reaction conditions. Leaching solution can be precipitated. The rock back- Other reagent systems are NaHS (liquid lumps) at stand is pumped out via the valve pump 216 and then process conditions in the reactor 212, preferably filtered on a drum filter 220, such that the rock back NaHS + '/ io mol NaîS • XH2O (as technical flakes), in which stood as a filter cake is thrown away. The rock is second stage K2S, K2S2 and K2S5 or mixtures thereof, at this point pretty well pulverized. 25 K2S prevails. A fairly typical amount of a rea-

The overhead products of the reactor 212 pass through a sieve, the gas catalyst consists of 20 g of 250 ml of support in the form, for example a York sieve 212a, and consist of ammo- of balls of the potassium aluminosilicate type of 4.8 mm. The niak, hydrogen sulfide, gas and distillates, depending on the catalyst used in the second reactor, have a very long operating temperature and the reagent used. Hydrogen sulfide and water are also present and are e.g. worked up as follows. The 30 den, the latter as water vapor. When treated in the two-temperature cold water condensable product gases stage, the sulfur content of the reaction products can be introduced into a second reactor 223 and reduced to less than 3%, such as 2%, in a first stage therein, a carrier reagent which is considered to be Catalyst works, implemented. To be, and the products can be in the API number range from explanation of a number of embodiments are two 40 °.

Reactors 223 and 230 shown. 35 Fig. 3 will now be considered again. Although the

In connection with a conventional carrying catalyst suspended in a basket 232, the reac process can be used as a two stage process, equally well in any column, any stream 221 being introduced into a reactor 223 which acts as a tower or reactor can be carried out, in which the plate column is shown, where the catalyst is distributed on trays supported catalysts. There may also be more than one arranged. The introduction takes place at the bottom of this reac- 40 column in parallel or in series, or it can be tors. It can be a reactor that uses alternating columns on top of the reactor. As shown in FIG. 3 212, but for ease of illustration, the basket is removable and rests on a front near the reactor 212. Stream 221 is at jump 234, with rim 235 of basket 232 being introduced as a funnel bottom of column 223, i.e. it is formed in direct current. Water is formed in the reactor 230. One introduced with additional water, as explained in Fig. 3. There are 45 other reactors, the same as 224, operating at a temperature - a reflux column 224 can be used. It works between 135 ° C and 150 ° C and treats the entire tet in a conventional manner to produce the desired product gas flow. However, all condensate is separated and cut or the desired product fraction removed. consists of hydrocarbons. The reagent is a hydrated

If the reactor 212 and column 223 with a single melt of K2S • 5H2O, and the gases will operate throughput, then the product streams from the 50 will be bubbled through this melt. The liquid hydrocarbons from the top of the reactor 223 are recovered, as by a reflux, above the melt, and are removed from a column 224, and a gas treatment, especially a level suitable for H2S. Similarly, two of the above workup can be done as shown in FIG. 4. Ammo- described reactors 230 are used alternately, niak is separated as follows, if in the boiler one at a time and the other, during the catasel water, such as 430, is changed as a bottom layer with a catalyst or the reagent and / or removed and hydrogen sulfide is found on top (if no alcohol is used it is finally reprocessed for the other.

or after the alcohol has been expelled). In Fig. 4 there is a schematic representation of a small amount of KOH or NaOH being used for the condensed hydrogen sulfide gas recovery. A reactor 442 was added to water, ammonia was driven out of it and then typically sheared with shale oil rock at 320 to 390 ° C in another container (not shown, in which water 60 was charged and a reagent in liquid or solid form, which was formed) . Hydrogen sulfide is very little water-soluble in the form of water vapor and hydrogen sulfide gas and therefore passes through. Thereafter, sulfur is treated and / or reacted as described above. Hydrogen further processed as shown in Fig. 4, i.e. After that, these gases are started in a condenser, like at-431. for example 426, cooled. A cooling jacket 424, which the condenser

However, as surrounded in the dashed section A-1 of FIG. 3, 65 426 facilitates cooling of the reaction gases. As shown, the reaction products from the reactor 212, initial and heavier products, can be processed as bottoms if the reactor is recovered with products of the capacitor 427. The gaseous products, if any liquid distillates, are operated are sent to the container 430, where water

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or alcohol (typically methanol or ethanol) as a KOH solution. 1 mole of kOH and 1 mole of water at 40 ° C are kept there. The alcohol solubility corresponds to 1 mol of KOH in 123 ml of methanol or 190 ml of ethanol. The selected solution in container 430 is kept cold and so the lighter gases pass through, such as the Ci-Cs hydrocarbons including hydrogen sulfide. When alcohol is used, C3 is absorbed and C4 and Cs are soluble, which is why a water solution is preferred.

In container 431, the contents are cooled to about -35 ° C and at this temperature liquid C4 and Cs hydrocarbons are removed. Although most of the C4 and Cs fractions are removed in container 431, something is still carried to container 432 where these residues are removed at -30 ° C with the Cî fraction in ethanol or methanol. A glass frit disk 433 removes residual mist from these components. At this stage, essentially only H2S and Ci and C2 fractions are contained in the gas stream, which is then introduced into container 435, which contains KOH and alcohol, typically ethanol or methanol in water solution. Hydrogen sulfide reforms therein the reagent, which is recovered as a precipitate, while the light fraction gases, predominant Ci and Ci hydrocarbons, pass through. With up to about 97% conversion of KOH to KHS, no H2S passes through, and thus is recovered as a reagent component and can be reused (or used in the system if KHS is converted to K2S5 by dissolving sulfur, forming equimolar amounts) will). If necessary, more than one wash tank 435 can be used to remove hydrogen sulfide. No H2S is blown into the air. The alcohol-water fraction from container 430, which is obtained during the start of the reaction, is used to replenish the alcohol carried away from container 435. However, this mixture must be cooled in the heat exchanger 436.

Although the recovery of alcohol and water was shown in Figure 4, the recovery scheme is equally applicable when the reagent is in a "dry" form, i.e. without alcohol dilution. In that case, alcohol is only present in container 435 where the reagent is recovered, and in 430 only water is present. Container 435 can operate below 40 ° C without alcohol while the exothermic reaction is being cooled and while the water content is maintained at or slightly below 2 moles per mole of KOH.

It should be understood that the above hydrogen sulfide recovery is applicable to the methods described with reference to FIGS. 1, 2 and 3.

This is also the reason that, in connection with the process as described in Example 3, the reagent that is introduced into the reactor vessel 212 via the screw 211 is a substantially dry reagent, i.e. a product that is in a concentrated form from which alcohol and water have been removed.

The alkali metal hydroxide, such as potassium hydroxide, is obtained from the spent and reconstituted reagent as shown in Fig. 2, or leached from the rock by adding water as shown in Fig. 3, where the sodium and potassium hydroxide from the spent Reagent is obtained.

The reagents used here are the empirical hydrates of the hydrogen sulfides, monosulfides and polysulfides of the elements of group IA of the periodic table of the element except hydrogen. Francium and cesium compounds are generally not used for various reasons. So the sodium, potassium, lithium and rubidium compounds are used more frequently. The potassium, rubidium

and sodium compounds are preferred. However, rubidium is not beneficial because of the cost. Sodium, like NaHS, is the cheapest, although potassium is the most desirable. For example, a product treated with KHS is about 3 to 5 ° API lighter due to the more effective ammonia and sulfur removal. For initially treated shale oil rock, sodium hydrogen sulfide is inexpensive because it is a melt under process conditions and because it is more stable with water under these conditions. Thus, in the first reactor 212, the kerogen fraction is best treated with NaHS because of the lower melting points at the process temperature.

During the reaction in the second reactor, such as 223, the reagent is actually a mixture of the empirical hydrates of the hydrogen sulfide and the sulfides (mono- and polysulfides) of the alkali metal used, and during the reaction there is an interconversion of these sulfur-containing forms (if the reaction temperature rises, some of these forms disappear because their decomposition temperatures have been exceeded, as will be further explained here). Accordingly, the reagent may initially be introduced into the reaction zone as the empirical hydrogen sulfide hydrate or as one or more of the sulfide hydrates or as a mixture of the empirical hydrogen sulfide and sulfide hydrates. The empirical hydrate reagents can also be obtained in situ, but they are preferably fed in their empirical hydrate form, but preferably at the higher hydrogen sulfide content, such as the hydrogen sulfide, when hydrogen sulfide is lost at higher temperatures, such as 200 to 220 ° C. Each of the alkali metal bisulfides and mono- and polysulfides can have more than one empirical hydrate, but unless otherwise stated, the term "hydrate" means all hydrates.

The amount of reagent used should be sufficient to provide suitable contact with the feed and the desired reaction rate. The maximum amount of shale oil rock that can be processed with a certain amount of reagent is different for each shale oil gesture information and can be determined with the regulations given here.

If the cost of the reagent, such as sodium hydrogen sulfide; because of their availability are less important, the reagent recovery can be omitted. Then the omission or maintenance of that stage must be considered separately.

It has been found, among other things, that if a shale oil rock reaction is performed with a certain minimum amount of reagent present, the reaction will give better results if all other conditions are the same. For this purpose, the stabilization of the reagent is best carried out with hydrogen sulfide present, based on the highest volume fraction of hydrogen sulfide in the reactor, which does not hinder the reaction. If large amounts of reagent are present, the hydrogen sulfide, as a fraction of the total reactor volume in gaseous form, cannot stabilize the reagent. On the other hand, if a large volume of the reactor is occupied by hydrogen sulfide, the reaction cannot proceed due to the absence of hydrogen from water. Excess reagent not only attacks the undesirable components in shale oil rock, such as iron in its various forms, but is also destabilized, i.e. converted into alkali hydroxides and sulfates and without attacking the carbon components, the reagent in the case of alkali hydroxides attacks, for example, iron components in the base material. If you don't remove the oxygen, sulfur, and remaining nitrogen atoms for the kerogen fraction of the shale oil rock, you can waste it

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Reagent reverse the process into an undesirable sequence of reactions. This consideration of competition is further influenced by the components in the different types of shale oil rock. These problems of the competitive reactions are partially solved or minimized by the following. Appropriate selection of a reagent, e.g. if cheap reagent, such as NaHS (an industrial raw material) is available, can be used to advantage, and then the reagent recovery is not critical. Hydrogen sulfide should be used in an amount that does not hinder the reaction (which is best determined by the rate at which the products are recovered). Water vapor or water is bubbled into the reactors, i.e. used as a fine mist in relation to the product obtained, for example according to a rough rule of thumb in an amount 15 of about 130 wt .-%, based on the amount of carbon obtained, but the actual proportions are as explained above. This also takes into account water of hydration or water present in the shale oil rock.

In general, the addition of hydrogen sulfide 20 is based on a space-time velocity basis and is typically in the range of about 10 to 30 ml / min / l reactor space, with about 20 ml / min / l being typical. In other words, Vi gMol and less H2S is added to every 1000 ml of water removed by the hydrogenation reaction.

The reasons for adding hydrogen sulfide result from the following reactions.

1.4 KOH + 4HzS - 4KHS + 4HzO if there is sulfur from shale oil,

2.4S + 6KOH - K2S2O3 + 2K2S + 3H2O vice versa

3. K2S2O3 + 3H2S - K2S5 H- 3H2O

The decomposition of K2S2 is as follows:

4.4K2S2 + 8H2O - 4KOH + 4KHS + 4S + 4HzO

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Thus, when H2S is present, KOH is converted to KHS, and when KOH forms the thiosulfate, the thiosulfate is converted to K2S5. Since KOH attacks, for example, gaseous iron salts, the obviously predominant or at least favored competitive reaction 45 with hydrogen sulfide minimizes the side reactions and makes the process attractive.

Other reactions are the following:

5.K2S5 - K2S4 + S (above 300 ° C)

6.K2S4 - K2S3 + S (above 460 ° C)

7. KHS + K2S + 3H2O - 3KOH H- 2H2S

8. K2S + H2O - KOH + KHS

9. KHS + H2O - H2S + KOH 10. KHS + KOH - K2S + XH2O

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(x can be, for example, 2.5, etc., depending on the temperature). Thus, there should be enough H2S to keep the reactions by mass action in a state where the reagent is stable, i.e. Sulfur is taken up when it is released from shale oil or shale oil rock or from the reagent, and hydrogen sulfide prevents the reagent from hydrolysis and minimizes the formation of free potassium hydroxide. In addition, the thiosulfate developed by the oxygen present in the shale oil rock is regenerated during the conversion to the desired K2S5. Thus, the reagent is kept at the desired level of hydrolysis by H2S.

Of the various reagents, the following are useful because of their stability and / or sulfur uptake: KHS, NaHS, K2S, K2S2, K2S3, and of these the order of preference is as follows: NaHS (due to price and availability), KHS, K2S2, K2S and then K2S3. The other sulfides show instability at their melting points, such as Na2S2 at 445 ° C, Na2S4 at 275 ° C, or give off sulfur at 760 mm, e.g. gives K2S5 at 300 ° C K2S4 + S, K2S4 at 460 ° C K2S3 + S and K2S3 at 780 ° C K2S2 + S. The melting points of the alkali sulfides explained above are as follows: For K2S 948 ° C, for K2S2 470 ° C, for K2S3 279 ° C (solidification point), for K2S4145 ° C, for K2S5 206 ° C and for K2S6190 ° C. The melting points for mixtures of sulfides (pure or electrical mixtures) are as follows: For K2S - K2S2 350 ° C, for K2S2 - K2S3 225 ° C, for K2S3 - K2S4 about 110 ° C and for K2S4 - K2S5 183 ° C. Based on the various explanations above, suitable temperature stability conditions are selected which are determined by the decomposition and / or melting point in order to allow the use of a solid reagent or a stable liquid reagent. Of course, the different hydrates of the alkali sulfides have different melting and / or decomposition points, which also applies to the eutectic mixtures. These temperature points can easily be determined thermographically, as is known to the person skilled in the art.

Thus, at peak operating temperatures such as 400 ° C, K2S5 gives sulfur (which is a useful phenomenon, as explained here in connection with the dehydrogenation of other process streams). Since the decomposition temperatures are lowered at lower pressures, shale oil rock conversion is fully feasible at atmospheric pressure, although some advantage is achieved by operating at elevated pressures, such as above 5 at. The additional costs and other expenses only make this way of working a less desirable method of performing the shale oil conversion process. Thus, for practical reasons, the range of pressure conditions can vary from about Vi at to about 5 at, but ambient atmospheric pressure is preferred. US Pat. No. 4,210,526 is relevant for the description of the various sulfides and their decomposition temperatures, including the reactions.

It is understood that there are many competitive reactions and the alkali metal sulfide chemistry is very complex. Although every attempt has been made to explain the process, the basic criterion was the feasibility of the process when applied to shale oil and preferably shale oil rock. This is shown by the examples below.

In the case of the potassium reagents, heating to a temperature of 105 to 110 ° C. under a water atmosphere results in an empirical hydrate melt which contains about 35% by weight of bound water. This melt is then dissolved in enough low boiling alcohol (preferably methanol or ethanol) to form a saturated solution (more dilute solutions can be used but require additional energy to evaporate the excess alcohol). In the case of potassium reagents, about 150 ml of methanol or a little more ethanol is required at ambient temperature to dissolve 1 gmol of KHS. Hydrogen sulfide is bubbled through the solution at a temperature not exceeding 60 ° C, resulting in a solution of the reagent in alcohol.

During the embodiments described above

637 688

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were dealt with with reference to the drawing, various aspects of these methods can be found in the following examples to facilitate understanding of these embodiments and to further support them.

example 1

200 g of shale oil was obtained by distilling shale oil rock which was treated in a first stage reactor. No hydrogen sulfide containing 50 ml of a methanol solution of empirical dihydrate of potassium hydrogen sulfide (0.38 g KHS / ml solution) was fed into the reactor. The first stage reactor was a vertical cylindrical vessel with a total volume of about 11 and equipped with a heating mantle. Analyzes of the shale oil, the products and the residue in the reactor are given below.

material

amount

Analysis of hydrogen

Nitrogen sulfur

Shale oil

200 g

9.90%

1.45%

6.23%

Fraction below

22 g

10.33%

1.16%

6.85%

280 ° C

Fraction 280-300 ° C

35 g

10.59%

0.85%

6.80%

Residue

100 g

8.33%

1.47%

5.76%

Uncondensed volatile substances totaling approximately 43 g were determined by difference formation. The metal content is given below (unless otherwise stated, the numbers mean parts per million (ppm). “N / D” means not ascertainable).

material

Analysis Na V

K

Fe

Ni

Approx

Shale oil

11 124

64

106

86

1223

Fraction below

1.2 5

5

N / D

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Fraction 280-300 ° C

0.61 19

4.6

N / D

N / D

-

Residue

21 56

2.89% 34

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The heavy metals such as vanadium, molybdenum and nickel are extracted as explained above.

Another approach to the untreated shale oil identified in Example 1 has been implemented. His analysis was as follows:

Untreated Hz C S C: H API N>

Shale oil 10% 78.65% 6.27% 1C: 1.53H 1.8 1.37%

Boiling point range, ° C

() 10% 20% 30% 40% 50% 60% 70% 80% 90% endpoint 142 255 286 316 328 338 352 353 (354 = 21.6% residue)

Analysis of the first 12% distillate from a shale oil of the above analysis treated in a manner as indicated above in a single reactor with K2S • XH2O formed from KHS fed to the reactor showed that the product had the following properties owned:

Degree API at 16 ° C 25.4

specific gravity at 16 ° C 0.9021

Sulfur,% 6.74

17517 13153 16484 0.001 80.15 11.32 6.74 0.68 1.11

1.2 ppm 1.1 pm

Example 2

Shale oil distilled from shale oil rock 15 Two tests were carried out with shale oil rock found in Israel. Insufficient oil was obtained in a single run to give a distillation range. The two attempts were combined to make enough oil for the distillation area.

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Trial No. 1

About 60 ml of the reagent solution described below was reacted with 1900 g of shale oil rock by merely mixing the rock with the reagent solution. A two layer reagent of the following composition was used. To 6 moles of KOH, dissolved in 12 moles of water, 108 ml of absolute ethanol and 4 moles of sulfur dissolved therein were added. When this solution was prepared (the exothermic reaction of water-dissolving KOH provided 30 the required heat), an additional 2 moles of S in 108 ml of absolute ethanol were added to obtain an empirical K2S2O3 + 2H2S2 + 3HîO. This reagent formed a two layer solution. One third of the solution, with the amounts of the solution in such proportions in which the two layers 35 are mutually related, was added to an equimolar amount (based on K) of a reagent thus prepared. KOH + 2H2O, the solution being saturated with H2S in cold conditions. Another mole of KOH was then dissolved in the solution. The solution melted at 40 60 ° C. The reagent was then K2S • 5H2O.

The rock was treated in the reactor with mechanical stirring with steam and H2S, 80 ml / min. The shale oil rock came from Israel.

The reaction was good, but at 320 ° C (approximately) the reaction became exothermic and the temperature rose to 440 ° C. The heat had occurred at 320 ° C, but the exothermic reaction had started below 320 ° C. Water vapor was turned off at 380 ° C, but the exothermic reaction continued until a peak temperature of 440 ° C was observed 50. Then 591 gas had been produced. Hydrogen made up 69% of the gas, CO2 made up 6% (mainly from the carbonates of the shale), the rest consisted of hydrocarbons with a carbon content between 1 and 6.77 ml condensate with an API of 29 and 55 and a sulfur content of 7.1 % were received.

Trial No. 2

About 60 ml solution of the following reagent was mixed with 2200 g shale oil rock from Israel. The reagent was 60 as described in Experiment # 1, except that KOH + 2H2O was saturated with H2S in cold conditions, another mole of KOH was added to give a solution. The solution was heated to above 180 ° C., then 0.83 mol of sulfur was reacted with this solution 65. The other catalyst was the same as that in Experiment No. 1 above, except that no further sulfur was added (over the 2 moles above). Equal amounts of the K-based solutions were added.

BTU 454 g each BTU 3.81 net BTU ash less than 5 carbon. Hydrogen sulfur nitrogen

Oxygen and Undetermined 10 Sodium Potassium

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The reactor for this, as in the previous experiment, was a round steel reactor with a capacity of about 3.81 and was heated and mechanically stirred. The oil distilled from the rock mainly at 220 to 240 ° C and at 280 to 320 ° C in the presence of water vapor and hydrogen sulfide, the latter at 80 ml / min.

Israeli shale oil rock contained 5% hydrocarbons ± 25% (of which 5%). The sulfur content of the rock was 2.5%.

The hydrocarbon condensate contained 6.25% sulfur, had an API of 31, and the volume of liquid collected was approximately 71 ml. There was an uncondensed distillate of 371 gas which was 66% hydrogen, 2% carbon dioxide, 1% carbon monoxide and 28 % Hydrocarbon containing carbon contents between 1 and 6. Part of the condensate was lost when an excess burst of water vapor blew some of the rock into the condensation tank.

The distillates from the two experiments were combined and 100 ml were subjected to a boiling point determination. The boiling range determination showed an initial boiling point (71 ° C.) and a final boiling point of 307 ° C. with a residue of 1.7% by weight. The 1.7% residue contained 3.7% sulfur. The sulfur content of the product with 0 to 50% boiling range was 7.25%, the sulfur content of the 50% of the product up to the end point was 4.1%. Thus, the sulfur content of Israeli shale oil extracted from the rock of the invention is greatest in the lower boiling fraction. The nitrogen content was reduced to 0.11%. The product was greenish-brown and clear.

As shown above, a milder reagent that causes an exothermic reaction at a higher temperature, such as 360 ° C, was obtained by combining K2S2 • XH2O (obtained by heating K2S • 2H2O at 100 ° C in the presence of sulfur) with one obtained two-layer reagent, the latter being prepared as above, except that

that no additional 2 moles of sulfur were introduced. Again, equimolar amounts of the two reagents were used based on the amount of potassium (on an elemental basis). The solution of the two-layer reagent described above was taken in the proportions in which the two layers are in relation to one another.

As can be seen from this example, mixtures of sulfides of the alkali series as well as mixtures of the sulfides of the alkali types, such as potassium, can be used.

Example 3

453 g of the shale oil rock, as in Example 2, were reacted with potassium hydrogen sulfide, KHS, in hydrate form and in the presence of water. The amount of reagent used was 60 ml solution of 0.4 g / ml KHS. The potassium hydrogen sulfide used was an alkanol solution (methanol and ethanol) of the potassium hydrogen sulfide and was removed by raising the temperature to about 135 ° C. At that time, some of the hydrogen sulfide had formed a potassium sulfide hydrate K2S • xh2Û (x is typically 5 under these conditions). Some of the reaction product, which was collected in series in two condensers, was carried away with the distillate. At about 160 ° C, the potassium sulfide hydrate decomposed and released large amounts of gas.

Significant amounts of liquid hydrocarbon condensate from the rock were obtained between 230 and 250 ° C, again at 320 to 350 ° C and at 370 ° C and finally at the peak temperature of 400 ° C. At the end of the experiment at 400 ° C there was little condensate. No precautions have been taken to collect gases. A total of 25 ml of oil product with a specific gravity of 0.89 and an API number of 26 was collected as a condensate. Since this shale oil rock was believed to contain 5% hydrocarbon, the extraction was almost complete, i.e. about 98.2%.

Example 4

453 g of the same shale oil rock was treated with NaHS flakes (technical quality). The amount of reagent was 100 g. These flakes melted at 112 ° C. The melt state was stretched using an inert atmosphere and in the presence of water vapor.

The hydrate melting at 112 ° C decomposed at a higher temperature with accompanying release of water to a lower hydrate which was a solid. Water was introduced into the reactor at a rate of about 6 ml / min. No hydrogen sulfide was added during the experiment described in Example 3 and in this example. 24.5 ml of the product was obtained in the same manner as in Example 3, and this condensate also had a specific gravity of 0.89 and an API number (American Petroleum Institute) of 26. A second experiment also gave a product with an API number of 26.

Washing the rock with water gave a green solution, and indeed a very deep green solution. This indicated the presence of alkaline iron compounds including other mineral complexes.

When hydrogen sulfide was used, the formation of these complexes (presumably ferrite-ferrate complexes) was significantly reduced so that there was no reagent consumption.

From the two examples above it can be seen that there was no noticeable difference between the quality and quantity of the hydrocarbon product obtained when sodium hydrogen sulfide (technical quality in flake form) was used with the drop of water in the reaction kettle and when alkanol solutions of potassium hydrogen sulfide and water vapor than the reagents were used in the process.

However, in later experiments it was found that significantly smaller amounts of reagent could be used when using hydrogen sulfide in the reaction vessel (which improved the economics of the process).

If the reaction was carried out in a single step, based on the above explanations, the API number for the condensate can range between about 20 and 32, with the range of about 25 to 30 being clearly achieved, and with the yields of the product is about 100% or more based on the amount of organic carbon in the shale oil rock. The presence of hydrogen sulfide is highly desirable to achieve these results.

For a two-step reaction with supported catalysts, the API numbers can be in the forties.

Example 5

466 g of shale oil of the type specified in Example 1 were treated with 18.6 g of reagent in a first reaction kettle and with 12.4 g of reagent in a second reaction kettle.

The reagents were as follows: KHS and K2S • XH2O in the first reaction kettle as well as in the second.

The reaction in the second reaction vessel was in the gas phase. The temperatures in the first reaction kettle were 390 ° C peak and in the second reaction kettle 220 ° C.

The analysis of the initial distillate from the second kettle was as follows:

Degree API at 16 ° C 22.6

specific gravity at 16 ° C 0.9180

Sulfur,% 5.94

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BTU 454 g each 17411

BTU 3.81 133 125 ash 0.008 each

Carbon 80.48

Hydrogen 10.66 Sulfur 5.94 Nitrogen 1.05 Oxygen 1.86 Sodium 0.32 ppm Vanadium N / D Potassium N / D Iron N / D

Analysis of the final distillation fraction:

Degree API at 16 ° C 19.5 specific gravity at 16 ° C 0.9371 sulfur,% 6.19 BTU per 454 g 17571

BTU 3.81 137124 net BTU 16470 each

Viscosity at 38 ° 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 Potassium N / D Iron ND / Nickel N / D

It should be noted that while the API number decreased (as should be the case with the last distillates), the hydrogen content still increased. The above reactions were carried out without the addition of hydrogen sulfide. The addition of hydrogen sulfide increases the product quality.

In subsequent experiments, it was found that a decrease in the amount of reagent did not affect the yield as long as hydrogen sulfide was present. As little as 7.5 ml of reagent (KHS base) could be used to treat 500 g of oil. The same was true for shale oil rock, i.e. approximately 7.5 ml (KHS-based) reagent treat 1100 g of rock, although the amount required to effectively coat rock 45 is an important consideration for practical reasons to ensure a thorough reaction with the rock. The optimal efficiency is achieved for each type of shale rock by a necessary series of tests with gradually decreasing amounts of reagent 50 and the appropriate use of hydrogen sulfide on the desired space-time and speed basis, as discussed above.

Some of the potassium hydrogen sulfide is decomposed into potassium hydroxide and hydrogen sulfide upon hydrolysis. At 55 the higher temperature, hydrogen sulfide is then obtained by suitable working up of the gas or re-conversion, as shown in FIG. 4. Potassium hydroxide provides a medium at temperatures of 360 ° C and higher, whereby the calcium carbonate of the limestone residue of the shale oil rock 60 reacts with the potassium sulfate of the reagent residue to form calcium sulfate and a mixture of potassium hydroxide and potassium carbonate. The potassium and sodium content of the shale oil rock residue is also extracted in hydroxide form at this point, i.e. by leaching, and is processed for reuse.

As shown above, water vapor is used at a temperature at which the reaction takes place, i.e. depending on the type of shale oil rock and the decomposition of its components and the desired product. Water can be sprayed into the reactors for the sodium hydrogen sulfide and sulfide series or reactions. Similarly, spraying water in the exothermic reactions helps control the reaction.

Although the reaction mass of shale oil rock and reagent can be stirred appropriately, it is best to pre-coat the rock with a reagent in the absence of oxygen because oxygen tends to destroy the reagent.

For this reason, it has also been found useful to use a liquid or a dissolved reagent. Liquid, still stable reagents can be used to coat the shale oil rock at or above the appropriate melting point of the selected reagent or the liquid electrical mixture thereof.

As explained above, the process can use the alkali hydrogen sulfides, alkali sulfides and alkali hydrogen sulfide hydrates as a reagent or as a "catalyst". Mixtures of alkali sulfides with another alkali sulfide, and mixtures of different sulfides with each other are within the inventive concept. Of course, the same considerations apply to every type of alkali metal sulfide hydrate. From a practical point of view, sodium and potassium sulfides as well as hydrates and mixtures of all of these in their respective series and mixtures with one another in series are considered. As discussed above, a specific sulfide and hydrates thereof can also be used, particularly for the treatment of initial reaction products for the second and any further stages, such as when subjected to the reaction temperatures above 135 ° C.

It is also contemplated that the other alkali compounds in the alkali metal series can be used, but they are not advantageous from a cost point of view, although rubidium sulfides are extremely active and indeed can be used well in special circumstances, such as as a supported catalyst, e.g. in alumina, etc. Cesium sulfides are another type in the alkali metal series, and they are less useful and also undesirable for reasons of cost.

In general, the number of moles of hydration water is determined thermographically by plotting the temperature against time and observing certain temperature-time values and the expulsion of water in the form of gas. These temperature values then indicate the stability of the reagent. ,

In addition to the above-mentioned supports for the above "catalysts", the following supports were also considered: spinel, potassium aluminum silicates in special fired bentonite clay, etc.

A reagent attack on the starting material as well as the cut out product fraction also depend on the chemical composition of the reagent. Specifically, the sulfur content of the alkali metal sulfides determines the hardness of the attack if all other conditions are the same. In particular, it should be noted that in the case of shale oil rock, the hydrogen sulfides have the ability to extract the oil from the rock without an excessive amount of gas production. Thus, this is the preferred way to extract kerogen-based hydrocarbon compounds from rock. These compounds can then be hydrogenated in the gas phase using the sulfide reagents described above, which are located on a catalyst support and then act as catalysts.

In addition, different hydrates of the same alkali sulfides cause different reagent formations, if all

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other conditions are the same. Of course, the hydrates of the above sulfides must be stable under the reaction conditions for the above application. The hardness 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 provides additional sulfur that is present when the hydrogen portion of water or hydrogen sulfide is released for hydrogen substitution or for incorporation into the hydrocarbon molecule containing nitrogen, sulfur, or oxygen. Mixtures of sulfides with different sulfur contents also result in a predetermined attack hardness. Hydrogen sulfide is also added to compensate for the loss of reagent.

Of course, the addition of water (water vapor) 15 also results in hydrogen substitution or an insertion in the hydrocarbon molecule.

If more bond cleavage is desired in the feedstock molecules, such as heavy final fractions of shale oil or more complex molecules in the shale oil rock, the catalyst composition, amount of water and amount of hydrogen sulfide can all be adjusted accordingly.

As also recognized and explained above, the cleavage products from the initial phase are best treated in gas phase reactions, i.e. in reactions with gas phase and solid phase (supported catalyst) in order to produce the desired product according to the above regulations.

According to the above examples and description, when treating shale oil rock, it is surprising that when the reagent is appropriately stabilized with hydrogen sulfide, the amount of the reagent used decreases. Unfavorable reactions due to the reagent attack on the rock base material masked the true reaction conditions, which are in fact far more favorable than could be found when considering the dilution factor of carbon in the rock and the rock components in general.

In addition, the bitumen fraction of the shale oil can easily be attacked by the same reagent that attacks the kerogens. Thus the joint production of hydrocarbons from these two sources is also very helpful in the overall economy of the process.

If the kerogens contain minerals such as vanadium, nickel, molybdenum, etc., the extraction of these, as already explained, further promotes the overall economy of the process.

In addition to the above, the presence of inorganic carbon, the potentially leachable constituents in the shale oil rock, such as sodium and potassium, etc., make the present process very superior to previous processes using heat, i.e. Distillation process.

As a result of the above explanations and detailed explanations, selective production of saturated and partially unsaturated compounds from the above shale oil or shale oil raw material can be realized, so that the need for the power generation and chemical industries can be satisfied in a variety of ways. This makes a large reserve of raw materials easily and economically accessible to ensure a continuous source of hydrocarbon.

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4 sheets of drawings

Claims (26)

637 688 PATENT CLAIMS 1. A process for the recovery of hydrogenated hydrocarbons from rock containing organic and inorganic hydrogenatable carbon components and minerals as the starting material, including the recovery of further components of this starting material, characterized in that in at least one step, the starting material with a reagent consisting of alkali metal hydro gene sulfide, alkali metal sulfide, alkali metal polysulfide or mixtures thereof or mixtures thereof with their hydrates, in the presence of water and / or water vapor and hydrogen sulfide, and the hydrocarbons including the other components are recovered. 2nd 2. The method according to claim 1, characterized in that one uses a reagent in a second stage, the other alkali metal bisulfides, alkali metal sulfides, alkali metal polysulfides, or mixtures thereof with their hydrates than in the first stage. 3rd 637 688 3. The method according to claim 2, characterized in that the hydrogensulfides, sulfides or polysulfides of potassium are used as sulfides of the other alkali metals. 4. The method according to claim 1, characterized in that the hydrocarbons are further treated in a further reaction zone in the presence of a reagent on a support and of water vapor and / or water and hydrogen sulfide and as an alkali metal bisulfide, alkali metal sulfide, alkali metal polysulfide or hydrate as a reagent the same or mixtures thereof are used. 5 5. The method according to claim 4, characterized in that one uses a lower temperature in the further reaction zone for the treatment of the hydrocarbons than in the first reaction zone, in which the starting material is reacted in the form of shale oil rock. 6. The method according to claim 4, characterized in that the reaction in the first reaction zone is exothermic. 7. The method according to claim 4, characterized in that one implements a shale oil rock with a content of at least 5 percent by weight of organic carbon. 8. The method according to claim 4, characterized in that the metal compounds contained in the starting material in the form of shale oil rock are obtained by leaching out the shale oil rock and extracting at least one reagent component and subsequent separation of the metal compound from the reagent component. 9. The method according to claim 4, characterized in that the metal compounds are obtained from the leached reagent. 10th 10. The method according to claim 1 for the recovery of hydrogenated hydrocarbons from carbon-containing rock starting material, characterized in that crushed rock at a temperature of less than 72 ° C with a reagent R from alkali metal hydrogen sulfide, an alkali metal sulfide, an alkali metal sulfide hydrate or mixtures thereof Pretreated in the presence of an alkali hydroxide and an alkanol, ammonia removed under vacuum while the mixture is being stirred, elemental sulfur formed during the stirring is removed, the temperature is raised to 135 ° C. and a mixture of an alkanol and water is distilled off and light hydrocarbon distillates and hydrogen sulfide are obtained , the reaction product freed from alcohol and water in a reaction zone at a temperature above 250 ° C and in the presence of one of the reagents R and from hydrogen sulfide and water and so further hydrocarbons hydrie rt and its volatility, and so selectively hydrogenated and / or dehydrated in the presence of one of the above selected reagents R and of water and / or hydrogen sulfide, and the reagent is recovered for reuse in the process, metal compounds contained in the starting material are recovered and the hydrocarbons are recovered . 11. The method according to claim 1 for the production of hydrogenated hydrocarbons and by-products from shale oil rock containing organic and inorganic hydrogenatable carbon components and minerals as the starting material, characterized in that (A) in a first step reacting the starting material with a reagent R, which consists of an alkali metal hydrogen sulfide, alkali metal sulfide, alkali metal polysulfide or a mixture thereof or a mixture of hydrates thereof, in the presence of water vapor and / or water and hydrogen sulfide, (B) the hydrocarbons obtained in stage (A) are reacted further in at least one reaction zone in the presence of one of the reagents R mentioned under (A), (C) hydrocarbons recover, (D) hydrogen sulfide wins and (E) metal compounds wins. 12. The method according to claim 11, characterized in that in step (B) the reagent R is used on a support. 13. The method according to claim 12, characterized in that a potassium hydrogen sulfide, potassium sulfide, potassium polysulfide, mixtures thereof or mixtures of the hydrates thereof are used as reagent R on a support. 14. The method according to claim 11, characterized in that one uses hydrogen sulfide mixed with hydrocarbon to form the reagent R again. 15 15. The method according to claim 11, characterized in that one carries out the method in the first stage under exothermic conditions at a temperature of about 320 ° C or about 360 ° C. 16. The method according to claim 11, characterized in that one obtains those of vanadium, cobalt, molybdenum or nickel as the metal compound. 17. A process for the extraction of hydrogenated hydrocarbons from shale oil or rock containing carbon compounds as the starting material, including the extraction of further components of this starting material, characterized in that (a) reacting the starting material with reagent R, selected from an alkali metal hydrogen sulfide, alkali metal sulfide, alkali metal polysulfide or alkali metal sulfide hydrate or mixtures of such compounds in the presence of alcohol or water and alcohol, so that ammonia and elemental sulfur are driven off and recovered, (b) the hydrocarbons obtained from stage (a) are further treated at an elevated temperature between 100 and 400 ° C. in the presence of the reagent mentioned under (a) and water vapor, thus obtaining a hydrocarbon material, and (c) the hydrocarbons including by-products are obtained from the implementation of stage (b). 18. The method according to claim 17, characterized in that in step (b) (l) the hydrocarbons obtained from step (a) are further hydrogenated in the presence of water and hydrogen sulfide and a reagent R and so further reaction products are obtained. 19. The method according to claim 17 or 18, characterized in that the reaction products obtained in step (b) or (b) (l) in a further step (b) (2) with a reagent R in the presence of water and hydrogen sulfide dehydrated to obtain a selected hydrocarbon composition. 20. The method according to any one of claims 17 to 19, characterized in that shale oil is used as the starting material. 20th 21. The method according to any one of claims 17 to 19, characterized in that shale oil rock is used as the starting material. 22. The method according to any one of the claims 17 to 19, characterized in that shale oil rock containing inorganic bitumen carbon is used as the starting material. 23. The method according to claim 19, characterized in that in step (b) (2) as reagent R at least one potassium sulfide is used on a support. 24. The method according to claim 23, characterized in that one uses for the carrier reagent potassium sulfides, such as potassium hydrogen sulfide, potassium sulfide, potassium polysulfides or mixtures thereof or mixtures thereof with their hydrates, the reaction at a temperature of 180 to 400 ° C is carried out. 25. The method according to any one of claims 17 to 24, characterized in that the elemental sulfur obtained in stage (a) is recycled into the process in the form of hydrogen sulfide. 25th 30th 35 40 45 50 55 60 65 26. The method according to claims 17 and 19, characterized in that one carries out several stages (b) (l), followed by several stages (b) (2), in which stages in the presence of a reagent R generates a certain hydrocarbon fraction is selected, the reagent R being selected depending on the reaction temperature.