CA1073389A - Removal of metals and coke during thermal hydrocracking of heavy hydrocarbon oils - Google Patents
Removal of metals and coke during thermal hydrocracking of heavy hydrocarbon oilsInfo
- Publication number
- CA1073389A CA1073389A CA269,020A CA269020A CA1073389A CA 1073389 A CA1073389 A CA 1073389A CA 269020 A CA269020 A CA 269020A CA 1073389 A CA1073389 A CA 1073389A
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- Prior art keywords
- particles
- hydrocracking
- reactor
- metals
- coal
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
REMOVAL OF METALS AND COKE DURING
THERMAL, HYDROCRACKING OF HEAVY HYDROCARBON OILS
Abstract An improved process is described for thermally hydrocracking heavy hydrocarbon oil, e.g. bitumen. According to the improvement, the hydrocracking is conducted in a cracking zone in the presence of small carbonaceous particles, e.g. coal, whereby metals and coke formed during the hydro-cracking reaction are deposited as a coating on the carbon-aceous particles and the coated particles are separated from the reaction system. This process is useful in minimizing coke buildup in the cracking zone and in removing metals which tend to act as catalyst poisons in subsequent catalytic treatments of the oil. The carbonaceous particles coated with coke, metals, and clay obtained can be used subsequently as fuel or subjected to gasification.
THERMAL, HYDROCRACKING OF HEAVY HYDROCARBON OILS
Abstract An improved process is described for thermally hydrocracking heavy hydrocarbon oil, e.g. bitumen. According to the improvement, the hydrocracking is conducted in a cracking zone in the presence of small carbonaceous particles, e.g. coal, whereby metals and coke formed during the hydro-cracking reaction are deposited as a coating on the carbon-aceous particles and the coated particles are separated from the reaction system. This process is useful in minimizing coke buildup in the cracking zone and in removing metals which tend to act as catalyst poisons in subsequent catalytic treatments of the oil. The carbonaceous particles coated with coke, metals, and clay obtained can be used subsequently as fuel or subjected to gasification.
Description
- ~733~
This invention relates to a process for thermally hydrocracking heavy petroleum oils containing a substantial amount of material which boils above 975F, for example bitumens obtained from oil sands.
Commericial interest in the catalytic hydrocracking of heavy oils to distillate fuels is increasing rapidly as supplies of conventional oil decline. Typical of these heavy oils are heavy residual oil and tars such as atmospheric and vacuum bottoms materials produced in petroleum refiners and 10 bitumens such as those from the oil sands in ~orthern Alberta.
Of course, in terms of quantities, the oil sands are of great interest as a source of distillate fuels.
Most of the residual oils which are likely candidates for^catalytic hydrocracking contain high concentrations of asphaltenes and organometallic compounds. For example, bitumen from the oil sands is a heavy, viscous, tarry material containing high concentrations of chemically combined impurities such as sulphur, nitrogen, nickel and vanadium and includes as much as 16% asphaltic material (pentane insolubles). Extensive refining and upgrading is required to convert this material to conven-tional fuels (dlesel fuels, domestic furnace oil, etc.).
Basically, the refining and upgrading consist of:
a) cracking processes to reduce molecular weight (convert the residuum to distillate fractions), and b) hydrogenation processes to stabilize the hydro-carbon fraction produced in the cracking stage and to remove sulphur and nitrogen impurities.
The only commercial operation presently being used on bitumen from oil sands accomplishes the cracking phase of the upgrading process by delayed coking. A fluid coking process will be used for the second commercial operation. With all the coking ~ .
processes the clay and metals impurities remain in the coke, and the coker distillate fractions are hydrogen treated in a second step. The quality of the synthetic crude generated by this technique is good but the yield is low.
The thermal hydrocracking process for converting bitumen to lower boiling distillate fraction is superior to coking processes in at least two major respects. Firstly, the quantity of distillate obtained is significantly larger.
Secondly, hydrocracking produces a higher quality of distillate than the coking processes. Reactions resulting in sulphur ; removal~ nitrogen removal and the hydrogenation of unsaturated - compounds, take place to a much greater extent during hydrocracking then during coking.
However, thermal hydrocracking does have a major disadvantage. With most residuum type feedstocks there is considerable coke formation which soon interferes with the operation of the hydrocracking reactor and there are also substantial metal accumulations in the reactor, particularly at high conversion levels.
It is, therefore, the object of the present invention to resolve the problem of metal deposition and sludge accumulation at high conversion levels in the thermal hydrocracking of heavy oils.
Thus, in accordance with the present invention there is provided an improved process for thermally hydrocracking heavy oil wherein the oil is subjected to thermal cracking at temperatures in excess of 350C and pressures in excess of 1000 psig in a cracking zone in the presence of a flow of free-hydrogen containing gas. The inventive feature comprises conducting the hydrocracking in the presence of small carbonaceous particles, whereby metals and coke formed during the hydrocracking reaction are deposited as a coating on the carbonaceous particles and separating the coated
This invention relates to a process for thermally hydrocracking heavy petroleum oils containing a substantial amount of material which boils above 975F, for example bitumens obtained from oil sands.
Commericial interest in the catalytic hydrocracking of heavy oils to distillate fuels is increasing rapidly as supplies of conventional oil decline. Typical of these heavy oils are heavy residual oil and tars such as atmospheric and vacuum bottoms materials produced in petroleum refiners and 10 bitumens such as those from the oil sands in ~orthern Alberta.
Of course, in terms of quantities, the oil sands are of great interest as a source of distillate fuels.
Most of the residual oils which are likely candidates for^catalytic hydrocracking contain high concentrations of asphaltenes and organometallic compounds. For example, bitumen from the oil sands is a heavy, viscous, tarry material containing high concentrations of chemically combined impurities such as sulphur, nitrogen, nickel and vanadium and includes as much as 16% asphaltic material (pentane insolubles). Extensive refining and upgrading is required to convert this material to conven-tional fuels (dlesel fuels, domestic furnace oil, etc.).
Basically, the refining and upgrading consist of:
a) cracking processes to reduce molecular weight (convert the residuum to distillate fractions), and b) hydrogenation processes to stabilize the hydro-carbon fraction produced in the cracking stage and to remove sulphur and nitrogen impurities.
The only commercial operation presently being used on bitumen from oil sands accomplishes the cracking phase of the upgrading process by delayed coking. A fluid coking process will be used for the second commercial operation. With all the coking ~ .
processes the clay and metals impurities remain in the coke, and the coker distillate fractions are hydrogen treated in a second step. The quality of the synthetic crude generated by this technique is good but the yield is low.
The thermal hydrocracking process for converting bitumen to lower boiling distillate fraction is superior to coking processes in at least two major respects. Firstly, the quantity of distillate obtained is significantly larger.
Secondly, hydrocracking produces a higher quality of distillate than the coking processes. Reactions resulting in sulphur ; removal~ nitrogen removal and the hydrogenation of unsaturated - compounds, take place to a much greater extent during hydrocracking then during coking.
However, thermal hydrocracking does have a major disadvantage. With most residuum type feedstocks there is considerable coke formation which soon interferes with the operation of the hydrocracking reactor and there are also substantial metal accumulations in the reactor, particularly at high conversion levels.
It is, therefore, the object of the present invention to resolve the problem of metal deposition and sludge accumulation at high conversion levels in the thermal hydrocracking of heavy oils.
Thus, in accordance with the present invention there is provided an improved process for thermally hydrocracking heavy oil wherein the oil is subjected to thermal cracking at temperatures in excess of 350C and pressures in excess of 1000 psig in a cracking zone in the presence of a flow of free-hydrogen containing gas. The inventive feature comprises conducting the hydrocracking in the presence of small carbonaceous particles, whereby metals and coke formed during the hydrocracking reaction are deposited as a coating on the carbonaceous particles and separating the coated
- 2 -!
lQ733!3'9 particles from the distillate products leaving the reactionsystem.
The carbonaceous material is preferably coal and it has been established that a wide variety of diEferent coals can be used, extending all the way from lignite to anthracite.
Although the size of the particles is not critical, it has been found that best resùlts are generally obtained if the particles ^ have diameters of less than about 5 mm.
The coal particles are added in small quantitites to the bitumen feed to a hydrocracking reactor and these particles act as a "getter" for the metals and coke formed. The particle size of the coal relative to the oil is such that it will wash out of the reaction system. This means that the coal particles can be continuously added and continuously withdrawn, thereby providing a mechanism for the removal of the coke and metals from the system.
As the residence time of the coal particles in the hydro-; cracking reactor increases, they become progressively smaller ih size. Also the conversion of the coal to liquid and gaseous products has been shown to progress to a greater extent in small particles than in large ones. When the particles have been in thereactor long enough to become su~iciently small in size, the upward velocity of the liquid exceeds the terminal settling velo-city of the particles and they are swept out of the reactor. In ; principle, the upward velocity of liquid in the reactor can be chosen by appropriately matching the reactor diameter with the volumetric feedrate. A low enough liquid velocity permits the particles to become sufficiently small, thereby maximizing coal hydrogenation, before they leave the reactor. It must be empha-sized that coal hydrogenation is a secondary consideration. The primary objective is to accumulate coke and metals, formed from compounds in the bitumen, so that they will be removed from the .... . .. . . . . . .. ..
~ 9733~9 reaction system with the particles. Coal hydrogenation is merely a desirable phenomenon which occurs simultaneously.
This procedure is able to lower the concentrations of metals and coke~forming compounds in the li~luid product to permit subsequent catalyeic processing without causing ` appreciable catalyst deactivatlon. Moreover, the solids '~ removed from the hydrocracking reactor can be burned directly to provide energy for the process or alternatively they can be gasified to produce both hydrogen and fuel gas.
While the principle purpose of the coal particles is as a "getter", there also appears to be some selective ~ -~
catalytic action by the coal. Also, as mentioned above, ~here ~ -~
appears to be some hydrogenation of the coal taking place under certain circumstances which add to the liquid yield of the process. Petrographic examination of the coated coal par ticles obtained from the reactor clearly established that the deposits of coke formed on the surface of the particles origi-nated primarily from the oil residuum rather than from the coal itself.
Reactors for the hydrocracking of heavy oils are, of course, already well known and many different types are des~
cribed in the literature. In the system utilized in this inven-tion, hydrogen and oil are combined at high pressure and are flowed continuously into the bottom of a tubular reactor. The reaction mixture flows up through the bed where hydrocracking occurs. The products flow out of the top of the reactor and are separated into liquid and vapour streams.
It is also possible to use a fixed bed reactor in which the coal particles Eorm the fixed bed. For this purpose, the particles should have a minimum size of about 500 ~m to prevent them from fusing together into a large solid mass. Of course, ~ 4 --~L~97331 ``
this problem does not occur in Lhe continuous flow system. r The oil is contacted with substantially large volumes of hydrogen, as for instance 500 to 50,000 standard cubic feet of hydrogPn per barrel of oil (SCF/BBL). Pressures employed in the process are in excess of l,OOO psig. and preferably in the range of about 1,500 psig. to 3,000 psig. partial pressure hydro-gen. Temperatures employed in the hydrocrclcking are in the range -~ of from about 350-to 500C with a temperature in the range of about 425 to 475C being preferred. The space velocity is ~ lO typically maintained in a range of from about 0.5 to 10 hr with about 0.7 to 5 hr 1 being preferred.
The following Examples are given by way of illustration only and are not to be construed as limiting the invention.
EXA~PLE l a) Materials - The bitumen used for these studies was obtained from Great Canadian Oil Sands Ltd. at Fort McMurray, Alberta.
This operation uses the Clark hot water process to separate the coarse sand from the bitumen and the bu]k of the residual clay in the water-separated bitumen is removed by dilution centri-20 fuging. The bitumen used for the present procedure was topped bitumen (diluent removed), typical of the material fed to the commercial delayed coking unit now in use. The general proper-ties of the bitumen are shown in Table 1 below.
~0733~39 . . ~ ` .
TABLE l ,~ Properties of Athabasca Bitumen -,, .
Specl~ic Grsvity 60/60F........... 1.000 A911 (wt %) 700C~ 70 lckel (ppm)O..................... ~ 76 :~
Vanadium (ppm~................... 191 Conradson Carbon Residue (wt %).. 12.6 Pentane Insolubles (wt %)........ 15.83 ~enzene Insoluble~ (wt %)........ 0.90 ,;
Carbon Disulphide Insolubles (wt %~ 0.88 Sulphur (wt %)................... 4.72 ;~ ~
Nitrogen (wt %).................. 0.42 ~`. `
Vlscos1ty, Kinematic (cSt) at 210~F 129.5 Visco~ity, KinematLc (cSt) at 130F 2041 Molecular Weight (calculated).... 7~2 Re~iduum (+975F) wt %........... 51 -- - :
b) Apparatus and Operating Procedure - A standard bench- -scale flow system designed to evaluate catalyst performance was used. ~ydrogen and bitumen at high pressure were combined and flowed continuously into the bottom of a fixed-bed reactor filled with -4~8 mesh (U.S. Standard Sieve No.) coal particles. -~
The coal was used as received and was not subJected to any pre-treatment. To begin the experiment the reactor was filled with the coal particies, pressurized at 2,000 psi and the hydrogen flow initiated. Approximately l-l/2 hours were required to bring the reactor up to standard tempe-rature and achieve steady-state conditions. The flow of bitumen to the reactor was begun as the coal temperature approached 250C. The reaction mixture flowed up through tlle bed of coal particles where both bitumen hydrocracking and coal hydrogenation occurred.
The reaction conditions are listed in Table 2 below ~733~9 ,.~
T~BLE 2 Hydrocracklng Reaction Co~ditlons ~ Temperature ............... 450 C (723 ~) ~ Pressure .................. 2000 pslg (13.9 MPa) H2 flowrate ............... 5000 scf/Bbl (0.0359 l/sec) Bitumen flowrate (at 60 F) 153.6 ~l/hr (42.7 ml/ks) Llquid Space Veloclty ... 1.0 hr~l (0.28 ks 1) .
The products flowed out of the top of the reactor and were separated into liquid and vapour streams~ The product was collected at standard conditions for three hours, then the reactor system was allowed to cool. The solids remaining in the reactor were removed carefully and subjected to a toluene extraction in Soxhlet apparatus to remove adhering bit~lmen and liquid hydrocarbon products. The solids were vacuum dried and finally weighed.
This procedure was carried out using two different .
sources of coal, the general properties of which are listed in Table 3 below:
Coals Used in Reaction Studies Canmore Source of Coal Cascade Area, Estevan Alberta ASTM Rank ................ semi-anthraclte lignite Proxlmate Analysl~ - wtZ
mol6ture ............... 0.78 18.26 a~h ~ 7.82 10.16 volatile matter ........ 13.39 35.62 f~ed carbon ......... 78.01 35.96 733~3~
.
- ~or the two di~ferent coal sourues, t~le ~uan~.ltl~es of solids charged to and removed from the reactor are shown in Table 4 while an analysis oE the residues obtained at the conclu sion of the experiment is shown in Table 5.
Quantlties of Solids Charged to and Removed from the Reactor . _ :
Source of Canmore Estevan Origlnal Coal Cascade Area, Alta. Saskatchewan ASTM Rank ................ , semi-anthracite lignlte Welght of coal charged to the reactor - grams ...... 91.3 100.0 Welght of resldue removed from the reactor - grams .... 86.5 47.3 -Residues Removed from the Reactor . ;
at the Conclusion of the Experiments . . _ . . _ . _ Source of Canmore Estevan Orlglnal Coal Cascade Area, Alta. Saskatchewan . . . ~
ASTM Rank ................... ~emi-anthracite llgnlte Resldue proximate analysls, wt %
molsture .................. 0.70 4.99 : ash ....................... 7.0R 24.59 ~ !
volatile matter ........... 13.44 24.02 fixed carbon .............. 78.78 46.40 . . . _ _ The metals removed from the bitumen using the two different coal sources are listed in Table 6.
" 1073389 . : .
TABI.E 6 Metals Removed from the Liquld Hydrocarbon . . ... _ Metals Content of Llquid ppm V ~i Bitumen Feedstock ..................... , 191 76 Product from Semi-Anthraclte Experlmenta 161 63 Product from Lignite Exper~ents ............ 82 37 -----fractions, the coal particles fused into a solid mass having the dimensions of the reactor. During the experiment with the -30+70 mesh size particles, a loosely fused disc was formed.
No fusloo of particles was observed with the two largest par-ticle si~es.
For a full comparison of possible differences with the use of different types of coal, a study was conducted using seven different coal solids having markedly different composi-tions and properties. The composition of each coal, its ASTM
Rank, its geographical location, its metal contents and both its proximate and ultimate analyses are shown in Table 7.
_ 9 _ :`
~6~733~9 : TABT.E 7 , ; Analyses of Coals Used ln Reactlon Studies . __ _ ,:
~ _~ ~ ~ c~
u ~ ~ ~ a o o o ASTM R~NK u g o ~ ~ ~ ~ a u~ ~ c ~ ~ ~ ~ ~ .~
,~ v v ~ ~o .C~ ~ ~ ~q r~
¢ v 5~ ¢ D D D
.. ____ _ _ SOURCE ~ ¢ ~
(Geographlcal ¢ ~ ~ ~ ~ v ~ ~ ~ ¢ ¢ a Locatlon) ~ u ~ ~ a ~ ~ ~ u ~ ~ ~ o ~ ~ ~ o ~ a ~u o ~ ~ c ~ u o u ~ u 3 ~ v ~ v ~ u ~ U ~ ~ D U ~ e; a~ ~ ~ n ~ ~ o ~ ~ ~
c~ VJ D )~ :~ ~ Ll ~ ~ C D D ~ E3 ~ ~ ~3 ~ v U~
t~ t~l ~1 n~ O ~ ~ ~ O O.) ~ ~1 ~ ~1 -a ~ u~ t~
_ ~ u ¢ ~ ~ ~ ~ ~ z ~ ~ ¢ 3 ~ ¢ ~ ~ d Proximate Analy~es molsture wt %0.78 0.67 1.41 11.96 17.62 22.9018.Z6 volatlle matter wt % 13.3919.7234.93 32.85 30.5929.15 35.o2 ash wt %7.82 10.252.34 10.08 10.74 11.4110.16 flxcd carbon wt %78.0169.3661.3245.11 41.05 36.6435.96 Ultlmate Analyses carbon wt %82.1978.2083.1158.26 52:48 48.6451.74 hydrogen wt %4.09 4.43 5.77 4.11 3.57 3.19 3.35 nltrogen wt %1.49 1.16 1.84 1.57 0.74 1.10 0.89 , sulphur wt %0.72 0.25 0.79 1.21 0.22 0.26 0.30 molsture wt %1.18 0.97 1.40 13.26 17.58 22.2914.88 ash wt %8.5211.782.83 10.07 12.04 10.9110.97 oxygen wt %1.813.21 4.26 11.52 13.37 13.6117.87 Metals nickel ppm 7.6 3.2 5.3 14 6.5 4.7 2.3 vanadium ppm <25 <25 <25 14.7 <25 C25 <25 lron ppm2200 2000 7500 7900 3000 2800 3300 Surface Area m /g2.39 1.36 0.55 4.07 6.49 5.35 1.93 ~338~
Coal hydrogenation and bitumen hydrocracking were carried out using tlle same equipment and conditions as described in Example 1. The product was collected and the solids remaining in the reactor were collected in the same manner as in Example 1.
Analyses of the solids remaining in the reactor are listed in Table 8.
Analyse~ of the Sollds Remaining at the Concluslon of the Experlment ~ ,~ ¢ ¢ ~ ~
ASTM Rank u ~ ~ ~ o o ~
.. n 3 ~ ~ ~ n n a :~
.
__ _ .__ Proxlmate Analyses molsture wt % 0.70 2.60 2.00 4.43 5.43 3.16 4.99 volatile matter wt % 13.44 17.51 15.46 21.69 23.27 20.67 24.02 ash wt %7.0814.204.7519.01 22.26 29.4524.59 flxed carbon wt %78.7865.6977.7954.8749,04 46.7246.40 Illtimate ~nalyses carbon wt %83.3477.3985.4967.2463.93 64.5062.57 hydrogen wt %3.933.913.83 3.29 3.52 3.734.00 nitrogen wt %1.261.411.80 1.75 0.95 1.581.35 sulphur wt 70.970.761.52 2.20 1.96 1.891.65 molsture wt %1.142.591.97 5.08 5~81 4.44.5.20 ash wt %7.5313.654.5719.45 24.26 22.6022.7~
oxygen wt %1.830.290.82 0.99 0.00 1.262.47 ~Metal6 nickel pp~38 56 105 195 147 123 127 vanadium pp~154 340 373 1312 900 778 734 iron ppm3,5004,60020,00015,5005,6004,9005,400 Sollds Remainlng in Reactor wt %94.888.271.2 55.2 47.7 50.747.3 Mode Particle Size ~m 1980 520 370 1980 1670 1820 840 ~Surface Area ~2/0.712.63 2.04 8.60 11.53 4.4017.65 ~:
~733~
~nalyses of the liquid products produced with the different coals are shown in Table 9 while Table 10 shows :
the results for various distillate fractions up to +975~F.
Table 11 shows material balances on the various ~netals whiLe Table 12 shows a comparison of metals and sulphur in 970 - 975F
gas oil and +975F pitch.
`:
10~733~9 :
~_ ~ ,~ ~
. ~ , ~ E ,~ ~ o o C~ ~ ~
C
> ~
~I E
., r~
U ~ ~ ~ -.~ _ _ o ~ ~ o~ ~ o~ o ~ ~ ~ ~ ~ :, C C ~ 3 ,~ _ ` o ~`~ .
~ ~o ~ :
o o ~ o ~r~ ~
lQ733!3'9 particles from the distillate products leaving the reactionsystem.
The carbonaceous material is preferably coal and it has been established that a wide variety of diEferent coals can be used, extending all the way from lignite to anthracite.
Although the size of the particles is not critical, it has been found that best resùlts are generally obtained if the particles ^ have diameters of less than about 5 mm.
The coal particles are added in small quantitites to the bitumen feed to a hydrocracking reactor and these particles act as a "getter" for the metals and coke formed. The particle size of the coal relative to the oil is such that it will wash out of the reaction system. This means that the coal particles can be continuously added and continuously withdrawn, thereby providing a mechanism for the removal of the coke and metals from the system.
As the residence time of the coal particles in the hydro-; cracking reactor increases, they become progressively smaller ih size. Also the conversion of the coal to liquid and gaseous products has been shown to progress to a greater extent in small particles than in large ones. When the particles have been in thereactor long enough to become su~iciently small in size, the upward velocity of the liquid exceeds the terminal settling velo-city of the particles and they are swept out of the reactor. In ; principle, the upward velocity of liquid in the reactor can be chosen by appropriately matching the reactor diameter with the volumetric feedrate. A low enough liquid velocity permits the particles to become sufficiently small, thereby maximizing coal hydrogenation, before they leave the reactor. It must be empha-sized that coal hydrogenation is a secondary consideration. The primary objective is to accumulate coke and metals, formed from compounds in the bitumen, so that they will be removed from the .... . .. . . . . . .. ..
~ 9733~9 reaction system with the particles. Coal hydrogenation is merely a desirable phenomenon which occurs simultaneously.
This procedure is able to lower the concentrations of metals and coke~forming compounds in the li~luid product to permit subsequent catalyeic processing without causing ` appreciable catalyst deactivatlon. Moreover, the solids '~ removed from the hydrocracking reactor can be burned directly to provide energy for the process or alternatively they can be gasified to produce both hydrogen and fuel gas.
While the principle purpose of the coal particles is as a "getter", there also appears to be some selective ~ -~
catalytic action by the coal. Also, as mentioned above, ~here ~ -~
appears to be some hydrogenation of the coal taking place under certain circumstances which add to the liquid yield of the process. Petrographic examination of the coated coal par ticles obtained from the reactor clearly established that the deposits of coke formed on the surface of the particles origi-nated primarily from the oil residuum rather than from the coal itself.
Reactors for the hydrocracking of heavy oils are, of course, already well known and many different types are des~
cribed in the literature. In the system utilized in this inven-tion, hydrogen and oil are combined at high pressure and are flowed continuously into the bottom of a tubular reactor. The reaction mixture flows up through the bed where hydrocracking occurs. The products flow out of the top of the reactor and are separated into liquid and vapour streams.
It is also possible to use a fixed bed reactor in which the coal particles Eorm the fixed bed. For this purpose, the particles should have a minimum size of about 500 ~m to prevent them from fusing together into a large solid mass. Of course, ~ 4 --~L~97331 ``
this problem does not occur in Lhe continuous flow system. r The oil is contacted with substantially large volumes of hydrogen, as for instance 500 to 50,000 standard cubic feet of hydrogPn per barrel of oil (SCF/BBL). Pressures employed in the process are in excess of l,OOO psig. and preferably in the range of about 1,500 psig. to 3,000 psig. partial pressure hydro-gen. Temperatures employed in the hydrocrclcking are in the range -~ of from about 350-to 500C with a temperature in the range of about 425 to 475C being preferred. The space velocity is ~ lO typically maintained in a range of from about 0.5 to 10 hr with about 0.7 to 5 hr 1 being preferred.
The following Examples are given by way of illustration only and are not to be construed as limiting the invention.
EXA~PLE l a) Materials - The bitumen used for these studies was obtained from Great Canadian Oil Sands Ltd. at Fort McMurray, Alberta.
This operation uses the Clark hot water process to separate the coarse sand from the bitumen and the bu]k of the residual clay in the water-separated bitumen is removed by dilution centri-20 fuging. The bitumen used for the present procedure was topped bitumen (diluent removed), typical of the material fed to the commercial delayed coking unit now in use. The general proper-ties of the bitumen are shown in Table 1 below.
~0733~39 . . ~ ` .
TABLE l ,~ Properties of Athabasca Bitumen -,, .
Specl~ic Grsvity 60/60F........... 1.000 A911 (wt %) 700C~ 70 lckel (ppm)O..................... ~ 76 :~
Vanadium (ppm~................... 191 Conradson Carbon Residue (wt %).. 12.6 Pentane Insolubles (wt %)........ 15.83 ~enzene Insoluble~ (wt %)........ 0.90 ,;
Carbon Disulphide Insolubles (wt %~ 0.88 Sulphur (wt %)................... 4.72 ;~ ~
Nitrogen (wt %).................. 0.42 ~`. `
Vlscos1ty, Kinematic (cSt) at 210~F 129.5 Visco~ity, KinematLc (cSt) at 130F 2041 Molecular Weight (calculated).... 7~2 Re~iduum (+975F) wt %........... 51 -- - :
b) Apparatus and Operating Procedure - A standard bench- -scale flow system designed to evaluate catalyst performance was used. ~ydrogen and bitumen at high pressure were combined and flowed continuously into the bottom of a fixed-bed reactor filled with -4~8 mesh (U.S. Standard Sieve No.) coal particles. -~
The coal was used as received and was not subJected to any pre-treatment. To begin the experiment the reactor was filled with the coal particies, pressurized at 2,000 psi and the hydrogen flow initiated. Approximately l-l/2 hours were required to bring the reactor up to standard tempe-rature and achieve steady-state conditions. The flow of bitumen to the reactor was begun as the coal temperature approached 250C. The reaction mixture flowed up through tlle bed of coal particles where both bitumen hydrocracking and coal hydrogenation occurred.
The reaction conditions are listed in Table 2 below ~733~9 ,.~
T~BLE 2 Hydrocracklng Reaction Co~ditlons ~ Temperature ............... 450 C (723 ~) ~ Pressure .................. 2000 pslg (13.9 MPa) H2 flowrate ............... 5000 scf/Bbl (0.0359 l/sec) Bitumen flowrate (at 60 F) 153.6 ~l/hr (42.7 ml/ks) Llquid Space Veloclty ... 1.0 hr~l (0.28 ks 1) .
The products flowed out of the top of the reactor and were separated into liquid and vapour streams~ The product was collected at standard conditions for three hours, then the reactor system was allowed to cool. The solids remaining in the reactor were removed carefully and subjected to a toluene extraction in Soxhlet apparatus to remove adhering bit~lmen and liquid hydrocarbon products. The solids were vacuum dried and finally weighed.
This procedure was carried out using two different .
sources of coal, the general properties of which are listed in Table 3 below:
Coals Used in Reaction Studies Canmore Source of Coal Cascade Area, Estevan Alberta ASTM Rank ................ semi-anthraclte lignite Proxlmate Analysl~ - wtZ
mol6ture ............... 0.78 18.26 a~h ~ 7.82 10.16 volatile matter ........ 13.39 35.62 f~ed carbon ......... 78.01 35.96 733~3~
.
- ~or the two di~ferent coal sourues, t~le ~uan~.ltl~es of solids charged to and removed from the reactor are shown in Table 4 while an analysis oE the residues obtained at the conclu sion of the experiment is shown in Table 5.
Quantlties of Solids Charged to and Removed from the Reactor . _ :
Source of Canmore Estevan Origlnal Coal Cascade Area, Alta. Saskatchewan ASTM Rank ................ , semi-anthracite lignlte Welght of coal charged to the reactor - grams ...... 91.3 100.0 Welght of resldue removed from the reactor - grams .... 86.5 47.3 -Residues Removed from the Reactor . ;
at the Conclusion of the Experiments . . _ . . _ . _ Source of Canmore Estevan Orlglnal Coal Cascade Area, Alta. Saskatchewan . . . ~
ASTM Rank ................... ~emi-anthracite llgnlte Resldue proximate analysls, wt %
molsture .................. 0.70 4.99 : ash ....................... 7.0R 24.59 ~ !
volatile matter ........... 13.44 24.02 fixed carbon .............. 78.78 46.40 . . . _ _ The metals removed from the bitumen using the two different coal sources are listed in Table 6.
" 1073389 . : .
TABI.E 6 Metals Removed from the Liquld Hydrocarbon . . ... _ Metals Content of Llquid ppm V ~i Bitumen Feedstock ..................... , 191 76 Product from Semi-Anthraclte Experlmenta 161 63 Product from Lignite Exper~ents ............ 82 37 -----fractions, the coal particles fused into a solid mass having the dimensions of the reactor. During the experiment with the -30+70 mesh size particles, a loosely fused disc was formed.
No fusloo of particles was observed with the two largest par-ticle si~es.
For a full comparison of possible differences with the use of different types of coal, a study was conducted using seven different coal solids having markedly different composi-tions and properties. The composition of each coal, its ASTM
Rank, its geographical location, its metal contents and both its proximate and ultimate analyses are shown in Table 7.
_ 9 _ :`
~6~733~9 : TABT.E 7 , ; Analyses of Coals Used ln Reactlon Studies . __ _ ,:
~ _~ ~ ~ c~
u ~ ~ ~ a o o o ASTM R~NK u g o ~ ~ ~ ~ a u~ ~ c ~ ~ ~ ~ ~ .~
,~ v v ~ ~o .C~ ~ ~ ~q r~
¢ v 5~ ¢ D D D
.. ____ _ _ SOURCE ~ ¢ ~
(Geographlcal ¢ ~ ~ ~ ~ v ~ ~ ~ ¢ ¢ a Locatlon) ~ u ~ ~ a ~ ~ ~ u ~ ~ ~ o ~ ~ ~ o ~ a ~u o ~ ~ c ~ u o u ~ u 3 ~ v ~ v ~ u ~ U ~ ~ D U ~ e; a~ ~ ~ n ~ ~ o ~ ~ ~
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t~ t~l ~1 n~ O ~ ~ ~ O O.) ~ ~1 ~ ~1 -a ~ u~ t~
_ ~ u ¢ ~ ~ ~ ~ ~ z ~ ~ ¢ 3 ~ ¢ ~ ~ d Proximate Analy~es molsture wt %0.78 0.67 1.41 11.96 17.62 22.9018.Z6 volatlle matter wt % 13.3919.7234.93 32.85 30.5929.15 35.o2 ash wt %7.82 10.252.34 10.08 10.74 11.4110.16 flxcd carbon wt %78.0169.3661.3245.11 41.05 36.6435.96 Ultlmate Analyses carbon wt %82.1978.2083.1158.26 52:48 48.6451.74 hydrogen wt %4.09 4.43 5.77 4.11 3.57 3.19 3.35 nltrogen wt %1.49 1.16 1.84 1.57 0.74 1.10 0.89 , sulphur wt %0.72 0.25 0.79 1.21 0.22 0.26 0.30 molsture wt %1.18 0.97 1.40 13.26 17.58 22.2914.88 ash wt %8.5211.782.83 10.07 12.04 10.9110.97 oxygen wt %1.813.21 4.26 11.52 13.37 13.6117.87 Metals nickel ppm 7.6 3.2 5.3 14 6.5 4.7 2.3 vanadium ppm <25 <25 <25 14.7 <25 C25 <25 lron ppm2200 2000 7500 7900 3000 2800 3300 Surface Area m /g2.39 1.36 0.55 4.07 6.49 5.35 1.93 ~338~
Coal hydrogenation and bitumen hydrocracking were carried out using tlle same equipment and conditions as described in Example 1. The product was collected and the solids remaining in the reactor were collected in the same manner as in Example 1.
Analyses of the solids remaining in the reactor are listed in Table 8.
Analyse~ of the Sollds Remaining at the Concluslon of the Experlment ~ ,~ ¢ ¢ ~ ~
ASTM Rank u ~ ~ ~ o o ~
.. n 3 ~ ~ ~ n n a :~
.
__ _ .__ Proxlmate Analyses molsture wt % 0.70 2.60 2.00 4.43 5.43 3.16 4.99 volatile matter wt % 13.44 17.51 15.46 21.69 23.27 20.67 24.02 ash wt %7.0814.204.7519.01 22.26 29.4524.59 flxed carbon wt %78.7865.6977.7954.8749,04 46.7246.40 Illtimate ~nalyses carbon wt %83.3477.3985.4967.2463.93 64.5062.57 hydrogen wt %3.933.913.83 3.29 3.52 3.734.00 nitrogen wt %1.261.411.80 1.75 0.95 1.581.35 sulphur wt 70.970.761.52 2.20 1.96 1.891.65 molsture wt %1.142.591.97 5.08 5~81 4.44.5.20 ash wt %7.5313.654.5719.45 24.26 22.6022.7~
oxygen wt %1.830.290.82 0.99 0.00 1.262.47 ~Metal6 nickel pp~38 56 105 195 147 123 127 vanadium pp~154 340 373 1312 900 778 734 iron ppm3,5004,60020,00015,5005,6004,9005,400 Sollds Remainlng in Reactor wt %94.888.271.2 55.2 47.7 50.747.3 Mode Particle Size ~m 1980 520 370 1980 1670 1820 840 ~Surface Area ~2/0.712.63 2.04 8.60 11.53 4.4017.65 ~:
~733~
~nalyses of the liquid products produced with the different coals are shown in Table 9 while Table 10 shows :
the results for various distillate fractions up to +975~F.
Table 11 shows material balances on the various ~netals whiLe Table 12 shows a comparison of metals and sulphur in 970 - 975F
gas oil and +975F pitch.
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~.~73389 TABLR 11 ~;
Material Balances on V, Nl, and Fe Metals r~ _ .Vanadium-mg Nickel-mg Iron-mg ASTM RANK _ . ._ __ OF COAL u v ~ v ~ v o 3 8 ~ o ~ ~ ~ o . ~ ~; ~ I ¢ o~ P~ ~ ¢ o ~ ~ ¢ g __ . _ Seml-Anthraclte 15 11-13 6.0 2.6 141 101 Medlum Volatlle Bltumlnous24 27-30 6.9 4.6 84 205 Hlgh Volatile A Bltuminous19 22-24 6.2 6.2 101 605 Subbituminous A _ 71 _ 9.4 _ 66 Subbltumlnous B 47 40-43 14 6.4 78 -33 Subbitumlnou~ C 35-38 _ 5.5 _ -30 Llgnl~e 56 37-35 20 5.8 107 -74 .. . . . .
~L~733~
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. u~ ~ z ~L(117338~ .
EX~MPLE 3 a) Materials - The bitumen ~eedstock was the same as that described in ~xample 1, and had the properties listed in Table 1.
The coal utilized was a sub-bituminous B obtained from the White-wood Mine in the Pembina area of Alberta. ~fter grinding to -200 mesh (U.S. Standard Sieve size) it was used without additional pretreatment. Its properties are listed in Table 7.
b) Apparatus and Operating Procedure - These experiments were performed in a continuous operation at steady state conditions.
The fine coal particles were mixed with the bltumen to form a bitumen-coal slurry. The slurry was maintained slightly above ambient temperature in an agitated feed tank from which it entered the slurry pump suction line. After leaving the slurry pump discharge port, the slurry was mixed with high pressure hydrogen and the mixture flowed into the bottom of a tubular reactor. The tubular reactor was maintained at conditions similar to those listed in Table 2. Both bitumen hydrocracking and coal hydrogen-ation reactions occurred in the reactor. The phenomenon of greatest interest was that the large number of coal particles in the reactor presented a large solid surface area on which both coke and metals could deposit. The reaction mixture left the reactor at the top and the vapour was subsequently separated from the liquid and the solids. Approximately 1-1/2 hours were required to establish standard operating conditions in the reactor. The bitumen and the hydrogen flowed through the reactor during the start-up period. ~fter the desired operating condi-tions had been attained, steady state conditions were maintained for 1 hour prior to the 3 hour sample period. At the conclusion of the experiments the reactor was cooled to ambient conditions and drained.
Following the shut down procedure the reactor was opened and visually inspected in order to determine whether or ~ 7331!3~
not coke had formed inside it. In those cases where coke formation did occ~r, the coke was carefully removed and weighed. The amount of coke found in the reactor at various pressures is shown in Table 13.
COKE FORMATION AS ~ FUNCTION OF PRESSURE
Pressure Weight of Coke psig_ % of Feedstock Weight 500 14.6 lOlO00 6.9 1500 4.4 2000 nil . .
~t 2000 psig no coke was found in the reactor at the conclusion of the experiment in which the bitumen-coal slurry was employed. In contrast when the same experiment was per-formed without the coal particles in the bitumen, the coke found in the reactor at the conclusion of the experiment amounted to 3.1 weight percent of the feedstock. This illus-trates the beneficial effect of the carbonaceous particles.
It must be emphasized that the amount of coke in the reactor is a function of the processing conditions used. For example at 1500 psig the amount of coke in the reactor could be increased, decreased or even eliminated by charging temperature, liquid space velocity, hydrogen flow rate, and other variables.
These examples show that low rank coals are hydrogenated to a greater extent than high rank coals and that as more coal is hydrogenated, a greater reactor void volume is created, so that pitch hydrocracking, desulphurization and other reactions occur to a greater extent with low rank coals than with high rank coals.
Changes in the composition of the solids caused by chemical reaction ~L~733~9 were as follows:
the oxygen to ash ratîo was lowered by a factor of 10;
the hydrogen to ash and carbon to ash ratios were lowered, the hydrogen to ash ratio to a greater extent than the carbon to ash ratio; and the nitrogen to ash ratio remained about the same and the sulphur to ash ratio increased.
The coking tendency of the liquid product as measured ; 10 by Conradson Carbon residue, produced in the p~resence of low -rank coals was considerably less than that produced using high rank coals. Essentially all the vanadium metal removed from the liquid was accumulated on the solids. The concentrations of coke precursors and metal in the liquid were found to be directly related to the +975F pitch content of the liquid.
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~.~73389 TABLR 11 ~;
Material Balances on V, Nl, and Fe Metals r~ _ .Vanadium-mg Nickel-mg Iron-mg ASTM RANK _ . ._ __ OF COAL u v ~ v ~ v o 3 8 ~ o ~ ~ ~ o . ~ ~; ~ I ¢ o~ P~ ~ ¢ o ~ ~ ¢ g __ . _ Seml-Anthraclte 15 11-13 6.0 2.6 141 101 Medlum Volatlle Bltumlnous24 27-30 6.9 4.6 84 205 Hlgh Volatile A Bltuminous19 22-24 6.2 6.2 101 605 Subbituminous A _ 71 _ 9.4 _ 66 Subbltumlnous B 47 40-43 14 6.4 78 -33 Subbitumlnou~ C 35-38 _ 5.5 _ -30 Llgnl~e 56 37-35 20 5.8 107 -74 .. . . . .
~L~733~
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EX~MPLE 3 a) Materials - The bitumen ~eedstock was the same as that described in ~xample 1, and had the properties listed in Table 1.
The coal utilized was a sub-bituminous B obtained from the White-wood Mine in the Pembina area of Alberta. ~fter grinding to -200 mesh (U.S. Standard Sieve size) it was used without additional pretreatment. Its properties are listed in Table 7.
b) Apparatus and Operating Procedure - These experiments were performed in a continuous operation at steady state conditions.
The fine coal particles were mixed with the bltumen to form a bitumen-coal slurry. The slurry was maintained slightly above ambient temperature in an agitated feed tank from which it entered the slurry pump suction line. After leaving the slurry pump discharge port, the slurry was mixed with high pressure hydrogen and the mixture flowed into the bottom of a tubular reactor. The tubular reactor was maintained at conditions similar to those listed in Table 2. Both bitumen hydrocracking and coal hydrogen-ation reactions occurred in the reactor. The phenomenon of greatest interest was that the large number of coal particles in the reactor presented a large solid surface area on which both coke and metals could deposit. The reaction mixture left the reactor at the top and the vapour was subsequently separated from the liquid and the solids. Approximately 1-1/2 hours were required to establish standard operating conditions in the reactor. The bitumen and the hydrogen flowed through the reactor during the start-up period. ~fter the desired operating condi-tions had been attained, steady state conditions were maintained for 1 hour prior to the 3 hour sample period. At the conclusion of the experiments the reactor was cooled to ambient conditions and drained.
Following the shut down procedure the reactor was opened and visually inspected in order to determine whether or ~ 7331!3~
not coke had formed inside it. In those cases where coke formation did occ~r, the coke was carefully removed and weighed. The amount of coke found in the reactor at various pressures is shown in Table 13.
COKE FORMATION AS ~ FUNCTION OF PRESSURE
Pressure Weight of Coke psig_ % of Feedstock Weight 500 14.6 lOlO00 6.9 1500 4.4 2000 nil . .
~t 2000 psig no coke was found in the reactor at the conclusion of the experiment in which the bitumen-coal slurry was employed. In contrast when the same experiment was per-formed without the coal particles in the bitumen, the coke found in the reactor at the conclusion of the experiment amounted to 3.1 weight percent of the feedstock. This illus-trates the beneficial effect of the carbonaceous particles.
It must be emphasized that the amount of coke in the reactor is a function of the processing conditions used. For example at 1500 psig the amount of coke in the reactor could be increased, decreased or even eliminated by charging temperature, liquid space velocity, hydrogen flow rate, and other variables.
These examples show that low rank coals are hydrogenated to a greater extent than high rank coals and that as more coal is hydrogenated, a greater reactor void volume is created, so that pitch hydrocracking, desulphurization and other reactions occur to a greater extent with low rank coals than with high rank coals.
Changes in the composition of the solids caused by chemical reaction ~L~733~9 were as follows:
the oxygen to ash ratîo was lowered by a factor of 10;
the hydrogen to ash and carbon to ash ratios were lowered, the hydrogen to ash ratio to a greater extent than the carbon to ash ratio; and the nitrogen to ash ratio remained about the same and the sulphur to ash ratio increased.
The coking tendency of the liquid product as measured ; 10 by Conradson Carbon residue, produced in the p~resence of low -rank coals was considerably less than that produced using high rank coals. Essentially all the vanadium metal removed from the liquid was accumulated on the solids. The concentrations of coke precursors and metal in the liquid were found to be directly related to the +975F pitch content of the liquid.
. . . .
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for thermally hydrocracking heavy hydrocarbon oil wherein the oil is subjected to thermal cracking at temperatures in excess of 350°C and pressures in excess of 1000 psig in a cracking zone in the presence of a flow of a free hydrogen containing gas, the improvement which comprises conducting the hydrocracking in the presence of small carbonaceous particles, whereby metals and coke formed during the hydrocracking reaction are deposited as a coating on the carbonaceous particles and separating the coated particles from the reaction system.
2. The process of claim 1 wherein the heavy hydrocarbon oil is bitumen.
3. The process of claim 2 wherein the carbonaceous particles are pulverized coal particles.
4. The process of claim 3 wherein the coal particles have a size of less than about 5 mm.
5. The process of claim 1, 2 or 3 wherein the heavy hydrocarbon oil, carbonaceous particles and hydrogen are fed into the bottom of a cracking zone and a reaction product mixture containing the coated particles is removed from the top of the cracking zone.
6. In a process for thermally hydrocracking bitumen from oil sands wherein the bitumen is subjected to thermal cracking at temperatures in excess of 350°C and pressures in excess of 1000 psig by upward flow in a tubular reactor in the presence of a flow of free hydrogen containing gas, the improvement which comprises introducing pulverized coal into the reactor whereby metals and coke formed during the hydrocracking reaction are deposited as a coating on the pulverized coal particles, and removing a reaction product mixture containing coated coal particles from the top of the reactor.
7. The process of claim 6 wherein the pulverized coal is introduced into the reactor as a slurry with the bitumen feed.
8. The process of claim 6 wherein the reaction product mixture is separated into a liquid and vapour stream.
9. The process of claim 8 wherein the coated coal particles are separated from the liquid product stream.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA269,020A CA1073389A (en) | 1976-12-31 | 1976-12-31 | Removal of metals and coke during thermal hydrocracking of heavy hydrocarbon oils |
| MX17188778A MX146308A (en) | 1976-12-31 | 1978-01-02 | IMPROVED PROCEDURE FOR THERMAL HYDROCARBON HYDRODESINTEGRATION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA269,020A CA1073389A (en) | 1976-12-31 | 1976-12-31 | Removal of metals and coke during thermal hydrocracking of heavy hydrocarbon oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073389A true CA1073389A (en) | 1980-03-11 |
Family
ID=4107637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA269,020A Expired CA1073389A (en) | 1976-12-31 | 1976-12-31 | Removal of metals and coke during thermal hydrocracking of heavy hydrocarbon oils |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1073389A (en) |
| MX (1) | MX146308A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0048098A2 (en) * | 1980-09-12 | 1982-03-24 | Mobil Oil Corporation | Upgrading of residual oil |
| US4330393A (en) | 1979-02-14 | 1982-05-18 | Chevron Research Company | Two-stage coal liquefaction process with petroleum-derived coal solvents |
| DE3117081A1 (en) * | 1981-02-12 | 1982-08-19 | Her Majesty in Right of Canada, vertr.durch the Minister ofEnergy, Mines and Resources, Ottawa, Ontario | METHOD FOR SIMULTANEOUS HYDROCRACKING AND DEMETALIZING HEAVY CARBON OILS |
| JPS57174388A (en) * | 1981-04-21 | 1982-10-27 | Canada Majesty In Right Of | Hydrogenolysis of heavy oil-fly ash slurry |
| US4370221A (en) * | 1981-03-03 | 1983-01-25 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Catalytic hydrocracking of heavy oils |
| US4376037A (en) | 1981-10-16 | 1983-03-08 | Chevron Research Company | Hydroprocessing of heavy hydrocarbonaceous oils |
| FR2514021A1 (en) * | 1981-10-07 | 1983-04-08 | Canada State | HYDROCRACKING OF HEAVY HYDROCARBONS WITH HIGH CONVERSION IN PIT |
| US4389301A (en) * | 1981-10-22 | 1983-06-21 | Chevron Research Company | Two-step hydroprocessing of heavy hydrocarbonaceous oils |
| DE3221822A1 (en) * | 1982-06-09 | 1983-12-15 | Minister of Energy, Mines and Resources, Ottawa, Ontario | Process for hydrocracking heavy oil |
| US4422922A (en) * | 1976-12-27 | 1983-12-27 | Chevron Research Company | Coal liquefaction and hydroprocessing of petroleum oils |
| US4487687A (en) * | 1979-05-19 | 1984-12-11 | Metallgesellschaft Ag | Method of processing heavy hydrocarbon oils |
| US4640765A (en) * | 1984-09-04 | 1987-02-03 | Nippon Oil Co., Ltd. | Method for cracking heavy hydrocarbon oils |
| WO2013126362A3 (en) * | 2012-02-21 | 2014-02-06 | 4CRGroup LLC | Two-zone, close-coupled, heavy oil hydroconversion process utilizing an ebullating bed first zone |
-
1976
- 1976-12-31 CA CA269,020A patent/CA1073389A/en not_active Expired
-
1978
- 1978-01-02 MX MX17188778A patent/MX146308A/en unknown
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422922A (en) * | 1976-12-27 | 1983-12-27 | Chevron Research Company | Coal liquefaction and hydroprocessing of petroleum oils |
| US4330393A (en) | 1979-02-14 | 1982-05-18 | Chevron Research Company | Two-stage coal liquefaction process with petroleum-derived coal solvents |
| US4487687A (en) * | 1979-05-19 | 1984-12-11 | Metallgesellschaft Ag | Method of processing heavy hydrocarbon oils |
| EP0048098A3 (en) * | 1980-09-12 | 1982-06-30 | Mobil Oil Corporation | Upgrading of residual oil |
| EP0048098A2 (en) * | 1980-09-12 | 1982-03-24 | Mobil Oil Corporation | Upgrading of residual oil |
| DE3117081A1 (en) * | 1981-02-12 | 1982-08-19 | Her Majesty in Right of Canada, vertr.durch the Minister ofEnergy, Mines and Resources, Ottawa, Ontario | METHOD FOR SIMULTANEOUS HYDROCRACKING AND DEMETALIZING HEAVY CARBON OILS |
| US4376695A (en) * | 1981-02-12 | 1983-03-15 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Simultaneous demetalization and hydrocracking of heavy hydrocarbon oils |
| US4370221A (en) * | 1981-03-03 | 1983-01-25 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Catalytic hydrocracking of heavy oils |
| JPS57174388A (en) * | 1981-04-21 | 1982-10-27 | Canada Majesty In Right Of | Hydrogenolysis of heavy oil-fly ash slurry |
| FR2514021A1 (en) * | 1981-10-07 | 1983-04-08 | Canada State | HYDROCRACKING OF HEAVY HYDROCARBONS WITH HIGH CONVERSION IN PIT |
| US4376037A (en) | 1981-10-16 | 1983-03-08 | Chevron Research Company | Hydroprocessing of heavy hydrocarbonaceous oils |
| US4389301A (en) * | 1981-10-22 | 1983-06-21 | Chevron Research Company | Two-step hydroprocessing of heavy hydrocarbonaceous oils |
| DE3221822A1 (en) * | 1982-06-09 | 1983-12-15 | Minister of Energy, Mines and Resources, Ottawa, Ontario | Process for hydrocracking heavy oil |
| US4640765A (en) * | 1984-09-04 | 1987-02-03 | Nippon Oil Co., Ltd. | Method for cracking heavy hydrocarbon oils |
| WO2013126362A3 (en) * | 2012-02-21 | 2014-02-06 | 4CRGroup LLC | Two-zone, close-coupled, heavy oil hydroconversion process utilizing an ebullating bed first zone |
Also Published As
| Publication number | Publication date |
|---|---|
| MX146308A (en) | 1982-06-03 |
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