CA1124195A

CA1124195A - Hydrocracking of heavy hydrocarbon using synthesis gas

Info

Publication number: CA1124195A
Application number: CA348,513A
Authority: CA
Inventors: Chandra P. Khulbe; Ramaswami Ranganathan; David J. Patmore; Keith Belinko; Barry B. Pruden
Original assignee: Canada Minister of Energy Mines and Resources
Current assignee: Canada Minister of Energy Mines and Resources
Priority date: 1980-03-26
Filing date: 1980-03-26
Publication date: 1982-05-25
Also published as: FR2479255A1; JPS5723681A; GB2072697B; GB2072697A; DE3111763A1; FR2479255B1; NL8101510A; MX158005A

Abstract

Hydrocracking of Heavy Hydrocarbon Using Synthesis Gas Abstract Of The Disclosure A process is described for the hydrocracking of a heavy hydrocarbon, such as bitumen from tar sands. A
slurry of the bitumen, preferably together with coal, in the presence of a hydrogen-rich synthesis gas is passed through a confined hydrocracking zone, and the effluent emerging from the zone is separated into a gaseous stream containing a wide boiling range of material and a liquid stream containing heavy hydrocarbons. This process provides increased liquid yields and increased H/C atomic ratios of liquid and solid, as well as significantly decreased hydrogen consumption.

Description

This invention related to hydrocracking and, more particularly, to the hydrocracking of heavy hydrocarbon oil, such as bitumen from tar sands, in the presence of synthesis gas~
Hydrocracking processes for the convention of heavy hydrocarbon oi]s to light and intermediate naphthas of good quality for reforming feed stock, fuel oil and gas oil are well known. These heavy hydrocarbon oils can be such materials as petroleum crude oil, atmospheric tar bottoms products, vacuum tar bottoms products, heavy recycle oils, shale oils, coal derived liquids, crude oil residuum, topped crude oils and the heavy bituminous oils extracted from tar sands. Of particular interest are the oils extracted from tar sands which contain wide boiling range materials from naphtha through kerosene, gas oil, pitch, etc., and which contain a large portion, usually more than 50 weight percent of material boiling above 524C., equivalent atmospheric boiling point.
The heavy hydrocarbon oils of the above type tend to contain nitrogenous and sulphurous compounds in quite - larye concentrations. In addition, such heavy hydrocarbon fractions frequently contain excessive quantities of organo-metallic contaminants which tend to be extremely detrimental to various catalytic processes that may sub-sequently be carried outl such as hydrofining. If the metallic contaminants, those containing nickel and vanadium q~'

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are most common, although other metals are often present.
These metallic contaminants, as well as others, are usually present within the bituminous material as organo-metallic compounds of relatively high molecular weight. A consider-able quantity of the organometallic complexes are linkedwith asphaltenic material and contains sulphur. Of course, in catalytic hydrocracking procedures, the presence of large quantities of asphalte~ic material and organic-metallic compounds interferes considerably with the activ-ity o~ the catalyst with respect to the destructive removalof nitrogenous, sulphurous and oxygenated compoundsO A
typical Athabasca bitumen may contain 53.76 wt. ~ material boiling above 524C., 4.74 wt. % sulphur, 0.59 wt. %
nitrogen, 162 ppm vanadium and 72 ppm nickel.
As the reserves of conventional crude oils decline, these heavy oils must be upgraded to meet the demands.
In this upgrading, the heavier material is converted to lighter fractions and most of the sulphur, nitrogen and metals must be removed. This is usually done by a coking process such as delayed or fluidized coking or by a hydrogen addition process such as thermal or catalytic hydrocracking. The distillate yield from the coking process is about 70 weight percent and this process also yields about 23 wt. % coke as by-product which cannot be used as fuel because of low hydrogen:carbon ratio, and high mineral and sulfur content. Depending on operating conditions, hydrogenation processes can give a distillate yield of over 87 wt. %.
In the case of catalytic hydrocracking r the asphaltenes and mineral matter present in the bitumen and heavy oils have harmful effects on operating life of the expensive catalysts used in catalytic hydrocracking, which results in increased operating and production costs. It has been found that procedures involving addition of hydro~en at high pressures and temperatures are useful, with high molecular weight compounds hydrogenating and/or hydro-cracking to produce materials of lower boiling ranges.

_3_ '~ 5 Simultaneous desulphurization, demetallization and denitrogenation reactions take place. For this purpose, reaction pressures of Up to 3500 psig and temperatures up to 490C. have been used.
In thermal hydrocracking, a major problem is solids deposit;on in the reactor, especially when operating at relatively low pressures, and this results in costly shutdowns. Deposits form at the top of the reactor where the partial pressure of hydrogen and ash content are lowest. Operating at high pressures, e.g. at 3500 psig and 470C., very significantly reduced reactor fouling.
Because a large portion of the capi~al and operating costs in a hydrocrackiny plant are related to hydrogen, efforts have been made to develop processing aids which enable the plant to operate at low pressures. Such a procedure has been described in Ranganathan et al, Canadian application Serial No. 289,320, filed October 24, 1977. These processing aids serve to suppress coking during conditions that would otherwise lead to severe operating problems. Another procedure involves simultaneous bitumen/coal hydrocracking as described in Ranganathan et al Canadian Application Serial No. 320,226 filed January 25, 1979.
A process known as Costeam for liquefying lignite in the presence of added catalysts is described in Appell, H.R., Moroni, E.C. and Miller, R.D. "COSTEAM Liquefaction of lignite". Am. Chem. Soc., Div. Fuel Chem. Preprints Vo.20, No.l 58-65, 1975. This process used a synthesis gas, reducing agent and moisture in the coal as the source of hydrogen. It has been observed that carbon monoxide is selected with respect to the reduction of carbonyl groups~
whereas cracking reactions occur to a greater extent with hydrogen. The high activity of carbon monoxide in reducing carbonyl groups is believed to be the reason that low ranked coals are liquefied more readily in the presence of çarbon rnonoxide than hydrogen. Low rank coals not only contain more carbonyl groups than higher ranked coals but also contain the organically bonded alkaline metals which are converted to formates~ the probable active reducing agents.
Schlinger et al, U~S. Patent 3,565,784 describes a continuous process for recovering oil Erom a slurry of raw oil shale in shale oil. Water and hot unquenched synthesis gas from the reaction zone of a partial oxidation yenerator are injected into the raw oil-shale oil slurry under pressure and the mixture is immediately introduced in a noncatalytic tubular retort maintained at a temperature in the range of 850 to 950F and at a pressure in the range of 300 to 1000 psig, for maximum yield of shale oil having a minimum nitrogen content. Substantially all of the hydrogen and a large fraction of the heat required in the tub~lar retort is provided by the synthesis gas.
In Schlinger et al, U.S. Patent 3,617,471 there is described a process in which synthesis gas and water are injected into shale oil at a comparatively moderate temperature and pressure, high quality shale oil being ,~Q produced with the addition of H2O reducing hydrogen consumption. In another Schlinger et al U.S. Patent

3,617,472 there is described a process for recovering shale oil from oil shale by retorting with synthesis gas.
This patent indicates that additional hydrogen is produced in oil shale retorts by the water gas shift reaction, the shale acting as a catalyst.
It is the object of the present invention to provide a process for the hydrocracking of heavy hydrocarbon oil, while decreasing costs by substituting the usual hydrogen with synthesis gas.
SUMMARY OF THE INVE:NTION ~
In accordance with the present invention, there is described a process for hydrocracking a heavy hydrocarbon oil, a substantial portion of which boils above 524C., ~5 which comprises:

a) passing a heavy hydrocarbon oil feed in the presence of a hydrogen-containing synthesis gas in an amount sufficient to provide 500-50,000 s.c.f. of hydrogen per barrel of said hydrocarbon oil through a conEined hydrocracking zone, said hydrocracking zone being main-tained at a temperature between about ~00 and 500C., a pressure of at least 500 psig. and a space velocity between about 0.5 and 4 volume of hydrocarbon oil per hour per volume of hydrocracking zone capacity, b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising vaporous hydrocarbons, H2O, H2 and carbon oxides and a liquid phase comprising heavy hydrocarbons, and c) separating said effluent into a gaseous stream containing vaporous hydrocarbons, H2O, H2, H2S and carbon oxides and a liquid stream containing heavy hydrocarbons.
While the process of this invention is particularly well suited for the treatment of bitumen or heavy oil, it is also very well suited for the treatment of topped bitumen, pitch, oil shale, refinery bottoms, residuum, etc. It can be operated at quite moderate pressures, e.g.
in the range of 500 to 3,500 psig, without coke formation in the hydrocracking zone.
The hydrocracking process of this invention can b~
carried out in a variety of known reactors with either up or down flow. Thus, the hydrocracking reactor zone can be an empty tubular reactor, an ebullated bed reactor or a fluidized bed reactor. The empty tubular reactor has been ~ound to be particularly convenient with the effluent from the top being separated in a hot separator and the gaseous stream from the hot separator being fed to a low temperature-high pressure separator where it is separated into a gaseous stream containing hydrogen and lesser amounts of gaseous hydrocarbons and a liquid product stream containing light oil products. It is also possible to have the reactors in stages where the first reactor is an empty tubular reactor and the second reactor contains an ebullated bed of catalyst extrudates.

-6~

The synthesis gas is typically a gas mixture containing H2 and CO as its main components, and containing 1-99 mol.~ H2t preferably at least 45 mol.~ H2, frequently together wlth some minor amounts of other gases such as CO2, H2O and H2S. According to a preferred embodiment, water may be present in the form of steam. The synthesis gas may be produced by almost any hydrocarbonaceous material suitable for charging a synthesis gas generator, e.gO natural gas, propane, butane, reduced crude, whole crude, etc. However, a portion of the oil product obtained from the process of the present invention is the preferred source of hydrocarbonaceous material. Likewise the oxidizing gas fed to the synthesis gas generator may be selected ~rom airl oxygen, oxygen-enriched air.
The heavy hydrocarbon feed can be processed as is together with synthesis gas, or a slurry of the heavy hydrocarbon oil and coal may be formed. The coal is typically included in amounts of 0.1 to 60% by weight.
~ny type of coal, such as lignite, sub-bituminous, bituminous, etc., or peat, can be used as the coal portion of the charge slurry. The coal can be used as is without any additive or at least a portion of it may be coated with up to about 20 wt.~ of a metal catalyst such as iron, cobalt, molybdenum, zinc, tin, tungsten, nickel or other catalytically active salts. The use of the catalytic ; materials improve the conversion of coal and bituman as well as the operability of the process, but the metal loading must depend on the cost of materials, tolerable ash content and optimum catalyst activity.
The catalyst can be coated on the coal by spraying an aqueous solution of a metal salt on the coal particles.
The coal may either be partially dried to reduce the moisture content before blending with the feed stock, or it may be used with a predetermined moisture content.
The coal particles can vary widely in size and are preferably less than 60 mesh (Canadian Standard Sieve), with a material which will pass through a 100 mesh sieve being particularly preferred. The particle si~e is determined primarily by the hydrodynamic characteristics of the reactor. The coal should be mixed with the bitumen in such a manner as to avoid formation of lumps and, if desired, additional homogeneous or heterogeneous catalyst may be mixed with the coal-bitumen slurry.
The additional catalysts are typically active hydro-genation and desulphurization catalysts. They may include such materials as Co~Mo-alumina and Ni-Mo alumina or metals from Groups VIb and VIII of the Periodic Table.
According to another feature of the invention, the heavy hydrocarbon feed may contain about 0.05 to 10 wt% oE
a coke suppressing agent. As such agent there may be mentioned high ash coal, coal washing rejects, fly ash, iron-coal and coal coated with metal catlysts.
According to a preferred embodiment, the bitumen is pumped through a heater and fed with synthesis gas through a vertical empty t~be reactorO The liquid-gas mixture from the top oE the hydrocracking ~one is separated in a hot separator maintained at a temperature in the range of about 200C up to the hydrocracking zone temperature and at the pressure of the hydrocracking zone. The heavy hydrocarbon product from the hot separator can be partially recycled to the hydrocracking zone or sent to secondary treatment.
The gaseous stream from the hot separator containing a mixture of hydrocarbon gases and hydrogen is further cooled and separated in a low temperature-high pressure separator~
By using this type of separator, the outlet gaseous stream obtained contains mostly H2, CO and CO2 with some impurities such as hydrogen sulfide and light hydrocarbon gases. This aseous stream is passed through a scrubber and the scrubbed hydrogen-rich stream is recycled as part of the synthesis gas feed to the hydrocracking process.
The liquid stream from the low temperature-high pres~
sure separator represents the light hydrocarbon product of the present process and can be sent for secondary treatmentO

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Some of the coal may be carried over with the heavy oil product from the hot separator and found in the 524C.
pitch fraction. This coal can conveniently be burned or gasified with the pitch.
For a better understanding of the invention, reference is made to the accompanying drawing which illustrates diagramatically a preferred embodiment of the present invention.
Heavy hydrocarbon oil feed and coal are mixed together in a feed tank 10 to form a slurry. This slurry is pumped via feed pump 11 through inlet line 12 into the bottom of an empty tower 13. Recycled synthesis gas and make up synthesis gas rom line 30 is simultaneously fed into the tower 13 through line 12. A gas-liquid mixture is with-drawn from the top of the tower through line 14 and intro~
duced into a hot separator 15. In the hot separator the effluent from tower 13 is separated into a gaseous stream 18 and a liquid stream 16. The liquid stream 16 is in the form of heavy oil which is collected at 17.
The gaseous stream from hot separator 15 is carried by way of line 18 into a high pressure-low temperature separator 19. Within this separator the product is separated into a gaseous stream rich in hydrogen which is drawn off through line 22 and an oil product which is drawn off through line 20 and collected at 21.
The hydrogen rich stream 22 is passed through a packed scrubbing tower 23 where it is scrubbed by means of a scrubbing liquid 24 which is cycled through the tower by means of pump 25 and recycle loop ~6. The scrubbed hydrogen rich stream emerges from the scrubber via line 27 and is combined with fresh make up synthesis gas added through line 28 and recycled through recycle gas pump 29 and line 30 back to tower 13.
Certain preferred embodiments of this invention will now be further illustrated by the following non-limitative example.

~t~
_g_ Example A series of tests were conducted in a reaction vessel in the form of a stirred autoclave having a capacity of 2 litres. The allowable working pressure was 34.5 MPa at a maximum temperature of about 485C. The content of the vessel was stirred by a magnetically operated impeller rotating at 1250 rpm.
The autoclave was heated by an external heating coil and the assembly was insulated. The inside temperature was measured by means of a thermocouple inserted into a well, extending from the top to about 5.1 cm from the bottom. The outside skin temperature was measured by a thermocouple placed against the vessel wall in the middle of the heated section.
As feedstock there was used a bitumen having the following properties:
Specific Gravity, 15/15C.1.013 Sulphur, Wt. % 4.74 Ash, wt. % 0.59 Conradson Carbon Residue, wt. % 17.9 Pentane insolubles, wt. %16.8 Benzene insolubles, wt. %0.52 Carbon, wto ~ 81.93 Hydrogen, wt. ~ 10.03 Nitrogen, wt. % 0.42 Vanadium, ppm by wt. 162 Viscosity, Kinematic, cSt at 38C or 100F 23.83 50C or 122F 69.78 55C or 130F 43.38 99C or 210F 162 Pitch, wt. % 53.76 Distillate, wt. % 46.24 Different fractions of the distillate - IBP to 205C, Vol. % 2.8 205 to 345C, Vol. % 11.8 345 to 524C, Vol. % 77.4 The catalyst used in the tests was an FeSO4/coal catalyst formed by spraying a solution of FeSO4 on sub-bituminous coal particles, resulting in a particulate catalyst having the following analysiso Carbon, wt. % 49.19 Hydrogen, wt. ~ 3.52 Nitrogen, wto ~ 0.62 Sulphur, wt. ~ 3.62 Vanadium 5 (ppm by wt) Nickel 13 (ppm by wt) Titanium 718 (ppm by wt) Iron, wt. % 5.8 The autoclave was charged with about 500g of bitumen and for certain of the runs about 10g (2 wt. ~ of feed) of the above catalyst was added to the bitumen. After elushing twice with hydrogen, the vessel was pressurized with a syn-thesis gas consisting of E~2~CO at ambient temperature to give approximately 14 MPa at 450C. The reactor was heated to 450C in about four hours and this temperature was main tained for one hour. After one hour at reaction temperature, the vessel was allowed to cool to room temperature.
At ambient temperature the gases were metered into a plastic gas holder and two representative samples were collected for analysis. The vessel was opened and total liquid and solid samples were collected for analysisO
To demonstrate that hydrogen can be successfully replaced by a much cheaper synthesis gas, experiments were conducted using a gas mixture containing CO and H2 in the molar ratio of 1:2. In order to provide simulated steam injection, about 10 grams of water was charged into -the reactor vessel with the bitumen.
On the above basis, a series of tests were carried out, one set of tests being without catalyst and the other set be-ing with the FeSO4/coal catalyst present. The operating con-ditions for six different tests are shown in Table 1. Test #l represents a run using hydrogen, Test #2 uses a synthesis gas containing CO and H2 in the ratio 1:2 and Test #3 is a repeat of Test #2 with water added to simulate steam injection, all 35 three tests being without catalyst. Tests #4, 5 and 6 are repeats of Tests #1, 2 and 3 with the catalyst present.
Table 2 shows the product yields from the six different experiments and it is particularly noteworthy that the liquid yields increased significantly when synthesis gas was used in ~. ~, 2 L ~

place of hydrogen. Pitch conversions remained relatively constant and hydrogen consumption decreased. The substan-tial drop in Test #3 indicates that hydrogen was generated by the water-gas shift reaction.
In Table 3 below there is shown the properties of the liquid products and with the use of synthesis gas, the H/C
atomic ratio increased, as did the yields of the different fractions.
Table 4 shows the properties of different fractions of the liquid product and the fraction falling between IBP
and 200C showed a slight increase in sulphur content, while all other properties remained substantially constant.
The properties of the solid product are shown in Table 5 and, although H/C atomic ratio was increased, sulphur and nitrogen contents were also increased.
An analysis of the gases is given in Table 6 and for Test #3, the CO2 concentration was highest because most of the CO was converted to CO2 from the water-gas shift reaction producing more available hydrogen. For the synthesis gas runs, the concentration of hydrocarbon gases decreased and this was probably due to conversion to liquid products.
From the above results, it is clear that in the hydro-cracking of bitumen and heavy oils and simultaneously hydrogenation of bitumen and coal, in the presence or absence of active catalysts, if hydrogen is replaced by synthesis gas the liqu;d yield and H/C atomic ratio of liquid and solid increases. There is little effect on the other properties. Furthermore, hydrogen consumption decreased by as much as 34%, probably because hydrogen i5 produced in the reaction zone from the moisture present in the coal or from the presence of steamO This means that in an upgrading process using synthesis gas, the high capital cost and operating cost involved in hydrogen generation, puri~ication and separate water/gas shift step, is significantly reduced. Another advantage is the pro-duction of lighter hydrocarbons produced from the chemical reaction of C, CO and H2O in the hydrocracking zone.

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;.1 . .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for hydrocracking a heavy hydrocarbon oil, a substantial proportion of which boils above 524°C which comprises:
(a) passing a heavy hydrocarbon oil feed in the pres-ence of a hydrogen-containing synthesis gas in an amount sufficient to provide 500 - 50,000 s.c.f. of hydrogen per barrel of said hydrocarbon oil through a confined hydro-cracking zone, said hydrocracking zone being maintained at a temperature between about 400 and 500°C., a pressure above 500 psig and a space velocity between about 0.5 and 4.0 volumes of heavy hydrocarbon oil per hour per volume of hydrocracking zone capacity, (b) removing from said hydrocracking zone a mixed effluent containing a gaseous phase comprising vaporous hydrocarbons, H2O, H2, H2S and carbon oxides and a liquid phase comprising heavy hydrocarbons, and (c) separating said effluent into a gaseous stream containing vaporous hydrocarbons, H2O, H2, H2S and carbon oxides and a liquid stream containing heavy hydrocarbons.

2. A process according to claim 1 wherein the heavy hydrocarbon oil feed is moved upwardly through a tubular reactor.

3. A process according to claim 1 wherein the hydro-cracking is conducted at a pressure in the range of 500 -3,500 psig.

4. A process according to claim 1, 2 or 3 wherein the mixed effluent is separated in a hot separator maintained at a temperature between 200°C and the hydrocracking zone temperature and the hydrocracking zone pressure.

5. A process according to claim 1 wherein the heavy hydro-carbon oil is selected from bitumen from tar sands/ oil shale, in situ production of heavy oil, refining bottoms and residuum.

6. A process according to claim 1 wherein the feed also contains 0.1 to 60 wt. % coal.

7. A process according to claim 6 wherein the coal is -60 mesh (U.S. Sieve).

8. The process according to claim 7 wherein the coal is selected from sub-bitumous, bituminous, and lignite coal and peat.

9. A process according to claim 6 wherein at least a portion of the coal is coated with up to about 20 wt. % of a metal catalyst.

10. A process according to claim 9 wherein the catalyst metal is in the form of a compound of iron, cobalt, molybdenum, zinc, tin, nickel or tungsten.

11. A process according to claim 6 wherein the hydrocracking is conducted in the presence of an active hydrogenation and desulphurization catalyst.

12. A process according to claim 11 wherein said catalyst is selected from Co-Mo-alumina, and Ni-Mo-alumina.

13. A process according to claim 11 wherein said catalyst is selected from metals from Groups VIb and VIII of the Periodic Table.

14. A process according to claim 1 wherein the feed also contains 0.05 to 10 wt % coke suppressing agent.

15. A process according to claim 14 wherein the coke suppressing agent is selected from high ash coal, coal washing rejects, fly ash, iron-coal and coal coated with metal catalysts.

16. A process according to claim 1 wherein a portion of the heavy oil product is recycled back to the hydrocracking zone.

17. A process according to claim 1, 2 or 6 wherein the synthesis gas comprises H2 and C0 as the main components.

18. A process according to claim 1, 2 or 6 wherein the synthesis gas comprises H2 and C0 as the main components with the H2 being present in an amount of at least 45 mole percent.

19. A process according to claim 1, wherein the reaction between the oil feed and synthesis gas takes place in the presence of water in the form of steam.

20. A process according to claim 19 wherein water is added by steam injection.