FI73458B - HYDROBEHANDLINGSFOERFARANDE AV KOLHALTIGT MATERIAL. - Google Patents

Description

1 73458

METHOD OF HYDRO-TREATMENT OF CARBON-CONTAINING MATERIALS

The invention relates to a process for the hydrotreatment of carbonaceous substances utilizing certain hydrates of alkali-5 metal sulfur compounds.

Many methods are known for treating petroleum oils and the like with alkali metal compounds and sulfides. For example, U.S. Patent No. 3,252,774 discloses a partitioned process for producing hydrogen-containing gases from liquid hydrocarbons by cracking by contacting the product in the presence of water vapor with a Ikti Limetal L i compound (e.g., sulfidi.su Lattec) at about 427-982 ° C: n temperature.

According to U.S. Patent No. 3,617,529, ai-15 is desulfurized from petroleum by contacting the oil at room temperature with an aqueous solution containing either sodium hydrogen sulfide alone or sodium hydrogen sulfide in combination with sodium hydroxide and ammonium hydroxide. The aqueous solution and oil are separated and the aqueous solution is treated to remove sulfur from the polysulfides formed during the contacting step.

U.S. Patent Nos. 3,787,3L5 and 3,788,978 disclose a process for desulfurizing petroleum oils. To remove sulfur, the oil is contacted together with hydrogen to form an alkali metal or metal alloy to form a sulfide. The sulfide is separated from the oil by treatment with hydrogen sulfide and the separated monosulfide is treated with sodium olysulfideΙ-Ιο to give a sulfide with a lower sulfur content, which in turn is electrolysed to sodium.

U.S. Patent No. 3,816,298 discloses a two-step process for converting heavy hydrocarbons (e.g., vacuum distillation residue) (partially by desulfurization, hydrogenation, and hydrocracking) to liquid hydrocarbons and a hydrogen-containing gas. The hydrocarbon fed in the first 35 steps is contacted with a gas containing hydrogen and carbon dioxide in the presence of one of a number of catalysts comprising alkali metal sulfides and hydrogen sulfides. The pressure should be above 10.5 aty and the average temperature 37.L-593 ° C. An example is the supply of feed water vapor (as well as hydrogen and carbon dioxide) using a 1 CO 2 catalyst at a pressure of 23.8 aty and a temperature of 488 ° C. The by-product, a solid carbonaceous material, precipitates on the catalyst and some of the catalyst is transferred to a second reaction step where it is treated with steam at a pressure of more than 10.5 aty and an average temperature of more than 649 ° C.

U.S. Patent No. 4,003,823 discloses another process for refining heavy hydrocarbons comprising contacting the hydrocarbons with alkali metal hydroxides at a hydrogen pressure of about 35-350 aty and a temperature of about 260-1093 ° C. Hydrogen sulfide can be added to the products removed from the reaction zone to convert the alkali metal sulfides in the reactor to hydrogen sulfides as a first step to regenerate the alkali metal hydroxides.

U.S. Patent No. 4,018,572 discloses a process for the desulfurization of fossil fuels in which the product is contacted with aqueous solutions of molten alkali metal polysulfides to form higher sulfur salts which are decomposed to regenerate less sulfur-containing polysulfides.

U.S. Patent No. 4,119,528 discloses another method for treating heavy carbonaceous products using potassium sulfide and hydrogen at pressures of about 35-350 aty and temperatures of 260-1093 ° C. Sulfur, low-boiling oils and potassium hydrogen sulphide are removed from the products, which can be converted back to potassium sulphide. Potassium sulfide 30 can be fed to the reactor as such or prepared in situ by reacting various potassium compounds with sulfur compounds such as hydrogen sulfide. Potassium sulfide can also be prepared by reducing potassium compounds such as hydrogen sulfide or polysulfides with hydrogen-like reducing agents. The sulfide can also be prepared from potassium hydrosulfide at high temperature by steam evaporation. It is preferable to use a mixture of potassium and sodium sulphides,

II

3,745,48 for sodium sulfide acts as a "receiver" of hydrogen sulfide formed during the reaction, which would otherwise react with potassium sulfide to form "inactive" potassium hydrosulfide. The following U.S. patents also cover the treatment of crude oil-5 fractions and the like with alkali metal compounds and sulfides: 1,300,816, 1,403,005, 1,729,943, 1,938,672, 1,974,724, 2,145,657, 2,950,245, 3 112 257, 3 185 641, 3 368 875, 3 354 081, 3 382 168, 3 483 119, 3 553 279, 3 565 792, 3 663 431, 3 745 109 and 10 4 007 109.

A problem with previous methods, including those mentioned above, is the cumbersome process conditions, such as high temperature and / or pressure, required to keep the yield of useful products high. The present invention is intended to solve previous problems.

It has now surprisingly been found that using an empirical hydrate reagent in the hydro-treatment process, which will be explained in more detail later, the yield of useful products is, only under relatively mild process conditions, much higher than in any known hydro-treatment, including the aforementioned methods. For example, the reaction temperature in the process of the invention need not exceed about 410 ° C, and the pressure required need not be different from atmospheric pressure. Since the conversion and the yield of useful products are also surprisingly high in the process according to the invention and its process conditions are cheaper, a reduction in consumer costs can be expected. The invention relates to the treatment of carbonaceous materials, characterized in that the carbonaceous material is contacted in a reaction vessel with a reagent comprising water vapor and an empirical hydrate of a sulfur-containing compound comprising alkali metal hydrogen sulfides, alkali metal monosulfides, or alkali metal polysulfides thereof.

None of the aforementioned U.S. patents discloses or recommends the use of empirical hydrates of alkali metal hydrogen sulfides, sulfides, 4,745,88, or polysulfides in the hydrotreatment (e.g., hydrogenation and hydrocracking) of carbonaceous materials in the sense of the invention.

5 As used herein, the term "carbonaceous material" includes oils, oil shale, oil sands and the like, but not carbon. Thus, the term "carbonaceous material" includes crude oils, normal pressure distillation residues (cracked and non-cracked), vacuum distillation residues 10 (viscosity decomposed and non-decomposed) and non-crude oil-based oils, "hydrotreating" includes hydrogenation. The term "empirical hydrate" is used because the reagents of this invention exist as hydrates such that they contain bound or associated water that is released at a certain temperature when the reagents are heated.

The use of water vapor in the process of the invention is essential because it preserves the reagents in their empirical hydrated (high activity) form.

20 The new method has many advantages. In addition to the advantages mentioned earlier, nitrogen and metal removal also take place simultaneously during the hydrotreatment. Depending on the reaction conditions and the reagents used, desulfurization can also take place; see. U.S. Patent No. 4,160,721, 25, which discloses a desulfurization process.

The efficiency and the degree of hydrotreatment achievable are very high. For example, in a preferred embodiment where hydrogen sulfide, among others, is introduced into a reaction zone where ice originally having an initial boiling point above 343 ° C is treated in a single run, substantially all of the products obtained boil below 343 ° C. This illustrates the high degree of cracking and the achievable relatively mild reaction conditions in the present invention.

Other advantages of the invention will become apparent from the following description.

The method of the invention comprises contacting a carbonaceous substance with a reagent.

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The carbonaceous material is usually used as the liquid phase, but according to preliminary research, contact in the gas phase can also be used. Water vapor is passed through the reaction mixture to keep the reagent in its empirically hydrogenated (highly reactive) form. (For carbonaceous materials with a high naphthenic acid content, the amount of water vapor must be kept to a minimum, as water tends to decompose them. In such cases, it is desirable to include hydrogen.) Free liquid water causes the reagent to decompose and the reaction conditions must therefore be selected. so that no significant amounts of liquid water are present. It is most preferred to select conditions such that virtually no liquid water is present in the reaction zone.

The reaction mixture is heated to evaporate the product to be treated and water vapor and product are removed from the reaction zone, cooled and separated. If desired, the product can be removed as a series of distillation fractions and the heavier (higher boiling point) fractions can be recycled for processing. Water vapor and evaporated product need not be removed continuously or at all; however, without intermittent removal, the pressure rises and causes condensation of water vapor. This in turn decomposes the reagent and stops the reaction. Thus, it is advisable to remove steam at least warily, with continuous removal being most preferred.

Processing can be performed on almost any type of equipment. For example, a tank reactor can be used. It is also possible to use an intermediate bottom column reactor 30 which allows product distillates to be taken either as an overflow or as by-products. The process can be carried out continuously or batchwise, in one or more reaction steps. The tank tension reactor is usually used for batch work, the midsole column is suitable for continuous work.

In a preferred embodiment, hydrogen sulfide is also introduced into the reaction zone in contact with the reaction mixture. This regenerates some of the reagent and results in better productivity. As will be explained later, hydrogen sulfide is generated during processing and is removed along with water vapor and vaporized product. Therefore, it is most useful to recycle the removed hydrogen sulfide to the reaction zone-5 zone.

Reaction temperatures are relatively low, generally about 40-410 ° C. For certain materials (e.g., vacuum distillation with residues), the actual reaction does not occur until at a relatively high temperature (e.g., 370 ° C). 10 Pressures need not be higher than normal atmospheric pressure, but design considerations may require the use of higher pressures, for example, because the diameter (and cost) of a column-type reactor can be reduced. Whatever conditions are used, they should not cause significant condensation of water vapor, and it is most preferred that substantially no water vapor condense.

The reagents used are empirical hydrates of hydrogen sulphides, monosulphides and polysulphides of the group IA elements, with the exception of hydrogen. Francium and cesium compounds are not commonly used. Thus, the most commonly used are sodium, potassium, lithium and rubidium compounds. Potassium, rubidium and sodium compounds are preferred, with potassium being most preferred.

(However, in a few cases, such as heavy Canadian crude oil, sodium reagents have been superior to potassium.) The most effective reagent has been found to consist of empirical hydrates of three hydrogen sulphides and comprising 14% rubidium hydroxide, 29% potassium hydroxide and 30% potassium hydroxide. (based on a total of two hydroxides and one hydrosulfide).

During the reaction, the reagent is, at low temperatures, in fact a mixture of the alkali metal hydrosulfide and the (mono- and poly-) empirical hydrates of the sulfides used, and during the reaction an internal conversion takes place between these sulfur-containing forms. (As the reaction temperature rises, some of these forms disappear when their 7 73458 Decomposition temperature is exceeded.) Thus, the reagent may be initially introduced into the reaction zone as an empirical hydrate of hydrogen sulfide or as one or more sulfide hydrates or empirical mixtures of hydrogen sulfide and sulfide. Empirical hydrate reagents can also be prepared in situ in the reaction zone, but are preferably fed in their empirical hydrate form. (Each alkali metal hydrogen, mono- and polysulfide may have more than one empirical hydrate and, unless otherwise indicated, the term "empirical hydrate" includes all hydrates.)

More specifically, for example, the potassium series contains six potassium sulfides, ^ S, K2S2 'K2S3' K2S4 'K2S5 K2S6, and one hydrogen sulfide, KHS. The molecule with the largest number of sulfur atoms can be considered to be "saturated" with respect to sulfur (e.g., K2sg) and less containing relatively unsaturated.

For example, taking potassium monosulfide (^ S), it crystallizes as an empirical pentahydrate. Under the reaction conditions of 162 ° C, the empirical pentahydrate decomposes into the empirical dihydrate with a violent and considerable release of three moles of water per mole of S. At 265-270 ° C, further decomposition to the lower empirical hydrate occurs as water is removed. Some amount of empirical hydrate water probably remains close to the melting point, 948 ° C. The release of water at certain temperatures is clear evidence of the binding of associated water, which is analogous to hydrate to water.

In the process according to the invention, nitrogen and metals are removed, while hydrogenation and hydrocracking take place. Nitrogen is removed from the system as ammonia vapor. The metals removed include vanadium, nickel, cobalt, and cadmium and remain in the reagent remaining in the reaction zone. If t ^ S is introduced or less sulfur-saturated reagents are used, desulfurization also takes place in the process.

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Increasing the sulfur-alkali metal ratio in the reaction zone (including sulfur in the carbonaceous material to be treated) tends to reduce the intensity of cracking and desulfurization. Low sulfur-alkali metal ratios 5 tend to increase cracking severity and enhance desulfurization. If hydrogen sulphide is introduced, the time of its addition also affects the cracking intensity. Starting the addition before all liquid water has drained (at about 110-135 ° C) reduces the intensity; Increasing after-10 keenward increases.

With potassium reagents, total ratios of between 0.5: 1 (corresponding to 100% ^ S) and 2.5: 1 (corresponding to 100%) can be used. For most carbonaceous materials, a more useful range is between 0.55: 1 and 1.5: 1 and preferably between 0.75 = 1 and 1 = 1. Lower ratios may be required in the case of materials which are difficult to crack, such as vacuum distillation residues.

If the combined sulfur-alkali metal ratio of the reagent and the carbonaceous material is too low, al-20 elemental sulfur may be added; if it is too high, an unsaturated reagent can be added.

The amount of reagent used should be sufficient to provide the necessary contact and the desired degree of reaction with the product. It is not known what is the maximum amount of product that can be treated with a given amount of catalyst, but as much as 500 g of vacuum distillation residue has been treated with 9.5 g of KHS (as empirical hydrate).

Reagents can be prepared in several ways.

The preparation of preferred potassium reagents is exemplified. Initially, sulfur is added in an excess of 15% to potassium in liquid ammonia. This gives potassium sulfide hydrate (empirical hydrate). A portion of the hydrate is then reacted with added sulfur to give an empirical hydrate of pentasulfide. The two hydrates are combined and used.

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Another method is to dissolve potassium hydroxide in water and add just enough low-boiling alcohol (e.g., ethanol, 1-propanol) to provide two layers. For example, 1 mole of KOH is dissolved in two to 5 moles of water. Sufficient alcohol (e.g., ethanol or higher) is added to provide two layers (total volume will be 160 mL or less) and elemental sulfur is added to the desired S / K ratio.

This second method yields almost exclusively empirical hydrates of sulfide-10 dienes, not hydrogen sulfides. A small amount of the hydrogen sulfide formed remains in the alcohol layer, with the aqueous layer containing only sulfides. The sulfides of the aqueous layer have been successfully used in hydrotreating. This proves the usefulness of sulfide reagents.

A third (and preferred method) comprises dissolving potassium hydroxide in an alcohol in which KOH is soluble and introducing hydrogen sulfide into this solution. Alcohols are usually primary alcohols, with methanol and ethanol being preferred, as KOH is more soluble in these than higher alcohols. The resulting mixture contains empirical hydrates of potassium hydrosulfide. (This method can also be used to prepare rubidium reagents. Sodium hydrogen sulfide reagents are not prepared in this way; instead, commercially available flakes of empirical NaH5 hydrate can be fed directly to the reaction zone.)

The preparation of the empirical hydrate reagent of potassium hydrogen sulfide according to a preferred method is pig-free: To a two-liter gas scrubbing bottle, add slightly less than 600 ml of ethanol to each and dissolve 3 moles of potassium hydroxide in both. Hydrogen sulfide is introduced into the first flask below the surface of the solution near the bottom and the gas bubbled through the solution is further fed to the second flask, respectively; then the following total reaction takes place: 35 H2S + KOH = KHS + H20 10 73458 This reaction is so rapid that if the flow is too small, the liquid is absorbed from the bottles back into the gas line. The flow of gas to the first flask is stopped as soon as H 2 S passes freely into the second flask, all the precipitate en-5 in the first flask has dissolved and the temperature in the first flask has dropped below 22 ° C. In this case, the first flask, which is disconnected from the system and sealed, contains a high-quality reagent (potassium hydrogen sulfide empirical dihydrate (KHS-21) in ethanol).

A typical batch working method for treating a carbonaceous material according to the present invention using a preferred potassium reagent in a preferred manner is as follows (crude oil as the carbonaceous material). the oil is introduced into the reaction vessel and nitrogen (or other inert kaa-15 sua) is continuously introduced into the oil to stir it during heating. (A mechanical stirrer, such as a magnetic stirrer, can be used as a substitute for the gas stirrer). If elemental sulfur is needed to increase the sulfur-alkali metal ratio, it can be added to the oil at this stage. A reagent mixture (empirical hydrate of potassium hydrogen sulfide in ethanol) is added. (Alternatively, excess sulfur may be added to the reagent mixture and not to the oil.) The temperature is raised to about 130 ° C and the steam supply is started. The water vapor flow need not be greater than 25 for visible bubbles to appear on the surface of the oil. If the conduction of water vapor causes sufficient mixing, the conduction of nitrogen can be stopped.

The excess steam is continuously and variably removed and contains alcohol and water from the reaction mixture, water-30 steam, hydrogen sulfide from the reaction, both vaporized and non-condensed hydrocarbon products from the treatment. (Assuming that the onset temperature of the reaction is reached.) The excess stream is cooled in a water condenser and the resulting condensate is passed to a liquid-liquid separator. Condensation-35 vapor can be introduced into a cold trap (e.g., at -15.5 ° C) to separate residual hydrocarbon products.

li 11 73458 As the oil temperature rises, various overheating products accumulate in the overflow. the nitrogen introduced into the oil begins to separate the alcohol and water associated with the reagent almost immediately after the addition of the reagent (at about 5 to 40 ° C). At 90 ° C, the first droplets of a separate hydrocarbon layer appear in a liquid-liquid separator. Prior to this, however, the light hydrocarbons formed (e.g., 3-, 4-, 5-, and 6-carbon compounds) have come out and at least some of them have dissolved in the alcohol separator.

At 135 ° C, the distillation of the alcohol and water in the reaction mixture is essentially complete. The water-alcohol layer in the separator is recommended to be removed and recycled to the feed water vapor generator. The process eventually returns the lighter hydrocarbons to the reaction vessel and seeks to reduce their additional yield. Alternatively, the water and alcohol can be separated and only the water recycled back to the steam generator. This prevents popping in the reaction vessel due to re-evaporation of the recycled alcohol. The temperature of the oil can be raised continuously or maintained at one or more temperatures (after the steam has started to flow at about 130 ° C). Maintaining a low temperature for a longer period of time promotes the intake of lighter products, but also results in better steam stripping of the heavier product from the reaction zone.

The following Table I shows the cumulative amounts of product obtained from the liquid-liquid separator in the case of a light crude oil containing 11.75% by weight of hydrogen using an empirical potassium hydrate having an S / K ratio = 1/1 30 and the oil was kept in each at the indicated temperature above 140 ° C for 15 minutes.

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Table I

oil temperature Cumulative products obtained as a percentage of the oil fed up to 140 ° C approx. 24% by weight ^ 180 ° C approx. 38% by weight

220 ° C

270 ° C about 59% by weight

320 ° C

340 ° C ca. 96% by weight The residue in the reaction vessel contained less than 2% by weight of starting material. Approximately 4.7 g of product accumulated during this run in a cold trap at -15.5 ° C.

It has been found that, with the exception of oils with a high naphthenic acid content, any light crude oil treated in a batch system to which no hydrogen sulfide is introduced has the hydrogen, nitrogen and sulfur contents of the various fractions in certain ranges. These expected values are shown in Table II below. ("Fraction below 140 ° C" is a hydrocarbon material obtained when the temperature of the oil to be treated is below 140 ° C. "Fraction 140-170 ° C" is obtained at product temperatures of 140-170 ° C, etc.)

Table II

Product fraction The amount of element in the product fraction (oil nitrogen- Hydrogen Nitrogen Sulfur 25 at room temperature) below 140 ° C 13.8-14.1% less than less than 0.05% 0.05% 140-170 ° C 13.4-13.6 % less than 0.07% 0.05% 30 170-270 ° C 13% 0.1% 0.36-0.48% 270-340 ° C 12.4-13.0% half of the initial 2/3 of origin

Various variations are possible in this reaction chain. One or more fractions may be recycled to the reactor for cracking. For example, it is possible to recycle all fractions obtained above 140 ° C and produce essentially only a net product of 140 ° C.

13 7 3 4 5 8

Another variation is the regeneration of the empirical hydrate reagent. This involves separating the hydrogen sulfide contained in the steam stream removed from the reactor and treating the potassium compounds remaining in the reactor. To separate the I-Sr from the steam-5 stream, it is passed through a water condenser, as before, and the uncondensed product is passed through the alcohol to remove lighter hydrocarbons, as they prevent the removal of hydrogen sulfide in the next step (washing alcohol solution can be recirculated to the steam generator). The remaining gas stream containing I 2 Stn is then passed to an alcoholic solution of alkali metal hydroxide, which removes hydrogen sulfide from the gas to form the regenerated empirical hydrate of the alkali metal hydrogen sulfide or sulfide in much the same manner as in the preferred fresh reagent preparation method. By using a multi-stage I ^ S scrubber, it is achieved that the steam leaving the last stage contains practically no hydrogen sulfide.

To recover the potassium in the reactor (if potassium reagents are used) and to regenerate the reagent, the solids in the reactor containing polysulfides and metal compounds formed during the reaction are removed and about 3 moles of water per mole of potassium are added to provide an aqueous solution. If desired, an amount of alcohol of less than 25 or an equivalent amount of water may be added. In the next step, the alcohol stabilizes the reagent precursors. The mixture is then cooled below 22 ° C to form some alkali metal hydroxide and hydrogen sulfide, which may be from a recycled H 2 S reactor, is bubbled through the mixture while cooling to keep the temperature below 22 ° C. This precipitates the sulfur from the solution and the solution is separated from the solids. The liquid is heated to remove most of the water and alcohol (if water has been used) and to provide an empirical molten potassium hydrate.

When potassium reagents are used, heating to 105-110 ° C in water vapor provides an empirical hydrate melt containing about 35% by weight bound water. Melt 14 73458 is dissolved in just a sufficient amount of low boiling alcohol (preferably methanol or ethanol) to a saturated solution. (Dilute solutions may be used, but this requires extra energy to evaporate the excess alcohol.) In the case of potassium reagents, about 150 ml of methanol or a little more ethanol is needed at room temperature to dissolve 1 mole of KHS. At 60 ° C, hydrogen sulfide is bubbled through the solution, resulting in an alcoholic solution of an empirical hydrate reagent. The solution is then ready for use in a hydrotreating reactor; however, it is desirable that the solution first wash the hydrocarbon products. This clarifies the distillates, removes free sulfur from them, and seeks to increase the efficiency of the reagent.

In a preferred embodiment, hydrogen sulfide is introduced into the reactor. Hydrogen sulfide presumably prevents the reagent from decomposing and inactivating and, as previously noted, depending on the time of feeding, the cracking severity either increases or decreases. The minimum and maximum amounts of hydrogen sulfide that can be used successfully are not currently known.

The following examples illustrate the invention.

Example 1 164.5 g of Texas crude oil, 2 g of elemental sulfur and 40 ml of a methanol solution containing 15.2 g of KHS and 7.6 g of water (water bound to the empirical dihydrate) were placed in a flask whose contents were stirred below the liquid surface near the bottom of the flask. nitrogen. The flask was heated in a heating mantle and a water vapor generator fed water vapor into the solution in the flask. Conduction of water vapor at 3 ° was started at a liquid temperature of about 120 ° C.

The effluent vapors were cooled in a water cooler and the condensate was collected in a flask. During the operation, the methanol-water condensate was returned to the steam generator at regular intervals. The carbon-35 hydrogen condensates (fractions) obtained at different temperatures were regularly removed and analyzed. Uncondensed steam was passed through a solution of 0.5 moles of KOH in 100 mL of methanol (which removed virtually all of H 2 O 4) through a water scrubber (to remove methanol and then through an isopropanol-carbonic acid ice bath (to remove some lighter hydrocarbons). Analysis results of crude oil and product fractions 5 below.

Analysis

Material Amount Hydrogen Nitrogen Sulfur

Crude oil 164.5 g 12.11% 0.14% 1.51%

Fraction below 140 ° C 29.4 g 13.87 7 <0.05% 0.05% 10 140-170 ° C Fraction 16.6 g 13.6% <0.05% 0.07% 170-275 ° C Part 25.7 g 13.1% 0.07 7, 0.8% 275-340 ° C Part 12.3% 12.3% 0.1% 1.1%

There was no carbonaceous residue in the reaction vessel and the condensate from the cold trap had a volume of 22 ml.

15 The results show that the process hydrogenates, removes nitrogen and sulfur. All product fractions contain (by weight fractions) more bound hydrogen, less bound nitrogen, and less bound sulfur than crude oil. (Cold trap distillate was not analyzed, but presumably has a greater mouth-20 fraction of bound water than crude oil.)

Example 2 200 g of Alaskan crude oil was treated using the same procedure as in Example 1, except that the steam supply was started at 135 ° C and no cold trap was used. Analyzes of crude-25 oil and products below (no actual oil residue left in the bottle).

Analysis

Material Amount Hydrogen Nitrogen Sulfur

Crude oil 200 g 12.04% 0.23% 1.5% 30 Unconcentrated 74 g

Fraction below 140 ° C 38.4 g 13.99% <0.05% <0.05% 140-180 ° C Fraction 20.1 g 13.77% <0.05% 0.07% 180-343 ° C Jae 59.1 g 12.8% 0.1% 0.9%

Example 3 35 175 g of Trinidad crude oil were treated with 30 ml of a reagent containing 11.4 g of KHS and 5.7 g of water (bound to the empirical hydrate). Due to its high naphthenic acid content, this oil is sensitive to decomposition due to water. For this reason, a minimum amount of steam was used (the steam generator was kept at 99 ° C at sea level) and gaseous hydrogen was also introduced. Crude oil and product analyzes are as follows.

Analysis

Material Amount Hydrogen Nitrogen Sulfur

Crude oil 175g 11.83% 0.32% 1.43%

Fraction below 180 ° C 13.01% 0.05% 0.24% 10 Hydrocarbons alcohol 33 vol.% 12.89% 0.06% 0.55% li-water condensate oil at 180-140 ° C Fraction 21% by volume of crude oil 12.39% 0.06% 0.58% 15 Residue in bottle 20% by volume of crude oil 11.87% 0.31% 1.43%

Due to the design of the apparatus, hydrogen could not be introduced close enough to the bottom of the reaction vessel to come into contact with the bottom material; this results in a 20% residue.

Example 4 150 g of light Arabic crude oil, 2 g of elemental sulfur and 40 ml of a methanol solution containing 15.6 g of KHS and 7.8 g of water (bound to the empirical hydrate) were run in a reaction flask as in Example 1, except that the water vapor conduction started at 130 ° C. Analyzes of crude oil and processed products below.

Analysis

Material Hydrogen Nitrogen Sulfur 30 Crude oil 12.25% 0.1% 1.8%

Fraction below 140 ° C 13.8% <0.05% 0.09% 140-170 ° C Fraction 13.5% <0.05% 0.12% 170-270 ° C Fraction 13.1% 0.07 % 2.3% 270-330 ° C Part 12.8% 0.11% 0.8% 35 17 7345 8

Example 5

Vacuum distillation residue (formed at 593 ° C with initial boiling point in vacuo) and a methanol solution containing 1 KHS (0.47 g KHS / ml solution) were placed in a reaction vessel. The contents of reactor 5 were heated and stirred with nitrogen at room temperature to 170 ° C, at which point the nitrogen flow was stopped and water vapor conduction was started. The run was stopped when the temperature reached 400 ° C, leaving 51% of the amount initially fed in the vessel. Analyzes of the residue taken and the 10 distillates taken below.

Analysis

Material Hydrogen TypDi Sulfur Residue 10.50% 0.52% 3.83%

Fraction below 110 ° C 12.02% 0.22% 2.61% 15 110-400 ° C Fraction 11.41% 0.21% 2.96%

Example 6

The direct vacuum distillation residue of Example 5 was again treated with KHS reagent, this time using hydrogen to stir the system, from room temperature to 240 ° C. A stream of water-20 steam was passed at 170 ° C. The run was stopped at 425 ° C, leaving 9% of coking material from the residue originally charged to the reactor. The analyzes of the residue, the two distillates collected and the residue remaining in the flask are given below.

25 Analysis

Material Hydrogen Nitrogen Sulfur Residue 10.50% 0.52% 3.83%

Fraction below 360 ° C 12.17% 0.13% 2.41% 360-425 ° C Fraction 12.29% 0.11% 1.95% 30 Residue in bottle and radiator washes 6.67% 0.23% 2 46%

Chromatographic analysis of the uncondensed gas stream showed it to contain 30.52% hydrocarbons, decomposed as follows.

35 is 7 3458

Compound (s) Hydrocarbon in gas stream%

Methane 59

Ethane + ethylene 21 propane + propylene 6 5 Butanes 6

Pentanes 2

The rest of the gas stream (69.48%) is believed to be air from the gas chromatography tube. The distillates were very light, corresponding to heating oil (# 2) or diesel fuel. In addition, the fact that no precipitate was present in the exhaust gas scrubber containing an alcoholic solution of KOH indicates that little or no carbon dioxide was evolved in the reactor.

Example 7 150 ml of a different vacuum distillation residue and 22 ml of a methanolic solution of the empirical hydrate of KHS (0.477 g KHS / ml solution) were placed in a reaction vessel and heated.

A nitrogen mixture was used from room temperature to 190 ° C, at which point it was stopped and a stream of water vapor 20 (superheated to 140 ° C) was started. One distillate was collected and kept at 100 ° C to remove water. Hydrocarbons not distilled with water were classified as "fraction 100-425 ° C" and distilled ones as "fraction below 100 ° C". Analyzes of the residue, the two hydrocarbon products and the 25 substances remaining in the flask below:

Analysis

Material Amount Hydrogen Nitrogen Sulfur Residue 150 ml 10.85% 0.44% 2.91%

Fraction below 100 ° C 27 ml 12.92% 0.07% 1.03% 30 100-425 ° C Fraction 110 ml 12.08% 0.25% 2.26% Residue in the flask 20 g 3.02% 1, 25% 4.47%

Example 8

Example 7 was repeated, the only change being the use of hydrogen instead of nitrogen, from room temperature to a final temperature of 425 ° C. At the end of the run, the bottle contained the same amount of residue (20 g). Analyzes of residue and single distillate below.

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Analysis

Material Hydrogen Nitrogen Sulfur Residue 10.85% 0.44% 2.91%

Distillate 12.91% 0.17% 1.95% Example 9 160 ml of the vacuum distillation residue used in Examples 7 and 8 and 25 g of dry, commercial NaHS flakes (technical grade) were placed in a reaction vessel. This material is in empirical hydrate form as such. Methanol was added to the water vapor-10 generator. Hydrogen stirring was used all the time in conjunction with the water vapor flow started at 220 ° C. Analyzes of residue and single distillate below.

Analysis 15 Material Hydrogen Nitrogen Sulfur Residue 10.85% 0.44% 2.91%

Distillation 12.07% 0.18% 2.53%

Example 10

The cracked residue and an alcoholic solution of the empirical hydrate of KHS (0.47 g KHS / ml solution) were placed in a reaction vessel.

Stirring with nitrogen was used from room temperature to 190 ° C, at which point the flow of nitrogen was stopped and conduction of water vapor was started. 13.3% of the residue (in the non-coking form) remained in the reaction vessel at the end of the run. The single distillate was kept at 100-100 ° C to evaporate the condensed water. With water to evaporate water that has evaporated. The hydrocarbons vaporized with water were separated and dried and are classified as a "fraction below 100 ° C". Analyzes of the residue and the two products below.

30 Analysis

Material Hydrogen Nitrogen Sulfur Residue 10.45% 0.53% 3.33%

Fraction below 100 ° C 12.55% <0.05% 1.91%

Fraction above 100 ° C 11.84% 0.2% 2.57% 35 ___ - T: 20 7 3 4 5 8

Example 11

Example 10 was repeated with the difference that hydrogen, not nitrogen, was used from room temperature to a final temperature of 450 ° C with the addition of a minimum amount of water vapor. Analyzes of residue 5 and three distillates below.

Analysis

Material Amount Hydrogen Nitrogen Sulfur Residue - 10.45% 0.53% 3.33%

Fraction 1 20% of total distillate 12.66% 0.08% 2.12%

Fraction 2 30% of total distillate 11.98% 0.15% 2.34%

Fraction 3 50% of total distillate 11.6% 0.25% 2.2% 15 Example 12

Example 11 was repeated with the modification that commercially available NaHS flakes (technical grade) placed directly in the reactor were used instead of the alcoholic solution of KHS and methanol was added to the steam generator. NaHS-20 flakes are originally in empirical hydrate form. Analyzes of the residue and the two distillates below.

Analysis

Material Hydrogen Nitrogen Sulfur Residue 10.45% 0.53% 3.33% 25 Fraction 1 12.36% 0.07% 1.99%

Jae 2 11.79% 0.18% 2.12%

Example 13

125 ml of the desulfurized cracked residue, 1.8 g of elemental sulfur and 25 ml of an ethanolic solution of KHS empirical hydrate (0.24 g KHS / ml solution) were placed in a flat-bottomed flask with a heated magnetic stirrer. The contents of the vessel were stirred rapidly and heated to 120 ° C to remove ethanol and water from the reagent and heating was continued. The water vapor flow was started at 130 ° C and continued to a final temperature of 325 ° C.

until. Analyzes of the residue, two distillates, and the residue in the flask below.

21 73458

Analysis

Material Amount Hydrogen Nitrogen Sulfur Residue 125 g 9.08% 0.45% 1.81%

Matalalämpöt. Fraction 57 ml 11.48% 0.06% 0.70% 5 High temperatures. Fraction - 9.77% 0.35% 1.91% Residue in the bottle - 8.75% 0.43% 1.91%

Example 14 In this run, hydrogen sulfide was introduced into a two-stage reactor to treat the vacuum distillation residue.

To the first reaction step, which was a vertical cylindrical vessel of about one liter capacity with a heat jacket, 50 ml of a methanolic solution of potassium hydrogen sulfide empirate dihydrate (0.38 g KHS / ml solution) was placed. To the second reaction step, which was a round-bottomed flask equipped with a heat jacket, 25 ml of reagent solution was placed. The I 2 S gas introduced into the first stage was introduced by a decomposition tube below the surface, close to the bottom. At the same time, the excess steam from the first stage was passed through the decomposition pipe below the liquid surface of the second stage. Steam-20 ry from the second stage was cooled and partially condensed in a water cooler.

At the beginning of the run, several hundred grams of the vacuum distillation residue was heated (to make it flowable) and passed directly into the addition vessel above the first stage reactor. A portion of the resin was allowed to drain into the reactor and both reactors were heated. At the same time, the introduction of water vapor, nitrogen and hydrogen sulfide into the first stage reactor was started. I ^ S flow could not be measured, but was estimated to be three moles per hour. As the temperature rose in the first step, the methanol and water of empirical hydration added with the reagent distilled off and entered a second step at 110 ° C to prevent water condensation there.

In the first step, the reaction took place at about 35,370 ° C. During the run, the temperature in the first stage rose from 370 ° C to 390 ° C and in the second stage from 110 to 270 ° C. A total of 286 g of residue was added to the first 22,734 5 8 steps during the run and less than 10 g remained at the end of the run. Analyzes of the vacuum distillation residue, the product remaining in the second reaction step and the product collected from the water cooler below, 5 Analysis

Material Amount Hydrogen Nitrogen Sulfur

Vacuum distillation residue 286 g 10.04% 0.64% 2.02%

Second stage product 57.1 g 11.22% 0.42% 1.48%

The final product 186.5 g 12.99% 0.50% 1.19% 10 The final product had an initial boiling point of 23 ° C and a maximum distillation temperature of 118 ° C. The uncondensed steam product was estimated to weigh about 35 g. The API values for the second stage and final products were 17.4 and 50.4 degrees at 15.5 ° C, compared to 6.0 for the vacuum distillation residue. Metal concentrations of 15 are given below (figures are ppitirnaj "N / D" means "not determinable").

Analysis

Material Na V K Fe Ni

Vacuum order balance 2.6 102 2.3 24 62 20 Second stage

product 0.35 N / D 2.9 N / D N / D

End product 1.6 N / D 46 0.93 N / D

Example 15

The shale oil was treated in the first 25 stage reactor of Example 14 with a methanolic solution of the empirical hydrate of KHS, water vapor and nitrogen, but not I 2 S. Analyzes of shale oil, products, and reactor residue remain below.

Analysis 30 Material Amount Hydrogen Nitrogen Sulfur

Shale oil 200 g 9.90% 1.45% 6.23%

Less than 280 ° C Fraction 22 g 10.33% 1.16% 6.85% 280-300 ° C Fraction 35 g 10.59% 0.95% 6.80% Residue 100 g 8.33% 1.47% 5.76% 35 The total unconsolidated volatiles were estimated to be 43 g. Metal concentrations below (unless otherwise stated, figures in ppm; "N / D" means "not determinable").

Il 23 734 5 8

Analysis

Material Na V K Fe Ni Ca

Shale oil 11 124 64 106 86 1223

Below 280 ° C Jae 1.2 5 5 N / D 20

5 280-300 ° C Part 0.61 19 4.6 N / D N / D

Residue 21 56 2.89% 34 565

Example 16 At 15.5 ° C, 10.5 API grade heavy crude oil was treated with reagent, water vapor and hydrogen sulfide in the apparatus and method of Example 14, except that the second stage reactor was not used and 100 ml of reagent solution was used. One product was obtained at 370-390 ° C. Crude oil and product analyzes below. At the end of the run, less than 2% of crude oil remained in the reactor.

15 Analysis

Material Hydrogen Nitrogen Sulfur

Crude oil 10.80% 0.40% 4.42%

Product 11,69% 0,13% 3,15%

The product had 24.3 API degrees at 15.5 ° C, an initial boiling point of 20,110 ° C and an end point (97% recovery) of 360 ° C. Metal pitches below (figures in ppm; "N / D" means "not determinable").

Analysis

Material Na V K Fe Ni 25 Crude oil 5 203 36 99

Product 0.06 N / D N / D 0.66 N / D

Claims (10)

24 73458 A process for the hydrogenation, hydrocracking, nitrogen removal or metal removal of a carbonaceous material to produce substantially normally liquid hydrocarbon products having a higher hydrogen content than the hydrocarbonaceous material, characterized in that the carbonaceous material is contacted in a reaction vessel simultaneously with a reactor and steam. consisting of an empirical hydrate of a sulfur-containing compound, comprising alkali metal hydrogen sulfides, alkali metal monosulfides, and alkali metal polysulfides, and mixtures thereof, the reaction conditions being such that free water is not formed in amounts necessary to decompose the reagent. Process according to Claim 1, characterized in that the steam is introduced into the reaction ethy after the contents of the vessel have been heated to a predetermined temperature, the water vapor retaining the reagent 20 in its empirical hydrate form. Process according to Claim 1 or 2, characterized in that the alkali metal is sodium, lithium, potassium or rubidium. Process according to one of Claims 1 to 3, characterized in that the alkali metal hydrogen sulphide reagent in the vessel comprises potassium hydrogen sulphide and / or sodium hydrogen sulphide. Method according to one of the preceding claims, characterized in that hydrogen sulphide is also introduced into the vessel. Process according to one of the preceding claims, characterized in that the temperature of the carbonaceous material in the reaction vessel is about 40 to 410 ° C and that the pressure in the vessel is about atmospheric pressure. Process according to one of the preceding claims, characterized in that hydrogen is also introduced into the reaction vessel. 25 7345 8 Process according to one of the preceding claims, characterized in that the initial inert sulfur is fed into the reaction vessel in order to adjust the sulfur / alkali metal ratio. Process according to one of the preceding claims, characterized in that the alkali metal is in an alcoholic solution. Process according to Claim 9, characterized in that the alcoholic solution is a solution of methanol, ethanol or propanol-1. 73458