WO2008055152A1 - Réacteur et procédé pour valoriser des hydrocarbures liquides lourds - Google Patents

Réacteur et procédé pour valoriser des hydrocarbures liquides lourds Download PDF

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Publication number
WO2008055152A1
WO2008055152A1 PCT/US2007/082992 US2007082992W WO2008055152A1 WO 2008055152 A1 WO2008055152 A1 WO 2008055152A1 US 2007082992 W US2007082992 W US 2007082992W WO 2008055152 A1 WO2008055152 A1 WO 2008055152A1
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Prior art keywords
water
reaction zone
reactor
hydrocarbon
reaction
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Ceased
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PCT/US2007/082992
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English (en)
Inventor
Zunqing He
Lin Li
Lixiong Li
Lawrence P. Zestar
Daniel Chinn
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Chevron USA Inc
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Chevron USA Inc
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Priority to CA002666390A priority Critical patent/CA2666390A1/fr
Priority to EA200970437A priority patent/EA200970437A1/ru
Publication of WO2008055152A1 publication Critical patent/WO2008055152A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to upgrading of hydrocarbons, especially heavy hydrocarbons such as whole heavy oil, bitumen, and the like using supercritical water.
  • Oil produced from a significant number of oil reserves around the world is simply too heavy to flow under ambient conditions. This makes it challenging to bring remote, heavy oil resources closer to the markets.
  • One typical example is the Hamaca field in Venezuela.
  • the diluent may be naphtha, or any other stream with a significantly higher API gravity (i.e., much lower density) than the heavy oil.
  • diluted crude oil is sent from the production wellhead via pipeline to an upgrading facility.
  • Two key operations occur at the upgrading facility: (1) the diluent stream is recovered and recycled back to the production wellhead in a separate pipeline, and (2) the heavy oil is upgraded with suitable technology known in the art (coking, hydrocracking, hydrotreating, etc.) to produce higher-value products for market.
  • suitable technology known in the art (coking, hydrocracking, hydrotreating, etc.) to produce higher-value products for market.
  • Some typical characteristics of these higher-value products include: lower sulfur content, lower metals content, lower total acid number (TAN), lower residuum content, higher API gravity, and lower viscosity. Most of these desirable characteristics are achieved by reacting the heavy oil with hydrogen gas at high temperatures and pressures in the presence of a catalyst.
  • Hydrogen-addition processes also have high operating costs, since hydrogen production costs are highly sensitive to natural gas prices. Some remote heavy oil reserves may not even have access to sufficient quantities of low-cost natural gas to support a hydrogen plant. These hydrogen-addition processes also generally require expensive catalysts and resource intensive catalyst handling techniques, including catalyst regeneration.
  • the refineries and/or upgrading facilities that are located closest to the production site may have neither the capacity nor the facilities to accept the heavy oil.
  • Coking is often used at refineries or upgrading facilities. Significant amounts of by-product solid coke are rejected during the coking process, leading to lower liquid hydrocarbon yield. In addition, the liquid products from a coking plant often need further hydrotreating. Further, the volume of the product from the coking process is significantly less than the volume of the feed crude oil.
  • a process according to the present invention overcomes these disadvantages by using supercritical water to upgrade a heavy hydrocarbon feedstock into an upgraded hydrocarbon product or syncrude with highly desirable properties (low sulfur content, low metals content, lower density (higher API), lower viscosity, lower residuum content, etc.).
  • the process neither requires external supply of hydrogen nor must it use catalysts. Further, the process in the present invention does not produce an appreciable coke by-product.
  • advantages that may be obtained by the practice of the present invention include a high liquid hydrocarbon yield; no need for externally-supplied hydrogen; no need to provide catalyst; significant increases in API gravity in the upgraded hydrocarbon product; significant viscosity reduction in the upgraded hydrocarbon product; and significant reduction in sulfur, metals, nitrogen, TAN 1 and MCR (micro-carbon residue) in the upgraded hydrocarbon product.
  • U.S. Patent No 4,840,725 discloses a process for conversion of high boiling liquid organic materials to lower boiling materials using supercritical water in a tubular continuous reactor.
  • the water and hydrocarbon are separately preheated and mixed in a high-pressure feed pump just before being fed to the reactor.
  • U.S. Patent No. 5,914,031 discloses a three zone reactor design so that the reactant activity, reactant solubility and phase separation of products can be optimized separately by controlling temperature and pressure.
  • the examples given in the patent were obtained using batch operation.
  • U.S. Patent No. 6,887,369 discloses a supercritical water pretreatment process using hydrogen or carbon monoxide preferably carried out in a deep well reactor to hydrotreat and hydrocrack carbonaceous material.
  • the deep well reactor is adapted from underground oil wells, and consists of multiple, concentric tubes.
  • the deep well reactor described in the patent is operated by introducing feed streams in the core tubes and returning reactor effluent in the outer annular section.
  • Waste streams typically contain both organic and inorganic materials. Although organic materials can be destroyed quickly through supercritical water oxidation, inorganic materials are insoluble in supercritical water.
  • U.S. Patent Nos. 5,560,823 and 5,567,698 incorporated by reference herein disclose a reversible flow reactor having two reaction zones which are alternately used for supercritical water oxidation while the remaining reaction zone is flushed with subcritical effluent from the active reaction zone.
  • U.S. Patent No. 6,264,844, incorporated by reference herein discloses a tubular reactor for supercritical water oxidation. The velocity of the reaction mixture is sufficient to prevent settling of solid.
  • 5,558,783, incorporated by reference herein, disclose a reactor design for supercritical wastewater oxidation. It contains a reaction zone inside the containment vessel and a permeable liner around the reaction zone. An oxidizer is mixed with a carrier fluid such as water. The mixture is heated and pressurized to supercritical conditions, and then introduced to the reaction zone gradually and uniformly by forcing it radially inward through the permeable liner and toward the reaction zone.
  • the permeable liner permits the continuous, gradual, uniform dispersion of a reactant and therefore promotes an even and efficient reaction.
  • the liner also isolates the pressure vessel from high temperature and oxidizing conditions found in the reaction zone, allowing a reduction in cost of the pressure vessel.
  • EP 1489046 discloses a double-vessel design with a reaction vessel placed inside a pressure vessel. Reaction takes place inside the reactor vessel at high temperature, pressure and corrosive environments. The outer pressure vessel will only see water.
  • 6,168,771 discloses a reactor design including an autoclave inside a pressure vessel.
  • the pressure between autoclave and pressure vessel is essentially equal to that inside the autoclave, therefore eliminating possible leaking of toxic material inside the autoclave.
  • heavy oil upgrading using supercritical water may be considered similar in some respects to waste treatment using supercritical water, and can be implemented using various elements of reactors designed for waste treatment, there are significant differences in requirement for reactor design for heavy hydrocarbon upgrading from that for waste treatment. Specifically, the following are among the many issues to be addressed in designing a reactor in which to conduct an effective process for heavy oil upgrading using supercritical water:
  • High density and viscosity One distinguishing feature of heavy oil is high density and viscosity. In fact, this is one of the primary reasons that the oil has to be upgraded.
  • the density of heavy oil is very close to liquid water, and viscosity can be as high as 10,000 cp. High density and viscosity, together with high concentration make the dispersion of heavy oil into supercritical water an important consideration.
  • the present Invention relates to an apparatus for upgrading a hydrocarbon by reaction with a fluid comprising water under supercritical water conditions comprising: means for dispersing and mixing the fluid comprising water and the hydrocarbon under conditions which disfavor thermal cracking and formation of coke; means for injecting a dispersed water-hydrocarbon mixture into a reaction zone under supercritical water conditions; a reaction zone having means for maintaining a uniform temperature within said reaction zone; means for controlling the residence time in the reaction zone within determined limits and means for avoiding the settling of inorganic solids within the reaction zone; and means for recovering an upgraded hydrocarbon.
  • Figure 1 is a process flow diagram of one embodiment of a process employing an apparatus of the present invention.
  • Figure 2 is a process flow diagram of another embodiment of a process employing an apparatus of the present invention.
  • Figure 3 is a process flow diagram of another embodiment of a process employing an apparatus of the present invention.
  • Figure 4 is a process flow diagram of another embodiment of a process employing an apparatus of the present invention.
  • FIG. 5 is a process flow diagram of another embodiment of a process employing an apparatus of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Water and hydrocarbons, preferably heavy hydrocarbons are the two reactants employed in a process according to the present invention.
  • Any hydrocarbon can be suitably upgraded by a process according to the present invention.
  • the preferred heavy hydrocarbons are heavy crude oil, heavy hydrocarbons extracted from tar sands, commonly called tar sand bitumen, such as Athabasca tar sand bitumen obtained from Canada, heavy petroleum crude oils such as Venezuelan Orinoco heavy oil belt crudes Boscan heavy oil, heavy hydrocarbon fractions obtained from crude petroleum oils particularly heavy vacuum gas oils, vacuum residuum as well as petroleum tar, tar sands and coal tar.
  • Other examples of heavy hydrocarbon feedstocks which can be used are oil shale, shale oil, and asphaltenes.
  • Sources of water include but are not limited to drinking water, treated or untreated wastewater, river water, lake water, seawater, produced water or the like.
  • the heavy hydrocarbon feed and a fluid comprising water that has been heated to a temperature higher than its critical temperature are contacted in a mixing zone prior to entering the reaction zone.
  • mixing may be accomplished in many ways and is preferably accomplished by a technique that does not employ mechanical moving parts. Such means of mixing may include, but are not limited to, use of static mixers, spray nozzles, sonic or ultrasonic agitation, or thermal siphons.
  • the oil and water should be heated and mixed so that the combined stream will reach supercritical conditions in the reaction zone.
  • One aspect of this invention is to employ a heating sequence so that the temperature and pressure of the hydrocarbons and water will reach supercritical reaction conditions in a controlled manner. This will avoid excessive local heating of oil, which will lead to solid formation and lower quality product.
  • the oil should only be heated up with sufficient amount of water present and around the hydrocarbon molecules. This requirement can be met by mixing oil with water before heating.
  • water is heated to a temperature higher than its critical temperature, and then mixed with oil.
  • the temperature of heavy oil feed should be kept in the range of about 100 0 C to 200 0 C to avoid thermal cracking but still high enough to maintain a reasonable pressure drop.
  • the water stream temperature should be high enough to make sure that after mixing with oil, the temperature of the oil-water mixture is still higher than the water supercritical temperature.
  • the oil is actually heated up by water. An abundance of water molecules surrounding the hydrocarbon molecules will significantly suppress condensation reactions and therefore reduce formation of coke and solid product.
  • the required temperature of the supercritical water stream, Tscw can be estimated based on reaction temperature, TR, and water to oil ratio. Since the heat capacity of water changes significantly in the range near its critical conditions, for a given reaction temperature, the required temperature for the supercritical water stream increases almost exponentially with decreasing water-to-oil ratio. The lower the water-to-oil ratio, the higher the Tscw- The relationship, however, is very nonlinear since higher T S cw leads to a lower heat capacity (far away from the critical point).
  • water is heated up to supercritical conditions. Then the supercritical water mixed with heavy oil feed in a mixer.
  • the temperature of heavy oil feed should be kept in the range of about 100 0 C to 200°C to avoid thermal cracking but still high enough to maintain reasonable pressure drop.
  • the temperature of the water-oil mixture would be lower than critical temperature of water; therefore a second heater is needed to raise the temperature of the mixture stream to above the critical temperature of water.
  • the heavy oil is first partially heated up by water, and then the water-oil mixture is heated to supercritical conditions by the second heater.
  • reaction zone in which they are allowed to react under temperature and pressure conditions of supercritical water, i.e. supercritical water conditions, in the absence of externally added hydrogen, for a residence time sufficient to allow upgrading reactions to occur.
  • the reaction is preferably allowed to occur in the absence of externally added catalysts or promoters, although the use of such catalysts and promoters is permissible in accordance with the present invention.
  • Hydrodrogen as used herein in the phrase, "in the absence of externally added hydrogen” means hydrogen gas. This phrase is not intended to exclude all sources of hydrogen that are available as reactants. Other molecules such as saturated hydrocarbons may act as a hydrogen source during the reaction by donating hydrogen to other unsaturated hydrocarbons. In addition, H 2 may be formed in-situ during the reaction through steam reforming of hydrocarbons and water-gas-shift reaction.
  • the reaction zone preferably comprises a reactor, which is equipped with a means for collecting the reaction products (syncrude, water, and gases), and a section, preferably at the bottom, where any metals or solids (the "dreg stream”) may accumulate.
  • Supercritical water conditions include a temperature from 374 0 C (the critical temperature of water) to 1000 0 C, preferably from 374 0 C to 600 0 C and most preferably from 374 0 C to 400°C, a pressure from 3,205 (the critical pressure of water) to 10,000 psia, preferably from 3,205 psia to 7,200 psia and most preferably from 3,205 to 4,000 psia, an oil/water volume ratio from 1 :0.1 to 1 :10, preferably from 1: 0.5 to 1 :3 and most preferably about 1:1 to 1:2.
  • the reactants are allowed to react under these conditions for a sufficient time to allow upgrading reactions to occur.
  • the residence time will be selected to allow the upgrading reactions to occur selectively and to the fullest extent without having undesirable side reactions of coking or residue formation.
  • Reactor residence times may be from 1 minute to 6 hours, preferably from 8 minutes to 2 hours and most preferably from 20 to 40 minutes.
  • a reactor designed for heavy oil upgrading using supercritical water in accordance with the present invention will preferably include the following features:
  • the reactor will have means for adequate oil-water mixing and dispersion. Contrary to the conventional thermal cracking in an uncontrolled fashion that will lead to excessive formation of light hydrocarbon and therefore lower liquid hydrocarbon yield at the temperature and pressure under supercritical water conditions, heavy hydrocarbons will hydrothermally crack into lighter components. Furthermore, hydrocarbon radicals formed from thermal cracking will also recombine and polymerize and eventually become coke. Water molecules, especially under supercritical conditions, can quench and stabilize hydrocarbon radicals and therefore prevent them from over cracking and polymerization. To avoid over cracking into light hydrocarbons and coke formation, the heavy hydrocarbon molecules are preferably surrounded by water molecules to the greatest practical extent. Therefore, the reactor includes means to assure adequate mixing of oil with water for the purpose of achieving a high yield of liquid hydrocarbons.
  • Such means should be chosen so as to be able to handle heavy oil feed which has low API gravity and high viscosity at high oil to water ratio.
  • such means can include, among others, (a) nozzles; (b) static mixer; (c) stirring vessel; (d) micro-channel device; and sonic and ultrasonic device.
  • reaction zone in accordance with the present invention will preferably:
  • reaction temperature is an intermediate product from selective, partial reaction. Therefore, it is extremely important to control reaction temperature to achieve high liquid hydrocarbon yield. Adequate control of reaction temperature can be achieved by providing enough heat transfer area, uniform feed distribution; or by quenching.
  • the present invention also employs a separation zone for product recovery.
  • the effluent stream from the reaction zone contains liquid hydrocarbon product, gas, water under supercritical conditions and solids.
  • the liquid hydrocarbons are generally separated from other components to achieve high yield.
  • the preferred way is to remove the solid first, and then bring the fluid phase containing hydrocarbon products, supercritical water and gas byproducts out of supercritical condition by lowing temperature, pressure or both so that hydrocarbon product and water will condense into liquid phase.
  • the solids are primarily inorganic materials formed during the reactions and can be separated from the supercritical fluid phase using separation techniques known in the art, which could be a disengaging zone in the reactor or a separate device such as settling vessel, filter, cyclone etc.
  • Another option for separating the solids is to bring the product stream out of supercritical regime by lowing temperature or pressure or both. Then the solid will precipitate.
  • a potential disadvantage of this option is that some of the inorganic components in the solid may dissolve in water, which may contaminate the liquid hydrocarbon product. It should be noted that depending on the specific applications, a reactor for heavy oil upgrading using supercritical water in accordance with the present invention may have more than one of each of the three components listed above.
  • Figure 1 shows an embodiment of the present invention, which has been used in a laboratory.
  • An inline mixer is used for mixing heavy oil with water.
  • it is a static mixer.
  • the reaction zone comprises a spiral tube reactor with large length to diameter ratio to attain high velocity inside the reactor, which is helpful to maintain oil-water dispersion.
  • This design also makes the fluid flow inside the reactor close to plug flow and therefore achieves narrow residence time distribution for selective conversion to desired liquid hydrocarbons. Inorganic solids in the feed and formed during the reaction will not dissolve in supercritical water. High velocity inside the reactor also prevents settling of those inorganic solids.
  • the small diameter of the reactor body also provides large specific surface area for heat transfer to maintain uniform temperature distribution inside the reactor.
  • the length of the reactor can be designed based on residence time needed for specific conversion.
  • a second vessel is added to settle the solids.
  • the temperature and pressure is maintained at the same values as those in the spiral tube so that the fluid in the second vessel is still at supercritical water conditions. Due to the larger cross-sectional area of the second vessel the fluid velocity is much lower. As a result, inorganic materials separated from the fluid will settle down in the vessel, and can be removed from the system.
  • the fluid containing hydrocarbon products, supercritical water and gas byproducts is cooled while maintaining at the same pressure as in the reactor, and hydrocarbon products and water are condensed in the high pressure separator.
  • a spiral tube with a high length to diameter ratio which may be from 50 to 10,000, preferably from 100 to 4,000 may be used as reactor body.
  • Use of such a reactor has the advantages of high velocity, narrow residence time distribution, and large surface for heat transfer.
  • the length to diameter ratio is a useful parameter to determine preferred reactor configurations.
  • the diameter may be determined by velocity needed to avoid solids precipitation and then the length can be selected to provide the desired residence time.
  • Other reactor configurations known to those in the art can be used to achieve similar effects, such as a serpentine reactor.
  • the separation zone for removing solid and recovering hydrocarbon products is a vessel with a dip tube.
  • Other fluid - solid separation devices known in the art can be used to achieve the separation effect, which includes, but not limited to, cyclone, filter, ceramic membrane, settling tank, etc.
  • the mixer, reaction and separation zones are separated. Such arrangement is convenient for laboratory research, and is used as an illustrative example. It is within the scope of the present invention and in some applications will be beneficial to integrate these three functions into one vessel.
  • the reactor may include more than one piece of each function devices.
  • Figure 2 shows an example.
  • heavy hydrocarbon molecules are preferably surrounded by sufficient water molecules.
  • high water to oil ratio will be helpful to maintain the desired environment.
  • high water to oil ratio also means high equipment and operating cost.
  • the embodiment shown in Figure 2 can achieve high water to oil ratio locally without increasing overall water to feed ratio. Instead of mixing all the feed oil with water at reactor inlet, this embodiment uses multiple injections of oil to maintain a desired water to oil ratio. Such a design is also helpful to control reaction temperature. By distributing feed oil more uniformly through the reactor length, reaction temperature will not increase too much due to the exothermic nature of the reactions.
  • Figure 3 shows yet another embodiment with more than one mixing and reaction zones.
  • a second mixer which may or may not be the same as the first mixer, is added between reaction zone to enhance the oil/supercritical water mixing. Again, multiple mixers and reaction zones can be used.
  • the upgrading reaction is exothermic.
  • a reactor with a large surface area helps to maintain uniform temperature distribution inside the reactor. Depending on feed properties, heat exchange through the surface area provided by the reactor may or may not be enough. Water can be used to quench the reaction stream and thereby control the reaction temperature.
  • Figure 4 shows an embodiment of using water to quench the reaction stream between two reaction zones.
  • the amount of water used for quenching should be enough to bring down the reaction temperature while the reaction stream after quenching still maintain supercritical conditions. Multiple reaction zones and water quenching may be necessary for some feeds.
  • the quenching water can also be used to for product recovery, as shown in Figure 5. After reaction the product stream is quenched by liquid water. The solid will be washed out by the water, and due to the temperature reduction caused by quenching water and the hydrocarbons will condense as liquid.
  • a single phase reaction product is withdrawn from the reaction zone, cooled, and separated into gas, effluent water, and upgraded hydrocarbon phases.
  • This separation is preferably done by cooling the stream and using one or more two-phase separators, three- phase separators, or other gas-oil-water separation device known in the art.
  • any method of separation can be used in accordance with the invention.
  • composition of gaseous product obtained by treatment of the heavy hydrocarbons in accordance with the process of the present invention will depend on feed properties and typically comprises light hydrocarbons, water vapor, acid gas (CO ⁇ and H 2 S), methane and hydrogen.
  • the effluent water may be used, reused or discarded. It may be recycled to e.g. the feed water tank, the feed water treatment system or to the reaction zone.
  • the upgraded hydrocarbon product which is sometimes referred to as "syncrude” herein may be upgraded further or processed into other hydrocarbon products using methods that are known in the hydrocarbon processing art.
  • the process of the present invention may be carried out either as a continuous or semi-continuous process or a batch process or as a continuous process.
  • the entire system operates with a feed stream of oil and a separate feed stream of supercritical water and reaches a steady state; whereby all the flow rates, temperatures, pressures, and composition of the inlet, outlet, and recycle streams do not vary appreciably with time.
  • the exact pathway may depend on the reactor operating conditions (temperature, pressure, O/W volume ratio), reactor design (mode of contact/mixing, sequence of heating), and the hydrocarbon feedstock.
  • Oil and supercritical water are contacted in a mixer prior to entering the reactor.
  • the reactor is equipped with an inner tube for collecting the products (syncrude, excess water, and gas), and a bottom section where any metals or solids comprising a "dreg stream" of indeterminate properties or composition may accumulate.
  • the shell-side of the reactor is kept isothermal during the reaction with a clamshell furnace and temperature controller.
  • Preferred reactor residence times are 20-40 minutes, with preferred oil/water volume ratios on the order of 1 :3.
  • Preferred temperatures are around 374°- 400 0 C, with the pressure at 3200-4000 psig.
  • the reactor product stream leaves as a single phase, and is cooled and separated into gas, syncrude, and effluent water. The effluent water is recycled back to the reactor. Sulfur from the original feedstock accumulates in the dreg stream for the most part, with lesser amounts primarily in the form of H 2 S found in the gas phase and water phase.
  • Elimination of the dreg stream means that a greater degree of hydrocarbon is recovered as syncrude, but it also means that metals and sulfur will accumulate elsewhere, such as in the water and gas streams.
  • a Hamaca crude oil was diluted with a diluent hydrocarbon at a ratio of 5:1 (20 vol% of diluent).
  • the diluted Hamaca crude oil properties were measured before reacting it with the supercritical water process as referred to in Example 1 and Fig. 2.
  • the properties of the crude were as follows: 12.8 API gravity at 60/60; 1329 CST viscosity @40°C; 7.66 wt% C/H ratio; 13.04 wt% MCRT; 3.54 wt% sulfur; 0.56 wt% nitrogen; 3.05 mg KOH/gm acid number; 1.41 wt% water; 371 ppm Vanadium; and 86 ppm Nickel.
  • the diluted Hamaca crude oil after the super critical water treatment was converted into a syncrude with the following properties: 24.1 API gravity at 60/60; 5.75 CST viscosity @40°C; 7.40 wt% C/H ratio; 2.25 wt% MCRT; 2.83 wt% sulfur; 0.28 wt% nitrogen; 1.54 mg KOH/gm acid number; 0.96 wt% water; 24 ppm Vanadium; and 3 ppm Nickel.
  • Substantial reductions in metals and residues were observed, with simultaneous increase in the API gravity and a significant decrease in the viscosity of the original crude oil feedstock. There were modest reductions in the Total Acid number, sulfur concentration, and nitrogen concentration which could be improved with further optimization of the reaction conditions.
  • the product syncrude had the following properties: 14.0 API gravity at 60/60; 188 CST viscosity @40°C; 8.7 wt% MCRT; 3.11 wt% sulfur; 267 ppm Vanadium; and 59 ppm Nickel. This comparison demonstrates the importance of the heating sequence of the present invention.
  • Undiluted Boscan crude oil properties were measured before reacting it with the supercritical water process of the present invention.
  • the properties of the crude were as follows: 9 API gravity at 60/60; 1,140 CST viscosity @40°C; 8.0 wt% C/H ratio; 16 wt% MCRT; 5.8 wt% Sulfur; and 1 ,280 ppm Vanadium;.
  • the undiluted Boscan crude oil after the super critical water treatment was converted into a syncrude with the following properties: 22 API gravity at 60/60; 9 CST viscosity @40°C; 7.6 wt% C/H ratio; 2.5 wt% MCRT; 4.6% sulfur; and 130 ppm Vanadium.
  • a simulated distillation analysis of the original crude oil vs. the syncrude products from different experimental runs shows that the syncrude prepared in accordance with the present invention clearly has superior properties than the original crude.
  • the syncrudes contain a higher fraction of lower-boiling fractions. 51% of the diluted Hamaca crude boils across a range of temperatures of less than 1000 0 F, while employing a process according to the present invention using supercritical water depending on process configurations, between 79 to 94% of the syncrude boils across a range of temperatures of less than 1000°F.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un réacteur pour mettre en oeuvre un procédé qui utilise de l'eau supercritique pour valoriser une charge d'hydrocarbures lourds de façon à obtenir un produit hydrocarboné valorisé ou un pétrole brut de synthèse présentant des propriétés hautement recherchées (faible teneur en soufre, faible teneur en métaux, densité réduite (densité API accrue), viscosité réduite, teneur réduite en résidus, etc.). Ce réacteur peut fonctionner en mode continu, semi-continu ou discontinu et il est équipé de moyens permettant d'effectuer un transfert de quantité de mouvement, de chaleur et de masse entre l'intérieur et l'extérieur du réacteur et à l'intérieur du réacteur.
PCT/US2007/082992 2006-10-31 2007-10-30 Réacteur et procédé pour valoriser des hydrocarbures liquides lourds Ceased WO2008055152A1 (fr)

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CA002666390A CA2666390A1 (fr) 2006-10-31 2007-10-30 Reacteur et procede pour valoriser des hydrocarbures liquides lourds
EA200970437A EA200970437A1 (ru) 2006-10-31 2007-10-30 Реактор и способ повышения качества тяжелых углеводородных нефтей

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US11/555,211 2006-10-31
US11/555,211 US20080099374A1 (en) 2006-10-31 2006-10-31 Reactor and process for upgrading heavy hydrocarbon oils

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WO2008055152A1 true WO2008055152A1 (fr) 2008-05-08

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017106182A3 (fr) * 2015-12-15 2017-12-28 Saudi Arabian Oil Company Systèmes de réacteurs supercritiques et processus de valorisation de pétrole
US10011790B2 (en) 2015-12-15 2018-07-03 Saudi Arabian Oil Company Supercritical water processes for upgrading a petroleum-based composition while decreasing plugging
US10066172B2 (en) 2015-12-15 2018-09-04 Saudi Arabian Oil Company Supercritical water upgrading process to produce paraffinic stream from heavy oil
US10066176B2 (en) 2015-12-15 2018-09-04 Saudi Arabian Oil Company Supercritical water upgrading process to produce high grade coke
US10577546B2 (en) 2017-01-04 2020-03-03 Saudi Arabian Oil Company Systems and processes for deasphalting oil
US10815434B2 (en) 2017-01-04 2020-10-27 Saudi Arabian Oil Company Systems and processes for power generation

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7842181B2 (en) * 2006-12-06 2010-11-30 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
JP5269089B2 (ja) 2007-11-28 2013-08-21 サウジ アラビアン オイル カンパニー 熱加圧水によって高ワックス質原油をアップグレードする方法
US20090145808A1 (en) * 2007-11-30 2009-06-11 Saudi Arabian Oil Company Catalyst to attain low sulfur diesel
US8142646B2 (en) 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
WO2009105749A2 (fr) * 2008-02-21 2009-08-27 Saudi Arabian Oil Company Catalyseur pour parvenir à une essence à faible teneur en soufre
US20110003901A1 (en) * 2008-12-30 2011-01-06 Chevron U.S.A. Inc. Ft water treating and recovery
US8394260B2 (en) * 2009-12-21 2013-03-12 Saudi Arabian Oil Company Petroleum upgrading process
US8197670B2 (en) * 2010-02-23 2012-06-12 Chevron U.S.A. Inc. Process for upgrading hydrocarbons and device for use therein
US8444843B2 (en) 2010-04-15 2013-05-21 Saudi Arabian Oil Company Electrocatalytic dissociation of water for hydrodesulfurization of hydrocarbon feedstock
US9005432B2 (en) 2010-06-29 2015-04-14 Saudi Arabian Oil Company Removal of sulfur compounds from petroleum stream
US9382485B2 (en) * 2010-09-14 2016-07-05 Saudi Arabian Oil Company Petroleum upgrading process
US9039889B2 (en) 2010-09-14 2015-05-26 Saudi Arabian Oil Company Upgrading of hydrocarbons by hydrothermal process
US9051521B2 (en) * 2010-12-23 2015-06-09 Stephen Lee Yarbro Using supercritical fluids to refine hydrocarbons
US8894846B2 (en) * 2010-12-23 2014-11-25 Stephen Lee Yarbro Using supercritical fluids to refine hydrocarbons
US8535518B2 (en) 2011-01-19 2013-09-17 Saudi Arabian Oil Company Petroleum upgrading and desulfurizing process
EP2702121B1 (fr) * 2011-04-27 2019-04-10 Saudi Arabian Oil Company Craquage de sulfones en utilisant de l'eau supercritique
DK2908942T3 (da) * 2012-10-22 2020-11-16 Applied Res Associates Inc Højhastighedsreaktorsystem
US9914885B2 (en) * 2013-03-05 2018-03-13 Saudi Arabian Oil Company Process to upgrade and desulfurize crude oil by supercritical water
EP4570883A3 (fr) * 2014-01-20 2025-12-10 Applied Research Associates, Inc. Procédé de réduction de point d'écoulement à haut rendement
US9567530B2 (en) * 2014-11-26 2017-02-14 Saudi Arabian Oil Company Process for heavy oil upgrading in a double-wall reactor
US9802176B2 (en) 2015-03-24 2017-10-31 Saudi Arabian Oil Company Method for mixing in a hydrocarbon conversion process
CA2941568A1 (fr) 2015-08-31 2017-02-28 University Of New Brunswick Procede de valorisation de liquides d'hydrocarbure lourd
US9926497B2 (en) 2015-10-16 2018-03-27 Saudi Arabian Oil Company Method to remove metals from petroleum
JP6886480B2 (ja) 2016-07-08 2021-06-16 アプライド リサーチ アソシエーツ， インコーポレイテッド 超臨界水分離プロセス
US10106748B2 (en) 2017-01-03 2018-10-23 Saudi Arabian Oil Company Method to remove sulfur and metals from petroleum
US10752847B2 (en) 2017-03-08 2020-08-25 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US10703999B2 (en) 2017-03-14 2020-07-07 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
US11021659B2 (en) 2018-02-26 2021-06-01 Saudi Arabia Oil Company Additives for supercritical water process to upgrade heavy oil
US10526552B1 (en) 2018-10-12 2020-01-07 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process
CN111665164B (zh) * 2019-03-05 2023-07-18 中国石油化工股份有限公司 测定co2在油水间传质系数的实验装置、系统及方法
US10920158B2 (en) * 2019-06-14 2021-02-16 Saudi Arabian Oil Company Supercritical water process to produce bottom free hydrocarbons
US20210069732A1 (en) * 2019-09-09 2021-03-11 Xtrudx Technologies, Inc. Supercritical hydrocyclotron and related methods
US11124707B2 (en) 2019-12-17 2021-09-21 Saudi Arabian Oil Company Production of liquid hydrocarbons from polyolefins by supercritical water
US11162035B2 (en) * 2020-01-28 2021-11-02 Saudi Arabian Oil Company Catalytic upgrading of heavy oil with supercritical water
US11345861B2 (en) * 2020-06-22 2022-05-31 Saudi Arabian Oil Company Production of linear olefins from heavy oil
US11866447B2 (en) 2022-02-03 2024-01-09 Saudi Arabian Oil Company Reactive deasphalting process
CN114561229A (zh) * 2022-02-28 2022-05-31 中海油天津化工研究设计院有限公司 一种节能的超临界水改质油品的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3353924A (en) * 1965-07-16 1967-11-21 Shell Oil Co Bed reactor with quench deck
US4402709A (en) * 1982-04-27 1983-09-06 Texaco Inc. Simultaneous production of clean dewatered and clean saturated streams of synthesis gas
US5914031A (en) * 1994-12-06 1999-06-22 L'electrolyse Process in a reducing medium of chemically transforming complex chemical structures in a supercritical fluid
US6887369B2 (en) * 2001-09-17 2005-05-03 Southwest Research Institute Pretreatment processes for heavy oil and carbonaceous materials
US20050167333A1 (en) * 2004-01-30 2005-08-04 Mccall Thomas F. Supercritical Hydrocarbon Conversion Process

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948755A (en) * 1974-05-31 1976-04-06 Standard Oil Company Process for recovering and upgrading hydrocarbons from oil shale and tar sands
US4005005A (en) * 1974-05-31 1977-01-25 Standard Oil Company (Indiana) Process for recovering and upgrading hydrocarbons from tar sands
US3988238A (en) * 1974-07-01 1976-10-26 Standard Oil Company (Indiana) Process for recovering upgraded products from coal
US3948754A (en) * 1974-05-31 1976-04-06 Standard Oil Company Process for recovering and upgrading hydrocarbons from oil shale and tar sands
US3960706A (en) * 1974-05-31 1976-06-01 Standard Oil Company Process for upgrading a hydrocarbon fraction
ZA753184B (en) * 1974-05-31 1976-04-28 Standard Oil Co Process for recovering upgraded hydrocarbon products
US3989618A (en) * 1974-05-31 1976-11-02 Standard Oil Company (Indiana) Process for upgrading a hydrocarbon fraction
US3983027A (en) * 1974-07-01 1976-09-28 Standard Oil Company (Indiana) Process for recovering upgraded products from coal
US4528100A (en) * 1983-10-31 1985-07-09 General Electric Company Process for producing high yield of gas turbine fuel from residual oil
US4557820A (en) * 1984-05-24 1985-12-10 The Standard Oil Company Conversion of high boiling organic materials to low boiling materials
US4559127A (en) * 1984-05-24 1985-12-17 The Standard Oil Company Conversion of high boiling organic materials to low boiling materials
US4594141A (en) * 1984-12-18 1986-06-10 The Standard Oil Company Conversion of high boiling organic materials to low boiling materials
US4840725A (en) * 1987-06-19 1989-06-20 The Standard Oil Company Conversion of high boiling liquid organic materials to lower boiling materials
US5252224A (en) * 1991-06-28 1993-10-12 Modell Development Corporation Supercritical water oxidation process of organics with inorganics
US5384051A (en) * 1993-02-05 1995-01-24 Mcginness; Thomas G. Supercritical oxidation reactor
CA2143404C (fr) * 1994-03-09 1999-05-04 Michael Siskin Methode pour eliminer les heteroatomes en milieu reducteur, dans de l'eau sous des conditions supercritiques
US5560823A (en) * 1994-12-21 1996-10-01 Abitibi-Price, Inc. Reversible flow supercritical reactor and method for operating same
US5567698A (en) * 1995-02-15 1996-10-22 Bristol-Myers Squibb Company Pyridinium thiomethyl substituted chepholosporin derivatives
JP3366820B2 (ja) * 1997-02-19 2003-01-14 株式会社日立製作所 酸化処理方法とその装置及び反応容器
CA2432160C (fr) * 2001-01-09 2010-04-13 Bj Services Company Compositions fluides de traitement de puits et procedes d'utilisation de celles-ci
JP3724438B2 (ja) * 2002-03-08 2005-12-07 株式会社日立製作所 超臨界水による重質油の処理方法と処理装置及び重質油処理装置を備えた発電システム
US6887389B2 (en) * 2002-10-23 2005-05-03 Wendell Judd Method and apparatus for recycling sewage sludge utilizing spent water-softener lime

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3353924A (en) * 1965-07-16 1967-11-21 Shell Oil Co Bed reactor with quench deck
US4402709A (en) * 1982-04-27 1983-09-06 Texaco Inc. Simultaneous production of clean dewatered and clean saturated streams of synthesis gas
US5914031A (en) * 1994-12-06 1999-06-22 L'electrolyse Process in a reducing medium of chemically transforming complex chemical structures in a supercritical fluid
US6887369B2 (en) * 2001-09-17 2005-05-03 Southwest Research Institute Pretreatment processes for heavy oil and carbonaceous materials
US20050167333A1 (en) * 2004-01-30 2005-08-04 Mccall Thomas F. Supercritical Hydrocarbon Conversion Process

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10384179B2 (en) 2015-12-15 2019-08-20 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
US10543468B2 (en) 2015-12-15 2020-01-28 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
US10011790B2 (en) 2015-12-15 2018-07-03 Saudi Arabian Oil Company Supercritical water processes for upgrading a petroleum-based composition while decreasing plugging
US10066172B2 (en) 2015-12-15 2018-09-04 Saudi Arabian Oil Company Supercritical water upgrading process to produce paraffinic stream from heavy oil
US10066176B2 (en) 2015-12-15 2018-09-04 Saudi Arabian Oil Company Supercritical water upgrading process to produce high grade coke
US10119081B2 (en) 2015-12-15 2018-11-06 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
US9920258B2 (en) 2015-12-15 2018-03-20 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
EP3415227A1 (fr) * 2015-12-15 2018-12-19 Saudi Arabian Oil Company Systèmes de réacteurs supercritiques et processus de valorisation de pétrole
WO2017106182A3 (fr) * 2015-12-15 2017-12-28 Saudi Arabian Oil Company Systèmes de réacteurs supercritiques et processus de valorisation de pétrole
US10344228B2 (en) 2015-12-15 2019-07-09 Saudi Arabian Oil Company Supercritical water upgrading process to produce high grade coke
US11021660B2 (en) 2015-12-15 2021-06-01 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
US10640715B2 (en) 2015-12-15 2020-05-05 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
US10995281B2 (en) 2015-12-15 2021-05-04 Saudi Arabian Oil Company Supercritical reactor systems and processes for petroleum upgrading
EP3415228B1 (fr) * 2015-12-15 2020-11-11 Saudi Arabian Oil Company Systèmes de réacteurs supercritiques et processus de valorisation de pétrole
US10815434B2 (en) 2017-01-04 2020-10-27 Saudi Arabian Oil Company Systems and processes for power generation
US10577546B2 (en) 2017-01-04 2020-03-03 Saudi Arabian Oil Company Systems and processes for deasphalting oil

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