KR850000672B1 - Process for hydrotreating carbonaceous material - Google Patents

Abstract

This invention relates to the process for hydrotreating carbonaceous material with alkali metal. To produce liquid carbonaceous material containing more hydrogen than raw carbonaceous material, hydrocracking, denitration and demetalation are performed by treating the carbonaceous material with vapour and the reactant of hydrate containing sulfur in a reactor. This process gives high yield products and does not need high temp. or high pressure.

Description

Hydrogen Treatment of Carbon Material

The present invention relates to a method of hydrotreating a carbon material using a hydrate of an alkali metal active compound. Many methods of treating petroleum with alkali metal compounds or sulfur compounds are known. For example, U. S. Patent No. 3,252, 774 describes a method of cracking liquid hydrocarbons in which a melt of an alkali metal compound (e.g. sulfide) is brought into contact with a raw material at 422 to 972 DEG C in the presence of steam to produce a hydrogen-containing gas. .

US Pat. No. 3,617,529 describes a method for removing sulfur particles from petroleum by contacting petroleum at ambient temperature with an aqueous solution containing only sodium hydroxide (NaHS) or a mixture of sodium and ammonium hydroxide. The aqueous solution and the oil are separated and the aqueous solution is treated to liberate sulfur from the polysulfide produced during the contacting step. US Pat. Nos. 3,787,315 and 3,788,978 describe the desulfurization process of petroleum. The oil is desulfurized by contact with an alkali metal or alloy in the presence of hydrogen to form sulfur compounds. The oil is treated with hydrogen sulfide to separate the sulfides and the separated monosulfide is treated with sodium polysulfide to produce a low sulfur content polysulfide which is electrolyzed to yield sodium.

U.S. Patent No. 3,816,298 describes a two-step process (partially desulfurization, hydrogenation, hydrocracking) of reforming heavy hydrocarbons (e.g., reduced pressure residues) into liquid hydrocarbons and hydrogen containing gases. In the first step, the hydrocarbon is contacted with hydrogen containing gas and carbon monoxide in the presence of a catalyst comprising alkali metal sulfides and hydrosulfides. The pressure and temperature should be at least 150 psig and 367 to 587 ° C, respectively.

One example describes the feeding of steam (as well as hydrogen and carbon monoxide) in the first stage with a K ₂ CO ₃ catalyst at 340 psig and 483 ° C. By-product solid carbonaceous material is deposited on the catalyst and part of it is sent to the second stage to contact the steam at a pressure of 150 psig and a temperature of 642 ° C. U.S. Patent No. 4,003,823 describes another process for reforming heavy hydrocarbons by contacting the hydrocarbon material with alkali metal hydroxides at a hydrogen pressure of 500 to 5000 psig and a temperature of 257 to 1082 ° C. In the first step of regenerating the alkali metal hydroxide, hydrogen sulfide is added to the product recovered from the reaction zone, and hydrogen sulfide is added to the product recovered from the reaction zone to convert the alkali metal sulfide produced in the reaction tank into a hydrosulfide.

US Pat. No. 4,018,572 describes a method for desulfurizing fossil fuels by contacting the fossil fuel material with a melt or aqueous solution of an alkali metal polysulfide to produce a high sulfur content salt.

Finally, US Pat. No. 4,119,528 describes another method of treating heavy hydrocarbons using potassium sulfide at a hydrogen pressure of 500 to 5000 psig and a temperature of 257 to 1082 ° C. The product is a low boiling desulfurized oil and potassium hydrosulfide which can be converted back to potassium sulfide.

Potassium sulfide may be prepared by injecting potassium sulfide itself into a reactor or by reacting a potassium compound with a sulfur compound such as hydrogen sulfide in a reactor. Potassium sulfide can also be prepared by reacting a potassium compound such as hydrosulfide or polysulfide (polysulfide) with a reducing agent such as hydrogen. The sulfides can also be prepared by high temperature steaming of potassium hydrosulfide. It is preferable to use a mixture of potassium sulfide and sodium sulfide, since sodium sulfide acts as a "getter" for the hydrogen sulfide produced during the reaction, otherwise hydrogen sulfide reacts with potassium sulfide to "inert" hydrosulfide. Potassium is produced.

The following U.S. patent also describes a process for treating petroleum with alkali metal compounds or sulfides: 1,300,816, 1,413,005, 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, 3,38,553,119, 3,382 3,119 3,565,792, 3,663,431, 3,745,109, 4,007,109.

The problem with the prior art is that strict process conditions such as high temperature and high pressure are required to obtain high yield products. So the present invention is to solve the above problems.

The inventors have found that the treatment of hydrates, which will be described in more detail later, allows the yield of effective products to be increased much more than with conventional treatments with relatively mild process conditions. For example, according to the present invention, the reaction temperature does not need to be higher than 410 ° C, and the pressure does not need to be higher than atmospheric pressure.

In addition, the production efficiency can be reduced because of high conversion efficiency and product yield. More specifically, the present invention provides a carbonaceous material characterized in that the carbonaceous material is treated in a reaction tank with a hydrate and a vapor of a sulfur-containing compound consisting of an alkali metal hydrosulfide, an alkali metal monosulfide or an alkali metal multi-compound and a mixture thereof. Provides a hydrotreating process of the material.

In the above-mentioned US patents, the process according to the invention describes the use of hydrates of alkali metal hydrosulfides, sulfides or polysulfides (polysulfides) for the hydrotreating (eg hydrogenation and hydrocracking) of the carbonaceous material. There is no suggestion. As used herein, "carbonaceous material" includes oil, shale, tar sand and the like and does not include coal.

Thus, "carbonaceous material" is intended to include crude oil, atmospheric residue oil (cracked or uncracked atmospheric residue oil), vacuum residue oil (decompressed residue oil with reduced viscosity or not viscosity) and non-petroleum oil. "Hydrogenation" includes hydrogenation and hydrocracking. It is essential to use steam in the present invention because it keeps the reactants in hydrated form (high-reactivity).

There are many advantages to the new process. In addition to the benefits already mentioned, denitrification and demetallization occur simultaneously by hydrotreating. In addition, depending on the process conditions under which the reactants are used, desulfurization may occur; (See US Pat. No. 4,160,721, which describes the desulfurization process.) The efficiency and degree of hydrotreatment is also very high. For example, one preferred example is residue oil having an initial boiling point of 343 ° C. or higher and hydrogen sulfide is supplied to the reaction zone for one pass and all output products boil at 343 ° C. or lower. A high degree of cracking can be achieved by the present invention under relatively relaxed conditions.

Other advantages of the present invention will appear in the description that follows. In general, the present invention consists in contacting a carbonaceous material with a reactant. The carbonaceous material will generally be used in the liquid state, but can also be used in the vapor state. Vapor is passed through the reaction mixture to maintain the reactants in hydrated (highly reactive) form (for carbonaceous materials that are high in naphthalic acid, the vapor bleeding is kept to a minimum because water decomposes these materials). It is advantageous that the hydrogen is co-fed.) Since free water decomposes the reactants, the reaction conditions should be chosen so that the free water does not exist in large amounts.

The reaction mixture is heated to steam the treated output, and the steam and the product are recovered from the reaction zone, cooled and separated. If desired, the product can be separated into a series of distillate and a heavy (high boiling) fraction that is recycled for aftertreatment. Steam and vaporized products do not have to be recovered or recovered at all. However, without periodic recovery, the pressure rises and condenses the vapor. Thereafter, the reactants are decomposed and the reaction is stopped. Therefore, it is desirable to remove the steam at least periodically and continuous removal is the most desirable.

The processing can be carried out in any type of apparatus. For example, tank reactors may also be used. Column reactors may also be used which allow the product fraction to be separated at the top. This process can be carried out in one or more reactions, either continuously or in batch mode. Tank reactors are generally operated batchwise and column reactors are operated continuously.

In a preferred embodiment, hydrogen sulfide is also supplied to the reaction zone and brought into contact with the reaction mixture. Hydrogen disulfide regenerates part of the reactants and further increases productivity. As described below, hydrogen sulfide is produced during the treatment and is recovered with the vapor and vaporized product. Recycling the recovered hydrogen sulfide to the reaction zone is a great advantage.

The reaction temperature is relatively low and is about 40 to 410 캜. Specific substances. For the reduced pressure residue), the reaction occurs only when the temperature is relatively high (about 370 ° C). The pressure does not need to be above atmospheric pressure, but a technical design that uses more pressure, for example, to reduce the diameter (and cost) of the columnar reactor may be considered. Whatever conditions are used, the conditions should be such that they do not condense a large amount of steam, and preferably it is essential not to condense the vapor at all.

The reactants used are hydrates of monosulfide (monosulfide) polysulfides (polysulfides) and hydrosulfides of periodic group 1A elements other than hydrogen. Francium and cesium compounds are not commonly used. Therefore, sodium, potassium, lithium rubidium compounds are often used. Potassium, rubidium and sodium compounds are windy and potassium is most preferred. For 14% rubidium hydroxide, 29% potassium hydroxide and 57% sodium hydrosulfide, the reaction consisting of 3 equivalents of hydrogen sulfide hydrate was found to be most effective.

During the reaction, at low temperatures the reactants are actually mixtures of sulfides (single and polysulfides) of alkali metals and hydrates of hydrosulfides, and these three sulfur-containing forms change mutually during the reaction (as the reaction temperature rises, Some forms of these disappear as the decomposition temperature is exceeded).

Thus, the reactants are initially introduced into the reaction zone as a hydrosulfide hydrate or one or more sulfide hydrates or a mixture of hydrosulfides and sulfides. Although hydrated reactants can be made in the reaction zone, it is preferred to add hydrates (alkali metal hydrides and single and polysulfides can each have more than one hydrate, unless otherwise specified, "hydrate" Means all hydrates). In particular, examples of potassium series include six sulfides K ₂ S, K ₂ S ₂ , K ₂ S ₃ , K ₂ S ₄ , K ₂ S ₅ , K ₂ S ₆ and one hydrosulfide, KSH. . Molecules containing the highest number of sulfur atoms (ie, K ₂ S ₆ ) may be considered “saturated” for sulfur and molecules containing sulfur atoms below it are relatively “unsaturated” for sulfur.

For example, potassium monosulfide (potassium mosulfide, K ₂ S), which is crystallized to pentahydrate (mulpentahydrate). The pentahydrate decomposes into a dihydrate (dihydrate) at a reaction condition of 162 DEG C and 3 per K ₂ S It can be seen that the mole of water is liberated at 265-270 ° C., which breaks down again to become a hydrate below it and the water is freed. This is to prove the presence of bound or hydrated combined water.

The process is denitrified and demetallized while hydrogenated and hydrocracked. Nitrogen leaves the system as ammonia vapor. The removed metals contain vanadium, nickel, cobalt and cadmium and remain in the reactants remaining in the reaction zone. In addition, the process is also desulfurized if H ₂ S is co-grade or low sulfur-saturated reactants are used.

In the reaction zone, increasing the overall ratio of sulfur to alkali metals (including sulfur of carbonaceous material) reduces the severity and cracking of cracking. Low sulfur to alkali metals increase cracking severity and desulfurization. The timing of addition when co-feeding hydrogen sulfide also affects the severity of cracking. Initiating addition prior to removal of all liquids (at about 110-135 ° C.) reduces the severity of cracking; Starting addition after removal increases the severity of cracking.

For the potassium reactant, it is used at a ratio of 0.5 / 1 (corresponding to 100% K ₂ S) to 2.5 / (corresponding to 100% K ₂ S ₅ ). However, for most carbon materials, the more useful range is 0.55 / 1 to 1.5 / 1 and the preferred range is 0.75 / 1 to 1/1. The limits of the preferred range are considered K ₂ S _{1 · 5} (0.75 / 1) and K ₂ S ₂ (1/1). The range for sodium series is 0.55 / 1 to 1/1. Low ratios will be needed when materials that are difficult to crack, such as vacuum residues, are processed. If the sulfur ratio of the reactant and carbon material to the alkali metal is very low, sulfur may be added; If very high, additional unsaturated reactants may be added.

The amount of reactants used should be sufficient to make proper contact with the raw material and to achieve the required reaction rate. Although the maximum amount of raw material that can be processed with a predetermined amount of catalyst is not known, the degree of 500 g of the vacuum residue is treated with KHS9.5 g.

The reactants can be prepared in several ways. It is intended to illustrate the preparation of preferred potassium reactants. First, an excess of 15% sulfur is added to potassium in liquid ammonia. This produces potassium sulfide hydrate. Some of these hydrates are reacted with additional sulfur to produce pentasulfide hydrates. Use these two hydrates in combination.

The fifth method dissolves potassium hydroxide in water and adds low boiling alcohol (eg ethanol, propanol-1) to form a layer. For example, 1 gram molar KOH is dissolved in 2 gram moles of water. Sufficient alcohol (e.g. ethanol or higher alcohols thereof) is added to form two layers (total volume less than 160 ml) and sulfur atoms are added to the required S / K ratio.

This fifth method produces almost sulfide hydrates and few hydrosulfides. The resulting traces of hydrosulfide remain in the alcohol layer and the water layer contains only sulfides. Sulphides in the water layer are used continuously in hydrotreating.

The third method (preferably) dissolves potassium hydroxide in alcohol, in which KOH is dissolved and then contacted with hydrogen sulfide solution. Alcohols are preferred as methanol and ethanol, because KOH is more soluble in these alcohols than other higher alcohols. The resulting mixture contains potassium hydrosulfide hydrate (this method can also be used to prepare rubidium reactants. Sodium hydrosulfide reactants are not prepared in this way, but instead commercially available flakes of commercially available NaSH hydrate Can be committed to). The preparation of potassium hydrosulfide hydrate by the preferred method is as follows. Two 1-liter cylinders are filled with less than 600 ml of ethanol and 3 gram-mole of potassium hydroxide is dissolved in each of them. The hydrogen sulfide source is connected to the first cylinder so that H ₂ S is injected into the vicinity of the bottom of the KOH-ethanol solution. Vapor generated from the first cylinder is attracted to the second cylinder and introduced near the bottom of the solution. The following overall reactions occur:

H ₂ S + KOH = KHS + H ₂ O

This reaction occurs rapidly, so if the H ₂ S outflow rate is too low, the solution in each cylinder will remain in its respective steam supply line. After H ₂ S passes through the second cylinder, the precipitate is dissolved in the first cylinder, and the temperature of the first cylinder is lowered to 22 ° C or lower, and then the gas flow to the primary cylinder is stopped. At this temperature, the first cylinder contains potassium hydrosulfide dihydrate (KHS. 2H ₂ O) in high quality reactant ethanol, which is removed from the system and sealed.

A typical batch process for the treatment of carbonaceous materials according to the present invention using potassium reactants prepared by the preferred method is as follows (petroleum is carbon material). The oil is introduced into the reaction vessel and continuously supplied with nitrogen (or other inert gas) into the oil to stir while heating the oil (a mechanical method such as a magnetic stirrer can be used instead of stirring the substrate, sulfur to alkali metals) If necessary to increase the ratio, sulfur is added at this point, and the reaction mixture (potassium hydrosulfide dihydrate in ethanol) is added (or extra sulfur may be added to the reaction mixture rather than oil). The temperature is raised to 130 ° C. and the steam is supplied The steam outflow is sufficient to generate bubbles visible on the oil surface The nitrogen supply can be stopped if the steam provides sufficient agitation.

The upper steam continues to be recovered and variously contains water and alcohol from the reaction mixture, steam from the reaction, vaporized and non-condensable hydrocarbon products from treatment with hydrogen sulfide. The upper steam is cooled with cooling water and the resulting condensate is sent to a liquid-liquid separator. The non-condensed vapor is sent to a cold trap (eg -50.6 ° C.) to further recover the hydrocarbon product.

As the temperature of the oil in the reactor rises, various top products are recovered in the top system. The nitrogen supplied in the oil begins to separate the alcohol and the water bound to the reactants as soon as the reactants are added (at about 40 ° C.). At 90 ° C., the first drop of separated hydrocarbon layer is seen in the liquid-liquid separator: however, the previously produced light hydrocarbons (eg 3-, 4-, 5-, 6-carbon atom compounds) have already been added to the top and at least Part of it is dissolved in alcohol in the separator.

At 135 ° C., the distillation of alcohol and water from the reaction mixture is usually complete. Preferably, the water-alcohol layer in the separator is recovered and recycled to a steam generator that supplies steam. Eventually, by returning the light hydrocarbons to the reaction vessel, they prevent them from being produced again. Alternatively, water and alcohol can be separated so that only water can be recycled to the steam generator. This prevents the "Dolby phenomenon" that occurs in the reactor by the regasification of the recycled alcohol.

The temperature of the oil may be continuously raised (after starting at about 130 ° C. of the steam outflow) or maintained at one or more temperatures. Table I below shows the amount of product recovered in the liquid-liquid separator when processing a light crude oil having a silver ratio 1/1 of 11.75% by weight hydrogen using potassium hydrate, the oil being about 140 It is kept for 15 minutes at its respective temperature of < RTI ID = 0.0 >

TABLE 1

Residual oil in the reactor is within 2% by weight of the feed oil. Approximately 4.7 g of product is recovered in the -50.6 ° C cold trap during this process. With the exception of high naphthenic acid oils, no matter what diesel is processed in the batch, the sulfur content of the various production fractions is limited to a certain range. Table II below shows these expected values ("oil below 140 ° C." is the hydrocarbon material recovered during the oil temperature below 140 ° C. "140-170 ° C. fraction" is the material recovered when the oil temperature is 140-170 ° C.). And so on).

Various changes are possible in the process sequence. One or more of the output fractions may be recycled into the reactor for cracking. For example, it is possible to recycle all of the output at temperatures above 140 ° C. and basically produce only 140 ° C. pure water.

Another change is to regenerate the hydration reactant. This involves recovering hydrogen sulfide from the steam stream recovered from the reactor and treating the potassium compound remaining in the reactor. In order to recover H ₂ S in the steam, the reaction vessel is connected to a cooler, and the condensed material is passed through an alcohol washing plant to remove light hydrocarbons, because the light hydrocarbons prevent the recovery of hydrogen sulfide in the next step. (The alcohol wash solution can be recycled to the steam generator).

Residual gas containing H ₂ S is supplied to the alkali metal hydroxide / alcohol solution which removes hydrogen sulfide from this gas stream when regenerating the alkali metal hydrosulfide or sulfide hydrate. Preferably, a double stage H ₂ S scrubber is used and the steam flowing out in the final stage does not contain hydrogen sulfide. To recover potassium from the reactor (if a potassium reactant was used) and to recover the reactant (solid formed during the reaction), a solid containing polysulfide and a metal compound was recovered from the reactor and added about 3 moles of water per mole of potassium. Make an aqueous solution. Optionally, alcohol is added below the volume of the aqueous solution. The alcohol stabilizes the reaction precursor in a continuous process. Cooling the mixture to 22 ° C. or lower produces a portion of the alkali metal hydroxide, and H ₂ S recycled from the operation reactor is cooled and injected into the mixture. If sulfur precipitates, the liquid is separated. The liquid is heated to remove most of the water and alcohol and leave a potassium hydration melt.

In the case of potassium reactants, it is heated to 105-110 ° C. to leave a hydrated melt containing about 35% by weight of bound water. The melt is only dissolved in a low enough boiling point of alcohol (preferably methanol or ethanol) to produce a saturated solution (more dilute solutions may be used but additional energy is required to evaporate excess alcohol). In the case of potassium reactants, 150 ml of methanol or ethanol at ambient temperature are needed to dissolve 1 gram of KHS. Hydrogen sulfide is injected into the solution at a temperature above 60 ° C. to form a hydrated reactant solution in alcohol. The solution is prepared for use in a hydrotreating reactor. However, preferably the solution is first used to wash the hydrocarbon product. This can purify the distillate, remove the free sulfur present therein and improve the effectiveness of the reactants.

In one example, hydrogen sulfide is fed to the reactor. H ₂ S clearly tends to inhibit decomposition or desulfurization of the reactants and may increase or decrease the severity of cracking as the outflow of H ₂ S begins. The minimum and maximum amounts of hydrogen sulfide that can advantageously be used are not known to date.

Example 1

40 ml of a methanol solution containing 164.5 g of Texas crude oil, 2 g of sulfur, 15.2 g of KHS, and 7.6 g of water (bonded to a hydrate) are placed in a flask and stirred by injecting nitrogen under the liquid surface to the bottom. The flask is heated with a mantle heater and steam is injected into the flask contents. Steam outflow is initiated when the liquid temperature is about 120 ° C. The upper steam is sent to a cold water condenser and the condensate is collected from the flask. In operation, the methane-water condensate is periodically returned from the water cooled condenser to the steam generator. Periodically remove and analyze hydrocarbon condensate (oil) at different oil temperatures. The non-condensed vapor is passed through a 0.5 mole KOH solution (all H ₂ S removed), water scubaber (methanol removed) and isopropanol-dry ice bezel (some light hydrocarbons removed) in 100 ml of methanol. The analysis of crude oil and its output fraction is as follows.

There is no hydrocarbon residue in the reaction flask and the condensate from the cold trap is 22 ml.

This data represents the hydrogenation, denitrification, and desulfurization processes. All output fractions contain more hydrogen than crude oil and less nitrogen and sulfur than crude oil.

Example 2

200 ml of Alaska crude oil is treated in the same manner as in Example 1 except that the steam outflow is started at 135 ° C. and no cold trap is used. The analytical values for crude oil and outputs are as follows (no oil residues are present in the flask).

Example 3

175 g of Trinidad crude is treated with 30 ml of a methanol reactant solution containing 11.4 g KHS and 5.7 g water (bound to hydrate). Due to the high content of naphthenic acid, this oil is likely to be degraded by water. Therefore, a minimum amount of steam is used (the steam generator is kept at sea level at 99 ° C.) and gaseous hydrogen is also added. Analytical values of crude oil and product are as follows.

Because of the device arrangement, hydrogen cannot be supplied sufficiently to the bottom of the reaction flask to contact the bottom one material; Therefore, 20% residue remains.

Example 4

40 ml of methanol solution containing 150 g of crude Arab crude oil, 2 g of sulfur, 15.6 g of KHS, and 7.8 g of water (bonded with a hydrate) were added to the reaction flask and proceeded as in Example 1, and the vapor flow started at 130 ° C. do. The analytical values of the crude oil and the collected output products are as follows.

Example 5

Put the residue under reduced pressure (calculated at the initial boiling point under reduced pressure at 593 ° C) and methanol solution of KHS (0.47 g KHS / ml solution) into the flask. After heating the contents from ambient temperature to 170 ℃ and stirring the contents with nitrogen supply, when the temperature reaches 170 ℃, the nitrogen supply is stopped and steam is released. This operation is stopped when the temperature of the residue reaches 400 ° C., with the remaining residue in the flask being 51% of the original charge. Analytical values of the residue and the two distillates are as follows.

Example 6

The reduced pressure residue oil of Example 5 was again treated with a KHS reactant and stirred while supplying hydrogen up to 240 ° C. at ambient temperature. The vapor flows out at 170 ° C. This action is stopped at 425 ° C, with the remaining coke content in the reactor reaching 9% of the original residue. Analytical values of the residue in the flask and the two distillates collected are as follows.

Chromatographic analysis of the non-condensable gas stream indicated that 30.52% of hydrocarbons were contained and the analysis is as follows.

The remainder of the gas stream (69.48%) is considered to be air in the gas chromatography tube. Condensate distillates are very light and lighter than # 2 heated oil or diesel fuel. In addition, the absence of a precipitate containing an alcohol solution of KOH in the effluent gas scubaber indicates that little carbon dioxide is produced in the reactor.

Example 7

150 ml of vacuum residue and a methanol solution (0.477 g KHS / ml solution) 22 containing KHS hydrate were added to the reactor and heated. Nitrogen agitation from ambient temperature to 190 ° C, stops the nitrogen supply at 190 ° C and starts outflow. A single feed is collected and maintained at 100 ° C. to remove water. Hydrocarbons that do not distill with water are referred to as "100-425 ° C fractions" and hydrocarbons that are distilled with water are referred to as "oils below 100 ° C". The analytical values of the residue and the two hydrocarbon products and the residue in the flask are as follows.

Example 8

Example 7 is repeated, using hydrogen instead of nitrogen from ambient temperature to 425 ° C. Finally, the same amount (20 g) of residual oil as in Example 7 remains in the flask. The analysis values of the residue and the single distillation are as follows.

Example 9

160 ml of the reduced-pressure residue oil of Example 7 and Example 8 and 25 g of commercially available NaHS flakes were placed in a reaction flask. Methanol is added to the steam generator. It stirs, supplying hydrogen, and supplies steam from 220 degreeC. The analysis results are as follows.

Example 10

Add cracking residue and alcohol solution (0.47g KHS / ml solution) of KHS hydrating agent to the reaction flask. Nitrogen agitate from ambient temperature to 190 ° C, stop supplying nitrogen at 190 ° C, and start outflow of steam. Finally, 13.3% of the residue remains in the flask. A single distillate is maintained at 100 ° C. to vaporize the condensed water. Hydrocarbons vaporized with water are recovered and dried and named as oil fractions below 100 ° C.

The analysis results are as follows.

Example 11

Example 10 is repeated using hydrogen instead of nitrogen. Use hydrogen up to 450 ° C from ambient temperature and use a minimum amount of steam. The analysis results are as follows.

Example 12

Place commercially available NaHS flakes directly into the reactor and repeat Example 11. Methanol is then added to the steam generator. NaHS flakes are originally in hydrate form. The analysis results are as follows.

Example 13

125 ml of cranked and desulphurized residue, 1.8 g of sulfur, 25 ml of ethanol solution (0.24 g KHS / ml solution) of KHS hydrate are placed in a flat bottom flask, and the flask is placed on a hot plate and a magnetic stir bar is added. Stir the flask contents and continue heating to 120 ° C. to remove ethanol and water. Start steam supply at 130 ° C and continue to 325 ° C. The analysis results are as follows.

Example 14

In this example, hydrogen sulfide is added to a two-stage reactor for the treatment of vacuum residue. 50 ml (0.38 g KHS / ml solution) of methanol solution of potassium hydrosulfide dihydrate are placed in a 1 L cylinder equipped with a mantle heater for the first stage reaction. 25 ml of the reaction solution is placed in a round flask of a step reaction equipped with a mantle heater.

The H ₂ S gas supplied in the first step is introduced under the liquid surface and injected into the supply pipe near the bottom of the container. Similarly, the upper steam from the first stage is supplied by the supply pipe to the monolithic surface of the second system. The steam from the second stage is cooled and partially condensed under a water cooler. First, several hundred grams of reduced-pressure residue oil is heated (to allow the residue to flow out) and placed in the addition vessel in the first reaction tank. Allow some of the residue to enter the reactor and heat both reactors. At the same time, steam, nitrogen and hydrogen sulfide are fed to the first stage reactor.

H ₂ S outflow cannot be measured, but was estimated at 3 g-mole / hour. As the reaction temperature of the first stage is increased, methanol and the hydrating substance added together with the reactant are distilled and enter the second stage. In the second stage, the condensation of water is 110 ° C. The reaction in the first stage starts at about 370 ° C. In the whole process, the temperature of the first step is increased from 370 ° C. to 390 ° C., and the reaction temperature of the second step is increased from 110 ° C. to 270 ° C. A total of 286 g of residue is added to the first stage and less than 10 g is finally left in the first stage. The analysis of the residue under reduced pressure and the product remaining in the secondary reaction stage and the product collected in the water cooler are as follows.

The final product has an initial boiling point of 23 ° C. and a maximum distillation temperature of 118 ° C. Non-condensing product vapor was estimated at about 35 g. The second stage and the final product were 17.4 and 50.4 API respectively compared to 6.0 of the vacuum residue at 15.4 ° C. The metal content is as follows (value is ppm and "N / D" indicates that nothing is detected).

Example 15

Shale oil is treated in a first stage reactor of Example 14 using methanol solution of KHS hydrate, vapor nitrogen, and no H ₂ S. The analysis results of the shale oil, the product, and the residue in the reactor are as follows.

The total amount of noncondensing volatiles is 43g. The metal content is as follows (value is ppm and "N / D" indicates no detection).

Example 16

The heavy crude oil of 10.5 degrees API at 15.4 ° C. is treated with reactants, steam and hydrogen sulfide using the process and apparatus of Example 14, using 100 ml of the reaction solution without the use of a second stage reactor. Single product is obtained at 370-390 ° C. The analysis results of crude oil and product are as follows. At the end, less than 2% of the crude oil remains in the reactor.

The product is API at 15.4 ° C. to 24.3 degrees with an initial boiling point of 110 ° C. and a final boiling point (97% recovery) of 360 ° C.

The metal content is as follows (value is ppm: "N / D" means no detection).

The scope of the present invention is added below to make the scope of the present invention clearer. The present invention provides an alkali metal hydrosulfide, an alkali metal monosulfide, and an alkali metal under conditions in which free water does not generate enough to decompose the reactants to produce a generally liquid hydrocarbon substance having an increased hydrogen content than the original carbonaceous material. A method of hydrotreating a carbonaceous material, characterized in that the carbonaceous material is treated with a reactant composed of a hydrate of a sulfur-containing compound made up of multiple compounds and mixtures thereof, and then subjected to hydrogenation, idcracking, denitrification or demetallization. to provide.

The present invention also includes heating the reaction vessel contents to a predicted temperature in the method, wherein steam is injected into the reaction vessel to maintain the reactants in hydrated form. The present invention also includes the above method wherein the alkali metal is sodium, lithium, potassium or rubidium.

The invention also includes a process wherein the alkali metal hydrosulfide in the above methods consists of potassium hydrosulfide and / or sodium hydrosulfide. The invention also includes a process wherein, in the above methods, hydrogen sulfide is also supplied to the reaction vessel. The invention also includes a method wherein the hydrogen sulfide produced in the reaction vessel is recovered and recycled back to the vessel. The invention also includes a method wherein the temperature of the carbonaceous material in the reaction vessel is about 40 to 410 ° C. and the pressure is about atmospheric pressure.

The invention also includes a method wherein hydrogen is also supplied to the reaction vessel. The present invention also includes a method characterized by feeding sulfur to the reaction vessel to control the ratio of sulfur to alkali metal. The invention also includes a method wherein the alkali metal is present in the alcohol solution.

The present invention also includes a method wherein the alcoholic solution is methanol, ethanol or propanol-1 solution. The present invention also includes a method comprising recovering a vapor containing hydrogen sulfide and a hydrocarbon from a reaction vessel and recovering the hydrocarbon from the recovered steam. The present invention also includes a method of using potassium hydrosulfide in a ratio of sulfur: potassium of 0.55 / 1 to 1.5 / 1 in a reaction vessel.

Claims (1)

For the production of hydrocarbons in liquid form with increased hydrogen content than the original carbonaceous materials, carbonaceous materials with reactants and vapors consisting of a hydrating agent of a sulfur-containing compound composed of an alkali metal hydrosulfide alkali metal monosulfide, an alkali metal polysulfide and a mixture thereof Hydrotreating under conditions where a large amount of free water is not produced in the reactor to carry out hydrocracking, denitrification, or demetallization.