NL8101510A - PROCESS FOR HYDRO CRACKING OF HEAVY HYDROCARBONS USING SYNTHESIS GAS. - Google Patents

Description

ί '' VC 1774

Method of hydrocracking of black hydrocarbon fan using synthesis gas.

The present invention relates to hydrocracking and more particularly to hydrocracking heavy hydrocarbon oil, such as tar sand bitumen, in the presence of synthesis gas.

Hydrocracking processes for converting heavy hydrocarbon oils into light and intermediate good quality naphthas for reforming feed material, fuel oil and gas oil are known. These heavy hydrocarbon oils can be such materials as crude oil, atmospheric tar residue products, vacuum tar residue products, heavy recycle oils, slate oils, coal liquids, crude petroleum residues, capped crudes and the heavy bituminous oils extracted from tar sands. Of particular interest are the oils extracted from tar sands containing materials with ample boiling ranges from naphtha via kerosene, gas oil, pitch, etc., and equivalent to a high proportion, usually greater than 50 wt%, with a boiling point above 524 ° C atmospheric boiling point.

The heavy hydrocarbon oils of the above-mentioned type generally contain nitrogenous and sulfur-containing compounds in fairly large concentrations. Furthermore, such heavy hydrocarbon fractions often contain excessively large amounts of organometallic impurities which are particularly detrimental to various catalytic processes which can be carried out subsequently, such as hydrofining. In the metallic impurities, those containing nickel and vanadium are the most normal, although other metals are often present. These metallic impurities, as well as others, are usually present in the bituminous material as relatively high molecular weight organometallic compounds. A significant amount of the organometallic complexes are coupled with asphaltenic material 81015 10 ** - 2 - and contain sulfur. Of course, in catalytic hydrocracking processes, the presence of large amounts of asphaltenic material and organometallic compounds will significantly interfere with the catalyst's activity in destructively removing nitrogen, sulfur and oxygen containing compounds.

A typical Athabasca bitumen may contain 53.76 wt% material boiling above 524 ° C, 4.74 wt% sulfur, 0.59 wt% nitrogen, 162 ppm vanadium and 72 ppm nickel.

As the reserves of normal crude oils are decreasing, these heavy oils must be reprocessed to meet demand. In this work-up, the heavier material is converted into lighter fractions and most of the sulfur, nitrogen and metals must be removed. This is usually done by a coking process such as delayed or fluxed coking or by a hydrogen addition process such as thermal or catalytic hydrocracking. The distillate yield from the boiling process is about 70 wt.% And this process also provides about 23 wt.% Coke as a by-product that cannot be used as a fuel because of the low hydrogen / carbon ratio and high mineral and sulfur content. Depending on the process conditions, hydrogenation processes can give a distillate yield of more than 87% by weight.

In the case of catalytic hydrocracking, the asphalts and mineral material contained in the bitumen and heavy oils have detrimental effects on the life of the expensive catalysts used in the catalytic hydrocracking, resulting in increased treatment and production costs. It has been found that methods using hydrogen addition at high pressures and tenperating are suitable for hydrogenating and / or hydrocracking high molecular weight compounds to produce materials with lower boiling rates.

Desulfurization, demetallization and denitrification reactions take place simultaneously. Reaction pressures up to 24 MPa and temperatures up to 490 ° C have been used for this purpose.

In thermal hydrocracking, a major problem is the deposition of solids in the reactor, especially when operating at relatively high pressures, resulting in costly shutdowns. There are deposits at the top of the reactor where the partial water pressure and asgenalta are lowest. Working at higher pressures e.g. at 5 24 MPa and 470 ° C, the deposition in the reactor is considerably reduced.

Because much of the capital and process costs in a hydrocracking plant relate to hydrogen, efforts have been made to develop tools that allow the plant to operate at lower pressures at IQ. Such a net method is described in

U.S. Patent 4,214,977. These methods also serve to suppress coke formation during conditions that would otherwise lead to serious process problems. Another method involves simultaneous bitumen / hydrocarbon cracking.

A method 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. 58-65, 1375. In this method, a synthesis gas, reducing agent and moisture in the carbon were used as the hydrogen source.

It was observed that carbon monoxide has been selected for the reduction of o-carbonyl groups, whereas cracking reactions to a greater extent take place with hydrogen. It is believed that the greater activity of carbon monoxide in the reduction of carbonyl groups is the reason that low-classified carbons liquefy more easily in the presence of carbon monoxide than of hydrogen. Low-classified carbons not only contain more o-carbonyl groups than higher-classified ones, but also contain the organically bound alkali metals which are converted into formates, the probably active reducing agents.

U.S. Patent 3,565,784 describes a continuous process for recovering oil from a slurry crude oil slate oil slurry. Water and hot quenched synthesis gas from the reaction zone of a partial oxidation-35 generator are injected into the crude oil / slate oil slurry under pressure 81015 * 10 - 4 - and the mixture is immediately introduced into a non-catalytic tubular retort, maintained at a temperature in the range of 455-510 ° C and a pressure in the range of 2-7 MPa for maximum yield of slate oil with a minimum nitrogen content, Virtually all hydrogen and a large part of the tubular retort required heat, is provided by the synthesis gas. .

United States Patent 3,517,471 discloses a method of injecting synthesis gas and water into slate oil at a relatively moderate temperature and pressure producing high quality slate oil with the addition of H 2 O reducing hydrogen consumption. Another US patent, 3,617,472, discloses a process for recovering slate oil from oil-containing slate by treating with synthesis gas in a reactor. This patent discloses that additional hydrogen is produced in slate oil retorts by the water gas shift reaction, the slate acting as a catalyst.

The object of the invention is to provide a process for hydrocracking heavy hydrocarbon oil while reducing costs by replacing the usual hydrogen with synthesis gas.

The invention relates to a hydrocracking process of a heavy hydrocarbon oil, a large portion of which boils above 524 ° C comprising: directing a heavy hydrocarbon oil feed in the presence of a hydrogen-containing synthesis gas in an amount sufficient to provide of 14 - 1400 m hydrogen per barrel of said hydrocarbon oil through a limited hydrocracking zone, which hydrocracking zone is maintained at a temperature between 400 and 500 ° C, a pressure of at least 3.5 MPa and a space velocity between 0.5 and 4 volumes 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, rLG, H 2 and Co oxides and a liquid phase comprising ά heavy hydrocarbons and c 3 just separating said effluent into a gaseous stream containing vaporous hydrocarbons, H 2 O, and Koolox yden 5 and a liquid stream containing heavy hydrocarbons.

Although the process of the invention is particularly suitable for treating bitumen or heavy oil, it is also particularly suitable for treating topped bitumen, pitch, oil shale, refinery residues, residues, etc.

It can be performed at very moderate pressures e.g. in the range of 3.5 - 24 MPa transmitter coking in the hydrocracking zone.

the hydrocracking process of the invention can be carried out in a variety of known reactors with either upstream or downflow. For example, the hydrocracking reaction zone may be an empty tubular reactor, a boiling bed reactor or a fluidized bed reactor. The empty tubular reactor has been found to be particularly suitable in that the effluent from the top is separated in a hot separator and the gaseous stream from the hot separator is fed to a low temperature high pressure separator in which it is separated into a gaseous stream. contains hydrogen and minor amounts of gaseous hydrocarbons and a liquid product stream containing light oil products. It is also possible to have the reactors in stages, the first reactor being an empty tubular reactor and the second reactor containing a boiling bed of catalyst extrudates.

Synthesis gas is typically a gas mixture containing HjO and CO as its main components and contains 1-99 mole% H 2> preferably at least 45 mole% often along with some minor amounts of other gases such as C 2, H 2 O and h 2 S. According to a preferred embodiment, water can be present in the form of steam. The synthesis gas can be produced by virtually any hydrocarbon material suitable for loading a synthesis gas regenerator, e.g. natural gas, propane, butane, reduced crude oil, total crude oil, etc. However, part of the oil product obtained in the process of the invention is the 81015 10-6 preferred source of hydrocarbon material. Likewise, the oxidizing gas supplied to the synthesis gas generator can be selected from air, oxygen and oxygen-enriched air.

The heavy hydrocarbon feed can be treated as is along with synthesis gas, or a slurry of the heavy hydrocarbon oil and coal can be formed. The coal is typically included in amounts of 0.1-60% by weight.

Any type of coal, such as lignite, subbituminous, bituminous, etc. or peat, can be used as the cage part of the loading suspension. The coal can be used as is without any addition or at least a portion of it can be coated with up to about 20% by weight of a metal catalyst such as iron, cobalt, molybdenum, zinc, tin, tungsten, nickel or other catalytically active salts. The use of the catalytic materials improves the conversion of coal and bitumen as well as the effectiveness of the process, but the metal loading must depend on the cost of materials, acceptable ash content and optimum catalyst activity.

The catalyst can be coated on the carbon by spraying an aqueous solution of a metal salt on the carbon particles. The carbon can either be partially dried to lower the moisture content for mixing with feed material or it can be used with a predetermined moisture content.

The carbon particles can vary widely in size and are preferably less than 60 mesh (Canadian standard sieve3, with a material passing through a 100 mesh sieve being particularly preferred. The particle size is mainly determined by the hydrodynamic properties of the reactor. The carbon should be mixed with the bitumen in such a way as to avoid the formation of chunks and any further homogeneous or heterogeneous catalyst may be mixed with the carbon bitumen slurry.

The catalysts added are typically active hydrogenation and desulfurization catalysts. They may include such materials as Co-Mo alumina and Ni-Ho alumina or metals of the groups VIb and VIII of the Periodic System.

81015 10 - 7 -

According to a characteristic feature of the invention, the heavy hydrocarbon feed may contain about 0.05-10 wt.% Of a KooKsonoer crusting agent. As such means can be mentioned high ash cage, Carbon scrub, fly ash, iron coal and coal coated with metal catalysts.

In a preferred embodiment, the bitumen is pumped through a heater and fed with synthesis gas through a vertical empty tube reactor. The liquid gas mixture from the top of the hydrocracking zone is separated in a hot separator maintained at 1D a temperature in the range of about 200 ° C to the hydrocracking zone temperature and at the pressure of the hydrocracking zone. The heavy hydrocarbon cool product from the hot separator can be partially recirculated to the hydrocracking zone or transported to a second treatment.

The gaseous stream from the hot separator, which contains a mixture of hydrocarbon gases and hydrogen, is further cooled and separated in a low temperature-high pressure salt. By using this type of separator, the resulting effluent gas stream mainly contains CO and CO2 with some impurities such as hydrogen sulfide and light hydrocarbon gases. This gaseous stream is passed through a scrubber and the washed hydrogen-rich stream is recycled as part of the synthesis feed to the hydrocracking process.

The liquid stream from the low temperature-high pressure separator is the light hydrocarbon product of the present process and can be used for additional treatment.

Some of the cabbage can be carried with the hot oil product from the hot separator and found in the 524 ° C + pitch-30 fraction. This cabbage can be conveniently burned or gassed with the pitch.

For a better understanding of the invention, reference is made to the drawing which diagrammatically illustrates 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 through supply pump 11 through supply line 12 into the bottom of an empty column 13. Recirculated synthesis gas and additional synthesis gas from line 30 is fed simultaneously into column 13 through line 12. A gas-liquid mixture is withdrawn from the top from the column through line 14 and introduced into a hot separator 15. In the hot separator, the effluent from column 13 is separated into a gaseous stream 18 and a liquid stream 16. The liquid stream 16 is in the form of a heavy oil 10 which is received at 17.

The gaseous stream from the hot separator 15 is introduced via line 18 into a high pressure low temperature separator 19.

In this separator, the product is separated into a gaseous stream rich in hydrogen which is discharged via line 22 and 15 and an oil product which is discharged via line 20 and collected at 21.

The hydrogen-rich stream 22 is passed through a packed washing tower 23, in which it is washed by means of a washing liquid 24 which is circulated through the tower using a pump 25 and recirculation line 26. The washed hydrogen-rich stream leaves the washing device via line 27 and is combined with fresh supplemental synthesis gas added through line 20 and recycled through recirculation gas pump 29 and line 30 back to column 13. Certain preferred embodiments of the invention will now be further illustrated by the following non-limiting example.

Example

A series of tests were performed in a 3 dm stirred autoclave reaction vessel. The permissible operating pressure was 34.5 MPa at a maximum temperature of about 485 ° C. The contents of the vessel were stirred with a magnetically driven stirrer, rotating at 1250 rpm.

The autoclave was heated by an external heating coil and the assembly was isolated. The internal temperature was determined by means of a thermocouple inserted into a shaft, protruding from the top to about 5.1 cm from the bottom. The outer skin temperature was determined by a thermocouple placed against the vessel wall in the center of the heated section.

The feed material used was a bitumen with the following properties: specific gravity, 15/15 ° C 1, G13 sulfur, wt.% 4.74 ash, wt.% 0.59

Conradson carbon residue, wt%. 17.3 10 pentane, insoluble, wt% 16.6 benzene insoluble, wt% 0.52 cod, wt% 51.33 hydrogen, wt% 10.03 nitrogen, wt% 0.42 vanadium, ppm CgewJ 182 kinematic viscosity, cSt at 38 ° C 23.33 50 ° C 69.78 55 ° C 43.38 20 99 ° C 1S2 pitch, wt% 53.76 distillate, wt% 46.24 different fractions of the distillate initial boiling point to 205 ° C, vol.% 2.8 25 205 - 345 ° C, vol.% 11.8 345 - 524 ° C, vol.% 77.4 □ The catalyst used in the test was a FeSO4. / carbon catalyst formed by spraying a solution of reSO 2 onto sub-bituminous carbon particles resulting in a particulate catalyst with the analysis below: carbon, wt% 49.19 hydrogen, wt% 3.52 nitrogen, wt .% 0.62 sulfur, wt.% 3.62 35 vanadium (cppm) 81 015 10 - 10 - nickel 13 [wppm] titanium 718 (wppm) iron, wt% 5.8

The autoclave was charged with about 500 g of bitumen and for some of the runs, about 10 g [2 wt%, based on the feed] of the above catalyst was added to the bitumen. After purging with hydrogen twice, the vessel was pressurized with a synthesis gas consisting of h 2 -CO at ambient temperature to obtain about 14 MPa at 450 ° C. The reactor was heated to 450 ° C in about 4 hours and this temperature was maintained for 1 hour. After 1 hour of reaction temperature, the vessel was allowed to cool to room temperature. At ambient temperature, the gases were dosed into a plastic gas container and two representative samples were collected for analysis.

The vessel was opened and the total of liquid and solid samples were collected for analysis.

To demonstrate that hydrogen can be successfully replaced by a much cheaper synthesis gas, tests were conducted using a gas mixture containing CO and H 2 in the 1: 2 mol-20 ratio. To provide a simulated steam injection, about 10 g of water into the reaction vessel with the bitumen.

A series of tests was carried out on the above basis, one series without a catalyst and the other set with a FeSO 2 / carbon catalyst present. The process conditions for six different runs are listed in Table A. Run No.1 is a run using hydrogen, Run No.2 uses a synthesis gas containing CO and H2 in a 1: 2 ratio, and Run No. 3 is a repeat of Run No.2 with added water to simulate steam injection while all three runs are without a catalyst. Runs 4, 5 and 6 are repeats of runs 1, 2 and 3 with the catalyst present.

Table B shows the product yields of the six different ones. and it is particularly noteworthy that the liquid yields increased significantly when using synthesis gas instead of hydrogen. Pitch conversions remained relatively constant 81015 10-11 - hydrogen consumption decreased. The major downturn in Run 3 indicates that hydrogen was generated by the water gas shift reaction.

Table C shows the properties of the liquid products and with the use of synthesis gas, the H / C atomic ratio increased as well as the yields of different fractions.

Table D shows the properties of different fractions of the liquid product and the fraction falling between the initial boiling point and 200 ° C showed a slight increase in sulfur content, while all other properties remained essentially constant.

The properties of the solid product are shown in Table E and although the H / C atomic ratio had increased, the sulfur and nitrogen contents had also increased.

An analysis of the gases is given in Table F sn for Run 3, the CC 2 concentration was highest because most of the CO had been converted to CO2 from the water gas shift reaction producing more available hydrogen. For the synthesis gas tests, the concentration of hydrocarbon gases decreased and this was likely due to conversion to liquid products.

From the above results it appears that in the hydrocracking of bitumen and heavy oils and simultaneous hydrogenation of bitumen and coal in the presence or absence of active catalysts, when hydrogen is replaced by synthesis gas, the liquid yield and the H / C atomic ratio of liquid and solid dust increases. There is little effect on the other properties. Furthermore, hydrogen consumption decreases by as much as 34% presumably because hydrogen is produced in the reaction zone from the moisture contained in the coal or from the presence of steam. This means that in a reprocessing process using synthesis the high capital and process costs involved in the hydrogen generation, purification and individual water / gas shift step are significantly reduced. Another advantage is the production of lighter hydrocarbons produced by the chemical reaction of C, CO and H 2 O in the hydrocracking zone.

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Claims (19)

A method of hydrocracking a heavy hydrocarbon oil, much of which boils above 524 ° C, wherein a heavy hydrocarbon oil feed in the presence of hydrogen is passed through a limited hydrocracking zone, which hydrocracking zone is maintained at a temperature between about 400 and 500 ° C, a pressure above 3.5 MPa and a space velocity between 0.5 and 4.0 volume of heavy hydrocarbon oil per hour per volume of hydrocracking zone capacity, characterized in that the hydrogen is supplied in the form of synthesis gas in an amount sufficient to provide 14-1,400 m hydrogen per barrel of the hydrocarbon oil through the hydrocracking zone, from said hydrocracking zone a mixed effluent containing a gaseous phase comprising vaporous hydrocarbons, h 2 O, 1, h ^ S and carbon oxides, and a liquid phase containing heavy hydrocarbons is removed and said effluent is separated into a gaseous stream containing vapor Some hydrocarbons, H 2 O, H 2 S and carbon oxides, and a liquid stream containing heavy hydrocarbons. A method according to claim 1, characterized in that the heavy hydrocarbon oil feed is moved upward through a tubular reactor 20. Process according to claim 1, characterized in that the hydrocracking takes place at a pressure in the range of 3.5 - 24 MPa. 4. Process according to claims 1-3, characterized in that the mixed effluent is maintained in a hot separator at a temperature between 200 ° C and the hydrocracking zone temperature and at the pressure of the hydrocracking zone. 5. Process according to claims 1-4, characterized in that the heavy hydrocarbon oil is selected from bitumen from tar sands, oil slate, in situ production of heavy oil, refining residues and residue. 6. Process according to claims 1-5, characterized in that the feed also contains 0.1-60% by weight of carbon. 81015 10 T 3 * - 21 - A method according to claim 5, characterized in that the Cool is -SC mesh CL1.S. Sieve]. A method according to claim 7, characterized in that the cage is selected from sub-bituminous, bituminous and lignite col and peat. Process according to claim B, mez characterized in that at least part of the carbon is coated with up to about 2G wt.% Of a metal catalyst. 10. Process according to claim 9, characterized in that the catalyst is metal in the form of a compound of iron, cobalt, molybdenum, zinc, tin, nickel or tungsten. Process according to claim 6, characterized in that the hydrocracking is carried out in the presence of an active hydrogenation and desulfurization catalyst. 12. Process according to claim 11, characterized in that said catalyst is selected from Co-Mo-alumina and Ni-Plo-alumina. Process according to claim 11, characterized in that said catalyst is selected from metals of groups VIb and VIII of the Periodic System. 14. Process according to claims 1 -13, characterized in that the feed also contains 0.05-10% by weight of a coke suppressant. A method according to claim 14, characterized in that the coke suppressant is selected from high ash coal, carbon wax waste, fly ash, iron coal and coal coated with metal catalysts. 25 1B. Process according to claims 1-15, characterized in that part of the heavy oil product is recycled back to the hydrocracking zone. Process according to claims 1 to 16, characterized in that it contains synthesis gas and CO as main components. Process according to claim 17, characterized in that it contains synthesis gas and CO as main components, in which it is present in an amount of at least 45 mol%. 19. Process according to claims 1-18, characterized in that the reaction between the oil supply and the synthesis gas takes place in the presence of water in the form of steam. 81015 10 y t »- 22 - A method according to claim IS, characterized in that water is added by steam injection. , v * 81015 10