CA1287591C

CA1287591C - Hydroconversion process

Info

Publication number: CA1287591C
Application number: CA000535545A
Authority: CA
Inventors: Clyde L. Aldridge; William E. Lewis; Roby Bearden, Jr.; Francis X. Mayer
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1986-04-30
Filing date: 1987-04-24
Publication date: 1991-08-13
Anticipated expiration: 2008-08-13
Also published as: EP0244244A3; AU7218887A; AU597055B2; BR8702115A; US4765882A; EP0244244A2; EP0244244B1; DE3775819D1; JPS6327596A; US4762607A

Abstract

ABSTRACT OF THE DISCLOSURE

A slurry catalytic hydroconversion process comprising at least two hydroconversion zones is pro-vided in which the heavy hydrocarbonaceous fresh oil feed is added to more than one hydroconversion zone.
Additional portions of catalysts or catalyst precursors are also added to the first hydroconversion zone and to additional hydroconversion zones wherein said additional hydroconversion zones are maintained at a temperature of at least 10°F higher than an immediate preceding hydroconversion zone.

Description

~ ~2bl75~31 BACKGROUND OF THE INVENTION

1. Field of the Invention The present invention relates to a slurry hydroconversion process conducted in two hydroconver-sion stages wherein the temperature of the second stage is at least 10F higher than the first stage.

2. Description_of Information Disclosures Slurry hydroconversion processes in which a catalyst is dispersed in a hydrocarbonaceous oil to convert the oil in the presence of hydrogen are known.

U.S. Patent 4,134,825 discloses a catalytic slurry hydroconversion process using a catalyst produced in the oil feed from a catalyst precursor.

U.S. Patent 4,151,070 discloses a staged hydroconversion process in which the liquid effluent of the first hydroconversion zone is separated into fractions and in which the heavy fraction is passed to a second hydroconversion zone. The first hydrocon-':~

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version zone is operated at a lower temperature than the second hydroconversion zone.

U.S. Patent ~o. 4,606,809 also discloses a staged hydroconversion process wherein the temp~rature of a second stage is higher than that of a first stage, except product is not removed between stages.

The exothermic nature of hydroconversion of heavy hydrocarbonaceous oils to lower boiling products is disclosed in U.S. Patent No. 3,622,497 wherein the effluent from the reaction chamber is substantially higher in temperature than the inlet temperature of the chamber. The temperature gradient from inlet to outlet is maintained at a temperature less than about ~50C.

The term "hydroconversion" is used herein to designate a process conducted in the presence of hydrogen in which at least a portion of the heavy con-stituents of the hydrocarbonaceous oil is converted to lower boiling hydrocarbon products while it may simultaneously reduce the concentration of nitrogenous compounds, sulfur compounds, and metallic contaminants.

It has now been found that adding the fresh oil feed to more than one hydroconversion zone of a plurality of serially connected hydroconversion zones wherein each subsequent zone is maintained at a tem-perature of at least 10F higher than the preceeding zone, will provide advantages, such as a decrease in hydrogen preheat and a decrease in overall catalyst requirement. Furthermore, the use of more than one hydroconversion zones, as well as the introduction of fre-h~feed into ~ore than one hydroconversion zones , ~ .. - . -.- . . . .- . . . , . . . : .
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contributes to the control of the exothermic reaction taking place in said zones.

SUMMARY OF THE INVENTION

In accordance with the invention J there is provided, in a slurry hydroconversion process comprising at leask two zones, wherein heavy hydrocarbonaceous oil is converted to lower boiling products, which process comprises the steps of:
(a) adding a catalyst or a catalyst prec-ursor to a chargestock comprising a first portion of fresh heavy hydrocarbonaceous oil comprising at least 10 wt.% of materials boiling above about 1050F~, to form a mixture;
(b) reacting the resulting mixture with a hydrogen-containing gas in a first hydroconversion zone operated at a temperature ranging from about 800F. to about 900DF. at hydrogen partial pressures from about 50 to 5, 000 psig to produce a first hydroconversion oil;
(c) introducing at least a portion of the effluent of said first hydroconversion zone, including at least a portion of said first hydroconverted oil into a second hydroconversion zone also operated at temperatures ranging from about 800F to about 900F and hydrogen partial pressures from about 50 to 5,000 psig to react with a hydrogen-containing gas and produce a second hydroconverted oil, the improvement which comprises:
(d) introducing a second portion of said fresh heavy hydrocarbonaceous oil to said second hydroconversion zone.
BRIEF DESCRIPTION OF THE DRAWING
The figure i5 a schematic flow plan of one embodimen~ of the invention.

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~ eferring to the figure, a heavy hydrocarbonaceous oil feed carried in line 10 in admixture with the catalyst or catalyst precursor introduced into the oil by line 12 is passed into hydroconversion zone 1 which is the first of a series of related hydroconversion zones.

The Heavy Hydrocarbon Oil Feed Suitable hydrocarbonaceous oil feeds include heavy mineral oils, whole or topped crude oils, including heavy crude oils; asphaltenes; hydrocarbon-aceous oil boiling above 650F (343.33C); petroleum atmospheric residuum (boiling above 650F); petroleum vacuum residua boiling above 1050F (565.56C); tars;
bitumen; tar sand oils; shale oils; liquid products derived from coal liquefaction processes, including coal liquefaction bottoms, and mixtures thereof. The process is particularly suitable to convert heavy crude oils and residual oils containing materials boiling above 1050F and which generally contain a high content of metallic contaminants (nickel, iron, vanadium) usually present in the form of organometallic con-taminants, a high content of sulfur compounds, nitrogenous compounds and a high Conradson carbon residue. The metallic content of such oils may range up to 2000 wppm or more and the sulfur content may range up to 8 wt. ~ or more. Preferably, the feed is a heavy hydrocarbon oil comprising materials boiling above 1050F, more preferably having at least about 10 wt. % materials boiling above 1050F. To any of these Eeeds may be added coal.

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All boiling points rererred to herein are equivalent atmospheric pressure boiling points unless otherwise specified. Whenever reference is ~ade herein to fresh feed, it is intended that it is not a recycle stream; however, the fresh feed may be a cracked oil derived from other processes.

The Hydroconversion Catal~st The hydroconversion catalyst introduced via line 12 and optionally via line 20 into the oil feed to form a dispersion of the catalyst in the oil may be any suitable hydroconversion catalyst or catalyst pre-cursor suitable for use in slurry processes (i.e., a process in ~hich the catalyst is admixed with the oil).
The catalyst may comprise a ~roup VB, Group VIB or Group VIII metal, metal oxide or metal sulfide and mixtures thereof and may be a supported or unsupported catalyst. Instead of introducing a preformed catalyst via line 12, a catalyst precursor may be used such as an oil soluble metal compound or a thermally decom-posable metal compound such as the catalyst precursors described in U.S. Patent 4,134,825. Catalysts comprising cobalt~ molybdenum, nickel, tungsten, iron and mixtures thereof on an alumina-containing support or on solid carbonaceous supports, such as coal or coke, are also suitable.

A hydrogen-containing gas is introduced into hydroconversion zone 1 by line 14. The hydrogen-containing gas may be pure hydrogen, but will ge~erally be an impure hydrogen stream such as a hydrogen-containing gas derive,d from a process, e.g., reformer offgas. Although the figure shows the hydrogen being introduced directly into the hydro-` ~ :
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:~2~7S~l conversion zone, it is to be understood that the hydrogen-containing gas of line 14 could be introduced into oil feed line 10 and passed into the hydro-conversion zone in admixture with the oil. In hydroconversion zone 1, the oil feed is subjected to hydroconversion conditions to convert at least a portion of the oil to lower boiling hydrocarbon products.

Slurry Hydroconversion Conditions Suitable operating conditions for all the slurry hydroconversion zones of the process are summarized in Table I.

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The hydroconversion zone effluent comprising a normally gaseous phase, a normally liquid phase and catalyst particles is removed from hydroconversion zone l by line 16. If desired, at least a portion of the gaseous phase may be removed from the effluent. The effluent of hydroconversion zone l comprising the nor-mally liquid phase is passed into hydroconversion zone 2 which is the second hydroconversion zone into which an additional portion of fresh oil chargestock is introduced by line 18. This second hydroconversion zone is maintained at a temperature of at least 10F
preferably, at least 20F, higher than that of the first hydroconversion zone 1. The fresh oil is a por-tion of the same oil that was introduced by line 10 into hydroconversion zone 1. An additional portion of catalyst or catalyst precursor may be introduced into fresh feed line 18 via line 20. An additional hydrogen-containing gas may be introduced into hydro-conversion zone 2. If the gas phase had been removed from the effluent of the first hydroconversion zone, then introduction of the required hydrogen would be made via line 22. As previously described, the hydro-gen of line 22 may be introduced into fresh feed line 18 or it may be introduced directly into hydrocon-version zone 2. The effluent of hydroconversion zone 2 is removed by line 24 and, if desired, may be passed with or without separation of gas phase from the liquid into additional hydroconversion zones (not shown) into which additional portions of fresh feed may be intro-duced. It should be noted that it is not required that the additional portion of fresh feed be introduced into a specific second hydroconversion zone. The additional portion of fresh feed may be introduced into any one of a series of hydroconversion zones or into each of the hydroconversion zones of a plurality of hydroconver--. .
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sion zones in series. The percentages of fresh feed introduced into the first hydroconversion zone, and to the subsequent hydroconversion zones are as follows:

% Fresh Feed to~ Fresh Feed to First Subsequent Hydroconversion Zone HydroconverSiOn Zones Broad PreferredBroad Preferred 25-95 wt.% 50-gO wt.%5-75 wt.% 10-50 wt.~

The actual conditions may be the same in the first, second or any subsequent hydroconversion zone, or may be different within the given ranqes.

The effluent of hydroconversion zone 2, which comprises a normally gaseous phase, a normally liquid phase (e.g., hydroconverted oil) and catalyst particles, is passed by line 24 into a gas-li~uid separation zone 3. The gaseous phase comprising hydrogen is removed by line 26. If desired, the gas may be recycled to any of the hydroconversion zones with or without additional cleanup.

Th`e normally liquid phase, which comprises hydroconverted hydrocarbonaceous oil and catalytic solids is passed to separation zone 4 for fractionation by conventional means such as distillation, into various fractions, such as light boiling, medium boiling and heavy bottoms fractions containing the catalytic solids. The light fraction is removed by line 30. The medium boiling fraction is removed by line 32. Thè heavy bottoms fraction is removed by line 3~4. If desired, at least a portion of the bottoms fraction may be recycled to hydroconversion zone 1 by :

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line 360 Alternatively, if desired, the bottoms frac-tion may be recycled to hydroconversion zones 1 or 2.
When the process comprises rnore than 2 hydroconversion zones, the heavy bottoms portion separated from the effluent of the last of these hydroconversion zones may be recycled to at least one of the hydroconversion æones.

The following examples are presented to illustrate the invention.

Seventy percent of a topped Cold Lake feed (780F~, containing 74.08 wt.% of 975F+ material) was hydroconverted in a first stage at 846F and 1923 psi H2 pressure at a feed rate of 0.59 V/V/Hr. (nominal holding time of 1.7 hr. excluding ~aporization effects). Molybdenum catalyst was provided in the amount of 225 wppm on feed by adding a concentrate of phosphomolybdic acid in Cold Lake crude. After this first stage, gaseous materials and volatile hydro-carbons were removed to yield 9.76 wt.~ of residual material containing the catalyst.

The remaining 30% of the fresh feed was then blended with the effluent from the first stage and the mixture passed to a second hydroconversion stage main-tained at 840F and 2000 psig with hydrogen for three hours (0.33 V/V/Hr.). After the two-stage treatment the conversion of material boiling above 975F in the total fresh feed to oil boiling below 975F plus gas was 90.3 wt.%, and toluene insolubles produced amounted to 2.1 wt.~ on total fresh feed.

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Cold Lake vacuum residuum was hydroconverted in a continuous pilot plant containing two tubular reactors of equal size at a total pressure of 2090 psig and at a space velocity adjusted to give 94.0~ conver-sion of the 1050+F material to 1050-F products. The temperature of the first reactor was maintained at 825F and that of the second reactor at 835F. Total hydrogen treat gas amounted to 9100 SCF/bbl of feed, two-thirds of which was added to the first reactor and one-third to the second reactor.

Phosphomolybdic acid dispersed as a concentrate in Cold Lake crude (0.5 wt.~ Mo) was added to the feed in an amount to provide 314 wppm Mo on feed, which was an amount just sufficient to provide adequate hydrogenation catalysis and to substantially prevent formation of any significant detectable amount of mesophase carbon. Eleven weight percent of bottoms (based on fresh feed) from this conversion was recycled with the feed. Yields of products as wt.~ on fresh feed are as follows: Cl-C4, 12.2~, Naphtha (C5-350F), 18.0%; Distillate (350-650F), 35.7~; Vacuum Gas Oil (650-1050F), 26.1%. The hydrogen consumption was 2040 SCF/bbl of fresh feed.

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An experiment was carried out according to Example 2 with conditions identical in all respects except that the temperature of the first reactor was maintaihed at ~170F and that of the second reactor at a38F. Conversion of 1050+F material to 1050-F
products was 93.6~. In this experiment it was possible to lower the ~olybdenum catalyst concentration to 250 - . , .
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wppm on fresh feed while providing adequate hydrogena-tion catalysis and substantially preventing formation of any significant detectable amount of mesophase carbon. Yields of products as wt.% on fresh feed were as follows: Cl-C4, 12.1~, Naphtha (C5-350F), 18.0%;
Distillate (350-650F), 34.7%; Vacuum Gas Oil (650-1050F), 27.0~. The hydrogen consumption was 2030 SCF/bbl of fresh feed.

Results from Examples 2 and 3 are tabulated for comparison:

TABLE II
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Exam~le 2(a) Example 3(b) 1050+F Conversion 94.0 93.6 Yields, wt.~ on Feed Cl-c4 12.2 12.1 Naphtha (C3-350F) 18.0 18.0 Distillate (350-650F) 35.7 34. 7 Vacuum Gas Oil 26.1 27.0 (650-1050F) Hydrogen Consumption, 2040 2030 SCF/bbl .
Mo Catalyst Requirement, 314 250 wppm _ (a) Average of three analytical balance periods.
(b)~ Average of slx analytical balance periods.

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Example 4 Experiments are run according to the procedure of Example 3 above except that the conversion of 1050F+ material to 1050F-products is controlled in all cases to 95%. The amount of temperature staging and the amount of feed going to the second of the two stages, which varies as shown in Table III below, will have a synegetic reduction in the amount of catalyst required to prevent formation of any detectable amount of mesaphase carbon.

Table III
Example Reactor l Reactor 2 Catalyst % Fresh % Fresh Requirement, Mo Feed F Feed Fon Fresh Feed A 100 830 0 830 a B 100 820 0 840 b C 70 830 30 830 c D 70 820 30 840 d wher~e a, b, c, and d are numeric values such that a>b>c>d.

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Claims

1. In a slurry hydroconversion process comprising at least two zones, wherein heavy hydrocarbonaceous oil is converted to lower boiling products, which process comprises the steps of (a) adding a catalyst or a catalyst precursor to a chargestock comprising a first portion of fresh heavy hydrocarbonaceous oil comprising at least 10 wt.% of materials boiling above about 1050°F., to form a mixture;
(b) reacting the resulting mixture with a hydrogen-containing gas in a first hydroconversion zone operated at a temperature ranging from about 800°F. to about 900°F. at hydrogen partial pressures from about 50 to 5,000 psig to produce a first hydroconversion oil;
(c) introducing at least a portion of the effluent of said first hydroconversion zone, including at least a portion of said first hydroconverted oil into a second hydroconversion zone also operated at temperatures ranging from about 800°F to about 900°F and hydrogen partial pressures from about 50 to 5,000 psig to react with a hydrogen-containing gas and produce a second hydroconverted oil, the improvement which comprises:
(d) introducing a second portion of said fresh heavy hydrocarbonaceous oil to said second hydroconversion zone.

2. The process of claim 1 wherein said slurry hydroconversion process is conducted in more than two slurry hydroconversion zones in series and wherein at least a portion of said fresh hydrocarbonaceous oil is introduced into said first hydroconversion zone and into at least one additional hydroconversion zone.

3. The process of claim 1 wherein said slurry hydroconversion process is conducted in more than two slurry hydroconversion zones in series and wherein at least a portion of said fresh hydrocarbonaceous oil is introduced into each of said hydroconversion zones.

4. The process of claim 1 or 2 wherein said slurry hydroconversion process is conducted in a plurality of slurry hydroconversion zones and wherein a heavy bottoms portion is separated from the effluent of the last of said hydroconversion zones and, thereafter, the separated bottoms portion is recycled to at least one of said hydroconversion zones.

5. The process of claim 1 or 2 wherein an additional portion of said catalyst or catalyst percursor is introduced into at least one of said hydroconversion zonesd other than said first hydroconversion zone.

6. The process of claim 1 wherein said hydroconversion catalyst precursor is an oil soluble metal compound or a thermally decomposable metal compound.

7. The process of claim 1 wherein said first portion of fresh heavy oil is from 25 to 90 weight percent of the total chargestock of said process.