JPH05501829A - High activity slurry catalyst method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] High activity slurry catalyst method Mutual explanation of related questions This application is filed on July 5, 1990, U.S. Application Cir. No. 548.157, No. 19 U.S. Application Cir. No. 586,622 filed Sep. 21, 1990 and Jan. 1990 This is a continuation-in-part application of U.S. Ser. No. 621,501, filed on February 3rd.

This application is also filed in U.S. Application Serial No. 388,790, filed August 2, 1989. It is also a continuation-in-part application, which is a continuation-in-part application filed on August 29, 1983. No. 527.414 (currently a U.S. patent 4.557,821) is a continuation-in-part application. This application was also filed on September 3, 1988. It is also a continuation-in-part of U.S. Application Ser. No. 252.839, filed on , ■ Continuation in part of U.S. Application Cir. No. 941.456, filed December 5, 986. (now U.S. Pat. No. 4,857,496), filed August 2, 1985. In a continuation-in-part application of U.S. Application Ser. No. 767.767 (abandoned) filed on the 1st No. 527,414, filed August 29, 1983. (now U.S. Pat. No. 4,557,821) is a continuation-in-part application.

This application is also filed in U.S. Application No. 275,235, filed November 22, 1988. It is also a continuation-in-part application of No. 1, filed August 21, 1985. This is a partial continuation of Application No. 767.822 (abandoned), filed in 1983. The U.S. application circular filed on August 29, 1985 is National Application Circular No. 767.760 (currently U.S. Pat. No. 4,824.821), Makoha 1 Continuation-in-Part of U.S. Application Ser. No. 527,414, filed Aug. 29, 983; No. 767.768, filed August 21, 1985 (currently in U.S. Pat. Allow 4. 710. 486), also filed on August 29, 1983, Partial Continuation of Application Circular No. 527,414: and filed August 21, 1985. U.S. Pat. No. 767.821 (currently U.S. Pat. No. 4.762,812); , a continuation in part of U.S. Application Cir. No. 527,414, filed August 29, 1983. The present invention relates to crude oil, heavy crude oil and residual oil and refractory heavy fractions, FCC decane. The present invention relates to catalytic hydrogenation treatment of heavy hydrocarbon oils including heavy oils and lubricating oils.

The invention also applies to shale oil, oil derived from tar sands and oil derived from coal. It also concerns the hydroprocessing of oil. The present invention provides such a hydrocarbon supply. Catalysts for the hydrotreatment of raw materials, the use of such catalysts and the production of such catalysts It is related to construction.

No. 527.414, filed August 29, 1983 (currently in U.S. Pat. permission 4.557,821) In other words, in the parent application of this application, heavy oil is hydrotreated. A catalytic method using a circulating slurry catalyst was disclosed. The catalyst is aqueous ammonia reacting a and molybdenum oxide to form aqueous ammonium molybdate; produced by reacting it with hydrogen sulfide to form a precursor slurry. It contained a dispersion of molybdenum sulfide. The precursor slurry is mixed with feed oil, hydrogen and and hydrogen sulfide and heated under certain conditions.

Species of hydrogen sulfide expressed as SCF of hydrogen sulfide in one bond of molybdenum different dosages were taught to be useful in forming precursor slurries ( 3rd column). 2 to 83 CF/LB was preferred. (Column 4).

Slurry in the presence of both hydrogen and hydrogen sulfide to obtain an active slurry catalyst as a catalyst. It was found necessary to mix the oil with the oil (columns 11-12). then oil - The slurry mixture is heated with hydrogen and at least two temperatures (column 24) under certain conditions. and sulfided using hydrogen sulfide. Charge the watered feed and catalyst to the hydroprocessing reactor did. The introduction of water is important, as is the addition of nickel to the slurry catalyst (fourth (Columns 2 to 44), which are advantageous for certain purposes (Columns 26 to 2711).

No. 941.456, filed December 15, 1986 (currently filed in the U.S. patent 4.857.496) That is, the parent application of this application Supply a one-temperature sequence for one hour to complete the final catalyst production before flowing into the reactor zone. Sulfurization processes are described that have two or three heating stages.

Each sulfurization stage was operated at a higher temperature than the previous stage. Supplying ammonia was removed from an intermediate stage of catalyst preparation before addition and further sulfurization.

U.S. filed on August 21, 1985 and filed on August 29, 1983. U.S. Application No. 767.760, which is also a partial continuation of National Application No. 527.414 (now U.S. Pat. No. 4,824,821), after the sulfidation has finished, aqueous ammonia Group VIB metals such as nickel or cobalt are added to the compound. The promotion of rally catalysts is described.

U.S. filed on August 21, 1985 and filed on August 29, 1983. U.S. Application No. 767.768, which is also a partial continuation of National Application No. 527,414 (now U.S. Pat. No. 4,710.486) discloses that oxygen is combined with a Group VIB metal. intermediate temperature sulfidation stage by stoichiometric substitution of 50-95% with sulfur. describes specific adjustments to the amount of sulfidation that occurs in the floor. to sulfur at high temperature stage. At least three stages of sulfidation were preferred with respect to additional replacement of oxygen by.

U.S. filed on August 21, 1985 and filed on August 29, 1983. U.S. Application No. 767.821, which is also a continuation-in-part of National Application Circular No. 527,414 (currently U.S. Pat. No. 4,762.812) describes a method for recovering spent molybdenum catalysts. is listed.

The parent application of this application, U.S. Application No. 275, filed on November 22, 1988, No. 235 is heavy oil or at least o, 1 cc/g, pore radius range or 10~ Group VrB for hydroprocessing of residual oils with a pore volume of 300 angstroms A metal sulfide slurry catalyst is described. U.S. Patent 4,376.037 and U.S. Pat. In National Patent No. 4,389,301, heavy oil is treated with additives of porous solid contact particles. The presence of the pond in the presence of an added and dispersed hydrogenation catalyst suspended in the oil Hydrogenation in one or two stages by contacting with hydrogen. For two-step conversion The liquid product of the first stage is usually hydrogenated in a catalytic hydrogenation reactor. distributed dispersing the prepared catalyst in an oil with a water-soluble salt of one or more transition elements; It can be added as an oil/water emulsion prepared by. Porous contact particles are Preferably alumina, porous silica gel and natural or treated clay etc. It is a cheap material. Examples of suitable transition element compounds are (NH4)2MOO4, Ammonium ptamolybdate and oxides and sulfurs of iron, cobalt and nickel Contains chemical substances. The second reaction zone has a packed bed or fixed bed; The entire feed of preferably passes upwards through the second zone.

In U.S. Patent 4,564.439, heavy oil is imported in a two-step, return-to-back process. Convert to fuel. The first stage is a dispersion with coke-suppressing activity and hydrogen. a hydrogen heat treatment zone for the feedstock mixed with demetalized contact particles; The stage is first a hydrogen catalytic reactor connected to the reactor. The aforementioned U.S. special The entire specification of the patent application is hereby incorporated by reference as if written by Petroleum. The need for refiners to utilize heavier and poorer quality crude feedstocks for their processing. is being discovered. As the need increases, the need also grows and rises in temperature. boils especially above about 1000°F and contains undesirable metals, sulfur and coke. those containing increasingly high levels of contaminants such as formation precursors. Processing a fraction of the inferior feedstock. These contaminants can be removed by conventional hydrotreating methods. The process considerably hinders the hydroprocessing of these heavier cuts. These hydrocarbons The most common metal contaminants found in elementary distillates are nickel, vanadium and iron. include. Various catalysts or hydrogen catalytic catalysts that tend to poison or deactivate those catalysts. Precipitate onto the medium. Furthermore, metals, asphaltenes and coke-precursors are It can fill the gaps in the media bed, reducing catalyst life and test time. Sara Asphaltenes also tend to reduce the susceptibility of hydrocarbons to desulfurization methods. . Such deactivated or blocked catalyst beds are replaced sooner.

As a practical matter, the test time in fixed bed residue desulfurization processes is limited by coke and/or metals present. Improved fixed bed performance, Catalyst life and improved 10'OO°F+ conversion plugs pores or The level of metal and coke precursors penetrating the catalyst pore volume containing the active catalyst moieties. can be obtained by reducing the number of

It would be beneficial to cure these problems with the least disruption and lowest cost. It will be. If, for example, a dispersed consumable catalyst is used, the catalyst It is effective at as low a concentration as possible in order to reduce the cost of treatment.

Low hydrogen to carbon ratio (i.e. less than about 1/8 by weight) and high carbon residue, Heavy oil characterized by contaminant content of sphaltenes, nitrogen, sulfur and metals If the parameters of the highly active slurry catalyst are known for the treatment of would be beneficial.

The performance of existing fixed bed reactors can be increased by the use of slurry catalysts. If so, that would also be beneficial.

Lube oil base stocks boil above about 500°F and below about 13,000F and generally It has a kinematic viscosity (measured at 100'C) of about 2C8 or higher. about 90 or more The above viscosity index is preferred (ASTM D 2270-86).

Lubricating oil base stocks are subject to modification, including methods such as hydrogen cracking or solvent extraction. It can be recovered from the waste zone as a distillate or a distillate fraction.

Lubricating oils generally made from hydrocarbon feedstocks boiling above about 1000°F The base material requires pretreatment prior to the remediation zone. One such pretreatment method The method is solvent deasphalting, which removes heavy hydrocarbonaceous components but also Otherwise, precipitates will form during lubricant processing. The use of these pretreatment methods is Adds additional pretreatment steps beyond the inventive method, leading to low yields of lubricating oil feedstock.

Distillates suitable for use as lubricant basestock feedstocks meet specific property specifications. It can be further processed as follows. Wax is removed to lower the pour point I can do it. Dewaxing can be accomplished by conventional methods known in the art, such as solvent dewaxing. or a catalytic membrane wax. The distillate recovered from the remediation zone is also Carbonization, which is further treated with a catalyst in the presence of hydrogen and undergoes oxidation during storage to form colored bodies. Hydrogen components can be removed.

Slurry catalyst method or heavy oil to produce lubricating oil base stock with high viscosity index. would also be beneficial.

Summary of the invention The present invention is produced by dispersing a slurry catalyst in hydrocarbon oil for hydrotreating. We supply highly active catalysts produced by The method involves fixed bed residual desulfurization, heating or Achieves higher nitrogen, sulfur, metal and residual oil conversions than existing slurry methods It has the advantage over conventional methods of

The method involves preparing an aqueous mixture of Group VIB metal compounds per bond of Group VIB metal. Contains hydrogen sulfide at a dosage of about 8 or more, preferably about 8 or more up to 143 CF. Sulfurize with gas to form a slurry, and heat the slurry with feed oil and hydrogen-containing gas It consists of mixing at elevated pressure. Moly per 12 SCF of hydrogen sulfide or 3 moles of sulfur Corresponds to about 1 mole of budene.

The present invention also provides an aqueous mixture of Group VIB metal compounds per bond of Group VIB metal. Slurry sulfurized with a gas containing hydrogen sulfide at a dosage of about 8 or more to 14 SCF and add the Group ■ metal compound to the slurry, and add the Group ■ metal compound to the slurry and the Group ■ metal compound. Dispersed Part V by mixing the product with feed oil and hydrogen-containing gas at elevated temperature and pressure. Also includes the production of Group IB metal sulfide catalysts.

High viscosity index lubricating oils are produced from heavy oils by our highly active slurry catalyst method. Ru. The lubricating oil produced has a surprisingly high viscosity index and good viscosity. our In the process, a highly active Group VIB metal sulfide catalyst slurry is added to the feed oil and An oil fraction boiling from the product at about 650°F in contact with hydrogen-containing gas at elevated temperature and pressure. Let's separate them and then explain them. The method also involves adding a Group I metal compound to the slurry. The slurry catalyst containing Group WB and Group II metals is supplied with oil and hydrogen. As a result, the feed oil is hydrotreated at a temperature of about 6500F. Preferably, the boiling product is separated from the lubricating oil base material and then defiltered. I will use it.

The lubricating oil fraction has a high viscosity index and good viscosity properties relative to the lubricating oil base material. .

Other methods using active catalyst slurries include heavy oil, active catalyst slurry and hydrogen-containing The gas is preferably heated upstream to said bed at a temperature greater than about 7000F under elevated temperature and pressure. In connection with the introduction of granular hydrodesulfurization-hydrodemetallization catalyst into a fixed bed or ebullated bed Consists of. Preferably, the Group I metal compound is added to the slurry prior to mixing with the heavy feed oil. Add.

Discrete porous contact particles can be added to the heavy oil feedstock.

In a two-stage process embodiment of the invention, heavy oil is added to the catalyst slurry in the first stage. and hydrogen at a temperature and time sufficient to achieve distillate pyrolysis in the product stream. touch The first stage distillate is then treated with a fixed bed or ebullated bed of desulfurization-demetallization catalyst. and hydrogen gas in a second step. The second stage catalyst bed promotes uniform metal deposition. can be divided into stages according to catalytic activity and/or temperature distribution in order to proceed. , and preferably the distillate stream flows up through the second stage catalyst bed. boiling floor smell Then, the catalyst is divided into stages using a staged reactor. In our method, metal is precipitated onto the slurry catalyst, and the catalyst is capable of absorbing low levels of the 1000°F fraction of heavy oil. Conversion rate provides demetallization profits.

Our method works well for heavy feed oils at 1000°F + when the conversion is less than 70%. It provides the advantage that the cous yield is less than about 1.0%. Conversion as high as 90% Even at low slurry catalyst concentrations (100-101,000 pp. The yield is below 2.5%.

Brief description of the drawing Figure 1 shows pretreatments with essentially the same ammonia to molybdenum ratio and varying degrees of shows the denitrification activity of various catalysts sulfided with Figures 2 and 3 are for sulfurization. Figure 2 shows an increase in denitrification rate constant and API gravity as a function of degree. Figure 4 shows the live This indicates that the molybdenum sulfide catalyst precursor that yields the aqueous gel is an aqueous gel. Ru. FIG. 5 illustrates the advantages of promoting active catalysts of the present invention using Group I metals.

Figure 6 shows the amount of coke produced by the present invention and coke produced by the competitive method. Coke yield (weight percent) versus amount of coke converted to lighter products Shown graphically as the amount of 1000°F fraction of the residue (volume percent) .

Figure 7 shows the percentage of vanadium metal removed from the residue by the present invention versus residue. The graph shows the 1000° F. fraction conversion rate.

Detailed description of preferred embodiments of the invention The activity of Group VIB metal slurry catalysts is a function of manufacturing conditions. Preferred Section VIB The group metal is molybdenum, but tungsten compounds are also catalytically useful.

Molybdenum is used herein for illustrative purposes or other Group VIB metal compounds. It does not exclude. The highly active slurry catalyst used in the present invention was developed in 1990. No. 548.157, filed May 5, the disclosure of which is incorporated by reference. and inserted it here.

In an improved method for producing molybdenum sulfide catalysts, acid The sulfidation of the aqueous solution formed by the pretreatment of molybdenum chloride is or hydrogen sulfide at a dose of at least 83 CF. This dose of sulfidation When hydrogen is used, the cleavage hydrogen of the hydrotreating process is present in the recycled gas stream. There is no need to In addition, the activation of the catalyst is It appears to be independent of the monia to molybdenum ratio.

High activity catalyst We determined that the activity of the final Group VIB metal catalyst converts the starting Group VIB metal into the final active catalyst. found that it is a special function of the activation conditions used to convert . In the following, we will exemplify and discuss our slurry catalysts by way of example and discussion. Mention is made of the preferred Group VIB metal, molybdenum and its compounds. However, I have mentioned Libden only by way of a preferred illustration; Other Group VIB metals and their compounds are not intended to be excluded.

As an improvement on the method of preparing the catalyst of the present invention, we used aqueous ammonia to activate the catalyst. per pound of molybdenum. It was discovered that this is caused by sulfidation with at least 8 SCF of hydrogen sulfide. . At this level of sulfidation, the cleavage hydrogen from the hydrotreating process is present in the recycled gas stream. There is no longer any need to do so. Further catalyst activation is used to form an aqueous mixture. This is achieved relatively independently of the ammonia to molybdenum ratio introduced.

sulfide The catalytic activity varies depending on the degree of sulfidation from about 8 or more to about 143 cF per molybdenum bond. This is achieved when hydrogen sulfide is used. This sulfidation dose is approximately 3 moles of sulfur to molybdenum. producing a catalyst precursor characterized by a ratio of of sulfidation in catalyst activation. The effectiveness is demonstrated in a first set of examples. In these examples, two tags Molybdenum oxide and aqueous ammonia under the same conditions and the same amount of ammonia It was produced by first reacting Monia. The aqueous mixture is then mixed with added oil. sulfided in the absence. Catalysts differ in the degree of sulphidation provided. first tie The sample was sulfided with hydrogen sulfide at a dose of 2.73 CF per pound of molybdenum. C-21). The second type of catalyst is more than 123 CF per pound of molybdenum. Sulfided with hydrogen sulfide (SC-25-2). Pre-treated with ammonia to remove these The conditions used to sulfidize the medium are summarized below.

Tables IA-IB are identical using both low sulfide catalyst 5C-21 and catalyst 5C-25-2. Compares the results of two tests conducted on the same feedstock under conditions. touch Medium Table IA conversion rate Catalysts sulfided at sulfidation doses higher than about 12 to 143 CF per bond of molybdenum The activity of the catalyst is higher or lower when tested in batch operation even with No. Table 1 shows the results of the pretreatment with essentially the same ammonia to molybdenum ratio. Denitrification activity of various catalysts presulfided with varying amounts of hydrogen sulfide is shown. . These pretreated and sulfided catalysts contain little sulfur without adding hydrogen sulfide. was screened in a batch reactor using a feed without in the absence of oil No further sulfurization of the catalyst except that carried out in the presulfidation step in won. The results shown in Table 1 are greater than 8 SCF per molybdenum bond. The criticality of sulfiding the catalyst with a dose of hydrogen sulfide is illustrated.

Ammonia pretreatment The catalyst was pretreated with 0.35 pounds of ammonia per pound of molybdenum. Manufactured without ammonia (ammonia to molybdenum ratio 0) in the solvent. A wide range of ammonia to molybdenum ratios were produced from a variety of materials. The result The result is that the catalytic activity is higher than that of ammonia versus molybdenum used to form the slurry catalyst. This shows that it is not related to the ratio of Ammonia to molybdenum ratio is approximately 0 ．． 16, a slight optimum condition is observed, but the catalyst is molybdenum oxide water. Even when the aqueous slurry is properly sulfurized without ammonia pretreatment, . However, pretreatment with ammonia provides better control of particle size than molybdenum oxide. This is preferably achieved when the densities are dissolved in aqueous ammonia.

Hydrogen sulfide requirements in hydrotreating Previous studies have shown that the partial pressure of hydrogen sulfide per bond of molybdenum is at least 20 ps i and hydrogen sulfide circulation is separated from the hydrotreating zone where the hydrogen sulfide circulation is greater than or equal to 53 CF. It was necessary to include a hydrogen-hydrogen sulfide cycle. However, in the present invention, oil In the absence of sulfur to hydrogen sulfide values of 8 or more to approximately 143 cF per bond of molybdenum. By increasing the amount of oxidation, active slurry catalyst is not only produced but also recirculated. The need for hydrogen sulfide to be present in the recycled gas stream is also eliminated.

Table ■ shows various tests conducted using both the low sulfide catalyst and the catalyst of the present invention. are shown and compared. As can be observed, stable and highly active catalysts obtained over a wide proportion of the hydrogen partial pressure and a wide proportion of the circulation at the inlet of the reactor. Ta. The active catalyst is sulfurized water from 271 psi to 3.5 per bond of molybdenum. An elementary partial pressure of 78-53 CF was obtained at any lower hydrogen sulfide.

Effect of hydrogen partial pressure on sulfidation In the examples described above, all catalysts are hydrogen sulfide contained in hydrogen gas. Sulfurized. I activated molybdenum sulfide catalyst where the sulfurization step is carried out in the absence of hydrogen. We have now shown that it can be manufactured if

To study this effect, a series of catalysts were tested with various sulfides in a hydrogen-free gas. Manufactured in doses. The catalyst was oxidized except that the sulfide gas stream contained no hydrogen. , produced with conventional sulfurization techniques described in the background section. 20 moles of sulfide gas % hydrogen sulfide and 80 mole % nitrogen. The resulting catalyst is in batch micro-activity units for their denitrification, hydrogenation and desulfurization activities Tested. The catalyst is heated under typical catalytic conditions while inserting a gas consisting of pure hydrogen. Tested. The results of this study were obtained using a catalyst sulfided under hydrogen partial pressure. It was compared to

Tables 2-3 show the increase in denitrification constant and API gravity as a function of the degree of sulfidation. are doing. Hydrogen sulfide and hydrogen sulfide with the same hydrogen sulfide composition as used in this study Similar results obtained using catalysts sulfided with mixtures of hydrogen gas also show that these Included in the table. The denitrification results showed that an active catalyst was obtained regardless of the hydrogen partial pressure. That's obvious.

In both cases, although active catalyst was produced, the activity of the slurry catalyst If the catalyst is prepared in the absence of hydrogen partial pressure, lower sulfidation dosages, i.e. 8 to 10 SCF of hydrogen sulfide per bond of budene occurred.

This value is based on the fact that it is in the presence of hydrogen partial pressure, that is, 12 to 14 S per molybdenum bond. When activated with hydrogen sulfide in CF, the sulfidation dose required to activate the catalyst It was slightly lower. Used to improve higher API gravity and liquid products The amount of hydrogen obtained was obtained using a sulfided catalyst under hydrogen partial pressure.

Ln　COm　m　el　m m el coΦmouth■ Effect of sulfidation on continuous operation We have demonstrated that the activation of slurry catalysts is based on ammonia molybdate and molybdenum oxide. It was shown that this occurs by sulfiding an aqueous solution or mixture. degree of sulfidation The activity increases as the degree increases. The highest activity is the degree of sulfidation or molybdenum 1 point. Approximately 123 CF of hydrogen sulfide per block was obtained. 1 pound of molybdenum Even with catalyst precursors sulfided at higher sulfidation doses than about 143 CF per The activity was neither higher nor lower when tested in the touch operation. batch o The effect of sulfidation dose on the activity of the system is important because the difference between It has been studied in continuous operation on quality oil.

Similar to the results in batch operation, the most active catalyst was either catalyst or molybdenum 1 lb. This occurred when the hydrogen sulfide was sulfided at a value of about 12 SCF per hydrogen sulfide. But batch Contrary to the results obtained in reactor studies, the activity of the catalyst system in continuous operation is The precursor is sulfided with hydrogen sulfide at a value of about 12 SCF per pound of molybdenum. was found to decrease according to

For catalysts pretreated with an ammonia to molybdenum weight ratio of 0.23, The initial gel formation is approximately 12 to 14 SCF of hydrogen sulfide per pound of molybdenum. Measuring happens. The effect of increasing sulfidation beyond this dose is due to the aqueous gelation of the catalyst precursor. It is to concentrate. By increasing the sulfurization operation beyond this dose, the sulfur It seems unlikely that it will be absorbed further. By what theory can we be controlled? Although not intended to limit or endorse the effects observed in continuous operations at high sulfidation doses Loss of activity is caused by larger particles produced at higher sulfidation doses It seems to be. As a result, loss of catalytic activity at high sulfidation doses is due to catalyst deposition and The reduction in reaction volume caused by the lower surface area of larger catalyst particles This is thought to be due to the small number of people.

composition The active catalyst precursor is characterized by a sulfur to molybdenum molar ratio of about 3; The final catalyst appears to be the active form of molybdenum disulfide. Catalyst precursor to final catalyst Decomposition of the material occurs under conditions typical of conventional side-walled heavy oil feed preheaters and No further sulfurization is necessary for activation. In addition, equilibrium calculations can be applied to slurry operations. Under the reactor conditions used, molybdenum disulfide is the preferred species. It shows.

The molybdenum sulfide catalyst precursor that yields the active catalyst is an aqueous gel (Figure 4); is an elastic agglomeration of ultramicroscopic particles or aqueous media in which they are dispersed and arranged in a network. Looks like a sex lump. Furthermore, the pH of the resulting aqueous precursor gel is within a wide range. Catalytic activity is independent of pH as it varies over a range of pH.

Optimal catalytic activity occurs when the catalyst precursor is sulfided at the point of initial gel formation. this Spreading sulfide on a dot plate produces a concentrated gel that is difficult to disperse in oil. The concentrated gel As water evaporates from the gel it tends to yield large xerogels, and the catalyst Transfer to oil. Large xerogels are produced from materials produced at the initial gel formation point. However, compared to those xerogels, they tend to generate larger solid particles. Kise A logel is defined as a gel that contains no or very little dispersion medium. Ru.

Promotion by Group ■ metals To enhance the denitrification activity of the active slurry catalyst of the present invention, the slurry is added to the feed oil and Adding the Group I metal compound to the slurry before mixing it with the hydrogen-containing gas at elevated temperature and pressure. is preferable. Such Group II metals are exemplified by nickel and cobalt. be done. The weight ratio of nickel or cobalt to molybdenum is approximately 1:100 to approximately It is preferable that the range is 1=2. The weight ratio of nickel to molybdenum is approximately 1:2. 5-1:1O or 4-10 weight percent promoter/molybdenum Most preferred. Group II metals, exemplified by nickel, usually form sulfates. preferably at a pH of about 10 or less, preferably about 8 or less. It is added to the slurry after sulfidation at a pl of less than or equal to pl. nitrates of group ■ metals; Carbonates or other compounds can also be used. Promotion of Group ■ metal compounds The advantages are illustrated in the examples below. The high activity of the slurry catalyst of the present invention From this point of view, further promotion by Group II metal compounds is very beneficial. .

To demonstrate the promoting effect of adding Group II metals to the sulfided catalyst, various amounts of Nickel and cobalt can be added to molybdenum as soluble nickel or cobalt sulfide. sulfurized catalyst gel and mixed.

The promoted catalyst then hydrotreats the nitrogen-rich and aromatic FCC circulating oil. By evaluating the ability of will be tested. Circulating oil is characterized by the following test results:

Feedstock inspection results FCC heavy circulating oil Figure 5 shows the promotion achieved by nickel on desulfurization and denitrification reactions. Ru.

Table ■ shows the crystallization from nickel and cobalt that promoted the active slurry catalyst of my invention. The results and operating conditions are summarized.

Table■ The present invention also provides low hydrogen to carbon ratios (i.e., less than about 1.8 by weight) and high carbon Heavy metals, characterized by their content of residual metals, asphaltenes, nitrogen, sulfur and metals. It also relates to the production of lubricating oil base materials from quality oil. Generally, heavy oil is about 65 The portion of crude oil that boils above 0°F. Heavy oils also boil above 1000°F. It is also those oils that contain 5% or more oil distillates. like this Examples of heavy oils are atmospheric and vacuum residues, asphaltene oils and heavy gas oils. Contains.

Catalyst to feedstock oil ratio The catalyst slurry/gel is pumped to the hydroprocessing reactor section where it is exposed to heavy oil. and in contact with hydrogen gas.

from about 0.05 to about 2.0% by weight molybdenum in oil based on the weight of the feedstock. It is preferred to use a highly active slurry catalyst system for lubricating oil production. Approximately 0 ．． Catalyst in oil concentrations of 3-2.0% are more preferred, with about 1% most preferred. concentration is used.

Hydrotreating The catalyst and heavy oil are brought into contact at elevated temperature and pressure. The mixture is heated at high temperature and under partial pressure of hydrogen. Usually about 775°F or above and a hydrogen partial pressure of about 700-4500 psi and preferably at about 830° F. and 2000 ps i, respectively. high It is under these conditions that levels of hydrogenation, demetalization, denitrification, desulfurization and conversion occur. It is. Conversion levels of up to 100% observed with conventional solids at equal catalyst-to-oil ratios. This is unexpected compared to what has been achieved in fixed bed technology. of these levels The conversion surprisingly produces the most important distillate product. In particular, 650° It is surprising that F+ products have unusually good lubricant properties. That is. A lubricating oil fraction boiling above about 650°F is separated from the product. Lubrication This fraction, which is ideally suited for the production of oil-based feedstocks, can then be processed.

Additional denitrification of this fraction can also be carried out, in which case it is It can also undergo hydrogenation finishing using techniques.

Let's take it off The products of highly active catalytic hydroprocessing are too also contains a lot of wax, i.e. has a low pour point, in which case our An absolutely necessary part of the law is the dewaxing stage. Dewaxing is solvent dewaxing or catalytic dewaxing. This can be done by conventional methods such as To promote catalytic dewaxing, Is there a need to remove additional nitrogen from the lubricating oil fraction, in which case hydrotreating or or utilized in a hydrofinishing step or incorporated into the overall process prior to dewaxing. Should.

The final product of this process has an unusually high viscosity index, especially in view of the nature of the feedstock. It was found that there may be. Traditionally, lubricating oil base materials are approximately 10 The method has a viscosity index of 0 or the number of It has been discovered that this can be surpassed.

Example■ To determine the suitability of a high activity slurry catalyst method for the production of lubricating oil base stocks. The method was applied to Hondo atmospheric resid feedstock. The feedstock is new The catalyst concentration in the oil was 1.1% by weight molybdenum based on the feed. catalyst was promoted using nickel at 10% by weight based on molybdenum.

The product is distilled to yield a C5-650°F product and a 650°F+ product. Ta. The 650°F+ product was evaluated as a lubricant basestock feedstock. Table ■ indicates the operation used. Contains a summary of conditions and yields obtained. Table V is feed and product testing The results are summarized. Table ■ summarizes the results from the lubricant test program .

Table■ Table V Feed <-----Product 1----> Hondo650°F + C5- 650°F650’F ten tables■ 1000°F - It is noteworthy that there was 100% conversion to product. be. Analysis shows high paraffins and low aromatics levels. The nitrogen content is Hydrofinishing may be necessary to remove product or nitrogen and provide good stability The clause indicates that it will be done.

When removing nitrogen, wax-rich oil is a good source for zeolite dewaxing. It is a material. In particular, the high yield of dewaxed oil with a viscosity index of 130 is noteworthy. there were.

This viscosity index is very low, especially the viscosity index of oil (i.e. 16 cS at 40'C) So it's extremely high. Generally V, I.

The scale looks too harsh on low viscosity oils.

2 step method Embodiments of the invention include a slurry hydrotreating step followed by fixed bed or ebullated bed desulfurization. Slurry hydrotreating is a two-step process consisting of a Initial cracking temperature, usually above 700'F, preferably 800-96 Operate at 0°F and most preferably 830-870°F. The second stage i.e. The desulfurization reactor is preferably oriented upwards to minimize the deposition of slurry catalyst in the bed. Operate with formulas. Superior performance is achieved in slurry reactors, i.e. in the first stage prior to heavy oil desulfurization treatment. achieved in this method by bulk demetallization and carbon residue conversion in one step. It will be done. Operation of the slurry reactor at temperatures above the initial cracking temperature of the bed reduces this Preferred for achieving metal and carbon residue reduction.

Slurry hydrogenation treatment The first stage, slurry hydrotreating, is carried out in a foam upward reactor, coil cracker or can be achieved in an ebullated bed reactor. Slurry catalyst systems contain small particles or or soluble compounds that produce small particles dispersed in the feedstock under reactor conditions. It will be. We introduce some important types of slurry systems in heavy oil hydroprocessing. distinguish between

Basically, it is used in slurry systems (having a diameter of 20 to 50 microns or less). ) small solid particles are catalytically active or inactive for aromatic carbon hydrogenation; It can also be autocatalytic for demetallization and can be a combination of the above. Inert gas Rally systems are particles that are inert to aromatic carbon hydrogenation and denitrification. this Some examples of such metals are mineral waste and spent Fcc catalyst or fines. . A known mineral waste for use in slurry systems is "red mud." In addition to the present invention In embodiments, the porous contact particles (i.e., inert) are Added separately to heavy oil feedstock. An example of such a porous contact particle is a spent F Contains cc catalyst particles or fine powder.

Slurry catalyst systems produce water by pyrolysis or by reaction with hydrogen/hydrogen sulfide gas mixtures. It can be produced during the plating process. These systems are oil-soluble or water-soluble metal compounds. consists of things. Water-soluble compounds can be mixed directly into the oil or emulsified with added surfactants. can do. In general, water-soluble compounds are cheaper than organic compounds. Therefore, it is preferable.

Autocatalytic slurry systems for demetalization reactions contain nickel/nickel that acts as a demetalization catalyst. exemplified by substances such as vanadium oxides or sulfides or oxysulfides and can therefore be classified as an autocatalytic metal. Nickel to oil and Addition of vanadium sulfide not only increases the demetalization reaction (autocatalytic demetalization The reaction also starts. However, the present invention is preferably promoted by Group I metal compounds. Group VIB metal-activated slurry catalysts are suitable for hydrogenation, denitrification, and carbonization of slurry catalyst systems. Provides substantial improvements to bare residue conversion and demetalization embodiments. With this invention The catalyst precursor produced by the method used has an extremely small particle size. Characterized by distribution.

The bulk of these particles is in the sub-micron range.

Processing conditions Embodiments of the invention operate in one or two stages.

In a one-stage operation, heavy oil is combined with an active catalyst slurry and a hydrogen-containing gas at an elevated temperature. Pressure contact, sufficient residence time in the catalytic reactor and measurable thermal cracking directly into a fixed bed or ebullated bed catalytic reactor at a temperature sufficient to achieve nothing. The process can be operated in two stages, the first of which is a fast thermal club such as a heating coil or a foam upward column or a boiling reactor to achieve The active catalyst slurry is mixed with heavy oil and water in a heat treatment reactor for sufficient time and temperature. contact with an element-containing gas. Such temperatures for heavy oil feedstocks is usually greater than or equal to about 700°F, preferably greater than or equal to about 750°F.

The concentration of active slurry catalyst in heavy oil is usually the weight of metal (molybdenum) versus heavy oil. From about 100 to 10,000 ppm expressed as weight of feedstock. 30% gold The demetalization of heavy oils above the metal level is even more difficult when the catalyst concentration is in this range. Surprisingly, the catalyst concentration is below about 500 ppm or 200 ppm. Even at times less than 50% conversion of the 1000'F+ fraction is obtained.

If the heavy oil 1000°F + conversion is less than 70%, the coke yield is approximately 1 % or less, and even more surprisingly, it has a high conversion rate of about 90%. Even at low slurry catalyst concentrations (100 to 100 Opp, the coke yield is It can be maintained at about 2.5% or less.

The process conditions for the second stage or fixed bed reactor are the preferred fluidized or catalytic bed reactor. heavy oil except for a common upward flow to minimize solids deposition in This is typical of desulfurization conditions. The second stage reactor can be a fixed bed, ebullated bed or moving bed reactor. be. The catalyst used in the second stage is the catalyst precipitated on the refractory metal oxide and/or is a hydrodesulfurization-demetallization catalyst such as one containing a Group I metal.

Examples of such catalysts are found in U.S. Pat. No. 4,455, incorporated herein by reference. 6.701 and 4.466.574. Typical l and 2 tier Processing conditions for floor operations are shown in Table 3.

Table■ Slurry hydrotreatment stage Fixed bed hydrotreating stage Total pressure 1500-4500 psigH2 pressure 1000-4500 psi.

Recirculation gas ratio: 1500-150005CFBLH3V, Vol/Hr/Vo l: 0.10-2.01/Hr active vs. inactive slurry catalyst Coke in amounts greater than 2.5 percent by weight based on string feed is used in the heat treatment of heavy oils. It is often formed during the process.

This coke is used in a fixed bed reactor to achieve the desired pressure drop through the reactor. will not help cause any increase and loss of catalyst activity and will finally close the reactor. I'll let you go. Therefore, any thermal pretreatment that occurs before that step as well as the fixed bed catalyst water It is desirable to minimize coke formation in the treatment reactor.

The use of the active catalyst of the present method in the thermal pretreatment step is ammonium hebutamolybdate. coke compared to pretreatment using other relatively inert slurry catalysts such as results in a considerable reduction in the formation of. This is explained in the comparative example in Table ■. There is. In Table ■, TCHC refers to relatively inert ammonium heptamolybdate. made by the thermal catalytic hydrogen conversion (TCHC) process using a slurry catalyst that is means a test that has been completed. In Table ■, the treatment test named ACTTVE is This corresponds to the use of the active slurry catalyst of the present invention. Thermal catalytic hydrogen conversion treatment (TCHC table ■), a relatively inert slurry catalyst is mixed with a succinimide surfactant. It was aqueous ammonium hebutamolybdate. used for activation treatment The reactor was an agitated autoclave growing a length-to-diameter ratio of 2.6. there were. (TCHC) Thermal catalytic hydrogen conversion research has been conducted with a length-to-diameter ratio of 20. It was carried out in a fuel reactor. The Maya feedstock used in both studies was 1000°F+ are substantially the same except for possible small differences in content. Ru. MB　y　a The first stage in which the vacuum residual oil uses a slurry catalyst that is relatively inert. Thermal catalytic hydrogen conversion processing (TCHC) (e.g., U.S. Pat. No. 4,564,4 39. 1 using U.S. Patent 4,761.220; U.S. Patent 4,389,301) 00° When processed, the coke yield is 4.5% and 85% conversion of 'tee' observed at a rate of The active catalyst of the present invention can be used in place of this relatively inert catalyst. with only 1.6% coke yield or 88% conversion of 1000'F+ fraction. be observed.

This decrease in coke yield is due to the concentration of slurry catalyst as illustrated in Figure 6. observed over a wide range of degrees and heat intensity. In FIG. 6, the present invention Coke yield for treatment and TCHC treatment is shown by 10000F+ conversion. As has been compared over a wide range of heat intensities. Activity of the invention Coke yield for slurry catalyst versus relatively inert TCHC treatment considerably lower than

Table■ Among other advantages, Table ■ removes metals from heavy oil more effectively than other methods. The ability of the method of the present invention to remove This superior metal removal benefit The point is that the operation of the second stage of catalytic hydrotreating is improved due to the increased catalyst life.

Also, demetallization is performed at relatively low temperature conditions and therefore free of feedstock prior to catalytic hydrotreating. Stabilization is achieved at relatively low levels.

FIG. 7 clearly shows the difference between this process and the thermal catalytic hydrogen conversion process. Figure 7 is a book The inventive active catalyst process provides demetallization at lower conversion levels than the inert slurry catalyst process. It indicates that it will be supplied. Lower conversions delivered before catalytic hydrotreatment leading to lower destabilization of things. The more severe the heat treatment of the feed, the more The resulting product becomes stable.

Active slurry catalyst fixed bed or ebullated bed residual oil hydrotreating unit Catalyst life is limited by metal or coke deposited on the catalyst. . Deposited metals and coke plug the catalyst pores, inhibiting hydrogenation, desulfurization, and carbon residue. Reduces catalyst activity for oil removal. Therefore, the lifetime of these catalysts is It can be increased by removing a portion of coke precursors. Demetallization and removal of coke precursors can be achieved with active slurry catalysts, which In some metals, the heavy oil is heated in the slurry before contacting the fixed bed or ebullated bed catalyst. deposited on the Lee catalyst. Instead, demetallization can be carried out by fixed-bed or ebullated-bed hydroprocessing. This can be achieved with an internal slurry catalyst.

Example■ The following example shows how the resid was treated with an active slurry catalyst before being fed to a fixed bed hydrotreating unit. The advantages of pretreating heavy oils with high metal content are explained. The feedstock is shown in the table ■ It was atmospheric pressure residual oil from Arabian heavy oil with test results. Table X is slurry Reactor followed by a two-stage system consisting of an upward fixed bed reactor and a slurry reactor. Operating conditions and results when processing this feed containing activated slurry catalyst It shows. For comparison purposes, in a fixed bed reactor without slurry catalyst. Also included are the results obtained for processing the feed.

The slurry catalyst contains I2wt% molybdenum and ammonia to molybdenum weight ratio. It was prepared by sulfurizing an aqueous ammonium molybdate solution containing:

The solution is hydrogen sulfide per pound of molybdenum at 150'F and 400 psig. Sulfurized with a hydrogen-hydrogen sulfide gas mixture equal to 135 standard cubic feet. sulfide The resulting nickel solution was then made to give a nickel to molybdenum weight ratio of 0.1. added to the slurry. Based on the weight of molybdenum slurry catalyst Dispersed in feed oil at ppm level.

For both tests, the fixed bed reactor was equipped with a staged catalyst system (i.e. 16 containing 1.5% cobalt, 6% molybdenum and 0.8% phosphorus. ．． 7% by volume catalyst A; 1% cobalt, 3% molybdenum and 0 on alumina ．． 16.7% by volume catalyst B containing 4% phosphorous and 3% nitric acid on alumina. 66.6% by volume catalyst containing Kel, 8% molybdenum and 1.8% phosphorus filled with C). The direction of flow is upward with catalyst A placed at the bottom of the reactor. Met. Catalyst B was placed on top of catalyst A and catalyst C was placed on top of catalyst B.

The catalyst was sulfided before use. Slurry reactors are It was an I liter autoclave equipped with a turbine to ensure good mixing. . The flow of gas, oil and catalyst was upward.

As seen in this example, the performance of a fixed bed unit is similar to that of a slurry reactor. It will be improved when it comes together.

Cranking conversion and carbon residue conversion are significantly increased and therefore more valuable. A certain product was obtained. Significant amounts of nickel and vanadium in slurry reactor When deposited on an active catalyst, the fixed bed catalyst The lifespan of will increase.

One effective way to increase distillate yield is to remove heavy waste from the hydroprocessing stage. The lax product is transferred to a delayed coker or a fluidized coker. - (fluid coker). In these processes, The heavy feed is cracked into light gas fractions and coke. Distillate products are common It is desirable to minimize the amount of coke as it is more valuable than coke. . If the 1000°F+ product from the above example is sent to a delayed coker , the coke yield is improved by using an active slurry catalyst before hydrotreating in a fixed bed unit. It can be reduced by pre-treating the feed. Fixed bed without slurry catalyst pretreatment Hydrotreating yields 41.4% by volume of 1000°F+ product. activated slurry With the medium a yield of only 21.5% by volume is obtained. Each of these products It contained 15.2% and 20.2% Conradson carbon. Therefore , delayed coke yield from these 1000°F+ products to the hydroprocessing unit. 10.1% and 6.9% by weight, respectively, calculated based on the new supply of right. The reduction in coke yield for pretreatment with activated slurry catalyst is , therefore 31%.

Table■ Table X Pre-sulfurization rate! 3CF H29/lb, M.

Pre-sulfurization rate, SCF H2S/Ib N.

0 5 10 Director 5 20 25 Pre-sulfurization rate, SCF 825/lb M.

Denitrification rate % 0 5 10 15 2O Ni/Mo,% 0 ri O+QqlQQ1g”jq qOgiichi no n～～-QO o　o　o　o　o　o　o　00　o　.

90')aQtwclrn~- international search report abstract High viscosity index lubricating oils are produced from heavy oils by using highly active slurry catalyst methods. will be built. The catalyst contains water sulfide at a dose of 83 CF or more per pound of Group VIB metal. It is produced by sulfiding an aqueous Group VIB metal compound with hydrogen.

Group VIB metals can be promoted with Group I metals to increase their activity.

Highly active slurry catalysts for hydrotreating heavy hydrocarbon oils are group VIB metals. Aqueous mixing of Group VIB metal compounds with about 8 to about 143 CF of hydrogen sulfide per bond. prepared from Group VIB metal compounds by sulfiding the compound.

Hydroprocessing of heavy oils involves the use of sulfur at doses of 83 CF or more per bond of Group VIB metal. Produced by sulfiding an aqueous Group VIB metal compound with a gas containing hydrogen oxide. improved by the use of highly active slurry catalysts. The slurry catalyst is placed in heavy oil. After introducing and subjecting the mixture to elevated temperature and partial pressure of hydrogen, the mixture is subjected to hydrotreating conditions. The process is carried out in a fixed or ebullated bed of hydrodesulfurization/hydrodemetalization catalyst.

Claims (36)

[Claims] 1. Method for producing a dispersed Group VIB metal sulfide catalyst for hydrocarbon oil hydrotreatment And (b) Contains hydrogen sulfide in amounts greater than about 8 SCF per pound of Group VIB metal. sulfiding an aqueous mixture of Group VIB metal compounds using a gas containing (b) mixing the slurry with supplied oil and hydrogen-containing gas under elevated temperature and different pressure; The method characterized in that. 2. The hydrogen sulfide dosage is about 8 to 14 SCF of sulfur per pound of Group VIB metal. 2. A method according to claim 1, wherein the hydrogen chloride is hydrogen chloride. 3. 2. A method according to claim 1, wherein said Group VIB metal is an oxide. 4. 2. A method according to claim 1, wherein said Group VIB metal is molybdenum. 5. The Group VIB metal compound is molybdenum oxide. A method according to claim 1. 6. 2. A method according to claim 1, wherein said Group VIB metal compound is an ammoniated salt. 7. According to claim 1, the Group VIB metal compound is ammonium molybdate. How to do it. 8. The aqueous mixture of Group VIB metal compounds comprises a Group VIB metal oxide in an aqueous aqueous mixture. A method according to claim 1 obtained by treatment with ammonia. 9. The aqueous mixture of Group VIB metal compounds contains molybdenum oxide in an aqueous ammonia mixture. A method according to claim 1 obtained by treating with. 10. A method according to claim 1, wherein said temperature increase is at least about 350 degrees Fahrenheit. 11. Claim wherein the slurry is in an initial gel stage prior to mixing with feed oil. Method according to 1. 12. The sulfiding is carried out with a gas containing a partial pressure of hydrogen, and the dose of hydrogen sulfide is The method according to claim 1, wherein the amount ranges from about 12 to 14 SCF per pound of Group IB metal. . 13. The sulfidation is carried out in the absence of hydrogen, and the amount of hydrogen sulfide is equal to the Group VIB metal 1. The method according to claim 1, wherein the amount is within the range of about 8-10 SCF per pound. 14. Method for producing a dispersed Group VIB metal sulfide catalyst for hydrocarbon oil hydroprocessing The law is (b) Contains hydrogen sulfide at a dose of approximately 8 to 14 SCF per pound of Group VIB metal. sulfiding an aqueous mixture of Group VIB metal compounds using a gas to form a slurry. (b) adding a group VIII metal compound to the slurry; (c) adding the group VIII metal compound to the slurry; and Group VIII metal compounds are mixed with feed oil and hydrogen-containing gas at elevated temperature and pressure. The method characterized in that: 15. 15. A method according to claim 14, wherein said slurry is present at an initial gel formation stage. 16. The Group VIII metal compound is added to the slurry at a pH of about 8 or less. 15. A method according to claim 14. 17. The Group VIII metal: Group VIB metal weight ratio is about 1:2 to about 1:10. 15. The method according to claim 14, wherein 0. 18. 15. A method according to claim 14, wherein said Group VIB metal is molybdenum. 19. Claims 14, 15, 16 and 17, wherein the Group VIII metal is nickel. Or the method according to 18. 20. Claims wherein the Group VIII metal compound is a sulfate, a nitrate, or a carbonate. Method according to Section 14. 21. Claims 14, 15, 16, 17 or 17, wherein the Group VIII metal is cobalt. Or the method according to 18. 22. A heavy hydrocarbonaceous feedstock in the presence of the catalyst of claim 1 and hydrogen at elevated temperature and pressure. A method for hydrotreating a heavy hydrocarbonaceous feedstock, the method comprising contacting a heavy hydrocarbonaceous feedstock. 23. A method for producing lubricating oil with a high viscosity index from heavy oil, the method comprising: (b) Contains hydrogen sulfide in a dose greater than 8 SCF per pound of Group VIB metal. sulfiding the aqueous mixture of Group VIB metal compounds using a gas of (b) The product of step (a) is mixed with heavy oil feedstock and hydrogen-containing gas at elevated temperature and pressure. and 0.01% or more by weight based on the weight of said feedstock. in contact with a group metal concentration to form a product; (c) separating a fraction having a boiling point above about 650°F from the product of step (b); (d) comprising various steps of dewaxing the fraction to produce the lubricating oil; The said method. 24. The heavy oil feedstock is heated with the product of step (a) at or above about 775°F. and at a hydrogen partial pressure of about 700 to 4500 psi. How to read. 25. Produced according to claim 23, which is hydrotreated before catalytic dewaxing. Products with lubricating oil boiling range. 26. A method for producing lubricating oil with a high viscosity index from heavy oil, the method comprising: (b) Contains hydrogen sulfide in amounts greater than about 8 SCF per pound of Group VIB metal. sulfiding an aqueous mixture of Group VIB metal compounds with a gas having (b) Adding a Group VIII metal compound to the product of step (a); (c) step (b) The product of heavy oil feedstock and hydrogen-containing gas at elevated temperature and pressure and said feedstock. contact with a Group VIB metal concentration of 0.01% by weight or greater based on the weight of to form a product; (d) separating a fraction having a boiling point above about 650°F from the product of step (c); (E) The method is characterized by comprising various steps of dewaxing the fraction to produce a lubricating oil. How to write. 27. A method according to claim 26, wherein the product of step (a) is present in the initial gel formation stage. . 28. Heavy hydrocarbon oils containing metal contaminants, active catalyst slurries and hydrogen-containing Containing gas is placed in a fixed bed or boiling bed of a hydrodesulfurization-hydrodemetalization catalyst under elevated temperature and pressure. , a heavy coal containing metal contaminants comprising introducing at a temperature above about 700°F. A method for hydrotreating hydrogenated oil, wherein the active catalyst slurry is a Group VIB For aqueous mixtures of metal compounds greater than 8 SCF per pound of Group VIB metal. Characterized by being produced by sulfidation using a gas containing an amount of hydrogen sulfide The said method. 29. Heavy hydrocarbon oils containing metal contaminants, active catalyst slurries, porous contacts Hydrodesulfurization of particles and hydrogen-containing gas under elevated temperature and pressure - fixed bed or metal hydride catalyst or containing metal contaminants by introducing them into an ebullated bed at temperatures above about 700°F. A method for hydrotreating heavy hydrocarbon oil, wherein the active catalyst slurry is Aqueous mixtures of Group VIB metal compounds starting at 8 SCF per pound of Group VIB metal manufactured by sulfiding with a gas containing large amounts of hydrogen sulfide. The said method characterized by. 30. A method for hydrotreating heavy hydrocarbon oil containing metal contaminants, the method comprising: (b) In the first stage, the pre-oil is mixed with the active catalyst slurry and hydrogen in the product stream. contact at a temperature and time sufficient to achieve moderate pyrolysis; (b) In the second stage, the previous product stream is converted into hydrogen and hydrodesulfurization-hydrodemetalization catalyst. contacting in a fixed bed or an effervescent bed at a temperature of about 700°F or above; The active catalyst slurry combines an aqueous mixture of Group VIB metal compounds with one portion of Group VIB metal. sulfidation using a gas containing hydrogen sulfide at a dose greater than about 8 SCF per The method, characterized in that it is produced by: 31. Claim 28, 29 or 30, wherein the oil stream flows upwardly through the fixed bed. How to read. 32. The fraction conversion rate of the heavy oil at 1000°F+ is less than 50%, and the nickel or the vanadium removal rate is 30% or more and the slurry catalyst concentration is According to claim 28, 29 or 30, from about 100 to 10,000 ppm in oil. Method. 33. The fraction conversion rate of the heavy oil at 1000°F+ is 50% or more, and the coke yield is The ratio is about 2.5 at a slurry catalyst concentration of about 100 to 10,000 ppm in the heavy oil. 31. A method according to claim 28, 29 or 30, wherein the method is less than or equal to %. 34. According to claim 31 or 32, the slurry catalyst concentration is about 500 ppm or less. How to do it. 35. According to claim 31 or 32, the slurry catalyst concentration is about 200 ppm or less. How to do it. 36. Claims 28 and 29, wherein a Group VIII metal compound is added to the slurry. Or the method according to 30.