Patent Description:
Supercritical water processes can upgrade heavy oil through radical-mediated reaction routes, where chemical bonds are broken by thermal energy and the cage effect exerted by supercritical water prevents coke formation. However, harsh operation conditions, such as high temperature and long residence times, are required to reach deep conversion of heavy oil. In conventional hydrocracking, deep conversion can refer to conversion of the vacuum residue between <NUM> % and <NUM> % but at the sacrifice of large amounts of hydrogen and a short life time of the catalyst. These harsh conditions generate large amounts of gas product as well as coke material. The increased production of gas product results in a loss of liquid yield. In supercritical water processes, deep conversion can be achieved by increasing the temperature and residence time, which can also increase the amount of coke production which results in a reduced process time due to plugging.

<NPL> discloses the upgrading of heavy oils using supercritical water. In one embodiment the heavy oil is first oxidised partially before the supercritical water treatment.

Disclosed are methods for upgrading petroleum. Specifically, disclosed are methods and systems for upgrading petroleum using pretreatment processes.

In a first aspect, a process for upgrading a heavy oil as defined in claim <NUM> is provided. The process includes the steps of introducing a heavy oil feed to a partial oxidation unit, introducing a water feed to a partial oxidation unit, introducing an oxidant feed to a partial oxidation unit, where the oxidant feed includes an oxidant, processing the heavy oil feed, the water feed, and the oxidant feed in the partial oxidation unit to produce a liquid oxidation product, where the liquid oxidation product includes oxygenates, introducing the liquid oxidation product to a supercritical water unit, introducing a water stream to the supercritical water unit, and processing the liquid oxidation product and the water stream in the supercritical water unit to produce an upgraded product stream, the upgraded product stream includes upgraded hydrocarbons relative to the heavy oil feed.

In certain aspects, the process further includes the steps of increasing the pressure of the heavy oil feed in a feed pump to produce pressurized oil feed, introducing the pressurized oil feed to a feed heater, increasing the temperature of the pressurized oil feed in the feed heater to produce a hot oil feed, mixing the water feed and the oxidant feed in a premixer to produce a mixed oxidant feed, introducing the mixed oxidant feed to an oxidant pump, increasing the pressure of the mixed oxidant feed in the oxidant pump to produce a pressurized oxidant feed, introducing the pressurized oxidant feed to a oxidant heater, increasing the temperature of pressurized oxidant feed to produce a hot oxidant feed, mixing the hot oil feed and the hot oxidant feed in an oxidation mixer to produce to produce a mixed oxidation feed, introducing mixed oxidation feed to an oxidation reactor, allowing the mixed oxidation feed to undergo oxidation reactions in the oxidation reactor to produce a reactor effluent, introducing the reactor effluent to an effluent cooler, reducing the temperature in the effluent cooler to produce a cooled effluent, introducing the cooled effluent to an effluent depressurizing device, and decreasing the pressure of the cooled effluent in the effluent depressurizing device to produce a depressurized effluent, introducing the depressurized effluent to a separator, and separating the depressurized effluent in the separator to produce a gas oxidation product and the liquid oxidation product, where the gas oxidation product includes unreacted oxidants.

In certain aspects, the process further includes the steps of increasing the pressure of the liquid oxidation product in a pump to produce a pressurized stream, introducing the pressurized stream to a heater, increasing the temperature of the pressurized stream in the heater to produce a hot stream, increasing the pressure of the water stream in a water pump to produce a pressurized water stream, introducing the pressurized water stream to a water heater, increasing the temperature of the pressurized water stream in the water heater to produce a supercritical water stream, mixing the hot stream and the supercritical water stream in a mixer to produce a mixed stream, introducing the mixed stream to a supercritical water reactor, allowing the hydrocarbons to undergo a set of conversion reactions in the supercritical water reactor to produce a reactor product, introducing the reactor product to a product cooler, reducing the temperature of the reactor product to produce a cooled product, introducing the cooled product to a depressurizing device, reducing the pressure of the cooled product in the depressurizing device to produce a depressurized stream, introducing the depressurized stream to a vapor-liquid separator to produce a gas product stream and a liquid stream, introducing the liquid stream to an oil-water separator, and separating the liquid stream in the oil-water separator to produce the upgraded product stream and a used water stream.

In certain aspects, the heavy oil feed is selected from the group consisting of petroleum, coal liquid, or biomaterials, and combinations of the same. In certain aspects, the oxidant is selected from the group consisting of air, oxygen gas, hydrogen peroxide, organic peroxides, and combinations of the same. In certain aspects, a molar ratio of oxygen atoms in the oxidant feed to carbon atoms in the heavy oil feed is between <NUM> and <NUM>. In certain aspects, the oxygenates are selected from alcohols, ketones, esters, ethers, carboxylic acids, and combinations of the same. In certain aspects, a temperature of the oxidation reactor is between <NUM> deg C and <NUM> deg C, and where a pressure is between <NUM> MPa and <NUM> MPa, such that water in the oxidation reactor is present in the liquid phase. In certain aspects, a liquid hourly space velocity is in the range between <NUM> hr-<NUM> and <NUM> hr-<NUM>. In certain aspects, the oxidation reactor includes an oxidation catalyst, where the oxidation catalyst includes an active component. In certain aspects, a ratio of a volumetric flow rate of the supercritical water stream to the hot stream is in the range between <NUM>: <NUM> and <NUM>:<NUM>. In certain aspects, a temperature of the supercritical water reactor is in the range between <NUM> deg C and <NUM> deg C.

In second aspect, a system for upgrading a heavy oil feed as defined in claim <NUM> is provided. The system includes a partial oxidation unit, the partial oxidation unit configured to process the heavy oil feed, a water feed, and an oxidant feed to produce a liquid oxidation product, where the oxidant feed includes an oxidant, where the liquid oxidation product includes oxygenates, a supercritical water unit fluidly connected to the partial oxidation unit, the supercritical water unit configured to process the liquid oxidation product and a water stream to produce an upgraded product stream, the upgraded product stream includes upgraded hydrocarbons relative to the heavy oil feed.

In certain aspects, the system further includes a feed pump, the feed pump configured to increase a pressure of the heavy oil feed to produce pressurized oil feed, a feed heater fluidly connected to the feed pump, the feed heater configured to increase a temperature of the pressurized oil feed to produce a hot oil feed, a premixer, the premixer configured to mix the water feed and the oxidant feed to produce a mixed oxidant feed, an oxidant pump fluidly connected to the premixer, the oxidant pump configured to increase the pressure of the mixed oxidant feed to produce a pressurized oxidant feed, an oxidant heater fluidly connected to the oxidant pump, the oxidant heater configured to increase the temperature of the pressurized oxidant feed to produce a hot oxidant feed, an oxidation mixer fluidly connected to the feed heater and the oxidant heater, the oxidation mixer configured to mix the hot oil feed and the hot oxidant feed to produce to produce a mixed oxidation feed, an oxidation reactor fluidly connected to the oxidation mixer, the oxidation reactor configured to allow the mixed oxidation feed to undergo oxidation reactions to produce a reactor effluent, an effluent cooler fluidly connected to the oxidation reactor, the effluent cooler configured to reduce the temperature of the reactor effluent to produce a cooled effluent, an effluent depressurizing device fluidly connected to the effluent cooler, the effluent depressurizing device configured to reduce the pressure of the cooled effluent to produce a depressurized effluent, and a separator fluidly connected to the effluent depressurizing device, the separator configured to separate the depressurized effluent to produce a gas oxidation product and the liquid oxidation product, where the gas oxidation product includes unreacted oxidants.

In certain aspect, the system further includes a pump, the pump configured to increase the pressure of the liquid oxidation product to produce a pressurized stream, a heater fluidly connected to the pump, the heater configured to increase the temperature of the pressurized stream in the heater to produce a hot stream, a water pump, the water pump configured to increase the pressure of the water stream to produce a pressurized water stream, a water heater fluidly connected to the water pump, the water heater configured to increase the temperature of the pressurized water stream to produce a supercritical water stream, a mixer fluidly connected to the heater and the water heater, the mixer configured to mix the hot stream and the supercritical water stream to produce a mixed stream, where the mixed stream includes hydrocarbons, a supercritical water reactor fluidly connected to the mixer, the supercritical water reactor configured to allow the hydrocarbons to undergo a set of conversion reactions to produce a reactor product, a product cooler fluidly connected to the supercritical water reactor, the product cooler configured to reduce the temperature of the reactor product to produce a cooled product, a depressurizing device fluidly connected to the product cooler, the depressurizing device configured to reduce the pressure of the cooled product to produce a depressurized stream, a vapor-liquid separator fluidly connected to the depressurizing device, the vapor-liquid separator to produce a gas product stream and a liquid stream, and an oil-water separator fluidly connected to the vapor-liquid separator, the oil-water separator configured to separate the liquid stream to produce the upgraded product stream and a used water stream.

These and other features, aspects, and advantages of the scope will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments and are therefore not to be considered limiting of the scope as it can admit to other equally effective embodiments.

In the accompanying Figures, similar components or features, or both, may have a similar reference label.

While the scope of the apparatus and method will be described with several embodiments, it is understood that one of ordinary skill in the relevant art will appreciate that many examples, variations and alterations to the apparatus and methods described here are within the scope and spirit of the embodiments.

Accordingly, the embodiments described are set forth without any loss of generality, and without imposing limitations, on the embodiments. Those of skill in the art understand that the scope includes all possible combinations and uses of particular features described in the specification.

The processes and systems described are directed to upgrading heavy oil feedstocks. The processes and systems described include partially oxidizing a heavy oil feedstock to produce oxygenates such as alcohol, ether, ester, and carboxylic compounds. Advantageously, the process order of partial oxidation unit followed by supercritical water unit results in improved performance of heavy oil upgrading in supercritical water unit. Advantageously, the partial oxidation unit provides a method of pretreating a heavy oil to generate carbon-oxygen bonds which can be broken in the supercritical water unit. Advantageously, the removal of gases formed in the partial oxidation unit can increase the efficiency of the system by reducing the potential for damage in the pump due to cavitation brought on by pumping gas-containing liquid. The presence of oxygen and other gases in the supercritical water unit can increase the amount of gas produced in the supercritical water unit while decreasing the liquid yield, thus, removing gases upstream of the supercritical water unit increases the liquid yield. Advantageously, the removal of solid particulates following the partial oxidation unit reduces the production of coke in the supercritical water unit. Advantageously, the upgrading process with partial oxidation pretreatment can increase the production of naphtha fraction and gas oil fractions in an upgraded product from the supercritical water unit, which can increase the API gravity. Advantageously, partial oxidation upstream of thermal cracking in supercritical water enhances overall liquid yield as compared to total oxidation and enhances conversion of heavy fractions and desulfurization reactions, denitrogenation reactions, and demetallization reactions. Advantageously, employing the partial oxidation unit upstream of the supercritical water unit reduces the amount of heat to be supplied to supercritical water reactor.

It is known in the art that hydrocarbon reactions in supercritical water upgrade heavy oil and crude oil containing sulfur compounds to produce products that have lighter fractions. Supercritical water has unique properties making it suitable for use as a petroleum reaction medium where the reaction objectives can include conversion reactions, desulfurization reactions denitrogenation reactions, and demetallization reactions. Supercritical water is water at a temperature at or greater than the critical temperature of water and at a pressure at or greater than the critical pressure of water. The critical temperature of water is <NUM>. The critical pressure of water is <NUM> megapascals (MPa). Advantageously, at supercritical conditions water acts as both a hydrogen source and a solvent (diluent) in conversion reactions, desulfurization reactions and demetallization reactions and a catalyst is not needed. Hydrogen from the water molecules is transferred to the hydrocarbons through direct transfer or through indirect transfer, such as the water-gas shift reaction. In the water-gas shift reaction, carbon monoxide and water react to produce carbon dioxide and hydrogen. The hydrogen can be transferred to hydrocarbons in desulfurization reactions, demetallization reactions, denitrogenation reactions, and combinations of the same. The hydrogen can also reduce the olefin content.

Without being bound to a particular theory, it is understood that the basic reaction mechanism of supercritical water mediated petroleum processes is the same as a free radical reaction mechanism. Radical reactions include initiation, propagation, and termination steps. With hydrocarbons, especially heavy molecules such as C<NUM>+, initiation is the most difficult step and conversion in supercritical water can be limited due to the high activation energy required for initiation. Initiation requires the breaking of chemical bonds. The bond energy of carbon-carbon bonds is about <NUM> kJ/mol, while the bond energy of carbon-hydrogen is about <NUM> kJ/mol. Due to the chemical bond energies, carbon-carbon bonds and carbon-hydrogen bonds do not break easily at the temperatures in a supercritical water process, <NUM> deg C to <NUM> deg C, without catalyst or radical initiators. In contrast, aliphatic carbon-sulfur bonds have a bond energy of about <NUM> kJ/mol. The aliphatic carbon-sulfur bond, such as in thiols, sulfide, and disulfides, has a lower bond energy than the aromatic carbon-sulfur bond.

Thermal energy creates radicals through chemical bond breakage. Supercritical water creates a "cage effect" by surrounding the radicals. The radicals surrounded by water molecules cannot react easily with each other, and thus, intermolecular reactions that contribute to coke formation are suppressed. The cage effect suppresses coke formation by limiting inter-radical reactions. Supercritical water, having low dielectric constant, dissolves hydrocarbons and surrounds radicals to prevent the inter-radical reaction, which is the termination reaction resulting in condensation (dimerization or polymerization). Because of the barrier set by the supercritical water cage, hydrocarbon radical transfer is more difficult in supercritical water as compared to conventional thermal cracking processes, such as delayed coker, where radicals travel freely without such barriers.

Sulfur compounds released from sulfur-containing molecules can be converted to H<NUM>S, mercaptans, and elemental sulfur. Without being bound to a particular theory, it is believed that hydrogen sulfide is not "stopped" by the supercritical water cage due its small size and chemical structure similar to water (H<NUM>O). Hydrogen sulfide can travel freely through the supercritical water cage to propagate radicals and distribute hydrogen. Hydrogen sulfide can lose its hydrogen due to hydrogen abstraction reactions with hydrocarbon radicals. The resulting hydrogen-sulfur (HS) radical is capable of abstracting hydrogen from hydrocarbons which will result in formation of more radicals. Thus, H<NUM>S in radical reactions acts as a transfer agent to transfer radicals and abstract/donate hydrogen.

As previously noted, aromatic sulfur compounds are more stable in supercritical water compared to more active aliphatic sulfur compounds. As a result, a feedstock having more aliphatic sulfur can have a higher activity in the early stage of thermal cracking in supercritical water. However, the amount of aliphatic sulfur in heavy oil feedstocks is insufficient to increase conversion of heavy oil at temperatures limited to <NUM> deg C and residence time of less than <NUM> minutes.

Aliphatic sulfur compounds are generally found in light naphtha and vacuum residue. In vacuum residue, aliphatic carbon-sulfur bonds are believed to be present in asphalthenic fraction. The amount of aliphatic sulfur compounds is less than aromatic sulfur compounds in common crude oils.

As used throughout, "external supply of hydrogen" refers to the addition of hydrogen to the feed to the reactor or to the reactor itself. For example, a reactor in the absence of an external supply of hydrogen means that the feed to the reactor and the reactor are in the absence of added hydrogen, gas (H<NUM>) or liquid, such that no hydrogen (in the form H<NUM>) is a feed or a part of a feed to the reactor.

As used throughout, "external supply of catalyst" refers to the addition of catalyst to the feed to the reactor or the presence of a catalyst in the reactor, such as a fixed bed catalyst in the reactor. For example, a reactor in the absence of an external supply of catalyst means no catalyst has been added to the feed to the reactor and the reactor does not contain a catalyst bed in the reactor.

As used throughout, "external supply of oxidants" refers to the addition of oxidants to the feed to the reactor or the addition of oxidants as a separate feed to a reactor. For example, a reactor in the absence of an external supply of oxidants means no oxidants have been added to the feed to the reactor in the form of a separate oxidant stream and the reactor does not contain a catalyst bed in the reactor.

As used throughout, "atmospheric residue" or "atmospheric residue fraction" refers to the fraction of oil-containing streams having a T10% of <NUM> (<NUM> deg F), such that <NUM>% of the volume of hydrocarbons have boiling points greater than <NUM> (<NUM> deg F) and includes the vacuum residue fraction. Atmospheric residue can refer to the composition of an entire stream, such as when the feedstock is from an atmospheric distillation unit, or can refer to a fraction of a stream, such as when a whole range crude is used.

As used throughout, "vacuum residue" or "vacuum residue fraction" refers to the fraction of oil-containing streams having a T10% of <NUM> (<NUM> deg F). Vacuum residue can refer to the composition of an entire stream, such as when the feedstock is from a vacuum distillation unit or can refer to a fraction of stream, such as when a whole range crude is used.

As used throughout, "asphaltene" refers to the fraction of an oil-containing stream which is not soluble in a n-alkane, particularly, n-heptane.

As used throughout, "coke" refers to the toluene insoluble material present in petroleum.

As used throughout, "cracking" refers to the breaking of hydrocarbons into smaller ones containing few carbon atoms due to the breaking of carbon-carbon bonds.

As used throughout, "upgrade" means one or all of increasing API gravity, decreasing the amount of impurities, such as sulfur, nitrogen, and metals, decreasing the amount of asphaltene, and increasing the amount of distillate in a process outlet stream relative to the process feed stream. One of skill in the art understands that upgrade can have a relative meaning such that a stream can be upgraded in comparison to another stream, but can still contain undesirable components such as impurities.

As used here, "conversion reactions" refers to reactions that can upgrade a hydrocarbon stream including cracking, isomerization, alkylation, dimerization, aromatization, cyclization, desulfurization, denitrogenation, deasphalting, and demetallization.

As used here, "partial oxidation" refers to oxidation reactions where the amount of oxygen present is limited, such that the extent of oxidation reactions is limited. While the carbons and heteroatoms present are subjected to the oxidation environment, in partial oxidation not all the carbons are transformed to carbon dioxide, unlike in a total oxidation environment. The extent of oxidation depends on the amount of oxygen present, the temperature, residence time, and catalyst in the oxidation reactor.

As used here, "deep conversion," a qualitative term, refers to the conversion of vacuum residue to greater than <NUM> %, and alternately greater than <NUM> % in the absence of an external supply of hydrogen and in the absence of an external supply of catalyst.

As used here, "gas-to-liquid processes" or "GTL processes" refer to processes to convert natural gas to liquid hydrocarbons, such as gasoline and diesel. An example of a GTL process is one with a Fischer-Tropsch reaction. Hydrocarbons produced in a GTL process can result in paraffinic hydrocarbons.

The following embodiments, provided with reference to the figures, describe the upgrading process.

Referring to <FIG>, a process flow diagram of an upgrading process is provided. Heavy oil feed <NUM>, water feed <NUM>, and oxidant feed <NUM> can be introduced to partial oxidation unit <NUM>. Heavy oil feed <NUM> can be from any hydrocarbon source derived from petroleum, coal liquid, or biomaterials. Examples of heavy oil feed <NUM> include whole range crude oil, distilled crude oil, residue oil, topped crude oil, refinery product streams, product streams from steam cracking processes, liquid hydrocarbons from gas-to-liquid (GTL) processes, liquefied coals, liquid products recovered from oil or tar sands, bitumen, oil shale, asphaltenes, and biomass hydrocarbons. Heavy oil feed <NUM> can include an oxygen content of less than <NUM> wt% and alternately less than <NUM> wt%. "Whole range crude oil" refers to passivated crude oil which has been processed by a gas-oil separation plant after being recovered from a production well. "Topped crude oil" can also be known as "reduced crude oil" and refers to a crude oil having no light fraction, and would include an atmospheric residue stream or a vacuum residue stream. "Refinery product streams" can include "cracked oil," such as light cycle oil, heavy cycle oil, and streams from a fluid catalytic cracking unit (FCC), such as slurry oil or decant oil, a heavy stream from hydrocracker with a boiling point greater than <NUM> (<NUM> deg F), a deasphalted oil (DAO) stream from a solvent extraction process, and a mixture of atmospheric residue and hydrocracker bottom fractions.

Water feed <NUM> can be a demineralized water having a conductivity less than <NUM> microSiemens per centimeter (µS/cm), alternately less <NUM>/cm, and alternately less than <NUM>/cm. In at least one embodiment, water feed <NUM> is demineralized water having a conductivity less than <NUM>/cm. Water feed <NUM> can have a sodium content less than <NUM> micrograms per liter (µg/L) and alternately less than <NUM>µg/L. Water feed <NUM> can have a chloride content less than <NUM>µg/L and alternately less than <NUM>µg/L. Water feed <NUM> can have a silica content less than <NUM>µg/L.

Oxidant feed <NUM> can be an oxidant-containing stream. Oxidants can include air, oxygen gas, hydrogen peroxide, organic peroxides, and combinations of the same. Oxidant feed <NUM> can include an aqueous fluid when the oxidant is hydrogen peroxide, organic peroxide, and combinations of the same. The aqueous fluid can include water. The concentration of oxidants in oxidant feed <NUM> can be adjusted and controlled to regulate the molar ratio of oxygen atoms in oxidant feed <NUM> to the carbon atoms in heavy oil feed <NUM>. The molar ratio of oxygen atoms in oxidant feed <NUM> to carbon atoms in heavy oil feed <NUM> can be in the range between <NUM> and <NUM>, <NUM> and <NUM> and alternately between <NUM> and <NUM>. Advantageously, adjusting the concentration of oxidants in oxidant feed <NUM> to achieve the molar ratio range of oxygen atoms to carbon atoms can reduce the amount of gas products formed in partial oxidation unit <NUM>. Reducing the amount of gas products, increases the liquid yield from the partial oxidation unit <NUM> and supercritical upgrading unit <NUM>.

Heavy oil feed <NUM>, water feed <NUM>, and oxidant feed <NUM> can be processed in partial oxidation unit <NUM> to produce liquid oxidation product <NUM> and gas oxidation product <NUM>. Gas oxidation product <NUM> is disposed. In at least one embodiment, oxidation product <NUM> can be sent to a flare stack to be disposed. Liquid oxidation product <NUM> can be introduced to supercritical upgrading unit <NUM> along with water stream <NUM>.

Water stream <NUM> can be a demineralized water having a conductivity less than <NUM> microSiemens per centimeter (µS/cm), alternately less <NUM>/cm, and alternately less than <NUM>/cm. In at least one embodiment, water feed <NUM> is demineralized water having a conductivity less than <NUM>/cm. Water feed <NUM> can have a sodium content less than <NUM> micrograms per liter (µg/L) and alternately less than <NUM>µg/L. Water stream <NUM> can have a chloride content less than <NUM>µg/L and alternately less than <NUM>µg/L. Water stream <NUM> can have a silica content less than <NUM>µg/L. Water stream <NUM> can be from the same source as water feed <NUM>, and alternately from a different source as water feed <NUM>.

Liquid oxidation product <NUM> and water stream <NUM> can be processed in supercritical upgrading unit <NUM> to produce used water stream <NUM>, upgraded product stream <NUM>, and gas product <NUM>. Upgraded product stream <NUM> can contain upgraded hydrocarbons relative to heavy oil feed <NUM>. The water content in upgraded product stream <NUM> can be less than <NUM> wt%.

Used water stream <NUM> can be treated and after treatment, can be disposed or recycled to the front end of the partial oxidation unit as the water feed or can be recycled to the supercritical water unit as the water stream. In at least one embodiment, treatment of used water stream <NUM> can include passing used water stream <NUM> through a reverse osmosis membrane.

Partial oxidation unit <NUM> can be described with reference to <FIG>.

Heavy oil feed <NUM> can be introduced to feed pump <NUM>. The pressure of heavy oil feed <NUM> can be increased in feed pump <NUM> to produce pressurized oil feed <NUM>. Feed pump <NUM> can be any type of pump capable of increasing the pressure of a heavy oil stream. Examples of feed pump <NUM> can include a metering pump, such as a diaphragm pump. The pressure of pressurized oil feed <NUM> can be between <NUM> MPa and <NUM> MPa and alternately between <NUM> MPa and <NUM> MPa. Pressurized oil feed <NUM> can be introduced to feed heater <NUM>.

The temperature of pressurized oil feed <NUM> can be increased in feed heater <NUM> to produce hot oil feed <NUM>. Feed heater <NUM> can be any type of heat exchanger capable of increasing the temperature of a heavy oil stream. Examples of feed heater <NUM> include shell and tube exchangers, double pipe type heat exchangers, plate-fin type heat exchangers. The temperature of hot oil feed <NUM> can be between <NUM> deg C and <NUM> deg C and alternately between <NUM> deg C and <NUM> deg C. Hot oil feed <NUM> can be introduced to oxidation mixer <NUM>.

Water feed <NUM> and oxidant feed <NUM> can be introduced to premixer <NUM> to produce mixed oxidant feed <NUM>. Premixer <NUM> can be selected from a simple mixer, a tank with impeller, and combinations of the same. Water feed <NUM> and oxidant feed <NUM> can be mixed in premixer <NUM> to produce mixed oxidant feed <NUM>. In embodiments in which the oxidant in oxidant feed <NUM> is oxygen gas or air, the oxygen content in mixed oxidant feed <NUM> can be controlled by the temperature and pressure in premixer <NUM>. The residence time in premixer <NUM> can be sufficient to decompose the oxidant to produce oxygen. By way of example, when the oxidant is hydrogen peroxide, the residence time in premixer <NUM> can be sufficient to decompose hydrogen peroxide to water and oxygen. The residence time in premixer <NUM> can be between <NUM> second and <NUM> minute. In at least one embodiment, premixer <NUM> can enable removal of undissolved gases. In at least one embodiment, removal of undissolved gases can be achieved through venting. Undissolved gases can include the oxygen gas or air that does not get mixed in mixed oxidant feed <NUM>. Mixed oxidant feed <NUM> can be introduced to oxidant pump <NUM>.

The pressure of mixed oxidant feed <NUM> can be increased in oxidant pump <NUM> to produce pressurized oxidant feed <NUM>. Oxidant pump <NUM> can be any type of pump capable of increasing the pressure of an aqueous fluid. Examples of oxidant pump <NUM> can include a metering pump, such as a diaphragm pump. The pressure of pressurized oxidant feed <NUM> can be between <NUM> MPa and <NUM> MPa and alternately between <NUM> MPa and <NUM> MPa. Pressurized oxidant feed <NUM> can be introduced to oxidant heater <NUM>.

The temperature of pressurized oxidant feed <NUM> can be increased in oxidant heater <NUM> to produce hot oxidant feed <NUM>. Oxidant heater <NUM> can be any type of heat exchanger capable of increasing the temperature of an aqueous fluid. Examples of oxidant heater <NUM> can include a shell and tube exchanger, electric heater, and gas fired heater. The temperature of hot oxidant feed <NUM> can be between <NUM> deg C and <NUM> deg C and alternately between <NUM> deg C and <NUM> deg C. Hot oxidant feed <NUM> can be introduced to oxidation mixer <NUM>. In at least one embodiment, hot oxidant feed <NUM> can be at supercritical conditions, such that the water in hot oxidant feed <NUM> is in a supercritical state. In at least one embodiment, hot oxidant feed <NUM> is at subcritical conditions, such that the water is in liquid state. Hot oxidant feed <NUM> is at operating conditions such that the water in oxidant feed is a supercritical fluid, or is in the liquid phase and is in the absence of steam.

Oxidation mixer <NUM> can combine hot oxidant feed <NUM> and hot oil feed <NUM> to produce mixed oxidation feed <NUM>. Oxidation mixer <NUM> can be any type of mixer capable of mixing a heavy oil stream and an aqueous stream. Examples of oxidation mixer <NUM> can include a line mixer, an agitator, and ultrasonic chamber. The volumetric ratio of water to heavy oil in mixed oxidation feed <NUM> can be between <NUM>:<NUM> and <NUM>:<NUM> volume by volume (vol/vol) at standard atmospheric temperature and pressure (SATP) and alternately between <NUM>:<NUM> and <NUM>:<NUM> vol/vol SATP. In at least one embodiment, the volumetric ratio of water to heavy oil in mixed oxidation feed <NUM> can be maintained such that mixed oxidation feed <NUM> contains a greater amount of water than oil, because maintaining a greater amount of water than oil minimizes the risk of run-away reactions due to the exothermic conditions of the oxidation reactions in oxidation reactor <NUM>. Water can act as a heat sink, to control temperature, in oxidation reactor <NUM>. The volumetric ratio of water to heavy oil in mixed oxidation feed <NUM> can be controlled to maintain the total oxygen to carbon molar ratio of liquid oxidation product <NUM>.

Mixed oxidation feed <NUM> can be introduced to oxidation reactor <NUM>. Oxidation reactor <NUM> can be any type of continuous-type reactor capable of supporting oxidation reactions. In at least one embodiment, paraffins and alkyl chains attached to aromatic cores in the heavy oil are susceptible to oxidation reactions. In at least one embodiment, aromatic and naphthenic rings exhibit stability such that they are not susceptible to oxidation reactions. The oxidation reactions can produce oxygenates, such that reactor effluent <NUM> can include oxygenates. Oxygenates can include alcohols, ketones, esters, ethers, carboxylic acids, and combinations of the same. In at least one embodiment, the greatest number of oxygenates are ketones having a carbonyl group (carbon double bonded with oxygen). Oxidation reactions differ from hydration reactions, because hydration reactions require a strong acid/base catalyst such as hydrogen sulfide or sodium hydroxide. Moreover, hydration reactions form alcohols alone, whereas oxidation reactions additionally form carboxylic acids and ketones. Examples of oxidation reactor <NUM> can include a fixed bed reactor and a CSTR type reactor. The temperature in oxidation reactor <NUM> can be between <NUM> deg C and <NUM> deg C and alternately between <NUM> deg C and <NUM> deg C. The pressure in oxidation reactor <NUM> can be between <NUM> MPa and <NUM> MPa. The operating conditions in oxidation reactor <NUM> can be controlled such that the water in oxidation reactor <NUM> can be maintained in a liquid phase.

Oxidation reactor <NUM> is operated at subcritical conditions, where the water is present in the liquid phase, such that the oxidation reactions result in the partial oxidation of carbon compounds. Due to the high rate of oxygen diffusivity in supercritical water, supercritical water is an efficient medium for oxidation reactions. At supercritical conditions, oxidation reactions can lead to the total oxidation of carbon compounds to carbon dioxide, resulting in loss of liquid. Thus, oxidation reactions in supercritical water conditions can result in a reduced liquid yield as compared to oxidation reactions in subcritical conditions. Additionally, the extent of oxygen incorporation into the heavy oil can be controlled in subcritical conditions to maintain a desired oxygen concentration in the reactor effluent. Controlling the extent of oxygen incorporation is more difficult in supercritical water due to the temperature. Total oxidation of the carbon compounds does not occur in oxidation reactor <NUM>. Heterogeneous catalysts are not stable at supercritical water conditions.

Hydrocarbons in mixed oxidation feed <NUM> can be upgraded due to the breaking of carbon-to-carbon bonds through oxidation.

Oxidation reactor <NUM> is in the absence of steam. The residence time in oxidation reactor <NUM> can be determined based on the extent of oxygen incorporation in the liquid products in the reactor effluent. The residence time measured as the liquid hourly space velocity (LHSV) can be in the range of between <NUM> per hour (hr-<NUM>) and <NUM> hr-<NUM> and alternately between <NUM> hr-<NUM> and <NUM> hr-<NUM>. In at least one embodiment, oxidation reactor <NUM> can operate in the absence of an external supply of catalyst. In at least one embodiment, oxidation reactor <NUM> can contain an oxidation catalyst and be a fixed bed reactor. Oxidation reactor <NUM> is not a fluidized bed reactor because the operating conditions are such that the water is maintained in the liquid phase, where fluidization is not easy.

Oxidation catalyst can include an active component and alternately an active component in combination with a support. The active component can be include transition metal oxides, precious metals, and lanthanoid oxides. The transition metal oxides can include iron (Fe), nickel (Ni), zinc (Zn), copper (Cu), zirconium, and combinations of the same. The precious metals can include platinum (Pt), gold (Au), silver (Ag) and combinations of the same. The lanthanoid oxide can include lanthium (La) oxide, cerium (Ce) oxide, and combinations of the same. The support can include silicon dioxide (SiO<NUM>), aluminum oxide (Al<NUM>O<NUM>), zeolites, and combinations of the same.

Reactor effluent <NUM> can include heavy oil, oxygenates, water, and oxidants. As noted, the total oxygen to carbon molar ratio in reactor effluent <NUM> can be controlled by adjusting the ratio of oxidant to heavy oil in the mixed oxidation reactor feed to the oxidation reactor, the temperature in the oxidation reactor, the residence time in the oxidation reactor, the catalyst in the oxidation reactor, and combinations of the same.

Reactor effluent <NUM> can be introduced to effluent cooler <NUM>. The temperature of reactor effluent <NUM> can be reduced in effluent cooler <NUM> to produce cooled effluent <NUM>. Effluent cooler <NUM> can be any type of heat exchanger capable of reducing the temperature of a mixed hydrocarbon and water stream. Examples of effluent cooler <NUM> include a shell and tube exchanger. The temperature of cooled effluent <NUM> can be between <NUM> deg C and <NUM> deg C. Cooled effluent <NUM> can be introduced to effluent depressurizing device <NUM>.

The pressure of cooled effluent <NUM> can be reduced in effluent depressurizing device <NUM> to produce depressurized effluent <NUM>. Effluent depressurizing device <NUM> can be any type of unit capable of reducing the pressure of a mixed hydrocarbon and water stream. Examples of effluent depressurizing device <NUM> include a pressure control valve, a back-pressure control valve, and a capillary element. The pressure of depressurized effluent <NUM> can be in the range from between ambient pressure and <NUM> MPa. Depressurized effluent <NUM> can be introduced to separator <NUM>.

Depressurized effluent <NUM> can be separated in separator <NUM> to produce liquid oxidation product <NUM> and gas oxidation product <NUM>. Separator <NUM> can be any type of unit capable of separating a stream in a gas phase and a liquid phase. Examples of separator <NUM> include a flash drum and a simple vessel. Separation in separator <NUM> means the whole product stream from the reactor effluent is not transferred to supercritical upgrading unit <NUM>. In at least one embodiment, a purge gas stream can be introduced to separator <NUM>. Purge gas stream can contain an inert gas. Examples of the inert gas in purge gas stream can include nitrogen, helium, argon, and combinations of the same. Introducing a purge gas stream to separator <NUM> can enhance the separation of gases in depressurized effluent <NUM> from the liquids in depressurized effluent <NUM>.

In at least one embodiment, cooled effluent <NUM> can be introduced to separator <NUM> without an intermediate depressurizing device. A purge stream, such as nitrogen gas, can be used in separator <NUM> to enhance the separation of the gas phase from the liquid phase. In such an embodiment, a pressure let down device can be located in the line withdrawing gas oxidation product <NUM> from separator <NUM>.

Gas oxidation product <NUM> contains, gases formed in oxidation reactor <NUM>, unreacted oxidants, water, and combinations of the same. The gases in gas oxidation product <NUM> can include carbon monoxide, carbon dioxide, light hydrocarbons and combinations of the same. Light hydrocarbons can include methane, ethane, butane, and combinations of the same. Separating the depressurized effluent <NUM> into liquid oxidation product and gas oxidation product results in removing unreacted oxidants as part of the gas oxidation product. Removing unreacted oxidants is advantageous because oxidants in supercritical water can reduce liquid yield and can cause corrosion problems in supercritical upgrading unit <NUM>.

Liquid oxidation product <NUM> contains heavy oil, oxygenates, water, and combinations of the same. In at least one embodiment, liquid oxidation product <NUM> is in the absence of oxidants. Liquid oxidation product <NUM> is in the absence of blown asphalt. The oxygenates can include organic oxygenates, where the organic oxygenates can be present in the water phase. The total oxygen to carbon molar ratio in liquid oxidation product <NUM> can be in the range between <NUM> and <NUM> and alternately in the range between <NUM> and <NUM>.

Supercritical upgrading unit <NUM> can be described in more detail with reference to <FIG>.

Liquid oxidation product <NUM> can be passed to filter unit <NUM>. Filter unit <NUM> can be any type of filtration unit capable of separating solid particles from a fluid stream. Filter unit <NUM> can include a filter. The solid particles can include metal compounds, coke, and combinations of the same. The metal compounds can include alkali, nickel, iron, vanadium, and combinations of the same. Filter unit <NUM> can separate solid particles with a size greater than <NUM> microns and alternately greater than <NUM> microns. Filter unit <NUM> can separate solid particles formed in partial oxidation unit <NUM> and solid particle present in heavy oil feed <NUM>. The solid particles in liquid oxidation product <NUM> can be separated in filter unit <NUM> to produce solid waste <NUM> and filtered stream <NUM>. Filtered stream <NUM> can be passed to pump <NUM>.

The pressure of filtered stream <NUM> can be increased in pump <NUM> to produce pressurized stream <NUM>. Pump <NUM> can be any type of pump capable of increasing the pressure of filtered stream <NUM>. Examples of pump <NUM> include a metering pump, such as a diaphragm pump. The pressure of pressurized stream <NUM> can be greater than the critical pressure of water. Pressurized stream <NUM> can be introduced to heater <NUM>.

The temperature of pressurized stream <NUM> can be increased in heater <NUM> to produce hot stream <NUM>. Heater <NUM> can be any type of heat exchanger capable increasing the temperature of pressurized stream <NUM>. Examples of heat exchangers capable of being used as petroleum heater <NUM> can include an electric heater, a fired heater, and a cross exchanger. The temperature of hot stream <NUM> can be less than <NUM> deg C, alternately less than <NUM> deg C, alternately between <NUM> deg C and <NUM> deg C and alternately between <NUM> deg C and <NUM> deg C. Maintaining the temperature of hot stream <NUM> at less than <NUM> deg C reduces the formation of coke hot stream <NUM> and in supercritical water reactor <NUM>.

Water stream <NUM> can be passed to water pump <NUM>. The pressure of water stream <NUM> can be increased in water pump <NUM> to produce pressurized water stream <NUM>. Water pump <NUM> can be any type of pump capable of increasing the pressure of water stream <NUM>. In at least one embodiment, water pump <NUM> is a metering pump, such as a diaphragm pump. The pressure of pressurized water stream <NUM> can be greater than the critical pressure of water. Pressurized water stream <NUM> can be introduced to water heater <NUM>.

The temperature of pressurized water stream <NUM> can be increased in water heater <NUM> to produce supercritical water stream <NUM>. Water heater <NUM> can be any type of heat exchanger capable of increasing the temperature of pressurized water stream <NUM>. Examples of heat exchangers that can be used as water heater <NUM> can include an electric heater and a fired heater. The temperature of supercritical water stream <NUM> can be equal to or greater than the critical temperature of water, alternately between <NUM> deg C and <NUM> deg C, and alternately between <NUM> deg C and <NUM> deg C.

Hot stream <NUM> and supercritical water stream <NUM> can be passed to mixer <NUM>. Mixer <NUM> can be any type of mixing device capable of mixing a petroleum stream and a supercritical water stream. Examples of mixing devices suitable for use as mixer <NUM> can include a static mixer, an inline mixer, such as tee fitting, and an impeller-embedded mixer. The ratio of the volumetric flow rate of hot stream <NUM> to supercritical water stream <NUM> can be determined based on the amount of water in liquid oxidation product <NUM>. The ratio of the volumetric flow rate of supercritical water stream <NUM> to hot stream <NUM> can be in the range between <NUM>:<NUM> and <NUM>:<NUM> at standard temperature and pressure (SATP). Advantageously, while the volume of water in liquid oxidation product <NUM> can be sufficient to allow conversion reactions to occur in supercritical water reactor <NUM>, the generation of supercritical water stream <NUM> can reduce the heat load in heater <NUM> while maintaining operating conditions in supercritical water reactor <NUM>. Hot stream <NUM> and supercritical water stream <NUM> can be mixed to produce mixed stream <NUM>. The pressure of mixed stream <NUM> can be greater than the critical pressure of water. The temperature of mixed stream <NUM> can depend on the temperature of supercritical water stream <NUM> and hot stream <NUM>. Mixed stream <NUM> can be introduced to supercritical water reactor <NUM>.

Supercritical water reactor <NUM> can include one or more reactors in series. Supercritical water reactor <NUM> can be any type of continuous-type reactor capable of allowing conversion reactions to occur. Examples of reactors suitable for use in supercritical water reactor <NUM> can include tubular-type, vessel-type, and combinations of the same. In at least one embodiment, supercritical water reactor <NUM> includes a tubular reactor, which advantageously prevents precipitation of reactants or products. Supercritical water reactor <NUM> can include an upflow reactor, a downflow reactor, and a combination of an upflow reactor and downflow reactor. In at least one embodiment, supercritical water reactor <NUM> includes an upflow reactor, which advantageously prevents channeling of reactants resulting in an increased reaction yield. According to the invention, supercritical water reactor <NUM> is in the absence of an external supply of hydrogen. Supercritical water reactor <NUM> is in the absence of an external supply of catalyst. Operating supercritical water reactor <NUM> in the absence of an external supply of hydrogen, an external supply of catalyst, and removing gases and unreacted oxidants from gas oxidation product <NUM> can reduce the extent of overcracking in supercritical water reactor <NUM>, overcracking of hydrocarbons can increase the amount of low economic value gases produced. Supercritical water reactor <NUM> is in the absence of an external supply of oxidants.

The temperature in supercritical water reactor <NUM> can be maintained at greater than the critical temperature of water, alternately in the range between <NUM> deg C and <NUM> deg C, and alternately in the range between <NUM> deg C and <NUM> deg C. The pressure in supercritical water reactor <NUM> can be maintained at a pressure greater than the critical pressure of water and alternately between <NUM> MPa and <NUM> MPa. The residence time of the reactants in supercritical water reactor <NUM> can between <NUM> minute and <NUM> minutes and alternately between <NUM> minutes and <NUM> minutes. The residence time is calculated by assuming that the density of the reactants in supercritical water reactor <NUM> is the same as the density of water at the operating conditions of supercritical water reactor <NUM>.

The reactants in supercritical water reactor <NUM> can undergo conversion reactions to produce reactor product <NUM>. In at least one embodiment, deoxygenation reactions, hydrolysis reactions, decarboxylation reactions, dehydration reactions, conversion reactions, and combinations of the same can occur in supercritical water reactor <NUM>. Deoxygenation reactions can include reactions that transform carbonyl groups, such as those found in ketones, to carbon monoxide, reactions that transform carboxylic groups to carbon dioxide, and combinations of the same. In hydrolysis reactions, ethers can be transformed into alcohols and esters can be transformed into alcohols and aldehydes. In decarboxylation reactions, a carboxyl group can be removed from any oxygenate releasing carbon dioxide due to the presence of supercritical water. In dehydration reactions, alcohols can be transformed to olefins. In at least one embodiment, the alcohols formed in hydrolysis reactions can be converted to olefins in dehydration reactions in the supercritical water reactor. Advantageously, the carbon-oxygen bonds of the oxygenates can be broken in the supercritical water reactor, which can enhance the conversion reactions. In at least one embodiment, supercritical water reactor <NUM> is in the absence of oxidation reactions. Reactor product <NUM> can be introduced to product cooler <NUM>.

The temperature of reactor product <NUM> can be reduced in product cooler <NUM> to produce cooled product <NUM>. Product cooler <NUM> can be any type of heat exchange device capable of reducing the temperature of reactor product <NUM>. Examples of product cooler <NUM> can include double pipe type exchanger and shell-and-tube type exchanger. The temperature of cooled product <NUM> can be between <NUM> deg C and <NUM> deg C and alternately between ambient temperature and <NUM> deg C and alternately between <NUM> deg C and <NUM> deg C. Cooled product <NUM> can be introduced to depressurizing device <NUM>.

The pressure of cooled product <NUM> can be reduced to produce depressurized stream <NUM>. Depressurizing device <NUM> can be any type of device capable of reducing the pressure of a fluid stream. Examples of depressurizing device <NUM> can include a pressure let-down valve, a pressure control valve, and a back pressure regulator. The pressure of depressurized stream <NUM> can be between atmospheric pressure and <NUM> MPa. Depressurized stream <NUM> can be introduced to vapor-liquid separator <NUM>.

Vapor-liquid separator <NUM> can be any type of separation device capable of separating a fluid stream into gas phase and liquid phase. Depressurized stream <NUM> can be separated in vapor-liquid separator <NUM> to produce liquid stream <NUM> and gas product stream <NUM>. Liquid stream <NUM> can be introduced to oil-water separator <NUM>.

Oil-water separator <NUM> can be any type of separation device capable of separating a fluid stream into a hydrocarbon containing stream and a water stream. Liquid stream <NUM> can be separated in oil-water separator <NUM> to produce used water stream <NUM> and upgraded product stream <NUM>. The conditions in oil-water separator <NUM> can be adjusted to control the amount of water in upgraded product stream <NUM>.

Additional equipment, such as storage tanks, can be used to contain the feeds to each unit. Instrumentation can be included on the process lines to measure various parameters, including temperatures, pressures, and concentration of water.

The Example was conducted by a lab scale unit with a system as shown in <FIG>. Two runs were performed with a heavy oil feed. In both runs, heavy oil feed <NUM> was an atmospheric residue of Arabian light crude oil. And water feed <NUM> was a demineralized water having a conductivity of <NUM>/cm.

In the first run, the heavy oil feed was processed in a supercritical upgrading unit. Heavy oil <NUM> was passed through a metering pump, at a rate of <NUM>/hr. The pressurized stream was heated to a temperature of <NUM> deg C in an electric heater. Water stream <NUM> was fed by a metering pump at a rate of <NUM>/hr. The temperature of the pressurized water stream was increased to <NUM> deg C in an electric heater. The supercritical water stream was mixed with the hot stream in a ¼ inch tee fitting and the mixed stream was introduced to the supercritical reactor. The supercritical reactor was two reactors in series, each with a tubular reactor with a <NUM> internal volume and downward flow direction. The temperature in the first reactor was <NUM> deg C and in the second reactor <NUM> deg C. The supercritical water reactor effluent was cooled to <NUM> deg C and the cooled product was depressurized in a back pressure regulator. The pressure between the pumps and the depressurizing device was maintained at <NUM> MPa. The depressurized stream was introduced to a vapor-liquid separator with nitrogen at a flow rate of <NUM> sccm. The liquid stream was introduced to an oil-water separator with a demulsifier. The fluid was agitated for <NUM> hours at <NUM> deg C and then allowed to settle for <NUM> hours, during which time the oil and water phases separated. Results are shown in Table <NUM>.

In a second run, an upgrading process that included a partial oxidation unit and a supercritical upgrading unit was used as describe. In the second run, oxidant feed <NUM> was a hydrogen peroxide solution, containing <NUM> wt% hydrogen peroxide in water. The mix rate of water feed <NUM> and oxidant feed <NUM> result in mixed oxidant feed <NUM> have a concentration of oxidant of <NUM> wt%. Mixed oxidant feed <NUM> was stored in a tank and withdrawn from a high pressure metering pump at a rate of <NUM>/hr. Heavy oil feed <NUM> was withdrawn from a storage tank at a temperature of <NUM> deg C and pumped through a high pressure metering pump at a rate of <NUM> liter/hour (L/hr). Pressurized oxidant feed <NUM> was heated to a temperature of <NUM> deg C in one heater and pressurized oil feed <NUM> was heated to a temperature of <NUM> deg C in a separate heater. The residence time of pressurized oxidant feed <NUM> in feed heater <NUM> was about <NUM> seconds which was sufficient to decompose all of the hydrogen peroxide into water and oxygen.

Hot oil feed <NUM> and hot oxidant feed <NUM> are mixed in oxidation mixer <NUM>, which was a ¼" tee fitting. Mixed oxidation feed <NUM> was introduced to oxidation reactor <NUM>. Oxidation reactor <NUM> was a CSTR with a <NUM> liter internal volume and temperature maintained at <NUM> deg C as measured by a dip tube-type thermocouple. Reactor effluent <NUM> was cooled in a double-pipe type cooler to <NUM> deg C and cooled effluent <NUM> was depressurized in a back pressure regulator. The pressure from the pumps through effluent depressurizing device <NUM> was maintained at <NUM> MPa. Depressurized effluent <NUM> was flushed by flowing nitrogen at the rate of about <NUM> standard cubic centimeters per minute (sccm) to remove gas-phase products and oxygen. The remaining liquid-phase product was agitated by a rotating turbine at <NUM> revolutions per minute (rpms) for five hours. The liquid-phase product was agitated to prevent settling of solid particles, because suspended solid particles can be filtered more easily than solid particles that have settled.

The agitated fluid was filtered by filter unit <NUM>, an inline filter having a <NUM> micron size and using a peristatic pump. Filtered stream <NUM> was stored in a storage tank having an agitator inside to produce a uniform oil-water distribution. Fluid was withdrawn from the storage tank and passed through pump <NUM>, a metering pump, at a rate of <NUM>/hr. Pressurized stream <NUM> was heated to a temperature of <NUM> deg C in an electric heater. Water stream <NUM> was fed by water pump <NUM>, a metering pump, at a rate of <NUM>/hr. The temperature of pressurized water stream <NUM> was increased to <NUM> deg C in an electric heater. Supercritical water stream <NUM> was mixed with hot stream <NUM> in a ¼ inch tee fitting and mixed stream <NUM> was introduced to supercritical reactor <NUM>. Supercritical reactor <NUM> was two reactors in series, each with a tubular reactor with a <NUM> internal volume and downward flow direction. The temperature in the first reactor was <NUM> deg C and in the second reactor <NUM> deg C. Reactor product <NUM> was cooled to <NUM> deg C and cooled product <NUM> was depressurized in depressurizing device <NUM>, a back pressure regulator. The pressure between the pumps and depressurizing device <NUM> was maintained at <NUM> MPa. Depressurized stream <NUM> was introduced to vapor-liquid separator <NUM> with nitrogen at a flow rate of <NUM> sccm. Liquid stream <NUM> was introduced to oil-water separator <NUM> with a demulsifier. The fluid was agitated for <NUM> hours at <NUM> deg C and then allowed to settle for <NUM> hours, during which time the oil and water phases separated. Results are shown in Table <NUM>.

In the table <NUM>°F corresponds to <NUM>.

Although the present invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereupon without departing from the principle and scope of the invention. Accordingly, the scope of the present invention should be determined by the following claims and their appropriate legal equivalents.

There various elements described can be used in combination with all other elements described here unless otherwise indicated.

The singular forms "a", "an" and "the" include plural referents, unless the context clearly dictates otherwise.

Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

Ranges may be expressed here as from about one particular value to about another particular value and are inclusive unless otherwise indicated. When such a range is expressed, it is to be understood that another embodiment is from the one particular value to the other particular value, along with all combinations within said range.

Claim 1:
A process for upgrading a heavy oil, the process comprising the steps of:
introducing a heavy oil feed to a partial oxidation unit;
introducing a water feed to a partial oxidation unit;
introducing an oxidant feed to a partial oxidation unit, where the oxidant feed comprises an oxidant;
processing the heavy oil feed, the water feed, and the oxidant feed in the partial oxidation unit to produce a liquid oxidation product and a gas oxidation product, where the liquid oxidation product comprises oxygenates, where the gas oxidation product comprises gases formed in the partial oxidation unit, unreacted oxidants, water, and combinations of the same, where the gas oxidation product is sent to be disposed;
introducing the liquid oxidation product to a supercritical water unit;
introducing a water stream to the supercritical water unit; and
processing the liquid oxidation product and the water stream in the supercritical water unit to produce an upgraded product stream, the upgraded product stream comprising upgraded hydrocarbons relative to the heavy oil feed, where the supercritical water unit is in the absence of an external supply of hydrogen.