CA1159788A - Upgrading hydrocarbonaceous oils with an aqueous liquid - Google Patents
Upgrading hydrocarbonaceous oils with an aqueous liquidInfo
- Publication number
- CA1159788A CA1159788A CA000393450A CA393450A CA1159788A CA 1159788 A CA1159788 A CA 1159788A CA 000393450 A CA000393450 A CA 000393450A CA 393450 A CA393450 A CA 393450A CA 1159788 A CA1159788 A CA 1159788A
- Authority
- CA
- Canada
- Prior art keywords
- oil
- aqueous liquid
- contacting
- free oxygen
- hydrocarbonaceous
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
Abstract
ABSTRACT OF THE DISCLOSURE
"UPGRADING HYDROCARBONACEOUS OILS
WITH AN AQUEOUS LIQUID"
A process for upgrading oils is disclosed, in which the oil to be upgrades is contacted with liquid phase water and free oxygen at an elevated temperature and at a pressure sufficient to maintain at least part of the water in the liquid phase.
"UPGRADING HYDROCARBONACEOUS OILS
WITH AN AQUEOUS LIQUID"
A process for upgrading oils is disclosed, in which the oil to be upgrades is contacted with liquid phase water and free oxygen at an elevated temperature and at a pressure sufficient to maintain at least part of the water in the liquid phase.
Description
-l 159788 UPGRADING HYDROCARBONACEOUS OILS
WITH AN AQUEOUS ~IQUID
BACKGROUND OF THE INVENTION
The present invention concerns a process for upgrading hydrocarbonaceous oils. More specifically, the invention concerns a process for upgrading heavy oils by contacting the oils with free oxygen and liquid phase water at an elevated temperature.
Heavy petroleum fractions such as residuals and heavy crude oils can be used as low grade commercial fuels or may be converted by thermal and catalytic conversion processes into more valuable, lighter hydrocarbons, parti-cularly gasoline. Heavy crudes and heavy oil fractionsare oten contaminated with substantial ccncentrations of detrimental materials. Common contaminants are organic nitrogen and sulfur compounds, metals, particularly nickel and vanadium, nondistillable, heat-sensitive coke precur-sors, such as asphaltenes, and the like. When heavy oilsare burned directly as fuel, combustion of the nitrogen and sulfur compounds results in formation of objectionable pollutants, nitrogen oxides and sulfur oxides. When heavy 25 oils are upgraded by conven~ional catalytic conversions, the presence o~ the nitrogen and sulfur compounds, and particularly the presence o the metals, results in rapid deactivation of catalysts, and causes the upgrading of residual oils to be undesirably expensive. Conventional methods for upgrading heavy oil fractions to provide more valuable hydrocarbons often consume substantial amounts of hydrogen. The cost of hydrogsn consumed is an economic drawback when hydroprocessing is employed for the upgrad-ing. When heavy crudes and oil fractions are subjected to conventional pyrolysis-type coking (e.g., delayed or fluid coking) at temperatures of 350C to 500C, large concen-trations of heat-sensitive, coke-forming materials, such as asphaltenes, can result in relatively low yields of the more valuable primary pr~oduct, distillates, and relatively high yields of the less valuable by-product, coke. The . .
presence of undesirably large concentrations of contaminants in coke derived by conventional coking of heavy oils detracts from the value of coke as a by-product. This is particularly true for sulfur. The quality of coke obtained from heavy oil high in contaminants may thus make it unsuitable for some uses, e.g., electrodes, because of poor specifications of such properties as coefficient of thermal expansion, electrical resistivity and sulfur content.
A general discussion of the wet air oxidation technology, is to be found in Mechanical Engineering, December 1979, page 30. A discussion of the regeneration of active carbon after use in waste water treating, by means of wet air oxidation, i9 to be found in the AICHE Symposium Series, Vol. 76, No. 192, (Recent Advances in Separation Technology - II), page 51 (AICHF, 1980).
A process for removing pyritic sulfur from coal by treatment with water and air at elevated temperature and pressure to convert the pyritic sulfur to water-soluble ferrous and ferric sulfate is disclosed in United States Patent No. 3,824,084. Use of silicates and an oxidizing agent (such ;~ as air, oxygen, hydrogen, peroxide, alkali metal sulfides, alkaline or metal sulfides) or a reducing agent (such as H2, C0, K2, S204, NaS204, and alkali metal polythionates) in an aqueous medium to desulfurize coal is disclosed in United States Patents No. 4,174,953 and No. 4,197,090.
Use of wet air oxidation to provide heat energy in the form of steam, as by wet oxidation of coal, is disclosed in United States Patents No. 4,211,174, No. 4,100,730, and 4,013,560.
Use of copper or silver ions to catalyze wet air oxidation of organic material in waste water is disclosed in United States Patent ;~ No. 3,912,626.
Treatment of papermill waste sludges to convert organic components to innocuous oxidation products and to provide for recovery of inorganic i filter materials for reuse is disclosed in United States Patent No. 3,876,497.
01 _3_ Essentially complete oxidation of solid or liquid combustible materials which are difficult to sus-pend in water, such as diesel fuel and nitroglycerine by direct injection into a wet air oxidation reactor is dis-closed in U.S. Patent No. 4,174,280.
None of the disclosures concerning wet air oxi-dation is concerned with upgrading of hydrocarbonaceous materials. Hydrocarbonaceous oils which are utilized in the disclosed wet air oxidation processes are simply essentially completely consumed to form highly oxidized materials, primarily carbon dioxide, water and the like.
SUMMARY OF THE INVENTION
..
The present invention concerns a process for upgrading a hydrocarbonaceous oil which comprises con-tacting the oil with free oxygen in the presence of an aqueous liquid at a temperature above about 175C and a pres~ure sufficient to maintain the aqueous liquid at least partially in a liquid phase.
I have found that surprising improvements in several properties of a heavy hydrocarbonaceous oil can be advantageously obtained by contacting the oil with free oxygen and liquid phase water at an elevated temperature.
The amounts of contaminants, such as metals, nitrogen and sulfur, in the oil can be substantially decreased. The viscosity of the oil can be substantially decreased. When the temperature is maintained generally below about 300C, the amount of nondistillable, coke-forming constituents of the oils, such as asphaltenes, can be substantially decreased. ~he process of present invention also permits the viscosity of heavy oils to be substantially decreased.
The present process can advantageously be performed at a temperature much lower than used in conventional heavy oil upgrading systems.
In one embodiment, the present invention con-cerns a process for producing coke from a hydroc~rbona-~ ceous oil, which comprises forming coke by contacting the ;l 40 oil with free oxygen in the presence of an aqueous liquid ~ at a temperature of at least 300C and a pressure , ' ,~:
`` 1 159788 01 _4_ sufficient to maintain the aqueous liquid at least partially in the liquid phase.
I have found that high-quality coke can be formed from a heavy hydrocarbonaceous oil by contact with liquid phase water and free oxygen at elevated temperature and pressure. The amounts of such contaminants as metals and sulfur in the resulting coke are advantageously low, and a desirable, low yield of coke, relative to distill-able hydrocarbons, is obtained. Advantageously, the coke formation can be carried out in a continuous manner, eli-minating the need for removal of coke from drums, as is done in delayed coking. Heat requirements for the present process can be provided completely by oxidation of heavy oil in the system.
DESCRIPTION OF THE DRAWING
The attached drawing is a schematic representa-0 tion of preferred embodiments of the present invention.
In an embodiment for mild hydrocarbon upgrading, there is shown a wet air oxidation reactor l. Aqueous liquid is introduced into the system through a conduit 3. A feed stream of hydrocarbonaceous oil to be upgraded 25 ~ is introduced to the system through a conduit 5 and is charged to the reactor l through a diesel injector (not shown~ at a rate of one part (by volume) of oil per four parts of aqueous liquid. Free oxygen-containing gas is introduced into the system through a conduit 7 and is mixed with the aqueous liquid in the conduit 3. The ~ water-oxygen mixture is passed into the reactor l. In the ;; ~ reactor the oil-water-oxygen mixture is maintained at suitable reaction conditions including an appropriate elevated temperature such as 204C and a pressure suffi-cient to maintain the aqueous phase as a liquid such as 50 atmospheres. The mixture flows upwardly through the reac-tor and is removed from the top of the reactor through a conduit 9. The mixture is then cooled in a heat exchanger ll, passed through a pressure reducing valve 13, and charged to gas separator vessel 15, in which the gases in :
l 159788 the mixture are separated from the aqueous and hydrocar-bonaceous liquids. The gases are removed from the top of the separator vessel 15 and passed out of the system through a conduit 17. The mixture of liquid aqueous and hydrocarbonaceous phases is withdrawn from the vessel 15 and passed through a conduit 19 into a phase separator, such as a settling vessel 21. The lighter oil phase rises to the top of the vessel 21 and is withdrawn from the vessel and recovered by means of a conduit 23. Aqueous liquid settles to the bottom of the vessel 21 and is with-drawn through a conduit 25.
In a coking embodiment, aqueous liquid, which may include fresh water, recycle water, or both, is intro-duced into the system through a conduit 3. A feed stream of heavy hydrocarbonaceous oil to be converted is intro-duced to the system through a conduit 5 and is mixed with the aqueous phase in the conduit 3. Free oxygen-contain-ing gas i5 introduced into the system through a conduit 7 and is passed into the lower portion of the reactor 1.
The oil-water mixture in the conduit 3 is passed into the reactor 1 above the oxygen inlet. In the reactor, the ; mixture is maintained at suitable reaction conditions including an elevated temperature above 300C, such as about 375C, and a pressure sufficient to maintain the aqueous phase as a liquid such as 70 atmospheres. The liquids and gases flow upwardly through the reactor and are removed from the top of the reactor through a con-duit 9. The mixture is then cooled in a heat exchanger 11, and is passed through a pressure reducing . , valve 13. The mixture is then charged to a gas separator vessel 15, in which gases in the mixture are separated from the liquids. Gases are removed from the top of the gas separator vessel and withdrawn from the system through a conduit 17. The mixture of aqueous and hydrocarbona-ceous liquid phases is then passed from the vessel 15 through a conduit 19 into phase separation means, such as a settling vessel 21. The generally lighter oil phase rises to the top of the vessel 21 and is withdrawn by :
`~:
~' :
1 15~788 Ol -6-means of a conduit 23. Aqueous liquid settles to the bottom of the vessel 21 and is withdrawn through a con-; 05 duit 25. The hydrocarbonaceous liquid is passed from the conduit 23 into a fractionator vessel 27. Lower-boiling, more valuable product hydrocarbons are vaporized, with-drawn overhead through a conduit 29, and recovered.
Higher-boiling, less valuable components of the oil are withdrawn from the bottom of the fractionator and recycled to the feed conduit 3 by way of a conduit 31. A reboiling slip stream from the liquid effluent in the conduit 31 is removed into a conduit 33, heated in a furnace 35, and returned to the fractionator through a conduit 37.
Referring again to the reactor vessel 1, reactions occur in the vessel which form solid coke particles. The coke particles sink to the bottom of the vessel, and are withdrawn as a slurry in aqueous liquid through a conduit 39. Coke is separated from most of the aqueous liquid in a centrifuge 41 and is withdrawn from the system as a concentrated aqueous slurry by way of a conduit 43.
Aqueous liquid is withdrawn from the centrifuge through a conduit 45. The aqueous streams in conduits 25 and 45 may, if desired, be recycled directly to the reactor 1, or may be mixed with fresh water in the conduit 5 or hydro-carbon feed in the conduit 3. The water recycle streams may be treated, as for removal of solids, mineral salts, and the like (by means not shown) prior to recycle, if desired. Various conventional elements necessary for carrying out the embodiment depicted in the drawing, such ~; as control means, pumping means, compressing means, and the like, are not shown or discussed. The disposition and use of such conventional elements will be apparent to those skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION
A wide variety of hydrocarbonaceous oils may be upgraded by the process of this invention. In general, any oil which contains an objectionable amount of oné or more undesirable contaminants can be upgraded. For exam-ple, an oil containing an undesirable concentration of one :
1 1~9788 Ol _7_ or more metalliferous contaminants can be upgraded, i.e.
demetallized, by reduction of the metals concentration.
05 Oils containing an undesirably high concentration of one or more sulfurous contaminants can be upgraded, i.e., desulfurized, by reduction of the sulfur concentration.
Oils containing an undesirably high concentration of one or more nitrogenous contaminants can be upgraded, i.e., denitrified, by reduction of their nitrogen concentration.
Oils having an undesirably high concentration of asphal-tenes can be upgraded, i.e. deasphalted by reduction of their asphaltenes concentration. Oils having a viscosity which is higher than desired can be upgraded to decrease their viscosity by treatment according to the present invention. Oils containing an undesirably high concentra-tion of relatively higher molecular weight hydrocarbona-ceous molecules can be upgraded according to the invention to provide a product having a decreased concentration of such higher molecular weight materials and an increased concentration of lower molecular weight hydrocarbons, as by cracking and decomposition of high mol~cular weight heteronuclear compounds, polycyclic aromatics, etc.
For example, high molecular weight, nondistillable com-pounds, such as asphaltenes, can be converted to distill-able hydrocarbon compounds and lower molecular weight com-pounds by upgrading according to the present invention.
In the coking embodiment, the oil is treated to provide coke and a distillate of lower contaminant level, lower molecular weight, and/or lower viscosity, etc, Although any oil contaminated with one or more of the contaminants discussed above or having an overly ;~ high boiling range or overly high viscosity, can be suita-bly upgraded according to the present invention, the pre-ferred feed oils are petroleum residuals, heavy petroleum ' crudes, shale oils, coal oils, tar sand oils (bitumens), and analogous natural or synthetic oils and oil fractions.
For example, preferred feeds include such petroleum frac-tions as atmospheric distillation bottoms streams, vacuum distillation bottoms streams, catalytic cracking product l 15978~ `
fractionator bottoms and slurry oils, and in general petroleum, coal oil, tar sand oil, shale oil, or the like or heavy fractions thereof, a substantial portion of which has a normal boiling point above 565C. Preferred heavy crude petroleum or tar sand oils for upgrading are those with one or more of the following properties: an API
gravity of less than 20; a Ramsbottom carbon residue factor of greater than 0.8; an asphaltenes (n-heptane insoluble fraction) content of greater than 3 weight per-cent; or a fraction of greater than l0 weight percent of the oil boiling above 565C. Preferred feeds include bitumen derived from tar sands, i.e., bituminous sands, and heavy crudes and tars such as those found in the Athabasca region of Canada and the Orinoco region of Venezuela.
Preferred feed oils include oils having a sub-stantial concentration of at least one metal selected from nickel and vanadium. These metals are usually present in crude oils and residual fractions in the form of organo-metallic compounds, such as metalloporphyrins.
Preferred feed oils include oils having a sub-stantial concentration of finely divided solid contami-nants, which may be solid organic material, solid inor-ganic material, or both. Examples of solids found in some preferred feed oils are clay, sand, silt and such salts as alkaline earth metal carbonates and silicates.
Preferred feed oils may be oils which are mixed with small or large concentrations of aqueous liquids. In fact, the present process provides a highly advantageous way to dispose of waste slop oils, oil-water emulsions, desalter separator cuff layers, contaminated oil bottoms from storage tanks and the like.
The aqueous liquid used in the treatment of the -~ present invention may simply be water or may be an aqueous solution or suspension of one or more inorga~ic or organic compounds or ions. In some cases, addition of solubie or suspended materials can be beneficial to carrying out the process in that the added material can catalyze reactions 01 _9_ which take place in upgrading an oil. Preferred additive materials include alkali metals, alkaline earth metals, 05 their ions and salts. Added extraneous materials, such as alkali and alkaline earth metals, can be mixed with the feed oil or with the oxygen-containing gas prior to con-tacting the gas, water and oil at high temperatures, or can preferably be premixed with the aqueous phase.
The temperature at which the present process is carried out should usually be maintained above about 175C. For upgrading without substantial coking, the reaction temperature is maintained between about 175C and 300C, particularly between about 195C and 260C. For coking, the process is carried out at a temperature suffi-cient to form coke from the feed oil. The temperatureshould usually be maintained above 300C, preferably between about 315C and ~40C, particularly between about 325C and 425C. In either case, the elevated operating temperature can be achieved solely by oxidation reactions which occur after the oil, water and molecular oxygen are contacted. One or more of the components can be preheated prior to contact with the other components. The mixture can also be heated by an external heat source after con-tact. Often, heat exchange between the hot effluent from the reaction zone and one or more of the aqueous feed, oilfeed or oxygen feed is advantageous in conserving heat energy.
It will be apparent that the reaction tempera-tures may not be uniform over the course of the reaction time in carrying out many embodiments of the present pro-cess, since oxidation reactions will tend to increase the temperature of the reaction mixture over the extent of the contact time, if free oxygen is not limited. Thus, in a batch-type non-coking reaction, the reaction temperature may start at a very low temperature, e.g. below 175C, and rise to a high level, e.g. above 300C at the end of the contact time. For coking, the temperature may start at a very low temperature, e.g. below 300C, and rise to a high level, which may even be above 540C by the end of the l 159788 contact time. A similar temperature profile will often be observed when a plug flow-type contacting scheme is employed. In general, however, the reactants should be maintained within the indicated temperature ranges for at least a major portion of the total contact time. Prac-tical contact times are usually those sufficient to allow consumption of at least a major portion of the free oxygen employed.
The pressure employed in the present process is at least sufficient to maintain at least a portion of the water, i.e., the aqueous phase, in the liquid state.
Preferably, a pressure is employed which is at least suf-ficient to maintain the major portion of water present in the reaction mi~ture as a liquid. Higher pressures have the advantage of permitting relatively larger amounts of free oxygen to be dissolved or diffused in the liquid aqueous phase, but increased capital and operating costs involved in the carrying out of higher pressure operations usually set a practical upper limit on the pressure that can economically be used.
According to the invention, free oxygen, i.e., molecular or atomic oxygen, or a precursor thereof, is contacted with oil and an aqueous liquid. To supply the free oxygen component for the process, pure molecular oxygen gas (2 or O3) can be used. Gases, such as air, which contain molecular oxygen mixed with one or more diluent gases, such as nitrogen, steam, carbon dioxide, etc., are also suitable for use. Solid, liquid or gaseous compounds of combined oxygen, which decompose or react to form atomic or molecular oxygen, such as hydrogen per-~d ~ oxide, may be used to supply the free oxygen component.
. ~
The free oxygen component, or a precursor thereof, can be mixed with the aqueous liquid prior to, simultaneously with, or after contact is established between the aqueous ., liquid and the feed oil. The amount of free oxygen ~ employed relative to the amount of oil should be suffi-! 40 cient to react with not more than a minor portion of the ~ `
oil. Preferably, the free oxygen should not constitute more than about 30 weight percent of the oil.
Contact of the feed oil with aqeuous liquid and with free oxygen can be carried out in a suitable conven-tional reactor or other suitable conventional vessel or container means, which should be sufficiently resistant to the temperatures, pressures, corrosive compounds and other reaction conditions which are encountered in carrying out the present invention. The oil, water and free oxygen components can be contacted in a batch-type system or, preferably, in a continuous type system. The oil, water and oxygen components can be contacted in cocurrent flow, in countercurren~ flow, in a stirred tank-type reaction system, or in another analogous contact system. Prefer-ably, contact is carried out in cocurrent flow through a reaction zone, particularly preferably in upflow through a vertically extending vessel. Preferably, at least a por-tion of the free oxygen employed is dissolved in the aqueous liquid prior to contacting the aqueous liquid with the oil to be treated.
Preferably, oil and aqueous liquid are contacted at an aqueous liquid-oil volume ratio in the range from about 0.5:1 to about 10:1. Particularly preferably, an aqueous liquid:oil volume ratio of about 1:1 to about 4:1 is used. Preferably, the feed oil i5 introduced into contact with the aqueous liquid in finely divided form, e.g. as droplets, as by using a mixer, diesel injector or the like.
The product oil can be separated from the water and gas by phase separation (settling, decantation, etc.) or fractional ~istillation or the like conventional separ-, ation technique. The product oil can be used advanta-geously in several ways. One advantageous use of the product of a non-coking process is as a feed for a thermal distillation or coking process. Suitable conventional coking techniques include delayed coking and fluidized coking. Another advantageous use for product oil is as a feed for a catalyti~ cracking operation, especially for an ' l 159788 FCC operation in which the oil is contacted with an acidic, zeolite or non-7eolite catalyst in the absence of 05 added molecular hydrogen. A further advantageous use for product oil is as a feed for a hydrogen treating process such as hydrodemetalation, hydrodenitrification, hydrode-sulfurization, hydrocracking or simple hydrogenation, in which the oil is contacted with a Group VIB and/or Group VIII metal on a porous carrier such as silica, alumina, clays and the like. Suitable hydrogen treating catalysts may include an acidic component such as silica-alumina, a zeolite, etc. The product oil formed in the present pro-cess can often be fractionated to provide high yields of such products as diesel fractions, jet fuels, gasolines, naphthas, etc.
As a byproduct of upgrading the feed oil, it may be advantageous to generate steam from a portion of the aqueous liquid, and the steam can be used to supply energy for electrical or mechanical power generation. It should be noted, however, that at least a portion of the aqueous phase should remain as a liquid at the end of the contact-ing period.
An atmospheric distillation residual oil frac-tion from an Arabian Heavy crude was upgraded according to the present invention in a series of bench scale tests using an upflow, vertical reactor system. The properties of the feed oil and product oils and the operating condi-tions used in each test are shown in the Table. In Test 2, 0.5 weight percent potassium hydroxide was dis-solved in the water prior to the test. In Tests 4 and 5 hydrogen peroxide was &dded to the water to provide the free oxygen component by decomposition. The API gravities for the products as reported in Tests 1 and 2 in the table were calculated from a TGA analysis. Distillation figures were also calculated from TGA analyses. Feed oil was mixed with water prior to introduction of the liquids into ; the upflow reactor in Tests 1 and 2. In Tests 3-6, oil was sprayed into the lower end of the reactor using a :
l 159788 diesel injector, while water was introduced along with hydrogen peroxide into the bottom of the reactor.
S Referring to the Table, it is apparent that upgrading an atmospheric distillation bottoms feed according to the present invention results in a substantially lighter prod-uct (higher API gravity, lower boiling range), with fewer heat-sensitive, nondistillable components such as asphal-tenes (lower Ramsbottom carbon), with reduced concentra-tion of metalliferous contaminants (Ni, V), a reduced concentration of sulfurous contaminants (weight per-cent S), a reduced concentration of nitrogenous contami-nants (weight percent N), and a substantially decreased Saybolt viscosity. The above-noted improvements were advantageously obtained at an operating temperature much lower than used in a conventional thermal cracking system.
An atmospheric distillation residual oil frac-; tion was co~ed according to the present invention in abench scale test. The temperature employed was 371C.
The pressure employed was 67 atmospheres. Oil was fed at a rate of 80 cc per hour. The feed was an Arabian Heavy atmospheric residual fraction containing 3.4 weight per-cent sulfur, 0.31 weight percent nitrogen, with a carbon content of 84.5 weight percent and a hydrogen content of 11.0 weight percent. The test was performed in a cocur-rent, upflow system in a simple reactor vessel. The coke formed in the reactor was analyzed and found to contain 4.9 weight percent sulfur, 0.46 to 0.49 weight percent nitrogen, 73.6 weight percent carbon and 4.~ weight per-cent hydrogen. It had a heat of combustion of 12,613 BTU/pound (293,000 kJ/kg).
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WITH AN AQUEOUS ~IQUID
BACKGROUND OF THE INVENTION
The present invention concerns a process for upgrading hydrocarbonaceous oils. More specifically, the invention concerns a process for upgrading heavy oils by contacting the oils with free oxygen and liquid phase water at an elevated temperature.
Heavy petroleum fractions such as residuals and heavy crude oils can be used as low grade commercial fuels or may be converted by thermal and catalytic conversion processes into more valuable, lighter hydrocarbons, parti-cularly gasoline. Heavy crudes and heavy oil fractionsare oten contaminated with substantial ccncentrations of detrimental materials. Common contaminants are organic nitrogen and sulfur compounds, metals, particularly nickel and vanadium, nondistillable, heat-sensitive coke precur-sors, such as asphaltenes, and the like. When heavy oilsare burned directly as fuel, combustion of the nitrogen and sulfur compounds results in formation of objectionable pollutants, nitrogen oxides and sulfur oxides. When heavy 25 oils are upgraded by conven~ional catalytic conversions, the presence o~ the nitrogen and sulfur compounds, and particularly the presence o the metals, results in rapid deactivation of catalysts, and causes the upgrading of residual oils to be undesirably expensive. Conventional methods for upgrading heavy oil fractions to provide more valuable hydrocarbons often consume substantial amounts of hydrogen. The cost of hydrogsn consumed is an economic drawback when hydroprocessing is employed for the upgrad-ing. When heavy crudes and oil fractions are subjected to conventional pyrolysis-type coking (e.g., delayed or fluid coking) at temperatures of 350C to 500C, large concen-trations of heat-sensitive, coke-forming materials, such as asphaltenes, can result in relatively low yields of the more valuable primary pr~oduct, distillates, and relatively high yields of the less valuable by-product, coke. The . .
presence of undesirably large concentrations of contaminants in coke derived by conventional coking of heavy oils detracts from the value of coke as a by-product. This is particularly true for sulfur. The quality of coke obtained from heavy oil high in contaminants may thus make it unsuitable for some uses, e.g., electrodes, because of poor specifications of such properties as coefficient of thermal expansion, electrical resistivity and sulfur content.
A general discussion of the wet air oxidation technology, is to be found in Mechanical Engineering, December 1979, page 30. A discussion of the regeneration of active carbon after use in waste water treating, by means of wet air oxidation, i9 to be found in the AICHE Symposium Series, Vol. 76, No. 192, (Recent Advances in Separation Technology - II), page 51 (AICHF, 1980).
A process for removing pyritic sulfur from coal by treatment with water and air at elevated temperature and pressure to convert the pyritic sulfur to water-soluble ferrous and ferric sulfate is disclosed in United States Patent No. 3,824,084. Use of silicates and an oxidizing agent (such ;~ as air, oxygen, hydrogen, peroxide, alkali metal sulfides, alkaline or metal sulfides) or a reducing agent (such as H2, C0, K2, S204, NaS204, and alkali metal polythionates) in an aqueous medium to desulfurize coal is disclosed in United States Patents No. 4,174,953 and No. 4,197,090.
Use of wet air oxidation to provide heat energy in the form of steam, as by wet oxidation of coal, is disclosed in United States Patents No. 4,211,174, No. 4,100,730, and 4,013,560.
Use of copper or silver ions to catalyze wet air oxidation of organic material in waste water is disclosed in United States Patent ;~ No. 3,912,626.
Treatment of papermill waste sludges to convert organic components to innocuous oxidation products and to provide for recovery of inorganic i filter materials for reuse is disclosed in United States Patent No. 3,876,497.
01 _3_ Essentially complete oxidation of solid or liquid combustible materials which are difficult to sus-pend in water, such as diesel fuel and nitroglycerine by direct injection into a wet air oxidation reactor is dis-closed in U.S. Patent No. 4,174,280.
None of the disclosures concerning wet air oxi-dation is concerned with upgrading of hydrocarbonaceous materials. Hydrocarbonaceous oils which are utilized in the disclosed wet air oxidation processes are simply essentially completely consumed to form highly oxidized materials, primarily carbon dioxide, water and the like.
SUMMARY OF THE INVENTION
..
The present invention concerns a process for upgrading a hydrocarbonaceous oil which comprises con-tacting the oil with free oxygen in the presence of an aqueous liquid at a temperature above about 175C and a pres~ure sufficient to maintain the aqueous liquid at least partially in a liquid phase.
I have found that surprising improvements in several properties of a heavy hydrocarbonaceous oil can be advantageously obtained by contacting the oil with free oxygen and liquid phase water at an elevated temperature.
The amounts of contaminants, such as metals, nitrogen and sulfur, in the oil can be substantially decreased. The viscosity of the oil can be substantially decreased. When the temperature is maintained generally below about 300C, the amount of nondistillable, coke-forming constituents of the oils, such as asphaltenes, can be substantially decreased. ~he process of present invention also permits the viscosity of heavy oils to be substantially decreased.
The present process can advantageously be performed at a temperature much lower than used in conventional heavy oil upgrading systems.
In one embodiment, the present invention con-cerns a process for producing coke from a hydroc~rbona-~ ceous oil, which comprises forming coke by contacting the ;l 40 oil with free oxygen in the presence of an aqueous liquid ~ at a temperature of at least 300C and a pressure , ' ,~:
`` 1 159788 01 _4_ sufficient to maintain the aqueous liquid at least partially in the liquid phase.
I have found that high-quality coke can be formed from a heavy hydrocarbonaceous oil by contact with liquid phase water and free oxygen at elevated temperature and pressure. The amounts of such contaminants as metals and sulfur in the resulting coke are advantageously low, and a desirable, low yield of coke, relative to distill-able hydrocarbons, is obtained. Advantageously, the coke formation can be carried out in a continuous manner, eli-minating the need for removal of coke from drums, as is done in delayed coking. Heat requirements for the present process can be provided completely by oxidation of heavy oil in the system.
DESCRIPTION OF THE DRAWING
The attached drawing is a schematic representa-0 tion of preferred embodiments of the present invention.
In an embodiment for mild hydrocarbon upgrading, there is shown a wet air oxidation reactor l. Aqueous liquid is introduced into the system through a conduit 3. A feed stream of hydrocarbonaceous oil to be upgraded 25 ~ is introduced to the system through a conduit 5 and is charged to the reactor l through a diesel injector (not shown~ at a rate of one part (by volume) of oil per four parts of aqueous liquid. Free oxygen-containing gas is introduced into the system through a conduit 7 and is mixed with the aqueous liquid in the conduit 3. The ~ water-oxygen mixture is passed into the reactor l. In the ;; ~ reactor the oil-water-oxygen mixture is maintained at suitable reaction conditions including an appropriate elevated temperature such as 204C and a pressure suffi-cient to maintain the aqueous phase as a liquid such as 50 atmospheres. The mixture flows upwardly through the reac-tor and is removed from the top of the reactor through a conduit 9. The mixture is then cooled in a heat exchanger ll, passed through a pressure reducing valve 13, and charged to gas separator vessel 15, in which the gases in :
l 159788 the mixture are separated from the aqueous and hydrocar-bonaceous liquids. The gases are removed from the top of the separator vessel 15 and passed out of the system through a conduit 17. The mixture of liquid aqueous and hydrocarbonaceous phases is withdrawn from the vessel 15 and passed through a conduit 19 into a phase separator, such as a settling vessel 21. The lighter oil phase rises to the top of the vessel 21 and is withdrawn from the vessel and recovered by means of a conduit 23. Aqueous liquid settles to the bottom of the vessel 21 and is with-drawn through a conduit 25.
In a coking embodiment, aqueous liquid, which may include fresh water, recycle water, or both, is intro-duced into the system through a conduit 3. A feed stream of heavy hydrocarbonaceous oil to be converted is intro-duced to the system through a conduit 5 and is mixed with the aqueous phase in the conduit 3. Free oxygen-contain-ing gas i5 introduced into the system through a conduit 7 and is passed into the lower portion of the reactor 1.
The oil-water mixture in the conduit 3 is passed into the reactor 1 above the oxygen inlet. In the reactor, the ; mixture is maintained at suitable reaction conditions including an elevated temperature above 300C, such as about 375C, and a pressure sufficient to maintain the aqueous phase as a liquid such as 70 atmospheres. The liquids and gases flow upwardly through the reactor and are removed from the top of the reactor through a con-duit 9. The mixture is then cooled in a heat exchanger 11, and is passed through a pressure reducing . , valve 13. The mixture is then charged to a gas separator vessel 15, in which gases in the mixture are separated from the liquids. Gases are removed from the top of the gas separator vessel and withdrawn from the system through a conduit 17. The mixture of aqueous and hydrocarbona-ceous liquid phases is then passed from the vessel 15 through a conduit 19 into phase separation means, such as a settling vessel 21. The generally lighter oil phase rises to the top of the vessel 21 and is withdrawn by :
`~:
~' :
1 15~788 Ol -6-means of a conduit 23. Aqueous liquid settles to the bottom of the vessel 21 and is withdrawn through a con-; 05 duit 25. The hydrocarbonaceous liquid is passed from the conduit 23 into a fractionator vessel 27. Lower-boiling, more valuable product hydrocarbons are vaporized, with-drawn overhead through a conduit 29, and recovered.
Higher-boiling, less valuable components of the oil are withdrawn from the bottom of the fractionator and recycled to the feed conduit 3 by way of a conduit 31. A reboiling slip stream from the liquid effluent in the conduit 31 is removed into a conduit 33, heated in a furnace 35, and returned to the fractionator through a conduit 37.
Referring again to the reactor vessel 1, reactions occur in the vessel which form solid coke particles. The coke particles sink to the bottom of the vessel, and are withdrawn as a slurry in aqueous liquid through a conduit 39. Coke is separated from most of the aqueous liquid in a centrifuge 41 and is withdrawn from the system as a concentrated aqueous slurry by way of a conduit 43.
Aqueous liquid is withdrawn from the centrifuge through a conduit 45. The aqueous streams in conduits 25 and 45 may, if desired, be recycled directly to the reactor 1, or may be mixed with fresh water in the conduit 5 or hydro-carbon feed in the conduit 3. The water recycle streams may be treated, as for removal of solids, mineral salts, and the like (by means not shown) prior to recycle, if desired. Various conventional elements necessary for carrying out the embodiment depicted in the drawing, such ~; as control means, pumping means, compressing means, and the like, are not shown or discussed. The disposition and use of such conventional elements will be apparent to those skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION
A wide variety of hydrocarbonaceous oils may be upgraded by the process of this invention. In general, any oil which contains an objectionable amount of oné or more undesirable contaminants can be upgraded. For exam-ple, an oil containing an undesirable concentration of one :
1 1~9788 Ol _7_ or more metalliferous contaminants can be upgraded, i.e.
demetallized, by reduction of the metals concentration.
05 Oils containing an undesirably high concentration of one or more sulfurous contaminants can be upgraded, i.e., desulfurized, by reduction of the sulfur concentration.
Oils containing an undesirably high concentration of one or more nitrogenous contaminants can be upgraded, i.e., denitrified, by reduction of their nitrogen concentration.
Oils having an undesirably high concentration of asphal-tenes can be upgraded, i.e. deasphalted by reduction of their asphaltenes concentration. Oils having a viscosity which is higher than desired can be upgraded to decrease their viscosity by treatment according to the present invention. Oils containing an undesirably high concentra-tion of relatively higher molecular weight hydrocarbona-ceous molecules can be upgraded according to the invention to provide a product having a decreased concentration of such higher molecular weight materials and an increased concentration of lower molecular weight hydrocarbons, as by cracking and decomposition of high mol~cular weight heteronuclear compounds, polycyclic aromatics, etc.
For example, high molecular weight, nondistillable com-pounds, such as asphaltenes, can be converted to distill-able hydrocarbon compounds and lower molecular weight com-pounds by upgrading according to the present invention.
In the coking embodiment, the oil is treated to provide coke and a distillate of lower contaminant level, lower molecular weight, and/or lower viscosity, etc, Although any oil contaminated with one or more of the contaminants discussed above or having an overly ;~ high boiling range or overly high viscosity, can be suita-bly upgraded according to the present invention, the pre-ferred feed oils are petroleum residuals, heavy petroleum ' crudes, shale oils, coal oils, tar sand oils (bitumens), and analogous natural or synthetic oils and oil fractions.
For example, preferred feeds include such petroleum frac-tions as atmospheric distillation bottoms streams, vacuum distillation bottoms streams, catalytic cracking product l 15978~ `
fractionator bottoms and slurry oils, and in general petroleum, coal oil, tar sand oil, shale oil, or the like or heavy fractions thereof, a substantial portion of which has a normal boiling point above 565C. Preferred heavy crude petroleum or tar sand oils for upgrading are those with one or more of the following properties: an API
gravity of less than 20; a Ramsbottom carbon residue factor of greater than 0.8; an asphaltenes (n-heptane insoluble fraction) content of greater than 3 weight per-cent; or a fraction of greater than l0 weight percent of the oil boiling above 565C. Preferred feeds include bitumen derived from tar sands, i.e., bituminous sands, and heavy crudes and tars such as those found in the Athabasca region of Canada and the Orinoco region of Venezuela.
Preferred feed oils include oils having a sub-stantial concentration of at least one metal selected from nickel and vanadium. These metals are usually present in crude oils and residual fractions in the form of organo-metallic compounds, such as metalloporphyrins.
Preferred feed oils include oils having a sub-stantial concentration of finely divided solid contami-nants, which may be solid organic material, solid inor-ganic material, or both. Examples of solids found in some preferred feed oils are clay, sand, silt and such salts as alkaline earth metal carbonates and silicates.
Preferred feed oils may be oils which are mixed with small or large concentrations of aqueous liquids. In fact, the present process provides a highly advantageous way to dispose of waste slop oils, oil-water emulsions, desalter separator cuff layers, contaminated oil bottoms from storage tanks and the like.
The aqueous liquid used in the treatment of the -~ present invention may simply be water or may be an aqueous solution or suspension of one or more inorga~ic or organic compounds or ions. In some cases, addition of solubie or suspended materials can be beneficial to carrying out the process in that the added material can catalyze reactions 01 _9_ which take place in upgrading an oil. Preferred additive materials include alkali metals, alkaline earth metals, 05 their ions and salts. Added extraneous materials, such as alkali and alkaline earth metals, can be mixed with the feed oil or with the oxygen-containing gas prior to con-tacting the gas, water and oil at high temperatures, or can preferably be premixed with the aqueous phase.
The temperature at which the present process is carried out should usually be maintained above about 175C. For upgrading without substantial coking, the reaction temperature is maintained between about 175C and 300C, particularly between about 195C and 260C. For coking, the process is carried out at a temperature suffi-cient to form coke from the feed oil. The temperatureshould usually be maintained above 300C, preferably between about 315C and ~40C, particularly between about 325C and 425C. In either case, the elevated operating temperature can be achieved solely by oxidation reactions which occur after the oil, water and molecular oxygen are contacted. One or more of the components can be preheated prior to contact with the other components. The mixture can also be heated by an external heat source after con-tact. Often, heat exchange between the hot effluent from the reaction zone and one or more of the aqueous feed, oilfeed or oxygen feed is advantageous in conserving heat energy.
It will be apparent that the reaction tempera-tures may not be uniform over the course of the reaction time in carrying out many embodiments of the present pro-cess, since oxidation reactions will tend to increase the temperature of the reaction mixture over the extent of the contact time, if free oxygen is not limited. Thus, in a batch-type non-coking reaction, the reaction temperature may start at a very low temperature, e.g. below 175C, and rise to a high level, e.g. above 300C at the end of the contact time. For coking, the temperature may start at a very low temperature, e.g. below 300C, and rise to a high level, which may even be above 540C by the end of the l 159788 contact time. A similar temperature profile will often be observed when a plug flow-type contacting scheme is employed. In general, however, the reactants should be maintained within the indicated temperature ranges for at least a major portion of the total contact time. Prac-tical contact times are usually those sufficient to allow consumption of at least a major portion of the free oxygen employed.
The pressure employed in the present process is at least sufficient to maintain at least a portion of the water, i.e., the aqueous phase, in the liquid state.
Preferably, a pressure is employed which is at least suf-ficient to maintain the major portion of water present in the reaction mi~ture as a liquid. Higher pressures have the advantage of permitting relatively larger amounts of free oxygen to be dissolved or diffused in the liquid aqueous phase, but increased capital and operating costs involved in the carrying out of higher pressure operations usually set a practical upper limit on the pressure that can economically be used.
According to the invention, free oxygen, i.e., molecular or atomic oxygen, or a precursor thereof, is contacted with oil and an aqueous liquid. To supply the free oxygen component for the process, pure molecular oxygen gas (2 or O3) can be used. Gases, such as air, which contain molecular oxygen mixed with one or more diluent gases, such as nitrogen, steam, carbon dioxide, etc., are also suitable for use. Solid, liquid or gaseous compounds of combined oxygen, which decompose or react to form atomic or molecular oxygen, such as hydrogen per-~d ~ oxide, may be used to supply the free oxygen component.
. ~
The free oxygen component, or a precursor thereof, can be mixed with the aqueous liquid prior to, simultaneously with, or after contact is established between the aqueous ., liquid and the feed oil. The amount of free oxygen ~ employed relative to the amount of oil should be suffi-! 40 cient to react with not more than a minor portion of the ~ `
oil. Preferably, the free oxygen should not constitute more than about 30 weight percent of the oil.
Contact of the feed oil with aqeuous liquid and with free oxygen can be carried out in a suitable conven-tional reactor or other suitable conventional vessel or container means, which should be sufficiently resistant to the temperatures, pressures, corrosive compounds and other reaction conditions which are encountered in carrying out the present invention. The oil, water and free oxygen components can be contacted in a batch-type system or, preferably, in a continuous type system. The oil, water and oxygen components can be contacted in cocurrent flow, in countercurren~ flow, in a stirred tank-type reaction system, or in another analogous contact system. Prefer-ably, contact is carried out in cocurrent flow through a reaction zone, particularly preferably in upflow through a vertically extending vessel. Preferably, at least a por-tion of the free oxygen employed is dissolved in the aqueous liquid prior to contacting the aqueous liquid with the oil to be treated.
Preferably, oil and aqueous liquid are contacted at an aqueous liquid-oil volume ratio in the range from about 0.5:1 to about 10:1. Particularly preferably, an aqueous liquid:oil volume ratio of about 1:1 to about 4:1 is used. Preferably, the feed oil i5 introduced into contact with the aqueous liquid in finely divided form, e.g. as droplets, as by using a mixer, diesel injector or the like.
The product oil can be separated from the water and gas by phase separation (settling, decantation, etc.) or fractional ~istillation or the like conventional separ-, ation technique. The product oil can be used advanta-geously in several ways. One advantageous use of the product of a non-coking process is as a feed for a thermal distillation or coking process. Suitable conventional coking techniques include delayed coking and fluidized coking. Another advantageous use for product oil is as a feed for a catalyti~ cracking operation, especially for an ' l 159788 FCC operation in which the oil is contacted with an acidic, zeolite or non-7eolite catalyst in the absence of 05 added molecular hydrogen. A further advantageous use for product oil is as a feed for a hydrogen treating process such as hydrodemetalation, hydrodenitrification, hydrode-sulfurization, hydrocracking or simple hydrogenation, in which the oil is contacted with a Group VIB and/or Group VIII metal on a porous carrier such as silica, alumina, clays and the like. Suitable hydrogen treating catalysts may include an acidic component such as silica-alumina, a zeolite, etc. The product oil formed in the present pro-cess can often be fractionated to provide high yields of such products as diesel fractions, jet fuels, gasolines, naphthas, etc.
As a byproduct of upgrading the feed oil, it may be advantageous to generate steam from a portion of the aqueous liquid, and the steam can be used to supply energy for electrical or mechanical power generation. It should be noted, however, that at least a portion of the aqueous phase should remain as a liquid at the end of the contact-ing period.
An atmospheric distillation residual oil frac-tion from an Arabian Heavy crude was upgraded according to the present invention in a series of bench scale tests using an upflow, vertical reactor system. The properties of the feed oil and product oils and the operating condi-tions used in each test are shown in the Table. In Test 2, 0.5 weight percent potassium hydroxide was dis-solved in the water prior to the test. In Tests 4 and 5 hydrogen peroxide was &dded to the water to provide the free oxygen component by decomposition. The API gravities for the products as reported in Tests 1 and 2 in the table were calculated from a TGA analysis. Distillation figures were also calculated from TGA analyses. Feed oil was mixed with water prior to introduction of the liquids into ; the upflow reactor in Tests 1 and 2. In Tests 3-6, oil was sprayed into the lower end of the reactor using a :
l 159788 diesel injector, while water was introduced along with hydrogen peroxide into the bottom of the reactor.
S Referring to the Table, it is apparent that upgrading an atmospheric distillation bottoms feed according to the present invention results in a substantially lighter prod-uct (higher API gravity, lower boiling range), with fewer heat-sensitive, nondistillable components such as asphal-tenes (lower Ramsbottom carbon), with reduced concentra-tion of metalliferous contaminants (Ni, V), a reduced concentration of sulfurous contaminants (weight per-cent S), a reduced concentration of nitrogenous contami-nants (weight percent N), and a substantially decreased Saybolt viscosity. The above-noted improvements were advantageously obtained at an operating temperature much lower than used in a conventional thermal cracking system.
An atmospheric distillation residual oil frac-; tion was co~ed according to the present invention in abench scale test. The temperature employed was 371C.
The pressure employed was 67 atmospheres. Oil was fed at a rate of 80 cc per hour. The feed was an Arabian Heavy atmospheric residual fraction containing 3.4 weight per-cent sulfur, 0.31 weight percent nitrogen, with a carbon content of 84.5 weight percent and a hydrogen content of 11.0 weight percent. The test was performed in a cocur-rent, upflow system in a simple reactor vessel. The coke formed in the reactor was analyzed and found to contain 4.9 weight percent sulfur, 0.46 to 0.49 weight percent nitrogen, 73.6 weight percent carbon and 4.~ weight per-cent hydrogen. It had a heat of combustion of 12,613 BTU/pound (293,000 kJ/kg).
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Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for upgrading a hydrocarbonaceous oil which comprises:
contacting said oil with free oxygen in the presence of an aqueous liquid at a temperature above about 175°C
and a pressure sufficient to maintain said aqueous liquid at least partially in the liquid phase.
contacting said oil with free oxygen in the presence of an aqueous liquid at a temperature above about 175°C
and a pressure sufficient to maintain said aqueous liquid at least partially in the liquid phase.
2. A process as defined in Claim 1 wherein said contacting is carried out at a temperature between about 175°C and about 300°C.
3. A process as defined in Claim 1 wherein said contacting is carried out at a temperature between 195°C
and 260°C.
and 260°C.
4. A process as defined in Claim 1 wherein said hydrocarbonaceous oil includes at least one metalliferous contaminant and said contacting decreases the concentra-tion of said metalliferous contaminant in said oil,
5. A process as defined in Claim 1 wherein said hydrocarbonaceous oil includes at least one nitrogenous contaminant and said contacting decreases the concentra-tion of said nitrogenous contaminant in said oil.
6. A process as defined in Claim 1 wherein said hydrocarbonaceous oil includes at least one sulfurous contaminant and said contacting decreases the concentra-tion of said sulfurous contaminant in said oil.
7. A process as defined in Claim 1 wherein the vis-cosity of said hydrocarbonaceous oil is decreased by said contacting.
8. A process as defined in Claim 1 wherein said hydrocarbonaceous oil comprises hydrocarbons and the average molecular weight of hydrocarbons in said oil is decreased by said contacting.
9. A process as defined in Claim 1 wherein at least one ion or salt of at least one metal selected from alkali metals and alkaline earth metals is present in said aqueous liquid during said contacting.
10. A process as defined in Claim 1 wherein said hydrocarbonaceous oil, said aqueous liquid and said free oxygen are mixed together at a temperature below about 175°C and the temperature of the resulting mixture is increased to greater than 175°C at least in part by heat energy supplied by reaction of at least a portion of said free oxygen with a portion of said hydrocarbonaceous oil.
11. A process as defined in Claim 1 wherein at least a portion of said free oxygen is dissolved in said aqueous liquid prior to contact with said hydrocarbonaceous oil.
12. A process as defined in Claim 1 wherein said aqueous liquid is present during said contacting at an aqueous liquid hydrocarbonaceous oil volume ratio of about 0.5:1 to about 10:1.
13. A process as defined in Claim 1 wherein said free oxygen is formed by decomposition of hydrogen peroxide.
14. A process as defined in Claim 1 wherein said hydrocarbonaceous oil is derived from oil shale.
15. A process as defined in Claim 1 wherein said hydrocarbonaceous oil is derived from coal.
16. A process as defined in Claim 1, comprising:
forming coke by contacting said oil with free oxygen in the presence of an aqueous liquid at a temperature of at least 300°C and a pressure sufficient to maintain said aqueous liquid at least partially in the liquid phase.
forming coke by contacting said oil with free oxygen in the presence of an aqueous liquid at a temperature of at least 300°C and a pressure sufficient to maintain said aqueous liquid at least partially in the liquid phase.
17. A process as defined in Claim 16 wherein said contacting is carried out at a temperature between 315°C
and 540°C.
and 540°C.
18. A process as defined in Claim 16 wherein steam is recovered as a by-product.
19. A process as defined in Claim 16 wherein at least two of said hydrocarbonaceous oil, said aqueous liquid and said free oxygen are mixed together at a temperature below about 300°C and the temperature of the resulting mixture is increased to greater than 300°C at least in part by heat energy supplied by reaction of at least a portion of said free oxygen with a portion of said hydrocarbonaceous oil.
20. A process as defined in Claim 16 wherein at least a portion of said free oxygen is contacted with said hydrocarbonaceous oil and said aqueous liquid after said oil and said aqueous liquid have been mixed together.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22175880A | 1980-12-31 | 1980-12-31 | |
| US221,758 | 1980-12-31 | ||
| US22223181A | 1981-01-02 | 1981-01-02 | |
| US222,231 | 1981-01-02 | ||
| US06/324,216 US4370223A (en) | 1980-12-31 | 1981-11-24 | Coking hydrocarbonaceous oils with an aqueous liquid |
| US324,217 | 1981-11-25 | ||
| US324,216 | 1981-11-25 | ||
| US06/324,217 US4428828A (en) | 1981-01-02 | 1981-11-25 | Upgrading hydrocarbonaceous oils with an aqueous liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1159788A true CA1159788A (en) | 1984-01-03 |
Family
ID=27499245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000393450A Expired CA1159788A (en) | 1980-12-31 | 1981-12-30 | Upgrading hydrocarbonaceous oils with an aqueous liquid |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1159788A (en) |
| DE (1) | DE3151614A1 (en) |
| GB (1) | GB2091758B (en) |
| NL (1) | NL8105848A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9896629B2 (en) | 2014-07-25 | 2018-02-20 | Saudi Arabian Oil Company | Integrated process to produce asphalt, petroleum green coke, and liquid and gas coking unit products |
| US10125319B2 (en) | 2011-07-31 | 2018-11-13 | Saudi Arabian Oil Company | Integrated process to produce asphalt and desulfurized oil |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4321808A1 (en) * | 1993-06-30 | 1995-01-12 | Kief Horst Dr Med | Enrichment of fuel |
| US6013176A (en) * | 1998-12-18 | 2000-01-11 | Exxon Research And Engineering Co. | Method for decreasing the metals content of petroleum streams |
| US6007705A (en) * | 1998-12-18 | 1999-12-28 | Exxon Research And Engineering Co | Method for demetallating petroleum streams (LAW772) |
| RU2158748C1 (en) * | 1999-10-20 | 2000-11-10 | Гандельман Леонид Яковлевич | Method of modification of motor fuel and device for its embodiment |
| JP3724438B2 (en) * | 2002-03-08 | 2005-12-07 | 株式会社日立製作所 | Method and apparatus for treating heavy oil with supercritical water, and power generation system equipped with heavy oil treatment apparatus |
| JP4098181B2 (en) | 2003-08-05 | 2008-06-11 | 株式会社日立製作所 | Heavy oil treatment method and heavy oil treatment system |
| US7435330B2 (en) | 2003-10-07 | 2008-10-14 | Hitachi, Ltd. | Heavy oil reforming method, an apparatus therefor, and gas turbine power generation system |
| US8066851B2 (en) | 2007-05-08 | 2011-11-29 | M-I L.L.C. | In-line treatment of hydrocarbon fluids with ozone |
| US10800981B2 (en) * | 2019-02-13 | 2020-10-13 | Saudi Arabian Oil Company | Process for producing diesel fuel from olefinic refinery feedstreams |
-
1981
- 1981-12-23 GB GB8138705A patent/GB2091758B/en not_active Expired
- 1981-12-24 NL NL8105848A patent/NL8105848A/en not_active Application Discontinuation
- 1981-12-28 DE DE19813151614 patent/DE3151614A1/en not_active Withdrawn
- 1981-12-30 CA CA000393450A patent/CA1159788A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10125319B2 (en) | 2011-07-31 | 2018-11-13 | Saudi Arabian Oil Company | Integrated process to produce asphalt and desulfurized oil |
| US9896629B2 (en) | 2014-07-25 | 2018-02-20 | Saudi Arabian Oil Company | Integrated process to produce asphalt, petroleum green coke, and liquid and gas coking unit products |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2091758B (en) | 1984-02-22 |
| GB2091758A (en) | 1982-08-04 |
| NL8105848A (en) | 1982-07-16 |
| DE3151614A1 (en) | 1982-08-26 |
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|---|---|---|---|
| MKEX | Expiry |