CA1195639A - Upgrading of heavy hydrocarbonaceous oil using carbon monoxide and steam - Google Patents
Upgrading of heavy hydrocarbonaceous oil using carbon monoxide and steamInfo
- Publication number
- CA1195639A CA1195639A CA000414120A CA414120A CA1195639A CA 1195639 A CA1195639 A CA 1195639A CA 000414120 A CA000414120 A CA 000414120A CA 414120 A CA414120 A CA 414120A CA 1195639 A CA1195639 A CA 1195639A
- Authority
- CA
- Canada
- Prior art keywords
- carbon monoxide
- oil
- catalyst
- containing gas
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
Abstract
Abstract A process is disclosed for the upgrading of heavy, viscous hydrocarbonaceous oil wherein said oil is contacted with carbon monoxide and steam at hydrocracking conditions in the presence of a catalyst comprising iron promoted by alkali metal carbonate or sulphide.
Description
~ 3 ~
This invention relates to the upgrading of heavy, viscous hydrocarbonaceous oils. More particularly, it relates to a process for the upgrading of that class of said oils comprising heavy oil having an API gravity less than about 25 degrees, in-situ oil sands bitumen and mineable oil sands bitumen, or al-ternatively the residua of those oils and of conventional crudes, by contacting them with carbon monoxide and steam, in the presence of a promoted iron catalyst.
In the environmen-t of decreasing availability of l() conven~ional crude oils, heavy oils and oil sands bitumen, for example Athabasca bitumen, are increasingly valuable as sources of liquid hydrocarbon fuels. That they yield upon dist~illa~ion a low amount of these liquid fuels is well-known. A number of processes have been proposed to improve their useful product yield, which fall into two L5 general categories, namely carbon rejection and hydrogen addition. In ~h~ la~ter category hydrogen donor diluents have been used to provide a high hydrogen concentration in a liquid system at hydrocracking ~emperatures without the usual need for high pressures necessary to compress molecular hydrogenO Residullm hydrocrackiny without the use ~n 0~ (IOnOrs iS well known in the ar~t, for example employing cobal-t nlolybden~lm catalysts having an alumina carrier, and using hiyh pressures ~o achieve a hydrogen concentration sufficient to minilnize coke laydown and consequent deactivation of the catalyst. Such processes require a source of hydrogen, which is commonly generated in a separate reactor. The Dynacracking process, descrihed by Fo No Dawson, Jr. in ENERGY PROCESSING/CANAOA (May-June, 1981), pp. 39-48, is a non-ca-talytic process which uses a reactor to whose first zone are fed preheated residuum, a hydrogen-containin~ gas and an inert carrier. Hydroconversion occurs, at about 538C, producing coke which is deposited on the carrier. The carrier moves down through a stripping zone to a gasificatiort zone where the coke is gasified at about 982C with steam and oxygen to produce the hydrogen-rich gasO
The commercial operation of that process is dependent on a speci-fic multi-zone reactor design.
Ternan et al in Canadian Patent No. 1 073 389 disclosed the hydrocracking of bitumen in the presence of finely-divided coa1 lU partic'les which acted as a seed, attrac-ting any coke formed during the reaction. The coal was said to have some catalytic action~ although there was no further disc'losure as regards the nature of the catalysis or its effect on, for example, product distribution or residuum conversion.
In UK specification GB 2 072 697, Patmore et al disclosed contacting a bitumen with hydrogen in the form of synthesis gas 7 optional'ly in the presence of a catalyst. Water was optionally but not necessarily present in the form of steam, and hydrogen preferably comprised at least 45 mole % of -the gas mixture. From these ~t) retluirelrlents it is clear that the substantially exclusive source of hy(lrO9erl WdS that alnount o~ moleculdr hydrogen contained in the sy~ s.
rn U.S. Pa~ent 3 728 252, Pitchford disclosed a desulphurization process for heavy hydrocarbon oils with or without 25 coal in the raw material, using carbon monoxide and optionally steamO
The sulphur was removed from the coal and hydrocarbon primarily ln the form of carbonyl su1phide, and an incidental improvement in carbon ~ 5~3~
residue and in API gravity took place, The heaviest oil ~reated was about 20 API. Iron catalyst was disclosed with no promoter, although a barium-promoted cobalt molybdate catalyst was also used. Coking became prominent at temperatures above 360C, for example 4.2 percen-t coke formed at 366C. It appears that that process was not an effective upgrading process for bitumen.
The process of the invention overcomes the need for a separate source of molecular hydrogen and enables use of an inexpensive catalyst by providing a process for the upgrading of heavy, viscous hydrocarbonaceous oil, comprising contacting said oil with a carbon monoxide-containing gas and steam at 'nydrocracking conditions, in the presence of a promoted iron catalyst, to yield a hydrocracked product.
In this specification all percentages and ratios are expressed by weight unless otherwise~indicated.
The process can be used to upgrade any crude oil whose gravity is 25 API or less, or atmospheric or vacuum residuum thereof, including Lloydminster, Pelican, Cold iake, Athabasca and Boscan, or to upyrade vacuum or atmospheric residua of conventional crudes~ that
This invention relates to the upgrading of heavy, viscous hydrocarbonaceous oils. More particularly, it relates to a process for the upgrading of that class of said oils comprising heavy oil having an API gravity less than about 25 degrees, in-situ oil sands bitumen and mineable oil sands bitumen, or al-ternatively the residua of those oils and of conventional crudes, by contacting them with carbon monoxide and steam, in the presence of a promoted iron catalyst.
In the environmen-t of decreasing availability of l() conven~ional crude oils, heavy oils and oil sands bitumen, for example Athabasca bitumen, are increasingly valuable as sources of liquid hydrocarbon fuels. That they yield upon dist~illa~ion a low amount of these liquid fuels is well-known. A number of processes have been proposed to improve their useful product yield, which fall into two L5 general categories, namely carbon rejection and hydrogen addition. In ~h~ la~ter category hydrogen donor diluents have been used to provide a high hydrogen concentration in a liquid system at hydrocracking ~emperatures without the usual need for high pressures necessary to compress molecular hydrogenO Residullm hydrocrackiny without the use ~n 0~ (IOnOrs iS well known in the ar~t, for example employing cobal-t nlolybden~lm catalysts having an alumina carrier, and using hiyh pressures ~o achieve a hydrogen concentration sufficient to minilnize coke laydown and consequent deactivation of the catalyst. Such processes require a source of hydrogen, which is commonly generated in a separate reactor. The Dynacracking process, descrihed by Fo No Dawson, Jr. in ENERGY PROCESSING/CANAOA (May-June, 1981), pp. 39-48, is a non-ca-talytic process which uses a reactor to whose first zone are fed preheated residuum, a hydrogen-containin~ gas and an inert carrier. Hydroconversion occurs, at about 538C, producing coke which is deposited on the carrier. The carrier moves down through a stripping zone to a gasificatiort zone where the coke is gasified at about 982C with steam and oxygen to produce the hydrogen-rich gasO
The commercial operation of that process is dependent on a speci-fic multi-zone reactor design.
Ternan et al in Canadian Patent No. 1 073 389 disclosed the hydrocracking of bitumen in the presence of finely-divided coa1 lU partic'les which acted as a seed, attrac-ting any coke formed during the reaction. The coal was said to have some catalytic action~ although there was no further disc'losure as regards the nature of the catalysis or its effect on, for example, product distribution or residuum conversion.
In UK specification GB 2 072 697, Patmore et al disclosed contacting a bitumen with hydrogen in the form of synthesis gas 7 optional'ly in the presence of a catalyst. Water was optionally but not necessarily present in the form of steam, and hydrogen preferably comprised at least 45 mole % of -the gas mixture. From these ~t) retluirelrlents it is clear that the substantially exclusive source of hy(lrO9erl WdS that alnount o~ moleculdr hydrogen contained in the sy~ s.
rn U.S. Pa~ent 3 728 252, Pitchford disclosed a desulphurization process for heavy hydrocarbon oils with or without 25 coal in the raw material, using carbon monoxide and optionally steamO
The sulphur was removed from the coal and hydrocarbon primarily ln the form of carbonyl su1phide, and an incidental improvement in carbon ~ 5~3~
residue and in API gravity took place, The heaviest oil ~reated was about 20 API. Iron catalyst was disclosed with no promoter, although a barium-promoted cobalt molybdate catalyst was also used. Coking became prominent at temperatures above 360C, for example 4.2 percen-t coke formed at 366C. It appears that that process was not an effective upgrading process for bitumen.
The process of the invention overcomes the need for a separate source of molecular hydrogen and enables use of an inexpensive catalyst by providing a process for the upgrading of heavy, viscous hydrocarbonaceous oil, comprising contacting said oil with a carbon monoxide-containing gas and steam at 'nydrocracking conditions, in the presence of a promoted iron catalyst, to yield a hydrocracked product.
In this specification all percentages and ratios are expressed by weight unless otherwise~indicated.
The process can be used to upgrade any crude oil whose gravity is 25 API or less, or atmospheric or vacuum residuum thereof, including Lloydminster, Pelican, Cold iake, Athabasca and Boscan, or to upyrade vacuum or atmospheric residua of conventional crudes~ that
2() is crudes wh~se gravity is greater numerically than 25 API. The -term "ul)-3ra(iing" in this speci~ication includes numerically increasing the API gravity, decreasing the viscosity and increasing the proportion of material boiling (at atmospheric pressure) below 5000; demetallizing and desulphurizing are also aspects of upgrading.
The gas feed to -the upgrading zone can be a mixture of steam and carbon monoxide. The process is operable also with steam and gas from other sources, for examp1e synthesis gas, the latter being a
The gas feed to -the upgrading zone can be a mixture of steam and carbon monoxide. The process is operable also with steam and gas from other sources, for examp1e synthesis gas, the latter being a
- 3 -3~
mixture of carbon monoxide and hydrogen, or with steam and ~urnace gases containing carbon monoxide. The source of steam can be liquid water or vapour. At hydrocracking temperatures ~he steam and carbon monoxide are in the gaseous state, having critical -temperatures below the specified temperature. Some gas is also dissolved in the liquid reaction mass because of the high pressure. Alternatively, carbon monoxide can be generated in situ by, for example, introducing a material that decomposes to form carbon monoxide at hydrocracking conditions, for example methanol or formaldehyde.
The ratio of available carbon monoxide, whether introduced as a carbon monoxide~rich gas or produced in situ, to heavy oil feedstock can be from about 0002:1 to 10.0:1. Lower proportions of carbon monoxide within this range yield a mildly wpgraded crude suitable, for example, for pipeline transporta-tion to a re-finery, and higher proportions yive a thoroughly upgraded product with high conversion of residuum to distillables, together with low or no coke production. A preferred ratio of ~arbon monoxide to oil for thorough upgrading is 0.2:1 to 5.0:1.
The process can be carried out in batch or continuous 2~ ope~ration. The space velocity in a continuous process can be from about 0.l -to 2~ h-1, preferably from about 0.5 to 3 h-1. In a batch process the residence time can be from about 3 minutes to 10 hours, preferably from 20 minutes to 2 hours.
The catalyst comprises promoted iron or iron compounds; if elemental iron or iron oxide is used it can convert to iron sulphide by reacting with sulphur values that can be present in the feedstock under -the reducing conditions present during hydrocracking, and continues its activity. The concentration of the iron catalyst, deFined as the concentration o-f Fe, can be from about 0.2% to 10% and preferably from about l~ to 5% based on the heavy oil feedstock. The promoter is selected from the group of known promoters for the iron-catalyzed water-gas shift reaction in which carbon monoxide and steam produce carbon dioxide and hydrogen. The known promoters include carbonates and sulphides of alkali metals. Potassium carbonate is preferred~ The promoter is added in a molar concentration from about l% to 20% of the iron catalys-t concentration. The source of at least a portion of the iron catalyst can be the heavy oil feedstock itself;
most of the heavy oils now known contain a small amount of ironO The catalyst is conveniently in finely divided form, from about 20 to 400 mesh (841 ~m to 37 ,um), preferably 40 to 325 mesh (420 ~m to 44 ,um), in which it can be readily dispersed in the heavy oil feedstock with agitation induced mechanically or by turbulent flo~, for example in d tubular reactor.
The lower temperature limit of -the process is relatecl to the temperature at which the particular heavy oil feedstock can be ~0 cracked; For some heavy oil teedstocks the lower limi~ of cracking is ahou~ 380"C, whereas other feedstocks do not crack below about 400C.
water--gas shift reaction in the reaction zone provides sufficient hy(irogen at temperatures within the stated limits to terminate the cracked radicals. The upper temperature limit is about 460C and ~5 preferably about 440C, and is affected by various factors, primarily -the production of coke.
The pressure limits are the same as for conventiona1 hydro-cracking, namely about 5 MPa to 20 MPa and preferably about 7 MPa to 14 MPa.
Optionally, the product stream can be distilled into one or more fractions boiling below about 400C to 570~C and a residuum fraction boiling above that temperature. One o~ the product streams can be used as raw material for a gasification reaction with oxygen-con-taining gas -to produce carbon monoxide and steam which can be used in -~he upgradiny zone. Advantageously the residuum stream is used for 1~ the purpose, because the residuum stream is usually the least valuable economically and contains the highest proportion of carbon, which is the source of the carbon monoxideO The residuum fraction produced by ~he process o~ -the in~ention is especially suitable for gasification because of its low hydrogen content: hydrogen in a yasification material is essentially wasted in forming water. The cut poin-t in clistillation can readily be adjusted so that the residuum or other gasification stream can supply all the necessary carbon monoxide -to the upgrading zone.
The process will be fur~her described by the tOl lowing ~xalnple~s, which illustrate preferred embodirnerrts of the invention.
I~xdll~e l . _~
A sample of Athabasca biturnen obtained by the hot water process was distilled so that its vacuum residuum had an initial boiling point of 501C. The residuum charac~eristics are shown in lable 1.
~L~3~ 3~
TABLE 1: CHARACTERIZATION OF BITUMEN RESIDUUM
Specific Gravity 1.075 Minimum Boiling Point, C at 101 kPa 50l Ash, Wt. % 1.5 Carbon, Wt . % 82 . 21 Hydrogen, Wt. % 9-59 Sulphur, Wt. % 6.52 Vanadium, ppm by weigh~ 336 Nickel, ppm by weight 111 An amount of 252.5 g of the vacuum residuum was charged to a two-litre autoclave together with 12.6 9 powdered ferric oxide, 1.3 9 powdered potassium carbonate and 43.8 g de-ionized water. The sealed vessel was -then flushed with carbon monoxide and pressurized to 3.0 MPa at 18C with 58.3 litres of carbon monoxide. The stirred vessel was brought to an internal temperature of 400C for 150 minutes. The pressure reached 1208 MPa ini~ially and 13.1 MPa af~er 40 minutes, falling to 12.7 MPa at the end of the run. Heating was discontinued and after cooling, the pressure in the autoclave was 3.8 MPa at 18C.
Two samples were taken during the metered discharge of the gas and analysed by low resolution mass spectrometry. The remaining material was separated into naphtha, distillate, gas oil, residuum, coke and inorganics and the water content measured. Product ratios are shown ~0 in Table 2 and ~uality in Table 3.
Ex~æ e 2 , _ _ The procedure of Example 1 was carried out using 234.5 g o-f Athabasca bitumen vacuum residuum, 11.7 9 ferric oxide, 1~2 9 potassium carbonate and 40.7 g water. The autoclave was pressurized with carbon monoxide to 2.8 MPa at 20C and raised to 430C, producing a pressure of 13.3 MPa. After 21 minutes, the system was cooled and 63~
depressurized and the gas content sampled. Thirty five (35.0) grams of water was added and the system repressurized with carbon monoxide -to 2.8 MPa at room temperature; the autoclave and contents were reheated and held at 430C for a further 30 minutes, when the depressurizing, recharging and repressurizing were repeated. The temperature was raised to 430C for a further 29 minutes, aFter which the pressure was 16.2 MPa. The times reported above and in Table 2 include -the total time at the indicated temperature plus a factor for thermal exposure a-t temperatures above 400C. The vessel was cooled and products were recovered and sampled as in Example 1.
xample 3 A 241.4 g sample of Athabasca bitumen vacuum residuum was charged along with 12.1 g ferric oxide, 1.2 g potassium carbonate and 41.9 g water into the autoclave, which was pressurized to 2.8 MPa with carbon monoxide and heated to 415C for a total of 220 minutes. In sllllildr fashion to Example 2, the autoclave was recharged with carbon monoxide and 35 g water three -times by repressuri~ing to 2.8 MPa at room temperature. The final pressure was 17.1 MPa. The autoclave was 2() cooled and pro~lucts were recovered and sampled as in Example 1 3~
TABLE 2: UPGRADING AT~IABASCA RESIDUUM
Example 1 Example 2 Example 3 Added Catalyst, % Fe on Resid. 3.5% 3.5% 3.5%
Temperature 400C 430C 415C
Time, minutes 150 90 220 Ni Demetallization 12% 70% 77%
V Demetallization 21% 85% 91%
Desulphurization 46% 60% 60%
Product distribution~ percent Gases 2.5 12.8 13.5 Naphtha (IBP-195C) 12.2 2507 2409 Distillate (195-315C) 13.0 16.3 17.7 Gas oil (315-504C) 27.6 24.3 24.5 Residuum (504C-~ 44.7 18.$ 18.9 Coke ~ 2.0 0.5 Conversion of Resi~. 55.3 81.2 8l.1 Hydro~en uptake, m /m3 139 346 3l4 Liquid product yield 52.8% 66.3% 67.1%
Table 2 shows the product yield and performance of the process at differing conditions. The products were highly dernetallized and had a reduced sulphur content. Up to 81% conversion was achieved and bo-th demetallization and desulphurization improved with increasing conversion. Hydrogen uptake -into the distillable produr~s was high, indicating high product saturation. For example, the ,roportion of paraffins in the distillate product of Example 1 was ~0 29~l%, comparcd to 8% for a distillate product from a typical fluid coked Athabasca whole bitumen. ~le hydrogen was added preferentially to ~he lighter products? the pitch formed in the hydrocracking reaction having low hydrogen content, an advantage when the pitch is to be burned directly or gasifiedO
g ~iSf~3~
TA3LE 3: PROPERTIES OF_ LIQUID PRODUCTS
Example 1 Example 2 Example 3 Naphtha (I~P-195C) Paraffins, Wt. % 53.8 . 54.9 53.5 Cycloparaffins, Wt% 11. 5 25.2 30.9 Bromine Number 42.8 18.6 20.7 Specific Gravity 0.751 0.75~ 0.764 Mono-ol ef i ns, Wt . % 21.2 8.8 5.7 Distillate (195-315C) Paraffins, Wt. % 29.l 26~3 26.6 Cyclo,oaraffins, Wt~ % 40.3 35.1 34.6 Bromine Number 29.6 17.2 15.9 Specific Gravity 0.871 0.875 0~876 Monoaromatics, Wt. % 18~4 24~6 24~8 Gas Oil (3l5-504~
FaraFfins, Wt. % ll.O 12.5 14.0 Cycloparaffins, Wt. % 26.0 18.0 22.7 Specific Gravity 0.970 00989 0.976 Monoaromatics, Wt. % 13.2. 13~8 13~1 Pitch (504C~) Hydrogen, Wt 8.41 6.73 7.10 Exam~les 4-7 Residua of several heavy crude oils were prepared in the same manner as the Athabasca of Exarnples 1 to 3~ to give materials havins an initial boiling point oF 504Co A typical experimental procedure is described below.
~0 A sample oF residuum (28l.2 9) was charged to a 2 litre autoclave together with 14.1 g ferric oxide, 1.4 9 potassium carbonate and ~8.5 9 deionized water. AFter nitrogen purging, the system was Flushe(l with carbon monoxide and 67 L oF carbon monoxide (at standard conditions) was added, raising the pressure to 3.3 MPa at 18C. The system was heated with stirring to an internal temperature of 415~Ca the pressure rising to 15.0 MPa initially and to a maximurn oF 15.2 MPa before falling finally to 15.0 MPa. After 50 minutes the system ~las allo~ed to cool to 19C, the pressure being 4.31 MPaO A volume of 3~D ' 95.5 L oF gas was drawn off and two samples analysed by lo~ resolution mass spectrometry. ~n amount o~ 40 9 of deionized ~ater was added and the vessel repressurized to 3.3 ~1Pa with carbon monoxide. The second heating period was also 50 minutes dura~ion. A further cycle of cooling, gas sampling, recharging with water and carbon monoxide and heating followed, to g;ve a total of 150 minu-tes at 415aCo Final product ~esting was the same as in Examples '-39 and the results are shown in Tables 4 and 5, TABIE 4: UPGRADING ~EAVY CRUDE OILS - PRGDUCT YIELDS
_ .
Example 4 _a¢~ Example 6 Example 7 ReSjd~J~Jm Pelican L. Cold Lake Lloydminster Boscan Source Canada Canada Canada Venezuela Temperature, C 415 415 415 ~15 Time, minutes 150 150 150 150 Ni demetallization, % 71 81 76 82 V demetallization, % 80 88 83 85 Desul~hurization, %58 57 53 60 15 Product distribution, percent Gases 13.1 9.2 8.8 11.0 N~phth~ (IBP-195C) 25.2 21.7 21.9 25.3 Distilla-te (195-315G) 15.9 17.6 15.7 15.2 Gas oil (315-504C) 26.2 24.9 32.3 29.7 Resid~u~ (504C+) 17.8 22.8 20.2 17.2 Coke 1.8 3.7 1~1 1.6 Conv ,sion of residuum, % 82.2 77,2 79.8 82.8 ~0 ~DS~3~
TABLE 5: UPGRADING HEAVy CRUDE OILS - PRODUCT PROPERTIES
_ Example 4 Example 5 Example 6 Example 7 Naphtha Paraffins 53~2% 53~4% 53~7% 53D9%
Cycloparaffins 24.9% 24.1% 23.2% 24.5%
Bromine Number 31. 6 32 ~ 0 23. 5 21 ~ 9 Specific Gravity 0~762 0~747 0~749 0~753 Mono-olefins 11.4% 11~0% 12~% 11~1%
- Distillate ~ Paraffins 28~7% 27~9% 2807% 26~4%
Cycloparaffins 33.2% 36.4% 38~0% 34.3%
Bromine Number 20.4 15~8 11.4 12~3 Spec;fic Gravity 0.881 0~870 0~866 0~87g Monoaromatics 21~1% 21.8% 21~2% 21~6%
Gas Oil Paraffins 15.0% 13~9% 16r5% 16~4%
Cycloparaffins 21. 5% 23 ~ 2% 28.8% 22.8%
Specific Gravity 0~972 Do961 0~961 0~962 Monoaromatics 10.8% 12.6% l3,7% 11~8%
From Tables 3 and 5 it is seen that the distillate contains a high level of saturates, being therefore very suitable For process-ing inLo di~sel fuel with a minimum amount of further treatment7 Because the process of the invention results in a net upgrading of middle distillates fed to the reactor, it can advantageously be used to upgrade full range bitumen, in addition to bitumen resid~lum.
~0 An advantage oF producing hydrogen by the water-gas shift reaction in presence oF the cracking oil feedstock is though-t to be tilat as fOrllled, the hydro9en is in an active state for a short time and is potentially more reactive than molecular hydrogen which must be cleaved in order to attach a sinyle hydrogen a-tom to a cracked radical. An advantage of the process of the invention is tha-t it uses an inexpensive catalyst9 iron oxide or sulphide, which can be discarded after a single batch run or a-Fter a single pass if a continuolls process is used. The iron catalyst can be recycled several times, an add-itional cos-~ advan-tage. No catalyst carrier or fluidized bed is necessary; the Finely divided catalyst is merely slurried in -the heavy oil Feeds-tock and passed -into -the reactor, good dispersion in the reaction mass being accomplished by agitation or by turbulent -flow through a tubular reactor, Another advantage is that the preFerred -feed gas, carbon rnonoxide, is readily available in many locations, as is synthesis gas, an alternat~ source of carbon monoxide. A Fur-ther advantage is that the produc-t residuum aFter distillin(g, being low in hydrogen content, is a good feedstock for 1~ gasi-fication and a-t a conversion oF about 70 percen-t or less, contains suffici~nt carbon to form the entire amount of carbon monoxide required For the water-gas shift reac-tion.
~()
mixture of carbon monoxide and hydrogen, or with steam and ~urnace gases containing carbon monoxide. The source of steam can be liquid water or vapour. At hydrocracking temperatures ~he steam and carbon monoxide are in the gaseous state, having critical -temperatures below the specified temperature. Some gas is also dissolved in the liquid reaction mass because of the high pressure. Alternatively, carbon monoxide can be generated in situ by, for example, introducing a material that decomposes to form carbon monoxide at hydrocracking conditions, for example methanol or formaldehyde.
The ratio of available carbon monoxide, whether introduced as a carbon monoxide~rich gas or produced in situ, to heavy oil feedstock can be from about 0002:1 to 10.0:1. Lower proportions of carbon monoxide within this range yield a mildly wpgraded crude suitable, for example, for pipeline transporta-tion to a re-finery, and higher proportions yive a thoroughly upgraded product with high conversion of residuum to distillables, together with low or no coke production. A preferred ratio of ~arbon monoxide to oil for thorough upgrading is 0.2:1 to 5.0:1.
The process can be carried out in batch or continuous 2~ ope~ration. The space velocity in a continuous process can be from about 0.l -to 2~ h-1, preferably from about 0.5 to 3 h-1. In a batch process the residence time can be from about 3 minutes to 10 hours, preferably from 20 minutes to 2 hours.
The catalyst comprises promoted iron or iron compounds; if elemental iron or iron oxide is used it can convert to iron sulphide by reacting with sulphur values that can be present in the feedstock under -the reducing conditions present during hydrocracking, and continues its activity. The concentration of the iron catalyst, deFined as the concentration o-f Fe, can be from about 0.2% to 10% and preferably from about l~ to 5% based on the heavy oil feedstock. The promoter is selected from the group of known promoters for the iron-catalyzed water-gas shift reaction in which carbon monoxide and steam produce carbon dioxide and hydrogen. The known promoters include carbonates and sulphides of alkali metals. Potassium carbonate is preferred~ The promoter is added in a molar concentration from about l% to 20% of the iron catalys-t concentration. The source of at least a portion of the iron catalyst can be the heavy oil feedstock itself;
most of the heavy oils now known contain a small amount of ironO The catalyst is conveniently in finely divided form, from about 20 to 400 mesh (841 ~m to 37 ,um), preferably 40 to 325 mesh (420 ~m to 44 ,um), in which it can be readily dispersed in the heavy oil feedstock with agitation induced mechanically or by turbulent flo~, for example in d tubular reactor.
The lower temperature limit of -the process is relatecl to the temperature at which the particular heavy oil feedstock can be ~0 cracked; For some heavy oil teedstocks the lower limi~ of cracking is ahou~ 380"C, whereas other feedstocks do not crack below about 400C.
water--gas shift reaction in the reaction zone provides sufficient hy(irogen at temperatures within the stated limits to terminate the cracked radicals. The upper temperature limit is about 460C and ~5 preferably about 440C, and is affected by various factors, primarily -the production of coke.
The pressure limits are the same as for conventiona1 hydro-cracking, namely about 5 MPa to 20 MPa and preferably about 7 MPa to 14 MPa.
Optionally, the product stream can be distilled into one or more fractions boiling below about 400C to 570~C and a residuum fraction boiling above that temperature. One o~ the product streams can be used as raw material for a gasification reaction with oxygen-con-taining gas -to produce carbon monoxide and steam which can be used in -~he upgradiny zone. Advantageously the residuum stream is used for 1~ the purpose, because the residuum stream is usually the least valuable economically and contains the highest proportion of carbon, which is the source of the carbon monoxideO The residuum fraction produced by ~he process o~ -the in~ention is especially suitable for gasification because of its low hydrogen content: hydrogen in a yasification material is essentially wasted in forming water. The cut poin-t in clistillation can readily be adjusted so that the residuum or other gasification stream can supply all the necessary carbon monoxide -to the upgrading zone.
The process will be fur~her described by the tOl lowing ~xalnple~s, which illustrate preferred embodirnerrts of the invention.
I~xdll~e l . _~
A sample of Athabasca biturnen obtained by the hot water process was distilled so that its vacuum residuum had an initial boiling point of 501C. The residuum charac~eristics are shown in lable 1.
~L~3~ 3~
TABLE 1: CHARACTERIZATION OF BITUMEN RESIDUUM
Specific Gravity 1.075 Minimum Boiling Point, C at 101 kPa 50l Ash, Wt. % 1.5 Carbon, Wt . % 82 . 21 Hydrogen, Wt. % 9-59 Sulphur, Wt. % 6.52 Vanadium, ppm by weigh~ 336 Nickel, ppm by weight 111 An amount of 252.5 g of the vacuum residuum was charged to a two-litre autoclave together with 12.6 9 powdered ferric oxide, 1.3 9 powdered potassium carbonate and 43.8 g de-ionized water. The sealed vessel was -then flushed with carbon monoxide and pressurized to 3.0 MPa at 18C with 58.3 litres of carbon monoxide. The stirred vessel was brought to an internal temperature of 400C for 150 minutes. The pressure reached 1208 MPa ini~ially and 13.1 MPa af~er 40 minutes, falling to 12.7 MPa at the end of the run. Heating was discontinued and after cooling, the pressure in the autoclave was 3.8 MPa at 18C.
Two samples were taken during the metered discharge of the gas and analysed by low resolution mass spectrometry. The remaining material was separated into naphtha, distillate, gas oil, residuum, coke and inorganics and the water content measured. Product ratios are shown ~0 in Table 2 and ~uality in Table 3.
Ex~æ e 2 , _ _ The procedure of Example 1 was carried out using 234.5 g o-f Athabasca bitumen vacuum residuum, 11.7 9 ferric oxide, 1~2 9 potassium carbonate and 40.7 g water. The autoclave was pressurized with carbon monoxide to 2.8 MPa at 20C and raised to 430C, producing a pressure of 13.3 MPa. After 21 minutes, the system was cooled and 63~
depressurized and the gas content sampled. Thirty five (35.0) grams of water was added and the system repressurized with carbon monoxide -to 2.8 MPa at room temperature; the autoclave and contents were reheated and held at 430C for a further 30 minutes, when the depressurizing, recharging and repressurizing were repeated. The temperature was raised to 430C for a further 29 minutes, aFter which the pressure was 16.2 MPa. The times reported above and in Table 2 include -the total time at the indicated temperature plus a factor for thermal exposure a-t temperatures above 400C. The vessel was cooled and products were recovered and sampled as in Example 1.
xample 3 A 241.4 g sample of Athabasca bitumen vacuum residuum was charged along with 12.1 g ferric oxide, 1.2 g potassium carbonate and 41.9 g water into the autoclave, which was pressurized to 2.8 MPa with carbon monoxide and heated to 415C for a total of 220 minutes. In sllllildr fashion to Example 2, the autoclave was recharged with carbon monoxide and 35 g water three -times by repressuri~ing to 2.8 MPa at room temperature. The final pressure was 17.1 MPa. The autoclave was 2() cooled and pro~lucts were recovered and sampled as in Example 1 3~
TABLE 2: UPGRADING AT~IABASCA RESIDUUM
Example 1 Example 2 Example 3 Added Catalyst, % Fe on Resid. 3.5% 3.5% 3.5%
Temperature 400C 430C 415C
Time, minutes 150 90 220 Ni Demetallization 12% 70% 77%
V Demetallization 21% 85% 91%
Desulphurization 46% 60% 60%
Product distribution~ percent Gases 2.5 12.8 13.5 Naphtha (IBP-195C) 12.2 2507 2409 Distillate (195-315C) 13.0 16.3 17.7 Gas oil (315-504C) 27.6 24.3 24.5 Residuum (504C-~ 44.7 18.$ 18.9 Coke ~ 2.0 0.5 Conversion of Resi~. 55.3 81.2 8l.1 Hydro~en uptake, m /m3 139 346 3l4 Liquid product yield 52.8% 66.3% 67.1%
Table 2 shows the product yield and performance of the process at differing conditions. The products were highly dernetallized and had a reduced sulphur content. Up to 81% conversion was achieved and bo-th demetallization and desulphurization improved with increasing conversion. Hydrogen uptake -into the distillable produr~s was high, indicating high product saturation. For example, the ,roportion of paraffins in the distillate product of Example 1 was ~0 29~l%, comparcd to 8% for a distillate product from a typical fluid coked Athabasca whole bitumen. ~le hydrogen was added preferentially to ~he lighter products? the pitch formed in the hydrocracking reaction having low hydrogen content, an advantage when the pitch is to be burned directly or gasifiedO
g ~iSf~3~
TA3LE 3: PROPERTIES OF_ LIQUID PRODUCTS
Example 1 Example 2 Example 3 Naphtha (I~P-195C) Paraffins, Wt. % 53.8 . 54.9 53.5 Cycloparaffins, Wt% 11. 5 25.2 30.9 Bromine Number 42.8 18.6 20.7 Specific Gravity 0.751 0.75~ 0.764 Mono-ol ef i ns, Wt . % 21.2 8.8 5.7 Distillate (195-315C) Paraffins, Wt. % 29.l 26~3 26.6 Cyclo,oaraffins, Wt~ % 40.3 35.1 34.6 Bromine Number 29.6 17.2 15.9 Specific Gravity 0.871 0.875 0~876 Monoaromatics, Wt. % 18~4 24~6 24~8 Gas Oil (3l5-504~
FaraFfins, Wt. % ll.O 12.5 14.0 Cycloparaffins, Wt. % 26.0 18.0 22.7 Specific Gravity 0.970 00989 0.976 Monoaromatics, Wt. % 13.2. 13~8 13~1 Pitch (504C~) Hydrogen, Wt 8.41 6.73 7.10 Exam~les 4-7 Residua of several heavy crude oils were prepared in the same manner as the Athabasca of Exarnples 1 to 3~ to give materials havins an initial boiling point oF 504Co A typical experimental procedure is described below.
~0 A sample oF residuum (28l.2 9) was charged to a 2 litre autoclave together with 14.1 g ferric oxide, 1.4 9 potassium carbonate and ~8.5 9 deionized water. AFter nitrogen purging, the system was Flushe(l with carbon monoxide and 67 L oF carbon monoxide (at standard conditions) was added, raising the pressure to 3.3 MPa at 18C. The system was heated with stirring to an internal temperature of 415~Ca the pressure rising to 15.0 MPa initially and to a maximurn oF 15.2 MPa before falling finally to 15.0 MPa. After 50 minutes the system ~las allo~ed to cool to 19C, the pressure being 4.31 MPaO A volume of 3~D ' 95.5 L oF gas was drawn off and two samples analysed by lo~ resolution mass spectrometry. ~n amount o~ 40 9 of deionized ~ater was added and the vessel repressurized to 3.3 ~1Pa with carbon monoxide. The second heating period was also 50 minutes dura~ion. A further cycle of cooling, gas sampling, recharging with water and carbon monoxide and heating followed, to g;ve a total of 150 minu-tes at 415aCo Final product ~esting was the same as in Examples '-39 and the results are shown in Tables 4 and 5, TABIE 4: UPGRADING ~EAVY CRUDE OILS - PRGDUCT YIELDS
_ .
Example 4 _a¢~ Example 6 Example 7 ReSjd~J~Jm Pelican L. Cold Lake Lloydminster Boscan Source Canada Canada Canada Venezuela Temperature, C 415 415 415 ~15 Time, minutes 150 150 150 150 Ni demetallization, % 71 81 76 82 V demetallization, % 80 88 83 85 Desul~hurization, %58 57 53 60 15 Product distribution, percent Gases 13.1 9.2 8.8 11.0 N~phth~ (IBP-195C) 25.2 21.7 21.9 25.3 Distilla-te (195-315G) 15.9 17.6 15.7 15.2 Gas oil (315-504C) 26.2 24.9 32.3 29.7 Resid~u~ (504C+) 17.8 22.8 20.2 17.2 Coke 1.8 3.7 1~1 1.6 Conv ,sion of residuum, % 82.2 77,2 79.8 82.8 ~0 ~DS~3~
TABLE 5: UPGRADING HEAVy CRUDE OILS - PRODUCT PROPERTIES
_ Example 4 Example 5 Example 6 Example 7 Naphtha Paraffins 53~2% 53~4% 53~7% 53D9%
Cycloparaffins 24.9% 24.1% 23.2% 24.5%
Bromine Number 31. 6 32 ~ 0 23. 5 21 ~ 9 Specific Gravity 0~762 0~747 0~749 0~753 Mono-olefins 11.4% 11~0% 12~% 11~1%
- Distillate ~ Paraffins 28~7% 27~9% 2807% 26~4%
Cycloparaffins 33.2% 36.4% 38~0% 34.3%
Bromine Number 20.4 15~8 11.4 12~3 Spec;fic Gravity 0.881 0~870 0~866 0~87g Monoaromatics 21~1% 21.8% 21~2% 21~6%
Gas Oil Paraffins 15.0% 13~9% 16r5% 16~4%
Cycloparaffins 21. 5% 23 ~ 2% 28.8% 22.8%
Specific Gravity 0~972 Do961 0~961 0~962 Monoaromatics 10.8% 12.6% l3,7% 11~8%
From Tables 3 and 5 it is seen that the distillate contains a high level of saturates, being therefore very suitable For process-ing inLo di~sel fuel with a minimum amount of further treatment7 Because the process of the invention results in a net upgrading of middle distillates fed to the reactor, it can advantageously be used to upgrade full range bitumen, in addition to bitumen resid~lum.
~0 An advantage oF producing hydrogen by the water-gas shift reaction in presence oF the cracking oil feedstock is though-t to be tilat as fOrllled, the hydro9en is in an active state for a short time and is potentially more reactive than molecular hydrogen which must be cleaved in order to attach a sinyle hydrogen a-tom to a cracked radical. An advantage of the process of the invention is tha-t it uses an inexpensive catalyst9 iron oxide or sulphide, which can be discarded after a single batch run or a-Fter a single pass if a continuolls process is used. The iron catalyst can be recycled several times, an add-itional cos-~ advan-tage. No catalyst carrier or fluidized bed is necessary; the Finely divided catalyst is merely slurried in -the heavy oil Feeds-tock and passed -into -the reactor, good dispersion in the reaction mass being accomplished by agitation or by turbulent -flow through a tubular reactor, Another advantage is that the preFerred -feed gas, carbon rnonoxide, is readily available in many locations, as is synthesis gas, an alternat~ source of carbon monoxide. A Fur-ther advantage is that the produc-t residuum aFter distillin(g, being low in hydrogen content, is a good feedstock for 1~ gasi-fication and a-t a conversion oF about 70 percen-t or less, contains suffici~nt carbon to form the entire amount of carbon monoxide required For the water-gas shift reac-tion.
~()
Claims (30)
1. A process for the upgrading of heavy, viscous hydrocarbonaceous oil, comprising contacting said oil with a carbon monoxide-containing gas and steam in a reaction zone at hydrocracking conditions, said hydrocracking conditions including a temperature at least 400°C and a pressure between substantially 5 MPa and 20 MPa, in the presence of a promoted iron catalyst, to yield a hydrocracked product.
2. A process as claimed in Claim 1 wherein said hydrocracking conditions include a temperature between substantially 400°C and substantially 460°C.
3. A process as claimed in Claim 2, wherein said temperature is between substantially 400°C and substantially 440°C
4. A process as claimed in Claim 1 wherein the ratio of carbon monoxide to hydrocarbonaceous oil supplied to said reaction zone is from substantially 0.02:1 to substantially 10:1, by weight.
5. A process as claimed in Claim 1 wherein the ratio of carbon monoxide to hydrocarbonaceous oil supplied to said reaction zone is from substantially 0.2:1 to substantially 5:1, by weight.
6. A process as claimed in Claim 1 wherein said pressure is between substantially 7 MPa and substantially 14 MPa.
7. A process as claimed in Claim 1 carried out for a residence time substantially from 0.05 to 10 hours.
8. A process as claimed in Claim 7 wherein said residence time is substantially from 0.3 to 2 hours.
9. A process as claimed in Claim 1 wherein said oil is raw crude having a gravity numerically less than substantially 25° API.
10. A process as claimed in Claim 1 wherein said oil is atmospheric residuum derived from crude oil having a gravity less than substantially 25° API.
11. A process as claimed in Claim 1 wherein said oil is vacuum residuum derived from crude oil having a gravity less than substantially 25° API.
12. A process as claimed in Claim 1 wherein said oil is vacuum residuum derived from crude oil having a gravity greater than substantially 25° API.
13. A process as claimed in Claim 1 wherein said catalyst is in finely divided form.
14. A process as claimed in Claim 13 wherein the particle size of said catalyst is from substantially 37 um to substantially 841 um.
15. A process as claimed in Claim 13 wherein the particle size of said catalyst is from substantially 44 um to substantially 420 um.
16. A process as claimed in Claim 1 wherein said carbon monoxide-containing gas comprises synthesis gas.
17. A process as claimed in Claim 1 wherein said carbon monoxide-containing gas consists essentially of carbon monoxide.
18. A process as claimed in Claim 1 wherein said carbon monoxide-containing gas comprises carbon monoxide generated in situ.
19. A process as claimed in Claim 18 wherein said carbon monoxide-containing gas comprises carbon monoxide generated in situ by decomposition of formaldehyde.
20. A process as claimed in Claim 18 wherein said carbon monoxide-containing gas comprises carbon monoxide generated in situ by decomposition of methanol.
21. A process as claimed in Claim 1 wherein said catalyst is present in a concentration, expressed as concentration of Fe, between substantially 0.2% and substantially 10% of said oil.
22. A process as claimed in Claim 21 wherein said catalyst is present in a concentration, expressed as concentration of Fe, between substantially 1% and substantially 5% of said oil.
23. A process as claimed in Claim 21 wherein said catalyst comprises iron oxide and alkali metal carbonate.
24. A process as claimed in Claim 23 wherein said alkali metal carbonate is present in a molar concentration between substantially 1% and substantially 20% of the concentration of said iron catalyst, expressed as moles of alkali metal to moles of iron.
25. A process as claimed in Claim 21 wherein said catalyst comprises iron sulphide and alkali metal carbonate.
26. A process as claimed in Claim 21 wherein said catalyst comprises iron oxide and potassium carbonate.
27. A process as claimed in Claim 25 wherein said catalyst comprises iron sulphide and potassium carbonate.
28. A process as claimed in Claim 1, further comprising the steps of:
(a) fractionally distilling said hydrocracked product to yield at least one fraction boiling below a temperature from substantially 400°C
to substantially 570°C, and a residuum fraction boiling above said temperature, (b) contacting one of said fractions with an oxygen-rich gas at gasification conditions to yield a recyclable carbon monoxide-containing gas, and (c) recycling said recyclable carbon monoxide-containing gas to comprise at least a portion of said carbon monoxide-containing gas to be contacted with said viscous hydrocarbonaceous oil.
(a) fractionally distilling said hydrocracked product to yield at least one fraction boiling below a temperature from substantially 400°C
to substantially 570°C, and a residuum fraction boiling above said temperature, (b) contacting one of said fractions with an oxygen-rich gas at gasification conditions to yield a recyclable carbon monoxide-containing gas, and (c) recycling said recyclable carbon monoxide-containing gas to comprise at least a portion of said carbon monoxide-containing gas to be contacted with said viscous hydrocarbonaceous oil.
29. A process as claimed in Claim 28 wherein said carbon monoxide-containing gas consists essentially of said recyclable carbon monoxide-containing gas.
30. A process as claimed in Claim 28 wherein said fraction that is contacted with said oxygen-rich gas is said residuum fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000414120A CA1195639A (en) | 1982-10-25 | 1982-10-25 | Upgrading of heavy hydrocarbonaceous oil using carbon monoxide and steam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000414120A CA1195639A (en) | 1982-10-25 | 1982-10-25 | Upgrading of heavy hydrocarbonaceous oil using carbon monoxide and steam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195639A true CA1195639A (en) | 1985-10-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000414120A Expired CA1195639A (en) | 1982-10-25 | 1982-10-25 | Upgrading of heavy hydrocarbonaceous oil using carbon monoxide and steam |
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| CA (1) | CA1195639A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316659A (en) * | 1993-04-02 | 1994-05-31 | Exxon Research & Engineering Co. | Upgrading of bitumen asphaltenes by hot water treatment |
| US5322617A (en) * | 1992-08-07 | 1994-06-21 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Energy, Mines And Resources | Upgrading oil emulsions with carbon monoxide or synthesis gas |
| US5326456A (en) * | 1993-04-02 | 1994-07-05 | Exxon Research And Engineering Company | Upgrading of bitumen asphaltenes by hot water treatment containing carbonate (C-2726) |
| US5868923A (en) * | 1991-05-02 | 1999-02-09 | Texaco Inc | Hydroconversion process |
| US5935419A (en) * | 1996-09-16 | 1999-08-10 | Texaco Inc. | Methods for adding value to heavy oil utilizing a soluble metal catalyst |
| US6059957A (en) * | 1996-09-16 | 2000-05-09 | Texaco Inc. | Methods for adding value to heavy oil |
| US7763160B2 (en) | 2003-12-19 | 2010-07-27 | Shell Oil Company | Systems and methods of producing a crude product |
| EP3608388A4 (en) * | 2018-04-28 | 2020-06-10 | Beijing Sanju Environmental Protection and New Material Co., Ltd. | Substandard oil product conversion process |
| EP3613830A4 (en) * | 2018-04-28 | 2020-07-15 | Beijing Sanju Environmental Protection & New Materials Co., Ltd. | Conversion process for organic matter |
| US11492563B2 (en) | 2018-04-28 | 2022-11-08 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an inferior oil |
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1982
- 1982-10-25 CA CA000414120A patent/CA1195639A/en not_active Expired
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5868923A (en) * | 1991-05-02 | 1999-02-09 | Texaco Inc | Hydroconversion process |
| US5322617A (en) * | 1992-08-07 | 1994-06-21 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Energy, Mines And Resources | Upgrading oil emulsions with carbon monoxide or synthesis gas |
| US5316659A (en) * | 1993-04-02 | 1994-05-31 | Exxon Research & Engineering Co. | Upgrading of bitumen asphaltenes by hot water treatment |
| US5326456A (en) * | 1993-04-02 | 1994-07-05 | Exxon Research And Engineering Company | Upgrading of bitumen asphaltenes by hot water treatment containing carbonate (C-2726) |
| US5935419A (en) * | 1996-09-16 | 1999-08-10 | Texaco Inc. | Methods for adding value to heavy oil utilizing a soluble metal catalyst |
| US6059957A (en) * | 1996-09-16 | 2000-05-09 | Texaco Inc. | Methods for adding value to heavy oil |
| US8070936B2 (en) | 2003-12-19 | 2011-12-06 | Shell Oil Company | Systems and methods of producing a crude product |
| US7879223B2 (en) | 2003-12-19 | 2011-02-01 | Shell Oil Company | Systems and methods of producing a crude product |
| US7763160B2 (en) | 2003-12-19 | 2010-07-27 | Shell Oil Company | Systems and methods of producing a crude product |
| US8163166B2 (en) | 2003-12-19 | 2012-04-24 | Shell Oil Company | Systems and methods of producing a crude product |
| US8394254B2 (en) | 2003-12-19 | 2013-03-12 | Shell Oil Company | Crude product composition |
| US8613851B2 (en) | 2003-12-19 | 2013-12-24 | Shell Oil Company | Crude product composition |
| EP3608388A4 (en) * | 2018-04-28 | 2020-06-10 | Beijing Sanju Environmental Protection and New Material Co., Ltd. | Substandard oil product conversion process |
| EP3613830A4 (en) * | 2018-04-28 | 2020-07-15 | Beijing Sanju Environmental Protection & New Materials Co., Ltd. | Conversion process for organic matter |
| US11198820B2 (en) | 2018-04-28 | 2021-12-14 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an organic material |
| US11492563B2 (en) | 2018-04-28 | 2022-11-08 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an inferior oil |
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