SE450128B - PROCEDURE FOR TRANSFORMING COBLE, PATH OR THREE TO THE POWDER - Google Patents

Description

TECHNICAL FIELD The present invention relates to the conversion of carbon into various useful constituents which either consist essentially of gaseous constituents or of both gaseous and liquid constituents in varying proportions comprising mainly liquid products, whereby suitable recovery of both reagent and hydrogen sulfide are included as part of the conversion process.

The invention also comprises the conversion of said gaseous constituents into other distillates. In particular, the invention relates to the conversion of carbon into desired conversion products such as hydrocarbons in liquid or gaseous form by reacting carbon in one or more steps with a special reagent which may be the same or different for each of the steps, however the reagent in each of the steps is present in the presence of water or steam as well as hydrogen sulfide. The process takes place at low or up to moderate temperatures and at a pressure between atmospheric pressure and a pressure below 5 psig (approx. 0.35 atm).

Furthermore, the invention relates to the conversion of carbon into various selected constituents thereof, either substantially gaseous constituents and gaseous and liquid constituents or substantially liquid constituents by means of specific reagents, whereby carbon or peat in the presence of said reagent, water, steam and hydrogen sulphide and optionally also sulfur, converted into useful decomposition products of coal or peat. These decomposition materials are either substantially gaseous hydrocarbons obtained in a one-step reaction or substantially liquid hydrocarbons obtained in a single-step reaction or gaseous and volatile products obtained from a single-step reaction. These products may be subjected to reactions in one or more further steps in the presence of various reagents, steam and hydrogen sulphide, with the aim of obtaining liquid distillates. Finally, at high temperatures, carbon in the presence of the reagent and in the presence of hydrogen sulfide and steam gives a certain amount of hydrogen.

BACKGROUND OF THE INVENTION It has become increasingly clear that liquid and gaseous hydrocarbon sources, such as petroleum and natural gas, are depleted at such a rate that intensive efforts are required to meet the needs of the future to produce alternative energy sources. , food or chemical raw materials. One of the most readily available sources of hydrocarbon material is carbon. To date, there have been no ready-made means to produce hydrocarbons from coal without extensive investments in capital and a 9k ° fl ° miscible base. Although various processes are known for converting coal at high temperatures, such as high temperature, i.e. above 60006, and high pressure, for example over 25 atmospheres carbon gasification, no readily available low temperature and low pressure processes have been available. through which carbon can be easily converted to its constituent hydrocarbons.

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 66h 4 210 526.

Further reference is made to the following literature: Letoffe, et al., Determination des Enthalpies de Formíon des Polysulfures de Potassium, Journal de Chimie Physique, 71, p. 427-430, 1974; 10 15 20 25 30 35 450 128 John S. Thomas and A. Rule (other articles in this series were authored by Thomas and Riding) The Polysulfides of the Alkali Metals, Journal Chemical Soc, Part 3 p. 1063 et seq., 1973; Blitz and Wílke-Dorfurt, Z. Anorg. Chem., Vol. 48, pp. 297, 1906 (see also ågí., 53, p. 43, 1905); van Krevelen, et al., 2221, 38, 256, 1959; B.K. Mazumdar, et al., Egil, 41, 121, 1962; something, Ann. cnim mys., 21, 72, 1900; W. Klemm, Z. Anorg. Chemm., P. 241, 281, 1939; F.W. Bergstrom, J. Amer. Chem. Soc., 147, 1926; F. Feher and H Berthold, Z. Anorg. Chem., P. 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. Chim. Phys. 22, 5, 1881; Marrony, J. Chim. Phys., 56, 214, 221.1959; Me Aline Auroux, C.R. Acad. Soc. Paris, 274 p. 1297-1300, March 1972; Kuster und Herberlein "Beitrage zur Kenntnisse der Polysulfide" Z. Anorg. Chem., P. 53-84, nov. DESCRIPTION OF THE INVENTION It has now been noted that when carbon is treated with a special reagent the carbon can be converted in the presence of this reagent and in the presence of water and / or steam and hydrogen sulfide to various hydrocarbon fractions which are either primarily of gaseous hydrocarbon fractions having 1 to 5 carbon atoms (C1 to C5), for example methane, ethane, ethylene, etc. or substantially liquid distillates or hydrocarbon fractions which are practically present in proportions between said extreme cases. At the same time, hydrogen is also produced.

At higher temperatures, more or mainly gaseous hydrocarbons are produced; in addition, using another reagent in another reactor, the gaseous hydrocarbons can be further reacted in the presence of steam and hydrogen sulfide to give other hydrocarbons which may be liquid or gaseous hydrocarbons. It has also been found that the conditions described above can be reversed by substituting the reagent and using substantially anhydrous and eutectic mixtures of sulfides as will be described in more detail.

Furthermore, it has surprisingly been found that an addition of hydrogen sulfide is significantly more favorable than the addition of sulfur because the hydrogen sulfide more effectively stabilizes the reagent and also promotes the conversion of thiosulfate or tetrationate (and 2e) to form 2 thiosulfate ions.

Some degradation of KHS to KZS takes place in the presence of water.

This degradation is partial. When hydrating carbon, both KHS and K2S should therefore be present. When sulfur is added, a less hydrolysed and therefore more water-stable polysulfide is needed, such as potassium pentasulfide. The hydrogen sulphide not only promotes stabilization. It also reduces the amount of reagent required.

It has further been observed that when mixtures of alkali sulphides are included in the reaction, these may be added in liquid form to the carbon in order to promote the reaction, for example in the form of mixtures of polysulphides or their hydrates. When K2S and various polysulfide forms react with carbon, it primarily attacks the oxygen, sulfur and nitrogen present in the carbon in bound form to expel these carbon constituents. When components in the form of derived hydrocarbons are formed in the presence of steam or water, the bond splitting of the various carbon constituents together with the removal of oxygen, nitrogen and sulfur makes it possible to introduce hydrogen and thus the formation of hydroaromatic, aromatic and aliphatic compounds with short chains. The reaction intensity can be adjusted so that one can continuously obtain different products from substantially gaseous to a product in substantially liquid form. The reactant used and the operating conditions are varied.

BRIEF DESCRIPTION OF THE DRAWINGS To illustrate the present invention, reference is made to the accompanying drawing figure which schematically shows the gas recovery chain in connection with the recovery of hydrogen sulfide.

DESCRIPTION OF PREFERRED EMBODIMENTS During the process and as soon as the desired working temperature has been reached and hydrogen sulfide or steam and hydrogen sulfide are introduced into the system, the inert gas such as helium or nitrogen, which is first used to purify the system from oxygen, is no longer needed. Hydrogen sulfide can be introduced through the steam line.

Fig. 1 shows a schematic view of the recovery of hydrogen sulphide gas.

A reactor 22, usually at a temperature of 350 ° C and up to 39 ° C, has been charged with carbon, a reagent in liquid form, water in the form of steam and hydrogen sulphide gas. A cooling jacket 24 surrounding the condenser 26 facilitates the cooling of the reaction gases. The heaviest initial products are recovered from the condenser bottom 27. The gaseous products are passed on to the vessel 30, in which there is water and alkanol (usually methane or ethane).

The vessel 30 receives water or alkanol from the reactor when reagent dissolved in alkanol is used. The mixture of water and alcohol in the vessel 30 is maintained at a temperature below the boiling point of the mixture to c hydrocarbons and thus the lighter gases such as Cl 5 including hydrogen sulfide can pass. In vessel 31, the contents are cooled to about -3500, at which temperature liquid Ca and C5 hydrocarbons are removed. Most of the C3 and C5 hydrocarbon fractions are removed in vessel 31 but a small proportion is transferred to vessel 32, where these hydrocarbons are removed at -30 ° C with the C3 hydrocarbon fraction in ethanol or methanol. Any remaining traces of these components are removed by means of a fried glass sheet 33. At this stage, essentially only H28 and C1 and C2 fractions are present in the gas stream, which is then introduced into a vessel containing KOH and alcohol, usually ethanol or methanol. in aqueous solution. In it, the hydrogen sulphide regenerates the reagent which is recovered in the form of a precipitate while the light fraction of gases mainly C1 and CZ hydrocarbons pass through.

About 972 and more H28 are recovered in the form of a reagent component and can be reused. No H28 is vented into the air. The alcoholic water fraction from vessel 30 is used to replenish the alcohol extracted from vessel 35. However, this mixture must be cooled in the heat exchanger 36.

As previously mentioned, hydrogen sulfide can be introduced into the reactor as a separate stream or together with steam. When introduced together with steam, it is at a point, i.e. at about 13,500 or above, but preferably hydrogen sulfide is introduced along with steam within the temperature range 170-19000 when steam is used. Steam is not introduced into the reaction vessel until a methanol-water mixture used to introduce the agent has been removed because the water-methanol mixture maintains the temperature within a specific temperature range during this distillation. Hydrogen sulfide is present from the beginning of the reaction.

After the introduction of steam or of steam and continued introduction of hydrogen sulphide, different types of lignite and sub-bituminous carbons, depending on their internal composition, have different distillation points during the production of considerable amounts of gaseous hydrocarbons. 10 15 20 25 30 35 450 128 Gas production increases significantly when the temperature reaches 360 ° C and when the final temperature is between 380 ° C and 45000, a very fast gas production is found which includes some production of hydrogen.

The temperature range 3600 to 38000 also produces carbonyl sulphide.

In the case of, for example, sub-bituminous carbons, 4.7% by weight of the total hydrocarbon gas may be carbonyl sulphide. When hydrogen sulphide is used, the production of carbonyl sulphide is suppressed, provided that other conditions remain unchanged.

Without establishing any particular theory, it is assumed that the reactions via water and hydrogen sulfide molecules yield hydrogen which reacts with carbon at the point where the carbon is freed from oxygen, sulfur or nitrogen. Thus, for the practice of the present invention, it is necessary that oxygen be present in the carbon. This advantage is also derived from the fact that sulfur and nitrogen are present in the carbon in the form of organic sulfur or organic nitrogen forms. In addition, higher grade carbon such as bituminous carbon cannot be so easily converted to gaseous hydrocarbons although as will be explained below this can still be done if the reaction scheme is appropriately modified.

The present invention preferably relates to the gasification of lignite and sub-bituminous carbon, but all types of carbon can be gasified, whereby liquid products can be obtained from these carbon. Wood shavings can also be gasified. Furthermore, wood (cellulose, lignite, sugar, etc.) can also be converted into gaseous or liquid products.

An anthracite carbon with a 92 Z carbon content can be easily converted in connection with a partial oxidation so that liquid and gaseous reaction products are obtained.

When potassium in carbon ash is converted to a hydrosulfide, this is done without loss of potassium hydrosulfide. The reagent balance of the reaction is very favorable, regardless of whether the reaction takes place batchwise or continuously. Furthermore, the amount of reagent used can be reduced in connection with hydrogen sulfide stabilization of the reagent and at the same time excess sulfur and excess potassium from the carbon can be used for, for example, the preparation of reagents or hydrogen sulfide.

It should be emphasized that in general sufficient amounts of sulfur, sulphide, hydrosulphide or polysulphide should be present to take up the sulfur evaporated from the coal by oxygen during the deoxidation to prevent the evaporated sulfur from dehydrating the coal at a temperature above 17500. The purity of the various reagent forms must also be maintained above 325 ° C, as a rise in temperature above this level results in a slow dehydration of the carbon by alkali metal hydroxide melting. Since sulfur causes the formation of polysulfides and the alkali polysulfide is less hydrolyzed with increasing sulfur content, the decomposition by steam (or other water) of the hydrolysis product is prevented, ie the hydrosulfide is thereby protected. However, the stabilization is best achieved by the addition of hydrogen sulfide as will be explained in more detail.

The hydrogen sulfide generated in connection with the addition of elemental sulfur to the alcoholic solution of alkali metal hydrogen sulfide and the reaction of the sulfur converted by oxygen during the conversion of carbon to hydrocarbon form is used to form additional alkali metal hydrogen sulfide starting from the alkali metal hydroxide in the process; however, hydrogen sulphide is also introduced into the reactor or reactors in order to stabilize the reagent, which means that the hydrogen sulphide may be present in excess in relation to the quantity required for the reaction.

A portion of the potassium hydrosulfide decomposes after the hydrolysis to form potassium hydroxide and hydrogen sulfide. This amount of potassium hydroxide is a medium at temperatures above 36006 or above which allows the calcium carbonate of the limestone (in the ash content of the carbon) to react with potassium sulphate (from the reagent residue) to form calcium sulphate and a mixture of potassium hydroxide and potassium carbonate. The potassium content of the carbon ash is also extracted in hydroxide form.

As shown above, steam is used at a temperature at which it is intended that the reaction should take place, i.e. that the temperature is selected taking into account the type of carbon and its degree of decomposition and the final product desired to be obtained. The water contained in carbon is also a source of water and / or steam.

As the amount of sulfur contained in the reagent increases, i.e. the amount of sulfur derived from carbon, from feed element sulfur and from the hydrogen sulphide, the reaction temperature is lowered. For example, the reaction temperature is lowered from 38,000 to 35,000 when, for example, the sulfur balance is representative of a produced theoretical compound K 2 S 3 which is maintained during the reaction. A consequence of this phenomenon is that larger molecules are produced, for example pentane, ie isopentane and pentane.

Furthermore, the class of the carbon affects the composition of the distillate in such a way that under otherwise equal conditions a larger proportion of liquid distillate is obtained when using more high-class carbon, for example in connection with the use of the theoretical K2S3 compound under the same temperature conditions.

Of course, the product composition changes when the temperature is varied.

Furthermore, as mentioned above, the product composition also changes when the amount of sulfur in the reagent changes.

Based on the above, one can thus vary the temperature, the sulfur content of the reagent, the use of different mixtures of reagents, for example liquid or dissolved forms of reagent, carbon class and the use of recycling of alcohol-absorbed distillates to obtain the desired product type.

The variations described above are within the following limit values: temperatures to a value between 425 ° C and 45000, with distillation starting at a value of 4000 or at a temperature between 4000 and 50 ° C; the sulfur content of the reagent (6XemPe1ViS for potassium) KZS but the sulfur content can go up to KZSS; sulfur or hydrogen sulfide additive; mixtures of these reagents; liquid or solid forms of reagents; contact of a product stream with another reagent composition including hydrogen sulfide and carbon class (preferably in the carbon class range comprising lignite and bituminous carbon). The results are less advantageous when applied to annracir. However, an aesthetic at 300 DEG C. is obtained using a reagent such as K2SA. Partial oxidation of high quality carbon can also be beneficial.

In addition, the quantity of recycled material can be varied. Thus, at a temperature of about 28,000 the product combination can be led to a composition which constitutes a liquid distillate with a boiling point below 180 ° C. At a reaction temperature of about 31006, paraffin distillate is formed using the alcohol recycling described above to the reaction vessel. As previously mentioned, and in connection with the said condition in terms of recycling, water, ie steam at a temperature of about 13,500 (and higher temperatures) and hydrogen sulphide must be present in order to advantageously cause the reaction to take place.

When the process is started at a temperature close to ambient temperature (and while raising the temperature), elemental sulfur or preferably hydrogen sulfide is added to the carbon or to the reagent in order to achieve the sulfur content selected for the reagent. Under these conditions, H28 formed in the system during the reaction between the sulfur and the reagent will be removed from the gas stream and the scrubbing system to re-form the reagent as shown in Fig. 1. At increasing temperature and without steam, the carbon hydrates from its own or reagent water content. For light distillates, water is added at 13,500. Usually, however, steam is added at the conversion temperature at which the hydrates of the reagent begin to be converted or converted to a lower hydrate. For potassium-based reagent, steam supply at 17000 is selected.

In summary it can be said that when oxygen is removed and nitrogen and organic sulfur and also water or to a lesser extent hydrogen sulphide (continuously produced by contact between water and the reagents) hydrogen is added to the carbon at the point where oxygen, sulfur and nitrogen have been removed from coal; the sulfur removed forms an alkali (eg potassium) polysulfide and at lower temperatures a mercaptan with the alkanol solvent. The mercaptans are absorbed in alcohol and in the KOH alcohol solution. This general reaction proceeds by reducing hydrogen sulfide gas to sulfur and water with a subsequent reaction of sulfur with KOH to form potassium thiosulfate and potassium thiosulfide. The potassium sulphide can then obtain additional sulfur from the hydrogen sulphide to form potassium polysulphide, which are the reagents used in the reaction.

The hydrocarbon compositions, i.e. gaseous fractions obtained at different temperature levels, can be further treated, for example in another reactor with a different reagent composition, thus a reagent composition with a higher sulfur content and at a lower temperature than that in the first stage, where the reaction temperature is between 34,000 and 390 ° C, whereby for example the temperature in the next step may be 28006 to 340 ° C with increasing sulfur content of the reagent. In the third step, the temperature can be 22s ° c: in 2so ° c and: 1so ° c: in 225 ° c. When the dehyarasization reaction competes with the hydrogen sulfide film, in the case of increasing sulfur content in the reagent and in the presence of sulfur, a dehydration of the product stream, which was originally gaseous, is obtained.

This flow can then be processed to obtain the desired product composition, ie a certain API number for a preselected product. In other words, it can be said that the originally gaseous products are transformed into products in accordance with demand.

As previously mentioned, the process described above can be improved by the addition of hydrogen sulphide at the stage when carbon or carbon products are hydrated, i.e. alkali metal sulphides, sulphide mixtures such as in their hydrate form, etc. The hydrogen sulphide addition appears to keep the selected reagent in a stable state. reaction that has been started with a certain reagent or mixture of reagents will occur, with minor variations and provided that the same starting material is used and that other conditions are kept unchanged, essentially the same products or mixture of products.

Thus, suitable stepwise arrangement of reagents as well as the composition of the reagents for each of the steps and also temperature conditions and water addition can be further improved by the addition of hydrogen sulfide to the process described above so that it becomes possible to include a wider range of products, a selected mixture of products and a more precise line of hydration (including dehydration of product flow / n /, if desired). Suitable alkali metal sulphides and mixtures of sulphides as well as mixtures of said sulphide hydrates in the presence of hydrogen sulphide give the desired reagent stability and the selected product. Thus, when the reagent is kept in a suitable "active" reagent state by the addition of hydrogen sulfide, the following advantages are obtained: reduced amount of reagent, better yields and better product control.

The reason for the hydrogen sulphide addition is shown in the reactions below. 1. 41 When carbon-derived sulfur is present, 2. 48 + 6KOH ---- 9 KZSZO3 + 2K2S + 3H2 4. axzsz '+ 81120 * Name + ams + as + 41120 It follows that when H28 is present KOH is converted to RHS and if any KOH forms thiosulfate then the thiosulfate is converted to KZSS.

Additional reactions are as follows:. U o 5. K2S5 -_¿} Kzsa + 5 (over 300 C) uo 6. KZS4 - à KZS3 + S (over 460 C) 7. KHS + KZS + BHZO - 7> 3KOH + ZHZS 8. Kzs + H20 -7 \ 1 10 15 20 25 30 35 450 128 14 9. KHS + H20 - $ H2S + KOH 10. Kns + Kon --- ¿> K2s - xnzo (x can be for example 2, 5, etc depending on the temperature).

Thus, sufficient H 2 S 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 the reagent or from the carbon and by the action of the hydrogen sulphide the hydrolysis of the reagent is avoided.

In addition, the thiosulfate generated by the oxygen in the carbon 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.

KZSZ, KZS and then K2S3. at their melting points, for example Na K 2 S 3; and among these, the order of preference is as follows: The other sulfides show no stability. o.

O 252 at 445 C, Na 2 S 4 at 275 C; or else sulfur is emitted at 760 mm, for example K 2 S at 30 ° C gives K s + s; KZS4 gives at 46 ° C K s + s; and K s3 gives at 70 ° C 2 4 2 3 K2S2 + S. 2 The melting points of the alkali metal sulfides mentioned above are as follows: N o o o. , o _ for KZS 348 C, K2S2 470 C, KZS3 279 C (solidification point), k2S4 145 C, Kzss 206 c; Kzsó the following (pure or eutectic mixtures): for K H _ 0 _ U _ for KZSZ - kZS3 225 C, for KZS3 KZSÅ 190 C. The melting points of the sulphide mixtures are o ZS - KZSZ 350 C, about 11 ° C; for K s - K s 2 4 2 5 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 a solid reagent or stable liquid reagent which can form a casing around the coal.

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 1s3 ° c. 10 15 20 25 30 35 450 128 15 without difficulty is determined thermographically, as is well known to those skilled in the art.

The carbon conversion process proceeds without reagent instability, ie alkali sulfide hydrate instability, because there is a greater tendency for carbon hydrogenation than for reagent decomposition. In addition, the addition of hydrogen sulfide helps in stabilizing the reagent. Furthermore, the reaction with carbon continues provided that an adequate quantity of reagent is present and the addition of hydrogen sulphide also helps to reduce the amount of reagent required, because the reagent is in a more stable form and thus the process is also improved for that reason. Under otherwise constant conditions, the use of hydrogen sulphide entails at least a doubling of product recycling.

In general, the hydrogen sulfide addition is based on a surface space, time and velocity basis and usually the addition amount will be from 40 and up to 120 ml / min / gal (about 10 ml / min / 1 to 30 ml / min / l) reactor space, with ml / min / l can be considered very common.

Expressed in another way, it can be said that in moles and less H S, 2 is added for 1000 ml of water which is removed by the hydrogenation reaction. The various sulfides and their decomposition temperatures, including the reactions, are set forth in U.S. Patent 4,210,526, issued July 1, 1980.

At the highest operating temperature, for example at 40,000, KZSS will yield sulfur (which can be considered a useful phenomenon as has been previously reported in connection with the dehydration of additional process flows). Because the decomposition temperatures are lowered at lower pressures, the column conversion becomes entirely possible at atmospheric pressure even though some advantages can be gained during operation at higher pressures. 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. Although the amount of reaction carbon and reagent can be stirred appropriately, it is most convenient to provide the carbon with a shell of reagent in the absence of oxygen, as the oxygen tends to destroy the reagent.

For this reason, it has also been found suitable to use a Liquid or a dissolved reagent. Liquid but stable reagents can be used to coat carbon at or above the appropriate melting point of the selected reagent or the liquid eutectic mixture thereof. For example, a mixture of K - KZS4 can be used S above 110 ° C in liquid form to envelop carbon. D: t3 has been found to be very useful as a solvent for the above reagent, glycerin. However, any solvent can be used which can dissolve the sulphides and which does not affect their activity. About 88 grams of KHS are dissolved to obtain a glycerin solution of a total of 200 ml. When the mixture is heated to 17500 (glycerin decomposes at temperatures above 190 ° C), H 2 O is expelled from the dissolved KHS mixture and the mixture will then contain K 2 S 'xH 2 O. Oxygen is also excluded from this reaction mixture. The mixture can then be suitably used to encapsulate carbon and thus be used as a reagent.

Since the intensity of the exposure to sulfur and nitrogen and the intensity of the effect of oxygen on carbon are a function of the composition and the amount of reactant, ie the composition of the substances participating in the chemical reaction and the amount of substances involved can be emphasized. Gas conversion of carbon is obtained when the decomposition of the carbon, ie when the reagent's attack on the carbon is most intense. With a lower degree of decomposition, lighter distillates are obtained.

At 17500 the sulfur begins to dehydrate carbon and therefore the presence of carbon is undesirable for column conversion. Therefore, a stable reagent is used under such conditions. However, in the case of regeneration, ie dehydration and mutual reaction of dehydrated varieties, this reaction is important because it allows pre-selected liquids with different boiling points (or pre-selected API numbers). Gases in the form of carbon derivatives are of course an ideal source of feed. As mentioned earlier, the carbon class also affects the reactions. In order to obtain less decomposition in low-class coal, a high sulfur content is used. To obtain a more complete gas formation, the amount of sulfur is reduced in Thus, KZS is used, whereas KZSS is used for less intensive attack, especially peat when it is involved in a reaction with KZSS, where it mainly produces naphthalene.

The above description of the process and of the present invention is further illustrated by the following examples, which are not to be construed as limiting the invention but rather as an illustration of an embodiment.

EXAMPLE 1 A reaction vessel having a capacity of 1 gallon is equipped with a steam line, heating and cooling devices, a thermocouple, stirrer and an outgoing line for reaction gases. Hydrogen sulphide is added together with steam and it can also be added separately. The products are recycled in a condenser, which is cooled in a suitable way at the same time as the gases are collected as previously shown in the figures.

To 800 grams of Kentucky%% 9% carbon, which is surrounded by helium gas in the vessel described, is added a liquid mixture of K2S3 ° Ch K25 'SHZO. The amount of reagent mixture added was 2 moles, i.e. one mole of each. One mole was KZS3 obtained from a mixture of KZS and KZSS in an aqueous solution adapted to the empirical formula KZS3. In addition, 4 grams of KOH were added, which had the task of evaporating NH3 under process conditions. The mixture was stirred to coat the carbon particles with the reagent.

Then steam was added together with H28 at 80 ml / min at a temperature of 5000. The reaction was exothermic and the temperature was not allowed to exceed 450 ° C and as far as possible the temperature was kept within the temperature range 350 ° C to 390oC. Steam was added at 13500, the flow corresponding to the hydrocarbon extraction or 130% thereof and the recovered product being a clear amber red solution which, when treated with 19 grams of KHS up to 240 ° C, was completely distilled to a water-clear liquid hydrocarbon distillate (almost 10 15 25 30 35 4> U7 C3 _; FJ OO water clear hydrocarbon) with water-like viscosity. A total of 324 ml of distillate was recovered, including 12 L (N.T.P.) of gas during the first reaction step. The product analysis was as follows: Boiling point ranges 1so ° F initial boiling point and 10% - 4eo ° F 202 - 479 ° F soz - 4ßs ° F 4oz - 492 ° F soz - soo ° F soz - sos ° F 702 - 522 ° F soz - s3s ° F 90% - se2 ° F 952 - 59z ° r 98.62 - s3z ° F 1.42 residue - heavy liquid EXAMPLE 2 In order to illustrate the effectiveness of the H25 additive, 110 grams of bituminous carbon (on a dry and ash-free basis) was reacted with solid NaHS (technical grade), or KHS (in aqueous solution), in a reaction vessel as previously described with the addition of H28 at 80 ml / min and 200 ml helium. Steam was added at a temperature above 137oC with a flow starting from compliance with 130% of the hydrocarbon condensate withdrawal. The addition of KOH suppresses ammonia reactions within the reactor and expels ammonia. The reaction becomes exothermic at 390 ° C. 252 l of gas and 70 ml of liquid hydrocarbon condensate were obtained before the reaction proceeded to exotherm above 39,000.

In experiments performed with lignite with and without H2S addition, the yield was more than doubled with H23 addition. Another reagent was illustrated in Example 1. The reaction proceeded to exotherm at 390 ° C. About 3 moles of H28 are required per mole of K2SZO3 formed. Furthermore, about 48 grams of carbon-based oxygen are consumed when one mole of KZSZOB is formed.

About 42% of wood is oxygen and about 2% of anthracite is oxygen. Between these limits, H28 is added based on the above reaction as a maximum, as other competing reactions occur.

The above is a rough indication as to the quantity of H25 required, but in practice smaller quantities are used, for example due to the primary side reaction of bicarbonate hydrogen which combines with oxygen to form water.

When KHS and / or NaHS are used, these produce significant amounts of gas and the reaction proceeds to an exothermic reaction above 390 ° C. KZSZ 'SHZO plus KZS (empirically, based on equal molar amounts of KZS' SHZO and KZS3) produce small quantities of gas and considerable amounts of liquid condensate from the same starting material but the reaction is initially exothermic, ie from about SOOC, and the reaction seems to be maintained at 39 °. c with small heat input. kzsz (obtained from a melt of KZS 'SHZO plus sulfur) mixed with an equal amount of KZS (obtained from hot KOH aqueous solution and sulfur in an amount ratio corresponding to 6KOH + 4S) as reagent produces a liquid distillate and gas. The reaction becomes exothermic at 24,000 if the same starting material is used. On all three occasions, the starting material was bituminous carbon -200 line number Kentucky No. 9 and the reaction conditions were otherwise identical, i.e. steam, H25 and helium were used as previously indicated. The foregoing shows the possibilities of obtaining gas, gas and distillate, as well as mainly distillate, and in addition it shows the great advantages of the exothermic reactions. During these exothermic reactions, negligible amounts of CO and CO 2 are formed. Hydrogen sulphide could not be traced in the gas flows after washing.

Apparently no COS was formed.

The above is further illustrated by the following examples. EXAMPLE 3 The following reagent was used on Kentucky No. 9 carbon: (1) KZS '5H2O + S theoretical: KZSZ (Kzs + KZSS) (2) Two layers (45) X (0.83) + GKOH (with water content) from each and one of (1) and (2) above used one mole of of the reagent.

Coal analysis: Table I Untreated Kentucky No. 9: Z Measured 2233 Humidity g¿â§ Ash 8.52 §¿Zå Volatiles §â¿§á 姿2Q Solid coal §§¿âí §§¿2â Sulfur 2¿§g 2¿ É2 ßcu / lb Jgggg 1323; (wh / kg) (1768) Btu / lb excl. ash _ 14569 (wh / kg)> (1938) Carbon Zl¿§Q 73.50 Hydrogen í¿§z â¿9g Nitrogen l¿â2 l¿§å Oxygen §¿åå §¿Íâ Chlorides 0.22 Q¿åå ..._ i :: '<__ SíO AIZO3 Fe2O3 TíO CaO Mg0 Na 0 K 0 Li O P205 S0 production Ash 15% 24.792 54. 13.722 _ 1.69% 0.722 0.852 0.352 Zeííš 135 PPM 9; åâš Qellå 21 Table lay Recycled product after the reaction: Greder API 6o ° F (1s.6 ° c) 16.9 specific weight eo ° F (1s, e ° c) o.9s3o Sulfur Z 0.17 BTU / lb (nn / kg) 181 5 (2413) BTU / gallon (wh / 1) 144089 (159939) Carbon 88.62 Hydrogen 10.19 Sulfur 0.17 Nitrogen 0.19 Oxygen 0.83 __ ** _ ..

Table III Distillation results of product according to Table II: Original boiling point 34ZoF 5% recovery 440 ° F 10% recovery 486oF zoz recovery 49z ° F. 30% recovery s1o ° F 40% recovery 528 ° F 50% recovery 538 ° F 602 recovery 544 ° F 702 recovery 578 ° F 802 recovery 610 ° F 902 recovery 670OF 952 recovery 710 ° F sink point 71o ° FZ Recovered 96.0 Z Residue 3.7 Z Loss 0.3 - .. ink-_ 172 ° c 22e ° c 2s2 ° c 2ss ° c 26s ° c 275 ° c 2s1 ° c zs4 ° c 3o3 ° c 3z1 ° c 3s4 ° c s76 ° c 37e ° c 128 22 Table IV Analysis of 0-502 of distillate product crade AP: ao ° F (1s, 6 ° c) gg specific weight eo ° F (1s, 6 ° c) o.9zs7 Sulfur ZQ¿l§ BTU / lb (wh / kg) ¿§§g1_ (24se) BTU / gallon (wh / 1) 144519 (160416) Carbon §Z¿lZ Hydrogen lQ¿Q§ Sulfur Q¿lâ Nitrogen Q¿l§ Oxygen 2.42 _- ** - _ -___- Table V Analysis of distilled product 502-end point Grades API 60 ° F (15.6 ° C) lg¿¿ specific gravity 6o ° r <1s, e ° c) o.9s6s Sulfur ZQ¿lí BTH / lb (wh / kg) 132 (2467) BTU / gallon 147788 (164o44) Carbon 90,451 Hydrogen 8,472 Sulfur O 142 Nitrogen 0.312 Oxygen 0.632 ..- kgk ..._ m 450 128 23 The above Example 3 illustrates a typical case of property improvement of carbon and conversion of coal into liquid products.

It has been shown above that an readily available source for the production of a wide range of hydrocarbons can be obtained from coal by means of a very flexible process, which can take place at low temperature and low pressure and which can also take place exothermically under certain conditions.

Claims (27)

10 15 20 30 35 450 128 24 PATENT REQUIREMENTS A process for the conversion of coal, peat or wood into gaseous hydrocarbons or volatile distillates or mixtures thereof by reacting carbon, peat or wood, using as hydrogen a hydrogen sulphide, a sulphide or a polysulphide of an alkali metal or a mixture of these reagents, characterized in that a conversion reaction takes place in the presence of water and hydrogen sulphide and optionally sulfur at a temperature between 50 ° C and up to 450 ° C in one or more steps, the temperature in each step being the same or different and wherein the reagent may be the same or different based on the sulfur content of the reagent and recovered volatile liquid distillates and hydrocarbon gases. Modification of the process according to claim 1, wherein an alkanol solution of an alkali metal hydrogen xylide, a sulphide or a polysulphide or mixtures thereof is used as reagent, characterized in that the conversion reaction takes place in one or more steps in the presence of water in the form of hydrate water, water or steam and in the presence of hydrogen sulphide, and that said reaction proceeds under exothermic conditions at least in the first step. The method of claim 2, wherein elemental sulfur is added to an alkanol solution of said alkali metal hydrogen sulfide. 4. A process according to claim 2, characterized in that the alkali metal hydrogen sulphide is potassium hydrogen sulphide. Process according to Claim 2, characterized in that the alkali metal hydrogen sulphide is sodium hydrogen sulphide. 6. A process according to claim 2, characterized in that said alkali metal hydrogen sulphide is a mixture of rubidium, potassium and sodium hydrogen sulphides and sulphides. 10 15 20 25 30 450 128 25 7. A process according to claim 2, characterized in that the hydrogen sulfide is recovered. Process according to Claim 2, characterized in that the carbon used is lignite carbon. 9. A method according to claim 2, characterized in that the carbon consists of sub-lignite, ie carbon of lower class. 10. A process according to claim 2, characterized in that the carbon consists of anthracite, partially oxidized anthrait, bituminous or sub-bituminous carbon, ie carbon of lower class. 11. ll. Process according to Claim 2, characterized in that peat is reacted. 12. A process according to claim 2, characterized in that the alkali metal is potassium. 13. A process according to claim 2, characterized in that the distillate is treated in another step with a reagent with a higher sulfur content in the presence of hydrogen sulphide. 14. A process according to claim 2, characterized in that the reaction is carried out at a temperature between 135 ° C and 450 ° C. Process according to Claim 14, characterized in that the reaction is carried out at a temperature between 170 ° C and 380 ° C. Process according to any one of claims 1 to 15, characterized in that the carbon, peat or wood is continuously introduced into a reaction zone, wherein they are enveloped by a reagent, and wherein said zone is kept at a temperature above 50 ° C and up to 450 ° C, 450 128 10 lb 20 25 30 35 26 26 that hydrogen sulphide, water or steam is introduced into at least one reaction zone at a temperature between 160 ° C and up to 450 ° C, that a reaction is carried out continuously in at least one zone at a predetermined temperature and having a predetermined reagent composition, said carbon, peat or wood or decomposition products thereof reacting with 1) a predetermined reagent based on the sulfur content of said reagent, its hydrate form or its melting points or 2) mixtures of said reagents in the presence of said introduced water, steam or hydrogen sulphide, that volatile and / or gaseous products are recovered from said reaction zone, that hydrogen sulphide is recovered from said reaction zone, that coal, peat and wood ash are recycled from said reaction zone, that reagent not participating in the reaction present in said coal, peat or wood ash and alkali metal constituents such as alkali metal hydroxides is recovered, and that a reaction is carried out, said alkali metal hydroxides having at least a portion of the hydrogen sulfide released during said reaction and and hydrogen sulfide is recovered, said hydrogen sulfide being added to the reaction and a sufficient quantity of said regenerated reagent being introduced into said reaction zone to continue said reaction of carbon, peat or wood or decomposition products thereof with said reagent. 10 15 20 25 30 35 450 128 27 17. A process according to claim 16, characterized in that a first reaction zone is kept at a fixed predetermined temperature for the production of gaseous hydrocarbons. 18. A process according to claim 16, characterized in that the reaction zone is maintained at a temperature suitable for recovering a suitable predetermined composition of liquid hydrocarbons. 19. A process according to claim 17, characterized in that the gaseous hydrocarbon is treated in a second reaction zone with another reagent in order to produce liquid distillate. Process according to Claim 17, characterized in that lignite carbon is used in the reaction. 21. A process according to claim 17, characterized in that potassium sulphide, potassium polysulphide, potassium hydrogen sulphide or a mixture thereof are used as reagents. 22. The method of claim 17, characterized in that said reaction is exothermic in a first reaction zone. 23. A process according to claim 17, characterized in that the temperature in said reaction zone is kept in different steps between 170 ° C and: in 450%. A process according to claim 17, characterized in that said hydrocarbon product in liquid or gaseous form is treated in different steps with said alkali reagent with increasing sulfur content of said reagent at discrete decreasing temperature ranges below 40,000 but at temperatures above 100 ° C. A process according to claim 24, characterized in that the gaseous hydrocarbon is washed in an alkali metal hydroxide solution whereby hydrogen sulphide is removed from said gaseous hydrocarbon as a reaction product with said alkali metal and further said reagent is recovered for reuse. 450 128 28 Process according to Claim 25, characterized in that a theoretical composition HZS3 on the basis of material balance is used as reagent. 27. A process according to claim 17, characterized in that anthracite carbon or oxidized anthracite carbon reacts with said reagent. au