DK143810B - PROCEDURE FOR HYDROCRAFTING OF AN ASPHALTIC CARBON HYDRAID CHARGE MATERIAL - Google Patents

Description

(19) DENMARK

i® (12) PRESENTATION (it) 11 * 3810 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 5133/72 (51) | nt.ci.3 C 10 G 47/06 (22) Filing day 17 · Oct. 1972 (24) Race day 17 · Oct. 1972 (41) Aim. available Apr 19 1973 (44) Submitted 1 Oct 2 1 981 (86) International application no.

(86) International filing day (85) Continuation day - (62) Master application no. -

(30) Priority Oct 18 1971, 190021, US Oct 18 1971, 190022, US

(71) Applicant UNIVERSAL OIL PRODUCTS COMPANY, Des Plaines, US.

(72) Inventor John George Gatsis, US: William Karl Theodore Gleim, US.

(74) Associate Engineering Company Budde, Schou & Co.

(54) Method of hydrocracking an asphalt-containing carbon = hydride charge material.

The present invention relates to a process for hydrocracking an asphaltene-containing hydrocarbon charge material for lower-boiling hydrocarbon products using a non-stoichiometric vanadium sulfide catalyst. More specifically, the present invention is directed to a combination process for continuous hydrocracking of bottom products from a distillation carried out at atmospheric pressure or v) under vacuum, crude oil residues, crude oils from which the most volatile parts have been removed. , petroleum extracts, crude oils extracted from tar sands and similar oils, all commonly referred to as S * "black oils" in the petroleum refining technique.

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These black oils contain high molecular weight sulfur-containing compounds in exceedingly large quantities and additionally excess amounts of nitrogen-containing compounds, high-molecular-weight organometallic complexes containing mainly nickel and vanadium, and asphalt-containing material. Asphalt-containing material is generally found to be complexed or bonded to sulfur and to some extent to the organometallic compounds. There is an abundant supply of such hydrocarbon material, most of which has a specific gravity at 15.6 ° C above 0.95. A significant amount has a specific gravity greater than 1.0. Black oils are usually characterized by a boiling range which shows that 10 V / Vol% (liquid volume percent) and usually more has a boiling point at normal pressure of over approx. 566 ° C.

In particular, the combination process of the present invention is directed to the hydrocracking of black oils for distillable hydrocarbon products. Specific examples of these black oils, illustrative of the types in which the present invention is particularly useful, include a bottom product from a vacuum tower having a specific gravity of 1.021 and containing 4.05% by weight S and 25.7% by weight asphaltenes, and a vacuum residue having a specific gravity of 1.009 and containing J>, 0 wt% S, 4.5ΟΟ ppm nitrogen and having a 20.0 V / V% distillation temperature of 568 ° C. The present invention enables for the first time hydrocracking of the majority of such material. This contrasts with refiners' previous experiences in processing this material. Thus, a typical known method of fixed mass could not treat such asphaltene-containing oils without a rapid deterioration in performance.

It is the object of the present invention to provide a more efficient method for hydrocracking heavy hydrocarbon material containing asphaltenes, in particular hydrocracking hydrocarbon-soluble asphaltenes for hydrocarbon-soluble, low-boiling normally liquid products, thereby obtaining continuous decontamination of black , unsupported non-stoichiometric vanadium sulfide catalyst with minimal catalyst deactivation.

Accordingly, the present invention provides a process for hydrocracking an asphalt-containing hydrocarbon charge material using a non-stoichiometric vanadium sulfide catalyst, the process of which is a) introducing a recycle stream obtained as described below. and comprises a solvent-low mixture of the catalyst and asphaltenes taken from a solvent extraction zone, and hydrogen in a conversion zone; b) in that conversion zone converts the stream with hydrogen at conditions selected to convert asphaltenes to lower boiling hydrocarbons; (d) introducing the residual, normally liquid portion of the effluent stream, including the vanadium sulfide, into the solvent extraction zone, and in this, the liquid portion deasphalting to provide a solvent-rich, normally liquid phase and a solvent-low mixture comprising non-stoichiometric vanadium sulfide and asphaltenes as the recycle stream; and (f) separating solvent from the solvent-rich stream from step (d), which solvent is preferably recycled, and recovering hydrocracked product.

In one embodiment, fresh feed material enters the reactor, the reactor effluent is deasphalted, and the solvent-poor fraction generated by the deasphalting is recycled to the reactor.

In another embodiment, the feedstock for the process is first deasphalted, then the solvent-containing asphaltene-containing fraction is charged to the reactor and the reactor effluent is recycled to the deasphalting means.

Particular embodiments relate primarily to operating conditions and the selected solvents used in the solvent extraction zone.

The basic idea involving the use of unsupported non-stoichiometric vanadium sulfide as a catalytic agent for the conversion of asphaltene-containing hydrocarbon-containing black oils is described in U.S. Patent No. 3,558,474. As disclosed in this patent 4,143,810, the non-stoichiometric vanadium sulfide exhibits an unusual degree of activity with respect to asphaltene conversion, while simultaneously eliminating a significant amount of the sulfur-containing and nitrogen-containing compounds. This patent does not disclose solvent desalination.

The examples given in U.S. Patent No. 3,558,474 employ all very large amounts of non-stoichiometric vanadium sulfide · precursor mixed with the reaction zone charge material. Example 5 of this patent shows the use of 832 g of vanadium tetra sulfide added to 1200 g of black oil. As one skilled in the art will recognize, it is not commercially profitable to put such exceedingly large amounts of any vanadium compound into a black oil.

In an attempt to reduce the exceedingly large amounts of vanadium compounds necessary in the practice of the invention of U.S. Patent No. 3 * 558,474, an attempt was made to recycle some of the catalyst and allow this recycled catalyst to replace the addition of vanadium tetra sulfide. The above patent specification does not disclose a method for catalyst recycling. Reactor discharge stream is sent to a hot flash evaporator separator, VLS, which is maintained at the reactor zone temperature but at a lower pressure. VLS liquid is recycled for combination with fresh hydrocarbon charge or the vanadium catalyst from this stream is recovered by filtration or treatment in deposition tanks or a series of centrifuges.

Both direct recirculation of VLS liquid as well as catalyst recycle recovered from this liquid by conventional methods were attempted. In each case, the catalyst activity was reduced by recycling.

This was a confusing phenomenon. The catalyst precursor was decomposed into non-stoichiometric vanadium sulfide. This catalyst worked well the first time it passed through the reactor, but its activity decreased by recycling. A chemical analysis of the catalyst showed that there was no change in composition. Furthermore, all the process conditions remained the same during the test.

It was postulated that some change in the physical form of the catalyst may have caused the decrease in activity. A microscopic analysis of the recycled catalyst confirmed that this was the problem.

Upon recirculation, the catalyst agglomerated into larger and larger particles. There was also found to be a build-up of carbonaceous material on the catalyst. These factors apparently reduced the effective surface area of the catalyst, which, as a result, decreased the reactor performance. Apparently, an almost colloidal dispersion of the catalyst is required for efficient conversion of black oils. Unfortunately, conventional methods for obtaining colloidal catalyst dispersions in a black oil could not be used in this process. A simple physical stirring of the catalyst in the oil left the agglomerated particles virtually undiminished in size. It would have been prohibitively expensive to buy and operate other mechanical means to achieve such colloidal dispersion, especially on a commercial scale.

At the same time, attempts were made to remove the carbonaceous material from the catalyst. Washing the catalyst with a "white oil" had little effect on the carbonaceous material.

Eventually, a resort was found. It appeared that asphaltenes not only removed some of the carbonaceous material, but that the asphaltenes also acted as support material for the catalyst. Surprisingly, the asphalene absorbs or adsorbs the catalyst, greatly increasing its surface area. Furthermore, the asphaltenes act as reasonably good solvents for the carbonaceous material observed on the catalyst. It is not known exactly why asphaltenes are so favorable to the catalyst recycling, but real improvements have been established. Thus, it is now possible to operate a slurry process for converting black oils economically if a deasphalting zone is operated in connection with the slurry process.

The deasphalting zone may be in either "countercurrent" or "co-current" relative to the slurry reactor depending on the feedstock and the variable operating factors. The terms "countercurrent" and "co-current" are used somewhat loosely because, as far as the catalyst is concerned, there is always a flow from the slurry reactor to the deasphalting means to the slurry reactor.

In one embodiment, the deasphaling method is countercurrent to the slurry method. Feedstock for the slurry reactor consists of the asphal ten-rich, solvent-poor fraction of the deasphalting means. The liquid discharge stream from the slurry reactor is then returned to the access to the deasphalting means. This flow system results in a slurry reactor of minimal size, although this is somewhat offset by an increase in the size of the deasphalting means which processes both the fresh feed and the liquid discharge stream from the slurry reactor. This flow is preferred whenever the charge material 6 may be subjected to such processing. Unfortunately, certain crude oils, e.g. Venezuelan crude oil, so many metals and so much asphalt-containing material that conventional deasphalting operations produce a product still unsuitable for further processing in conventional units.

Conventional units with fixed masses, e.g. desulphurisation units, can tolerate up to approx. 50 ppm metals or vanadium in the feed, and in some cases even above. If the feedstock contains more metal than this, it cannot be treated directly over the fixed mass of desulfurization catalyst. Deasphalting removes approx. 2/5 of the metal, so that black oils containing up to approx. 150 ppm metal can be deaphalted to produce an asphalt-free fraction which can be subjected to further treatment.

Deasphalting alone results in a great loss of liquid product because most deasphalting processes remove almost a volume of heavy oil for each volume of asphalt removed. The present invention, where the deasphalting zone is countercurrent to the reactor, enables the production of a low metal asphalt-free oil in a yield of approx. 100 V / Vol- ^. Furthermore, due to the activity of the recycled asphaltenes in "stealing" metals from the fresh feed charge, the deasphalting zone can remove up to 3/2 of the metals in the feed rather than 2/3, as is the case with conventional units.

If the black oil feedstock contains extremely large amounts of metal, neither conventional deasphalting nor deasphalting followed by slurry treatment of the asphalt fraction produces an oil of tolerable metal content. In these cases, it is necessary to pass the black oil material through the slurry reactor prior to the deasphalting, in order to benefit from the metal removal activity of the slurry process.

These results are summarized below: 7 143810 ppm Metal in the feed Preferred processing steps__ 0-50 Can be processed in conventional fixed mass units.

50 - 150 Treated in units with fixed mass without de-escalation only with great difficulty. Deasphalting enables treatment with fixed mass of an asphalt-free oil, but with large volume loss due to deasphalting.

50 - 250 Optimal range for use of deasphalting followed by slurry reactor.

25Ο + Slurry reactor followed by deasphalting is necessary.

(0 to 25Ο) (As above, if a product with very low metal content, i.e. slurry followed by deasphalting is desired).

Thus, it is still possible to practice the present invention with the deasphalting zone countercurrent to the slurry reactor in some cases where deasphalting alone would not work. The recycled asphaltenic material from the slurry reactor in some cases acts as a "thief" and steals some of the metals from the feedstock that would otherwise remain in the solvent-rich fraction from the deasphalting zone.

For the treatment of raw materials of extremely high metal content or to obtain a product with the lowest metal content, operation with the slurry reactor in countercurrent to the deasphalting zone is preferred for better metal removal. Thus, the crude fraction for the process is first fed to the slurry reactor and then to a deasphalting zone. The solvent-rich product phase from the deasphalting step has a very low vanadium content and can be treated without difficulty in conventional fixed mass units. The practice of the present invention is still necessary because the catalyst must be reused. Deaphalization of the slurry effluent stream ensures that there is a fine dispersion of catalyst in the asphalt phase from the deasphalting means. This asphal phase is then recycled to the approach to the slurry reactor.

A further economic advantage of this specific slurry process consists in converting the metals present in the oil into catalyst.

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If other metals were used as catalyst, e.g. Mo, and if it was not possible to convert the metals in the oil to catalyst, a large portion of the bottom fractions of the deasphalting means had to be branched continuously into a large catalyst regeneration unit.

This catalyst regeneration unit was to consist of a large costly inorganic metal refinery where the residual oil was first dissolved from the catalyst and the catalyst then liberated for Ni, Pe and V followed by regeneration.

In practicing the present invention, it is no longer necessary or desirable to achieve $ 100 conversion per asphaltene - passage. Because the asphaltenes are recycled, it is now possible to settle for a smaller conversion per passage and yet still achieve nearly $ 100 conversion of asphaltenes entering the system.

Although operating to achieve nearly $ 100 conversion per passage is possible and approximately obtained according to U.S. Pat.

5.558 · 474 on the basis of passage once again, it is to be avoided in the practice of the present invention. Conversion of from $ 15 to $ 85 per passage of asphaltenes ensures that there is sufficient asphalt material in the slurry outlet stream to maintain catalyst activity and also to prevent excess amounts of asphaltenic material. The exact amount of conversion per passage desired at any given installation depends on the characteristics of the black oil being treated, as well as on the efficiency and type of the deasphalting unit used.

It is to be recognized that the prior art is full of a wide variety of techniques for solvent implementation - deasphalting of asphalt-containing hydrocarbon resin materials.

For the sake of brevity, no attempt is made here to depict the solvent-deasphalting technique exhaustively.

Suitable liquid deasphalting solvents include condensed, normally gaseous hydrocarbons such as propane, n-butane, isobutane or mixtures thereof, and ethane, ethylene, propane, propylene, n-butylene, isobutylene, pentane, isopentane and mixtures thereof.

A particularly preferred solvent-deasphalting operation uses butane or pentane in a solvent-to-oil ratio of about 4: 1 and at a temperature of approx. 5 or 6 ° C below the critical temperature of the solvent.

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The concentration of non-stoichiometric vanadium sulfide in the charge to the reactor is preferably at least approx. 1/2 weight percent, calculated on an elemental vanadium basis. Use of smaller catalyst results in extremely low conversion per passage of the asphalt. Concentrations in excess do not appear to improve overall performance, not even with highly contaminated charge materials with a particularly high asphalin content. Therefore, the upper limit of the vanadium sulfide is approx. 25% by weight.

The colloidal slurry of catalyst and charge material is mixed with at least approx. 35 ° volume of hydrogen at 15 ° C and 1 atm per minute. volume of charge material at 15 ° C. Operation with less hydrogen circulation than this amount produces very poor results. In the preferred operation of the slurry flow process, the hydrogen bubbles up through a continuous liquid phase. Due to the presence of a continuous liquid phase, it is conceivable that only the hydrogen partial pressure in the reaction zone is significant, but this is not correct. Hydrogen transfer to the liquid is to some extent diffusion-limited. Thus, some minimum amount of hydrogen bubbling through the liquid slurry seems necessary. Operation with less than the above-mentioned minimum saturated hydrogen circulation produces extremely poor results. Operating at 1000-2000 Vol / Vol is preferred and approx. 13ΟΟ Vol / Vol seems to be optimal at the commonly used pressures. Use of more hydrogen than 2000 Vol / Vol is not harmful, but does not appear to improve the operation of the process. Compression costs become exceedingly large with hydrogen circulation failure exceeding 10,000 Vol / Vol, so that 10,000 Vol / Vol is an upper limit on hydrogen circulation in practice.

The reaction zone pressure can range from approx. 25 to approx. 500 atmospheres. Higher pressures tend to favor the hydrogenation reactions that occur. Higher pressures also to a certain extent reduce the capital and operating costs of the recycled hydrogen compressors frequently used in the process. Unfortunately, higher pressures require a more solidly constructed reaction vessel.

Although the reactions carried out are predominantly exothermic, the temperature of the exit stream from the reaction zone is significantly higher than the inlet temperature. Furthermore, a minimum temperature of approx. 300 to approx. 400 ° C for the reaction to take place. Inlet temperatures above 435 ° C should be avoided because higher temperatures favor dehydrogenation over hydrogenation.

ιη 143810 ίο

For example, simply heating cyclohexane to 350 ° C will generate benzene and hydrogen, even if no catalyst is present. Higher temperatures generally increase the reaction rate, but this is offset by an unfavorable change in equilibrium. For the same reasons, the residence time in the reaction zone and the inlet temperature should be such that the outlet temperature is not higher than approx. 500 ° C. Although useful results are obtained at a maximum reaction temperature of 500 ° C, a preferred operating method limits the maximum reaction temperature to approx. 450UC.

Although the present process can be carried out in an elongated reaction zone where the slurry and hydrogen are introduced into its upper part and the discharge stream is removed from a lower part, an upward flow system is preferred. A major advantage lies in the extremely heavy part of the charge material, especially the part having a boiling point at normal pressure of over approx. 566 ° C, has a noticeably longer residence in the reaction zone, which facilitates the conversion of this heavy fraction of the charge.

The slurry reactor effluent stream, including the vanadium sulfide catalyst and unreacted asphaltenes, is introduced into a suitable separation system from which a hydrogen rich gaseous phase is recovered, preferably for recycling to the slurry reactor feed. The hydrogen separation system is not considered to be an essential feature of this combination process. It may consist of one or more containers from which hydrogen and other normally gaseous streams are extracted separately. The normally liquid portion of the product effluent, including again the vanadium sulfide catalyst and unreacted asphaltenes, is preferably introduced into the upper portion of a solvent deaphalting zone where it contacts countercurrently with a suitable selective solvent introduced into the lower portion thereof. The solvent deasphalting zone can also process the entire feed stream for the process. Thus, the feed material for the deasphasing means may consist of fresh feed material and liquid discharge stream from the slurry reactor.

The solvent deasphalting zone operates at a temperature of from ca. 10 to approx. 300 ° C, preferably from ca. 35 to approx. and the pressure is in the range of ca. 5 to approx. 75 atm, preferably from 15 to 40 atm. The precise operating conditions generally depend on the physical characteristics of the feed material for the deasphalting means as well as the solvent selected. Generally, the temperature and pressure are chosen such that the deasphalting takes place in the liquid phase and ensures that all the catalyst particles are removed in the solvent-heavy, heavy phase. Suitable solvents include ethane, methane, propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, heptane and the like hydrocarbons. Similarly, the solvent may be a normal liquid naphtha containing hydrocarbons having from ea. 5 to approx. 14 carbon atoms per and preferably a naphtha fraction having a final boiling point of less than ca. 95 ° C.

The solvent-rich, normally liquid phase is introduced into a suitable solvent recovery system, the design and conditions of which are thoroughly described in the prior art. Similarly, the solvent-poor, asphaltenic phase is introduced into the slurry reactor. This is true regardless of whether the deasphalting zone is in the "countercurrent" or "co-current" of the slurry reactor. Black oil conversion is found to be favorably affected when carried out in the presence of hydrogen sulfide. Therefore, it is within the scope of the present invention to include from ca. 2.5 to approx.

25.0 mole percent hydrogen sulfide in the hydrogen entering the storage reactor.

An embodiment is shown in the drawing by means of a simplified flow diagram illustrating the practice of the present invention with the "co-flow" deasphalting zone of the slurry reactor.

Charge material in line 1 is mixed with the recycle hydrogen from a line 2 and the supplemental hydrogen from a line 5 asphaltenes are withdrawn from the reactor 5 via a conduit 6 and introduced into a suitable hydrogen separation system 7. Normally liquid reactor discharge stream, e.g. Hexane and heavier hydrocarbons, including vanadium sulfide catalyst and unreacted asphaltenes, are withdrawn from hydrogen separation zone 7 via a conduit 8 and introduced through it into the upper part of a deasphalting zone 9 ·

A suitable selective solvent, e.g. n-butane, is introduced into the lower part of the deasphalting means 9 via a conduit 10, 12, 143810

Supplementary solvent can be added to line 10 via line 11. The solvent-rich, normally liquid material withdrawn from the upper part of the deaphalting means 9 via line 12 is introduced into a solvent recovery system lj5 where the solvent is recovered and recycled via line 10. liquid product outlet stream is withdrawn from the process via line 14.

The precipitated vanadium sulfide catalyst and unreacted asphaltenes are withdrawn from the deasphalting means 9 via line 4 and recycled for combination with the charge material and hydrogen. Since most black oil charge materials contain significant amounts of metals, primarily nickel and vanadium, which exist as metallic porphyrias, a branched stream is preferably taken out via line 15 and sent to a suitable metal extraction unit. This technique prevents the unauthorized build-up of metals in the system.

The hydrocarbon charge material used in these examples is a bottom fraction from a vacuum column with a specific gravity of 1.028, an initial boiling point of 286 ° C, a 10.0 V / Vol-fo distillation temperature of 144 ° C and a 24.0 V / Vol -% distillation temperature of 566 ° C. The batch material contains 13.3 weight percent asphaltenes, 4.88 weight percent sulfur, 0.48 weight percent nitrogen, 400 ppm vanadium and 70 ppm nickel, the latter being available as organometallic porphyrins.

EXAMPLE 1 In this example, which serves as comparative example 3, 200 g / ml is mixed. hourly charge material with 0.535 m / hour hydrogen, measured at 15 ° C and 1 atm, or approx. 2,680 Vol / Vol. 17.0 mole percent hydrogen sulfide is present in the recycle gas. The reaction zone pressure is 205 atm and the maximum temperature in the reaction zone is 443 ° C. The normally liquid portion of the product exit stream is deaphalted with propane at a temperature of 67 ° C and a pressure sufficient to maintain liquid phase operation.

Approx. 3.2% by weight catalyst to convert a crude oil with a specific gravity of 1.008 from which the most volatile parts have been removed. The crude oil contains 10.53 weight percent asphaltenes, 2.80 weight percent sulfur and 578 ppm metals. The vanadium sulfide catalyst is treated to remove all benzene-soluble material and asphaltenes and the asphaltene-free catalyst is reused twice. The results are listed in Table I.

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Table I

Treatment; of crude oil, from which the most volatile parts are f, the iron.

product Features

Experiment No. Specific Density Weight # Asphaltenes Weight # S

1 0.937 0.19 0.95 2 0.948 2.01 1.49 3 0.955 2.40 l, 8l

The catalyst deactivation is quite evident. In Experiment # 3, specific gravity increased to 0.955, residual asphaltenes increased to 2.40% by weight, and 1.8% by weight of S remained in the product.

The batch material is then changed to be the bottom fraction described above from a vacuum column. 7.9% by weight of vanadium sulfide catalyst is recycled four times after removal of benzene-soluble material and residual asphaltenes. Table II below shows the results of the last three recycling operations.

Table II

Treatment of Bottom Fraction from a Vacuum Column Product Features

Experiment No. Specific Density Weight # Asphaltenes Weight # S

4 0.947 1.74 1.62 5 0.942 1.74 1.73 6 0.937 1.70 1.79

The catalyst deactivation is particularly noteworthy with regard to the concentration of the remaining asphalt. With the fresh catalyst, more than 99 # of the crude asphaltenes are converted, while the above numbers indicate approx. 87 # asphaltene conversion.

Example 2 In the next test series, the catalyst concentration is reduced to 2.8 - 3.5% by weight, calculated as elemental vanadium, and tem. the temperature is lowered to approx. 425-430 ° C. The only other operational change 14 is in accordance with the present invention, where the catalytic vanadium sulphide is immediately recycled from the deasphalting means with the unreacted asphaltenes.

The vanadium sulfide catalyst is reused twice. The catalyst concentration in the first experiment (7) is 3? 5% by weight and in the two recycling experiments (8) and (9) 2.8% by weight. The results are given in Table III below.

Table III

Processing of a Bottom Fraction from a Vacuum Column Product Properties

Experiment No. Specific Density Weight- ^ asphal tener Weight -j ^ S

7 0.958 0.05 2.07 8 0.940 0.17 2.48 9 0.940 0.09 2.12

These results clearly show the benefits provided by using the combination process of the present invention and the results are quite unexpected considering that the catalyst concentration has been reduced from 7.9 to 2.8% by weight.

In a subsequent example, the process flow system is modified in accordance with another embodiment of the present invention.

The batch material is first deasphalted, and the solvent-poor, asphaltenic fraction is sent to the conversion zone alone.

The conversion zone discharge stream is sent to a hydrogen separation system. Normally liquid discharge stream is then recycled to the approach to the deasphalting zone which processes the charge material. Thus, the deasphalting zone depletes both the charge material and the reactor discharge fluid. Asphaltenes converted in the conversion zone are recovered as a product in the solvent-rich phase recovered from the deasphalting means.

Example 3

The charge material, which is a bottom fraction from a vacuum column as described above, is mixed with unreacted asphaltenes and non-stoichiometric vanadium sulfide and subjected to n-butane deasphalting at a temperature of approx. J0 ° C and a pressure sufficient to maintain operation 1 liquid phase. Ca. 70 V / Vbl- $ of the original charge material is removed in a solvent-rich phase and introduced into a suitable solvent recovery system. The remaining components of the heavy oil, precipitated asphaltenes and non-stoichiometric vanadium sulphide, in an amount of approx. 3.0% by weight of elemental vanadium is introduced into the lower part of a reaction zone maintained at a maximum temperature of approx. 425 ° C and a pressure of ea. 205 atm. The batch is mixed with a hydrogen-rich gas to provide approx. 3000 Vol / Vol. This gas contains approx. 15.0 mole percent H2S.

After separating the reaction product effluent stream to recover hydrogen for recycling to the reaction zone, the liquid is mixed with fresh hydrocarbon charge material and introduced into the solvent-desphalation zone. 100 hours of operation a branched current of approx. 10 V / Vol- $ of the reactor liquid effluent stream and sent after removal of hydrocarbon soluble products to a metal recovery system.

Analyzes of the normally liquid product, viz. the asphaltene-free phase from the deasphalting zone and including hydrocarbon recovered from the branched stream when used indicates a recovery of the initial catalyst activity. At about. 50 hours of operation, the concentration of the remaining asphalt is approx. $ 1.25, at 142 hours of operation it has dropped to approx. $ 0.50, at 175 hours of operation, the remaining amount of asphalt amounts to approx. $ 0.25, and after approx. 200 hours the concentration is approx. 0.10 $,

The foregoing clearly shows the method by which the present invention is carried out, as well as the advantages provided by its use. The liquid product of the present invention is practically asphalt-free and greatly reduced in terms of metal content, and it is an ideal batch material for subsequent treatment in hydrodesulfurization or hydrocracking units with fixed mass.

Claims (3)

16 143810 A process for hydrocracking an asphalt-containing hydrocarbon charge material using a non-stoichiometric vanadium sulfide catalyst, characterized in that a) introduces a recycle stream obtained as described below and comprises a solvent-poor mixture of the catalyst extracted from the asphaltene and the asphaltene catalyst. and hydrogen in a conversion zone; b) in this conversion zone, the stream converts hydrogen with conditions selected to convert asphaltenes to lower boiling hydrocarbons; c) separates a hydrogen-containing stream from the conversion zone exhaust stream; d) introduces the remaining, normally liquid portion. of the effluent stream, including the vanadium sulfide, in the solvent extraction zone and in it the deasphalts the liquid portion to provide a solvent-rich, normally liquid phase and a solvent-low mixture comprising non-stoichiometric vanadium sulfide and asphaltenes which e) introduces the asphalt-containing hydrocarbon charge material into the circulation system by mixing this material with at least one stream selected from (1) the recycle stream for steps a) and (2) the normally liquid portion of the conversion zone exhaust stream, and f) separating solvent from the solvent-rich stream. step d), which solvent is preferably recycled and recovered hydrocracked product. Process according to claim 1, characterized in that the ratio of hydrogen to hydrocarbon in the conversion zone is from approx. 350 to approx. 10,000, preferably from ca. 1,000 to approx. 2,000 volumes of hydrogen at 15 ° C and 1 atm. volume of hydrocarbon at 15 ° C, the reaction zone pressure is from about 5 to approx. 75 atm, preferably from 15 to 40 atm, and the reaction zone temperature is from approx. 300 to approx. 500 ° C. Process according to claim 1 or 2, characterized in that the non-stoichiometric vanadium sulfide, calculated