Patent Application
20250059453
Embodiments of the present disclosure generally relate to upgrading petroleum-based compositions, and more specifically relate to supercritical reactor systems, methods, and uses for upgrading petroleum-based compositions via deep de-sulfurization.
Petroleum is an important source of energy; however, most petroleum is heavy petroleum, meaning that is contains a high amount of impurities, such as sulfur, asphaltenes, or, eventually, coke. Therefore, heavy petroleum is often upgraded before it can be used as a commercially available product. Supercritical water has been shown to be an effective reaction medium for heavy petroleum upgrading without requiring an external supply or feed of hydrogen because supercritical water reactions are highly selective towards breaking heavy fractions to produce upgraded products without generating coke.
Sulfur is the most abundant heteroatom in hydrocarbon oils, specifically the sour type, bituminous type, and residual. Current environmental regulations mandate extreme sulfur reduction in hydrocarbon oils. In hydrocarbon oils, sulfur typically exists as organic sulfur but could also exist as elemental and di-hydrogen sulfide to a minor extent. The types of organic sulfur species that are present in hydrocarbon oils are classified as mercaptans, sulfides, disulfides, thiophenes, dibenzothiophenes, benzothiophenes, and substituted dibenzothiophenes. Of the sulfur species present, the most difficult to remove are the dibenzothiophenes and substituted dibenzothiophenes, which are commonly referred to as refractory sulfur compounds. Refractory sulfur compounds form clusters of polyaromatic-sulfurous compounds in the heavy fractions of the hydrocarbon oils and are termed polycyclic aromatic sulfur heterocycles (PASH), generally having a molecular weight in the range of 250 to 310 g/mol.
PASH species are very difficult to remove due to their complexity and stability. The refractory nature of these sulfur compounds pose limitations for effective heat and mass transfer. Therefore, the possibility of removing these sulfur species would conventionally require a deep hydrotreating process with severe operating conditions facilitated by high hydrogen partial pressures, high hydrogen consumption, and frequent catalyst replacement or regeneration.
Traditionally, the reduction of sulfur species in hydrocarbon oils requires deep hydrotreating that requires catalyst and high hydrogen partial pressures to effectively treat the oils. These processes have a high operating cost due to the required high hydrogen partial pressures and catalysts utilization and replacement/regeneration. On its own, oil produced through upgrading by supercritical water contains olefinic and heavy aromatic components that compromise oil stability. Embodiments described herein utilize the synergy between the benefits of mild hydrogenation and the hydrothermal effect of supercritical water to upgrade and desulfurize oils without requiring high hydrogen partial pressures and without the need for a catalyst.
The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, in which:
Embodiments of the present disclosure are directed to processes for upgrading hydrocarbon streams in a supercritical water hydrogenation reactor in combination with a mild hydrotreating step for improved deep-desulfurization of hydrocarbon streams.
As used throughout the disclosure, “supercritical” refers to a substance at or above a pressure and a temperature greater than or equal to that of its critical pressure and temperature, such that distinct phases do not exist and the substances may exhibit the fast diffusion of a gas while dissolving materials like liquid. As such, supercritical water (ScW) is water having a temperature and pressure greater than or equal to the critical temperature and the critical pressure of water. At a temperature and pressure greater than or equal to the critical temperature and pressure, the liquid and gas phase boundary of water disappears, and the fluid has characteristics of both liquid and gaseous substances. Supercritical water is able to dissolve organic compounds like an organic solvent and has excellent diffusibility like a gas. Regulation of the temperature and pressure allows for continuous “tuning” of the properties of the supercritical water to be more liquid-like or more gas-like. Supercritical water has reduced density and lesser polarity, as compared to liquid-phase subcritical water, thereby greatly extending the possible range of chemistry that can be carried out in water. Water above its critical condition is neither a liquid nor gas but a single fluid phase that converts from being polar to non-polar.
As used throughout this disclosure, “upgrade” means to increase the API gravity, decrease the amount of impurities, such as sulfur, nitrogen, and metals, decrease the amount of asphaltene, and increase the amount of the light fraction. Supercritical water has various unexpected properties as it reaches supercritical boundaries. Supercritical water has very high solubility toward organic compounds and has an infinite miscibility with gases. Furthermore, radical species can be stabilized by supercritical water through the cage effect (that is, a condition whereby one or more water molecules surrounds the radical species, which then prevents the radical species from interacting). Without being limited to theory, stabilization of radical species helps prevent inter-radical condensation and thereby reduces the overall coke production in the embodiments disclosed and described herein. For example, coke production can be the result of the inter-radical condensation. In certain embodiments, supercritical water generates hydrogen gas through a steam reforming reaction and water-gas shift reaction, which is then available for the upgrading reactions.
Moreover, the high temperature and high pressure of supercritical water may give supercritical water a density of 0.123 grams per milliliter (g/mL) at 27 MPa and 450° C. Contrastingly, if the pressure was reduced to produce super-heated steam, for example, at 20 MPa and 450° C., the superheated steam would have a density of only 0.079 g/mL. At that density, the hydrocarbons may interact with the super-heated steam to evaporate and mix into the vapor phase, leaving behind a heavy fraction that may generate coke upon heating. The formation of coke or coke precursor may plug the lines and must be removed. Therefore, supercritical water is superior to steam in some applications.
Specific embodiments will now be described with reference
The hydrocarbon-based composition 105 may refer to any hydrocarbon source derived from petroleum, coal liquid, or biomaterials. Possible sources for hydrocarbon-based composition may include crude oil, distilled crude oil, reduced crude oil, residue oil, topped crude oil, product streams from oil refineries, product streams from steam cracking processes, liquefied coals, liquid products recovered from oil or tar sands, bitumen, oil shale, asphaltene, biomass hydrocarbons, and the like. Many compositions are suitable for the hydrocarbon-based composition. In some embodiments, the hydrocarbon-based composition 105 may comprise heavy crude oil or a fraction of heavy crude oil. In other embodiments, the hydrocarbon-based composition 105 may include atmospheric residue (AR), atmospheric distillates, vacuum gas oil (VGO), vacuum distillates, or vacuum residue (VR), or cracked product (such as light cycle oil or coker gas oil). In some embodiments, the hydrocarbon-based composition may be combined streams from a refinery, produced oil, or other hydrocarbon streams, such as from an upstream operation. The hydrocarbon-based composition 105 may be decanted oil, oil containing 10 or more carbons (C10+ oil), or hydrocarbon streams from an ethylene plant. The hydrocarbon-based composition 105 may, in some embodiments, be liquefied coal or biomaterial-derivatives, such as bio fuel oil. In some embodiments, used lubrication (lube) oil or brake fluids may be used.
The hydrocarbon-based composition 105 may, in some embodiments, be naphtha or kerosene or diesel fractions. Such fractions may be used but may not be upgraded as efficiently by the supercritical water. Contaminated hydrocarbon fractions may also be used. In some embodiments, fractions with saltwater contamination may be used as the hydrocarbon-based composition 105. For instance, crude oil in market typically has a salt content below about 10 PTB (pounds of salt per 1000 barrels of oil). The salt in saltwater may be precipitated by the supercritical water to produce a desalted product, which may be desirable in some embodiments.
The hydrocarbon-based composition 105 may have a T5 true boiling point (TPB) of less than 500° C. of less than 450° C., of less than 400° C., of less than 380° C., or of less than 370° C. In embodiments, the hydrocarbon-based composition 105 may have a T5 TBP of from 351° C. to 500° C., from 375° C. to 500° C., from 400° C. to 500° C., from 425° C. to 500° C., from 450° C. to 500° C., from 475° C. to 500° C., from 351° C. to 475° C., from 375° C. to 475° C., from 400° C. to 475° C. from 425° C. to 475° C., from 450° C. to 475° C. from 351° C. to 450° C., from 375° C. to 450° C. from 400° C. to 450° C. from 425° C. to 450° C., from 351° C. to 425° C., from 375° C. to 425° C., from 400° C. to 425° C., from 351° C. to 400° C., from 375° C. to 400° C., or from 351° C. to 375° C.
The hydrocarbon-based composition 105 may have a T90 TPB of less than or equal to 750° C., less than or equal to 700° C., or less than or equal to 650° C. In embodiments, the hydrocarbon-based composition 105 may have a T90 TPB from 601° C. to 750° C., from 625° C. to 750° C., from 650° C. to 750° C., from 675° C. to 750° C., from 700° C. to 750° C., from 725° C. to 750° C., from 601° C. to 725° C. from 625° C. to 725° C. from 650° C. to 725° C., from 675° C. to 725° C., from 700° C. to 725° C. from 601° C. to 700° C. from 625° C. to 700° C., from 650° C. to 700° C., from 675° C. to 700° C. from 601° C. to 675° C., from 625° C. to 675° C. from 650° C. to 675° C., from 601° C. to 650° C., from 625° C. to 650° C., or from 601° C. to 625° C. It should be understood that the T90 TPB is greater than the T5 TPB previously described.
The hydrocarbon-based composition 105 may have an API gravity from 5° to 11°, from 6° to 11°, from 7° to 11°, from 8° to 11°, from 9° to 11°, from 10° to 11°, from 5° to 10°, from 6° to 10°, from 7° to 10°, from 8° to 10°, from 9° to 10°, from 5° to 9°, from 6° to 9°, from 7° to 9°, from 8° to 9°, from 5° to 8°, from 6° to 8°, from 7° to 8°, from 5° to 7°, from 6° to 7°, or from 5° to 6°.
The hydrocarbon-based composition 105 may include greater than 2.1 weight percent (wt. %) or greater than 2.7 wt. % total sulfur content by weight of the hydrocarbon-based composition 105. In embodiments, the hydrocarbon-based composition 105 may include from 2.1 wt. % to 5.0 wt. %, from 2.3 wt. % to 5.0 wt. %, from 2.5 wt. % to 5.0 wt. %, from 2.7 wt. % to 5.0 wt. %, from 3.0 wt. % to 5.0 wt. %, from 3.3 wt. % to 5.0 wt. %, from 3.5 wt. % to 5.0 wt. %, from 3.7 wt. % to 5.0 wt. %, from 4.0 wt. % to 5.0 wt. %, from 4.3 wt. % to 5.0 wt. %, from 4.5 wt. % to 5.0 wt. %, from 4.7 wt. % to 5.0 wt. %, from 2.1 wt. % to 4.7 wt. %, from 2.3 wt. % to 4.7 wt. %, from 2.5 wt. % to 4.7 wt. %, from 2.7 wt. % to 4.7 wt. %, from 3.0 wt. % to 4.7 wt. %, from 3.3 wt. % to 4.7 wt. %, from 3.5 wt. % to 4.7 wt. %, from 3.7 wt. % to 4.7 wt. %, from 4.0 wt. % to 4.7 wt. %, from 4.3 wt. % to 4.7 wt. %, from 4.5 wt. % to 4.7 wt. %, from 2.1 wt. % to 4.5 wt. %, from 2.3 wt. % to 4.5 wt. %, from 2.5 wt. % to 4.5 wt. %, from 2.7 wt. % to 4.5 wt. %, from 3.0 wt. % to 4.5 wt. %, from 3.3 wt. % to 4.5 wt. %, from 3.5 wt. % to 4.5 wt. %, from 3.7 wt. % to 4.5 wt. %, from 4.0 wt. % to 4.5 wt. %, from 4.3 wt. % to 4.5 wt. %, from 2.1 wt. % to 4.3 wt. %, from 2.3 wt. % to 4.3 wt. %, from 2.5 wt. % to 4.3 wt. %, from 2.7 wt. % to 4.3 wt. %, from 3.0 wt. % to 4.3 wt. %, from 3.3 wt. % to 4.3 wt. %, from 3.5 wt. % to 4.3 wt. %, from 3.7 wt. % to 4.3 wt. %, from 4.0 wt. % to 4.3 wt. %, from 2.1 wt. % to 4.0 wt. %, from 2.3 wt. % to 4.0 wt. %, from 2.5 wt. % to 4.0 wt. %, from 2.7 wt. % to 4.0 wt. %, from 3.0 wt. % to 4.0 wt. %, from 3.3 wt. % to 4.0 wt. %, from 3.5 wt. % to 4.0 wt. %, from 3.7 wt. % to 4.0 wt. %, from 2.1 wt. % to 3.7 wt. %, from 2.3 wt. % to 3.7 wt. %, from 2.5 wt. % to 3.7 wt. %, from 2.7 wt. % to 3.7 wt. %, from 3.0 wt. % to 3.7 wt. %, from 3.3 wt. % to 3.7 wt. %, from 3.5 wt. % to 3.7 wt. %, from 2.1 wt. % to 3.5 wt. %, from 2.3 wt. % to 3.5 wt. %, from 2.5 wt. % to 3.5 wt. %, from 2.7 wt. % to 3.5 wt. %, from 3.0 wt. % to 3.5 wt. %, from 3.3 wt. % to 3.5 wt. %, from 2.1 wt. % to 3.3 wt. %, from 2.3 wt. % to 3.3 wt. %, from 2.5 wt. % to 3.3 wt. %, from 2.7 wt. % to 3.3 wt. %, from 3.0 wt. % to 3.3 wt. %, from 2.1 wt. % to 3.0 wt. %, from 2.3 wt. % to 3.0 wt. %, from 2.5 wt. % to 3.0 wt. %, from 2.7 wt. % to 3.0 wt. %, from 2.1 wt. % to 2.7 wt. %, from 2.3 wt. % to 2.7 wt. %, from 2.5 wt. % to 2.7 wt. %, from 2.1 wt. % to 2.5 wt. %, from 2.3 wt. % to 2.5 wt. %, or from 2.1 wt. % to 2.3 wt. % total sulfur content by weight of the hydrocarbon-based composition 105.
The hydrocarbon-based composition 105 may include greater than 0.51 wt. % or greater than 0.9 wt. % total nitrogen content by weight of the hydrocarbon-based composition 105. In embodiments, the hydrocarbon-based composition 105 may include from 0.51 wt. % to 2.00 wt. %, from 0.75 wt. % to 2.00 wt. %, from 1.00 wt. % to 2.00 wt. %, from 1.25 wt. % to 2.00 wt. %, from 1.50 wt. % to 2.00 wt. %, from 1.75 wt. % to 2.00 wt. %, from 0.51 wt. % to 1.75 wt. %, from 0.75 wt. % to 1.75 wt. %, from 1.00 wt. % to 1.75 wt. %, from 1.25 wt. % to 1.75 wt. %, from 1.50 wt. % to 1.75 wt. %, from 0.51 wt. % to 1.50 wt. %, from 0.75 wt. % to 1.50 wt. %, from 1.00 wt. % to 1.50 wt. %, from 1.25 wt. % to 1.50 wt. %, from 0.51 wt. % to 1.25 wt. %, from 0.75 wt. % to 1.25 wt. %, from 1.00 wt. % to 1.25 wt. %, from 0.51 wt. % to 1.00 wt. %, from 0.75 wt. % to 1.00 wt. %, from 0.51 wt. % to 0.75 wt. % total nitrogen content by weight of the hydrocarbon-based composition 105.
The hydrocarbon-based composition 105 may include greater than 0.51 wt. % or greater than 1.00 wt. % asphaltene (heptane-insoluble) by weight of the hydrocarbon-based composition 105. In embodiments, the hydrocarbon-based composition 105 may include from 0.51 wt. % to 2.0 wt. %, from 0.75 wt. % to 2.00 wt. %, from 1.00 wt. % to 2.00 wt. %, from 1.25 wt. % to 2.00 wt. %, from 1.50 wt. % to 2.00 wt. %, from 1.75 wt. % to 2.00 wt. %, from 0.51 wt. % to 1.75 wt. %, from 0.75 wt. % to 1.75 wt. %, from 1.00 wt. % to 1.75 wt. %, from 1.25 wt. % to 1.75 wt. %, from 1.50 wt. % to 1.75 wt. %, from 0.51 wt. % to 1.50 wt. %, from 0.75 wt. % to 1.50 wt. %, from 1.00 wt. % to 1.50 wt. %, from 1.25 wt. % to 1.50 wt. %, from 0.51 wt. % to 1.25 wt. %, from 0.75 wt. % to 1.25 wt. %, from 1.00 wt. % to 1.25 wt. %, from 0.51 wt. % to 1.00 wt. %, from 0.75 wt. % to 1.00 wt. %, from 0.51 wt. % to 0.75 wt. % asphaltene (heptane-insoluble) by weight of the hydrocarbon-based composition 105.
The hydrocarbon-based composition 105 may include greater than 5 parts per million (ppm) or greater than 6 ppm metals. In embodiments, the metals may be vanadium, nickel, or both. In embodiments, the hydrocarbon-based composition may include from 5 ppm to 100 ppm, from 10 ppm to 100 ppm, from 20 ppm to 100 ppm, from 40 ppm to 100 ppm, from 60 ppm to 100 ppm, from 80 ppm to 100 ppm, from 83 ppm to 100 ppm, from 90 ppm 100 ppm, from 5 ppm to 90 ppm, from 10 ppm to 90 ppm, from 20 ppm to 90 ppm, from 40 ppm to 90 ppm, from 60 ppm to 90 ppm, from 80 ppm to 90 ppm, from 83 ppm to 90 ppm, from 5 ppm to 83 ppm, from 10 ppm to 83 ppm, from 20 ppm to 83 ppm, from 40 ppm to 83 ppm, from 60 ppm to 83 ppm, from 80 ppm to 83 ppm, from 5 ppm to 80 ppm, from 10 ppm to 80 ppm, from 20 ppm to 80 ppm, from 40 ppm to 80 ppm, from 60 ppm to 80 ppm, from 5 ppm to 60 ppm, from 10 ppm to 60 ppm, from 20 ppm to 60 ppm, from 40 ppm to 60 ppm, from 5 ppm to 40 ppm, from 10 ppm to 40 ppm, from 20 ppm to 40 ppm, from 5 ppm to 20 ppm, from 10 ppm to 20 ppm, or from 5 ppm to 10 ppm metals.
The hydrocarbon-based composition 105 may have a viscosity at 50° C. of greater than 100 centiStokes (cSt) or greater than 500 cSt. In embodiments, the hydrocarbon-based composition 105 may have a viscosity at 50° C. from 101 cSt to 700 cSt, from 150 cSt to 700 cSt, from 200 cSt to 700 cSt, from 250 cSt to 700 cSt, from 300 cSt to 700 cSt, from 350 cSt to 700 cSt, from 400 cSt to 700 cSt, from 450 cSt to 700 cSt, from 500 cSt to 700 cSt, from 550 cSt to 700 cSt, from 600 cSt to 700 cSt, from 650 cSt to 700 cSt, from 101 cSt to 650 cSt, from 150 cSt to 650 cSt, from 200 cSt to 650 cSt, from 250 cSt to 650 cSt, from 300 cSt to 650 cSt, from 350 cSt to 650 cSt, from 400 cSt to 650 cSt, from 450 cSt to 650 cSt, from 500 cSt to 650 cSt, from 550 cSt to 650 cSt, from 600 cSt to 650 cSt, from 101 cSt to 600 cSt, from 150 cSt to 600 cSt, from 200 cSt to 600 cSt, from 250 cSt to 600 cSt, from 300 cSt to 600 cSt, from 350 cSt to 600 cSt, from 400 cSt to 600 cSt, from 450 cSt to 600 cSt, from 500 cSt to 600 cSt, from 550 cSt to 600 cSt, from 101 cSt to 550 cSt, from 150 cSt to 550 cSt, from 200 cSt to 550 cSt, from 250 cSt to 550 cSt, from 300 cSt to 550 cSt, from 350 cSt to 550 cSt, from 400 cSt to 550 cSt, from 450 cSt to 550 cSt, from 500 cSt to 550 cSt, from 101 cSt to 500 cSt, from 150 cSt to 500 cSt, from 200 cSt to 500 cSt, from 250 cSt to 500 cSt, from 300 cSt to 500 cSt, from 350 cSt to 500 cSt, from 400 cSt to 500 cSt, from 450 cSt to 500 cSt, from 101 cSt to 450 cSt, from 150 cSt to 450 cSt, from 200 cSt to 450 cSt, from 250 cSt to 450 cSt, from 300 cSt to 450 cSt, from 350 cSt to 450 cSt, from 400 cSt to 450 cSt, from 101 cSt to 400 cSt, from 150 cSt to 400 cSt, from 200 cSt to 400 cSt, from 250 cSt to 400 cSt, from 300 cSt to 400 cSt, from 350 cSt to 400 cSt, from 101 cSt to 350 cSt, from 150 cSt to 350 cSt, from 200 cSt to 350 cSt, from 250 cSt to 350 cSt, from 300 cSt to 350 cSt, from 101 cSt to 300 cSt, from 150 cSt to 300 cSt, from 200 cSt to 300 cSt, from 250 cSt to 300 cSt, from 101 cSt to 250 cSt, from 150 cSt to 250 cSt, from 200 cSt to 250 cSt, from 101 cSt to 200 cSt, from 150 cSt to 200 cSt, or from 101 cSt to 150 cSt.
As shown in
The pressurized hydrocarbon-based composition 116 may then be heated in one or more hydrocarbon pre-heaters 120 to form pressurized, heated hydrocarbon-based composition 124. In one embodiment, the pressurized, heated hydrocarbon-based composition 124 has a pressure greater than the critical pressure of water and a temperature greater than the critical pressure of 75° C. Alternatively, the temperature of the pressurized, heated hydrocarbon-based composition 124 is between 10° C. and 300° C., or between 50° C. and 250° C., or between 75° C. and 225° C. or between 100° C. and 200° C., or between 125° C. and 175° C., or between 140° C. and 160° C. According to embodiments, the pressurized, heated hydrocarbon-based composition 124 should not be heated above about 350° C., and in some embodiments, the pressurized, heated hydrocarbon-based composition should not be heated above 300° C. to avoid the formation of coking products. See Hozuma, U.S. Pat. No. 4,243,633, which is incorporated by reference in its entirety. While some coke or coke precursor products may be able to pass through process lines without slowing or stopping the process 100, the formation of these potentially problematic compounds should be avoided if possible.
Embodiments of the hydrocarbon pre-heater 120 may include a natural gas fired heater, heat exchanger, or an electric heater or any type of heater known in the art. In some embodiments, not shown, the pressurized, heated hydrocarbon-based composition 124 may be heated in a double pipe heat exchanger. For example, and not by way of limitation, the double pipe heat exchanger may heat the pressurized, heated hydrocarbon-based composition 124 after it has combined with a heated water stream 126 and/or a heated hydrogen stream 129 to form a combined feed stream 132.
The water stream 110 may be any source of water, such as a water stream having conductivity of less than 1 microSiemens (μS)/centimeters (cm), such as less than 0.1 μS. The water stream 110 may also include demineralized water, distilled water, boiler feed water (BFW), and deionized water. In at least one embodiment, water stream 110 is a boiler feed water stream. Water stream 110 is pressurized by water pump 114 to produce pressurized water stream 118. The pressure of the pressurized water stream 118 is at least 22.1 MPa, which is approximately the critical pressure of water. Alternatively, the pressure of the pressurized water stream 118 may be between 23 MPa and 35 MPa, or between 24 MPa and 30 MPa. For instance, the pressure of the pressurized water stream 118 may be between 25 MPa and 29 MPa, 26 MPa and 28 MPa, 25 MPa and 30 MPa, 26 MPa and 29 MPa, or 24 MPa and 28 MPa.
The pressurized water streams 118, 218, and 318 may then be heated in a water pre-heater 122 to create heated water stream 126. According to embodiments, the temperature of the heated water stream 126 is greater than 100° C. In embodiments, the temperature of the heated water stream 126 may be from 100° C. to 370° C., from 100° C. to 350° C., from 100° C. to 300° C. from 100° C. to 250° C. from 100° C. to 200° C., from 100° C. to 150° C., from 150° C. to 370° C. from 150° C. to 350° C., from 150° C. to 300° C. from 150° C. to 250° C. from 150° C. to 200° C. from 200° C. to 370° C., from 200° C. to 350° C., from 200° C. to 300° C., from 200° C. to 250° C., from 250° C. to 370° C., from 250° C. to 350° C., from 250° C. to 300° C. from 300° C. to 370° C. from 300° C. to 350° C., or from 350° C. to 370° C.
Similar to hydrocarbon pre-heater 120, suitable water pre-heaters 122 may include a natural gas fired heater, a heat exchanger, and an electric heater. The water pre-heater 122 may be a unit separate and independent from the hydrocarbon pre-heater 120.
The hydrogen stream 127 may be any source of hydrogen. The hydrogen stream 127 may be heated in a hydrogen pre-heater 128 to create heated hydrogen stream 129. According to embodiments, the temperature of the heated hydrogen stream 129 is greater than 100° C. In embodi-ments, the temperature of the heated hydrogen stream 129 may be from 100° C. to 370° C., from 100° C. to 350° C., from 100° C. to 300° C., from 100° C. to 250° C., from 100° C. to 200° C. from 100° C. to 150° C., from 150° C. to 370° C., from 150° C. to 350° C., from 150° C. to 300° C., from 150° C. to 250° C., from 150° C. to 200° C., from 200° C. to 370° C., from 200° C. to 350° C., from 200° C. to 300° C., from 200° C. to 250° C., from 250° C. to 370° C., from 250° C. to 350° C., from 250° C. to 300° C., from 300° C. to 370° C., from 300° C. to 350° C., or from 350° C. to 370° C.
Similar to hydrocarbon pre-heater 120 and water preheater 122, suitable hydrogen pre-heaters 128 may include a natural gas fired heater, a heat exchanger, and an electric heater. The hydrogen pre-heater 128 may be a unit separate and independent from the hydrocarbon pre-heater 120 and the water pre-heater 122.
The heated water stream 126, the heated hydrogen stream 129, and the pressurized, heated hydrocarbon-based composition 124 may then be mixed in a feed mixer 130 to produce a combined feed stream 132. The feed mixer 130 can be any type of mixing device capable of mixing the heated water stream 126 and the pressurized, heated hydrocarbon-based composition 124. In embodiments, the feed mixer 130 may be a mixing tec. The feed mixer 130 may be an ultrasonic device, a small continuous stir tank reactor (CSTR), or any suitable mixer. The volumetric flow ratio of each component fed to the feed mixer 130 may vary. It should also be understood that in one or more embodiments, which are not shown, multiple feed mixers may be used to individually mix the pressurized, heated hydrocarbon-based composition 124, the heated hydrogen stream 129, and the heated water stream 126 in any combination. In embodiments, the volumetric flow ratio of the heated hydrocarbon-based composition 124 to the heated water stream 126 may be from 1:10 to 1:1, from 1:10 to 1:5, from 1:10 to 1:2, from 1:5 to 1:1, from 1:5 to 1:2, or from 1:2 to 1:1 at standard ambient temperature and ambient pressure (SATP). In embodiments it is desirable that the volumetric flow rate of water is greater than the volumetric flow rate of hydrocarbons. Without being bound by any particular theory, it is believed that heavy oils such as residual and bituminous types are rich in fractions that contain asphaltenes and heavy polycondensed aromatic molecules. These fractions yield a high viscosity. Mixing hot compressed water, such as supercritical water, reduces the viscosity and improves the oil's mobility through the developed mixed oil/water phase. Therefore, having a water flow rate that is higher than an oil flow rate improves the mixture mobility especially for highly viscous oils. Furthermore, increasing the water-to-oil ratio improves the caging effect of water molecules surrounding the asphaltenic and polycondensed aromatic molecules and increases the distance between them to prevent their propagation and association. In embodiments, the hydrogen-to-oil volumetric flow can be from 10 to 5000 cubic feet of heated hydrogen stream 129 to one barrel of heated hydrocarbon-based composition 124, at SATP.
The combined feed stream 132 may then be introduced to the supercritical water hydrogenation reactor 150 that is configured to upgrade the combined feed stream 132. The supercritical water hydrogenation reactor 150 may be an upflow, downflow, or horizontal flow reactor. An upflow, downflow or horizontal reactor refers to the direction the supercritical water and hydrocarbon-based composition flow through the supercritical water hydrogenation reactor 150. An upflow, downflow, or horizontal flow reactor may be chosen based on the desired application and system configuration. Without intending to be bound by any theory, in downflow supercritical reactors, heavy hydrocarbon fractions may flow very quickly due to having a greater density, which may result in shortened residence times (known as channeling). This may hinder upgrading, as there is less time for reactions to occur. Upflow supercritical reactors have a uniform increased residence time distribution (no channeling), but may experience difficulties due to undissolved portion of heavy fraction and large particles, such as carbon-containing compounds in the heavy fractions, accumulating in the bottom of the reactor. This accumulation may hinder the upgrading process and plug the reactor. Upflow reactors typically utilize catalysts to provide increased contact with the reactants; however, the catalysts may break down due to the harsh conditions of supercritical water, forming insoluble aggregates, which may generate coke. Horizontal reactors may be useful in applications that desire phase separation or that seck to reduce pressure drop, however; the control of hydrodynamics of internal fluid is difficult. Each type of reactor flow has positive and negative attributes that vary based on the applicable process; however, in some embodiments, an upflow or downflow reactor may be favored.
The supercritical water hydrogenation reactor 150 may operate at a temperature greater than the critical temperature of water and a pressure greater than the critical pressure of water. In one or more embodiments, the supercritical water hydrogenation reactor 150 may have a temperature of between 380° C. to 480° C., or between 390° C. to 450° C. The supercritical water hydrogenation reactor 150 may be an isothermal or non-isothermal reactor. The reactor may be a tubular-type vertical reactor, a tubular-type horizontal reactor, a vessel-type reactor, a tank-type reactor having an internal mixing device, such as an agitator, or a combination of any of these reactors. Moreover, additional components, such as a stirring rod or agitation device may also be included in the supercritical water hydrogenation reactor 150.
The supercritical water upgrading process is aided by the addition of the heated hydrogen stream 129 to convert a greater amount of heavy hydrocarbons into lighter hydrocarbons. The supercritical water upgrading process and the addition of the heated hydrogen stream have a synergistic effect because the supercritical water dissolves the oil; maximizes mixing of the combined feed stream 132 (oil, water, and hydrogen components); ruptures hydrocarbon and heteroatom chemical bonds; cages asphaltenes and large hydrocarbon radicals (thereby preventing their polymerization); and provides high pressure that brings hydrogen to hydrocarbon and heteroatom radicals' moieties to further rupture chemical bonds and saturate the free hydrocarbon and heteroatom radicals; and the hydrogen addition facilitates rupturing hydrocarbon and heteroatom chemical bonds and saturates the free hydrocarbon and heteroatom radicals generated by the combined effect of supercritical water and the added hydrogen. Specifically, the hydrogen addition may suppress gummy olefin, asphaltene, and coke generation.
The presence of thiols and disulfides in the hydrocarbon-based stream 105 facilitates the desulfurization process by the ScW hydrogenation process. The sulfur-sulfur bond shown in reaction (1) has a bond dissociation energy of about 270 KJ/mol, which is much lower than that of a carbon-carbon bond. In the below reaction, S is sulfur, R is carbon or hydrogen, and n refers to the length of the carbon chain, and the black dot symbolizes a radical species.
R—S—SRn→RS+RnS Reaction 1
Disulfide compounds such as dimethyl disulfide and diethyl disulfide ac as initiators for radical chain reactions without catalyst presence. The case of sulfide bonds rupturing by the thermal energy of the ScW induces cracking of high molecular weight components in the hydrocarbon oil without the need for catalyst with an attendant evolution of H2S. When hydrocarbons are subject to the high temperature of the ScW, the sulfur-sulfur bonds are the first chemical bonds to be broken. As the number of sulfur atoms increases, the S—S dissociation energy decreases, as shown below in Table 1.
Hydrogenation in the ScW hydrogenation reaction medium reduces hydrogen abstraction from hydrocarbon molecules. Thus, it is believed that the hydrocarbon and sulfide radicals that are thermally generated from Reaction 1 above induce the atomic hydrogen abstraction reaction from molecular hydrogen (H2) under high hydrogen partial pressure, shown in below in Reaction 2.
RS+H2→RSH+H Reaction 2
The resulting free atomic hydrogen radical is highly reactive to saturate other generated free radicals. Thus, the above Reactions 1 and 2 result in the below global reaction.
RS-SR+3H2→2RSH+2H2 Reaction 3
Furthermore, the combination reaction between the atomic hydrogen radical from Reaction 2 and the generated hydrocarbon sulfide radical from Reaction 1 is favored by a relatively high exothermic reaction (˜92 KJ/mol), which favors generating mercaptan thiols shown below in Reaction 4.
RnS+H→RnSH Reaction 4
The thiol group then reacts with hydrogen to form d-hydrogen sulfide, as shown in Reaction 5.
2RSH+H2→2RH+2H2S Reaction 5
H2S is known to facilitate hydrogen transfer at temperatures as low as 171° C. Hydrocarbon radicals generated by thermal bond scission could abstract atomic hydrogen from H2S as shown by Reaction 6:
R—S-R+H2S+2H2→2RH+2H2S Reaction 6
Hydrocarbon oil reactions in ScW is also subjected to combination of steam reforming and water-gas shift reactions as shown by Reactions 7, 8, and 9 below.
Reaction 7: Steam Reforming Reaction
CH4+H2O→CO+3H2
Reaction 8: Water-Gas Shift Reaction (WGSR)
CO+H2O→CO2+H2
Reaction 9: Water-Gas Shift Reaction (WGSR)
CO+H2S→COS+H2
Therefore, oil desulfurization in ScW processes reduces hydrogen abstraction from hydrocarbons by availing hydrogen through steam reforming reactions and WGSRs, in addition to reducing the association of large molecules and condensation reactions.
Therefore, there exists recognizable synergy between supercritical water and added hydrogen to upgrade and improve hydrocarbon oils. It is contemplated that the super-critical water hydrogenation reactor 150 may dissolve the hydrocarbons and hydrogen in supercritical water and break the M-S bonds (having a bond energy of approximately 290 KJ/mol), M-M bonds, H—H bonds, and MS-SM bonds (having a bond energy of approximately 260 KJ/mol), and hydrogenate the generated hydrocarbon and heteroatom radicals. Within the supercritical water hydrogenation reac-tor 150, it is contemplated that large hydrocarbon molecules (including asphaltene aggregates) are dissolved, broken, dispersed, and hydrogenated in the oil medium, in addition to hydrocarbon upgrading by improving properties such as API gravity and reducing properties such as density, viscosity, and heteroatoms (including metals).
Upon exiting the supercritical water hydrogenation reactor 150, the upgraded product 152 may have a T5 true boiling point (TPB) of less than 350° C. or of less than 300° C., In embodiments, the upgraded product 152 may have a T5 TPB of from 251° C. to 350° C., from 260° C. to 350° C., from 270° C. to 350° C., from 280° C. to 350° C., from 290° C. to 350° C., from 300° C. to 350° C., from 310° C. to 350° C., from 320° C. to 350° C., from 330° C. to 350° C., from 340° C. to 350° C., from 251° C. to 340° C., from 260° C. to 340° C., from 270° C. to 340° C., from 280° C. to 340° C., from 290° C. to 340° C., from 300° C. to 340° C., from 310° C. to 340° C., from 320° C. to 340° C., from 330° C. to 340° C., from 251° C. to 330° C., from 260° C. to 330° C., from 270° C. to 330° C., from 280° C. to 330° C., from 290° C. to 330° C., from 300° C. to 330° C., from 310° C. to 330° C., from 320° C. to 330° C., from 251° C. to 320° C., from 260° C. to 320° C., from 270° C. to 320° C., from 280° C. to 320° C., from 290° C. to 320° C., from 300° C. to 320° C., from 310° C. to 320° C., from 251° C. to 310° C., from 260° C. to 310° C., from 270° C. to 310° C., from 280° C. to 310° C., from 290° C. to 310° C., from 300° C. to 310° C., from 251° C. to 310° C., from 260° C. to 310° C., from 270° C. to 310° C., from 280° C. to 310° C., from 290° C. to 310° C., from 300° C. to 310° C., from 251° C. to 300° C., from 260° C. to 300° C., from 270° C. to 300° C., from 280° C. to 300° C., from 290° C. to 300° C., from 251° C. to 290° C., from 260° C. to 290° C., from 270° C. to 290° C., from 280° C. to 290° C., from 251° C. to 280° C., from 260° C. to 280° C., from 270° C. to 280° C. from 251° C. to 270° C., from 260° C. to 270° C., or from 251° C. to 260° C.
In embodiments, upgraded product 152 may have a T90 TPB is from 500° C. to 600° C., from 510° C. to 600° C., from 520° C. to 600° C., from 530° C. to 600° C., from 540° C. to 600° C., from 550° C. to 600° C., from 560° C. to 600° C., from 570° C. to 600° C., from 280° C. to 600° C. from 590° C. to 600° C. from 500° C. to 590° C., from 510° C. to 590° C. from 520° C. to 590° C. from 530° C. to 590° C., from 540° C. to 590° C., from 550° C. to 590° C., from 560° C. to 590° C. from 570° C. to 590° C. from 280° C. to 590° C., from 500° C. to 580° C. from 510° C. to 580° C. from 520° C. to 580° C., from 530° C. to 580° C. from 540° C. to 580° C. from 550° C. to 580° C. from 560° C. to 580° C., from 570° C. to 580° C., from 500° C. to 570° C. from 510° C. to 570° C. from 520° C. to 570° C., from 530° C. to 570° C., from 540° C. to 570° C., from 550° C. to 570° C., from 560° C. to 570° C., from 500° C. to 560° C. from 510° C. to 560° C. from 520° C. to 560° C., from 530° C. to 560° C., from 540° C. to 560° C., from 550° C. to 560° C., from 500° C. to 550° C. from 510° C. to 550° C. from 520° C. to 550° C., from 530° C. to 550° C., from 540° C. to 550° C. from 500° C. to 540° C. from 510° C. to 540° C. from 520° C. to 540° C., from 530° C. to 540° C. from 500° C. to 530° C., from 510° C. to 530° C. from 520° C. to 530° C., from 500° C. to 520° C. from 510° C. to 520° C., or from 500° C. to 510° C. It should be understood that the T90 TPB is greater than the T5 TPB previously described.
The upgraded product 152 may have an API gravity from 12° to 24°, from 14° to 24°, from 16° to 24°, from 18° to 24°, from 20° to 24°, from 22° to 24°, from 12° to 22°, from 14° to 22°, from 16° to 22°, from 18° to 22°, from 20° to 22°, from 12° to 20°, from 14° to 20°, from 16° to 20°, from 18° to 20°, from 12° to 18°, from 14° to 18°, from 16° to 18°, from 12° to 16°, from 14° to 16°, or from 12° to 14°.
The upgraded product 152 may include less than 2.00 wt. % total sulfur content by weight of the upgraded product 152. In embodiments, the upgraded product 152 may include from 1.01 wt. % to 2.00 wt. %, from 1.25 wt. % to 2.00 wt. %, from 1.50 wt. % to 2.00 wt. %, from 1.75 wt. % to 2.00 wt. %, from 1.01 wt. % to 1.75 wt. %, from 1.25 wt. % to 1.75 wt. %, from 1.50 wt. % to 1.75 wt. %, from 1.01 wt. % to 1.50 wt. %, from 1.25 wt. % to 1.25 wt. %, or from 1.01 wt. % to 1.25 wt. % total sulfur content by weight of the upgraded product 152.
The upgraded product 152 may include less than 0.50 wt. % total nitrogen content by weight of the upgraded product 152. In embodiments, the upgraded product 152 may include from 0.11 wt. % to 0.50 wt. %, from 0.15 wt. % to 0.50 wt. %, from 0.20 wt. % to 0.50 wt. %, from 0.25 wt. % to 0.50 wt. %, from 0.30 wt. % to 0.50 wt. %, from 0.35 wt. % to 0.50 wt. %, from 0.40 wt. % to 0.50 wt. %, from 0.45 wt. % to 0.50 wt. %, from 0.11 wt. % to 0.45 wt. %, from 0.15 wt. % to 0.45 wt. %, from 0.20 wt. % to 0.45 wt. %, from 0.25 wt. % to 0.45 wt. %, from 0.30 wt. % to 0.45 wt. %, from 0.35 wt. % to 0.45 wt. %, from 0.40 wt. % to 0.45 wt. %, from 0.11 wt. % to 0.40 wt. %, from 0.15 wt. % to 0.40 wt. %, from 0.20 wt. % to 0.40 wt. %, from 0.25 wt. % to 0.40 wt. %, from 0.30 wt. % to 0.40 wt. %, from 0.35 wt. % to 0.40 wt. %, from 0.11 wt. % to 0.35 wt. %, from 0.15 wt. % to 0.35 wt. %, from 0.20 wt. % to 0.35 wt. %, from 0.25 wt. % to 0.35 wt. %, from 0.30 wt. % to 0.35 wt. %, from 0.11 wt. % to 0.30 wt. %, from 0.15 wt. % to 0.30 wt. %, from 0.20 wt. % to 0.30 wt. %, from 0.25 wt. % to 0.30 wt. %, from 0.11 wt. % to 0.25 wt. %, from 0.15 wt. % to 0.25 wt. %, from 0.20 wt. % to 0.25 wt. %, from 0.11 wt. % to 0.20 wt. %, from 0.15 wt. % to 0.20 wt. %, or from 0.11 wt. % to 0.15 wt. % total nitrogen content by weight of the upgraded product 152.
The upgraded product 152 may include less than 0.50 wt. % asphaltene (heptane-insoluble) by weight of the upgraded product 152. In embodiments, the upgraded product 152 may include from 0.21 wt. % to 0.50 wt. %, from 0.25 wt. % to 0.50 wt. %, from 0.30 wt. % to 0.50 wt. %, from 0.35 wt. % to 0.50 wt. %, from 0.40 wt. % to 0.50 wt. %, from 0.45 wt. % to 0.50 wt. %, from 0.21 wt. % to 0.45 wt. %, from 0.25 wt. % to 0.45 wt. %, from 0.30 wt. % to 0.45 wt. %, from 0.35 wt. % to 0.45 wt. %, from 0.40 wt. % to 0.45 wt. %, from 0.21 wt. % to 0.40 wt. %, from 0.25 wt. % to 0.40 wt. %, from 0.30 wt. % to 0.40 wt. %, from 0.35 wt. % to 0.40 wt. %, from 0.21 wt. % to 0.35 wt. %, from 0.25 wt. % to 0.35 wt. %, from 0.30 wt. % to 0.35 wt. %, from 0.21 wt. % to 0.30 wt. %, from 0.25 wt. % to 0.30 wt. %, or from 0.21 wt. % to 0.25 wt. % asphaltene (heptane-insoluble) by weight of the upgraded product 152.
The upgraded product 152 may include less than 83 parts per million (ppm) metals. In embodiments, the metals may be vanadium, nickel, or both. In embodiments, the upgraded product 152 may include from 0.51 ppm to 5.00 ppm, from 1.00 ppm to 5.00 ppm, from 1.50 ppm to 5.00 ppm, from 2.00 ppm to 5.00 ppm, from 2.50 ppm to 5.00 ppm, from 3.00 ppm to 5.00 ppm, from 3.50 ppm to 5.00 ppm, from 4.00 ppm to 5.00 ppm, from 4.50 ppm to 5.00 ppm, from 0.51 ppm to 4.50 ppm, from 1.00 ppm to 4.50 ppm, from 1.50 ppm to 4.50 ppm, from 2.00 ppm to 4.50 ppm, from 2.50 ppm to 4.50 ppm, from 3.00 ppm to 4.50 ppm, from 3.50 ppm to 4.50 ppm, from 4.00 ppm to 4.50 ppm, from 0.51 ppm to 4.00 ppm, from 1.00 ppm to 4.00 ppm, from 1.50 ppm to 4.00 ppm, from 2.00 ppm to 4.00 ppm, from 2.50 ppm to 4.00 ppm, from 3.00 ppm to 4.00 ppm, from 3.50 ppm to 4.00 ppm, from 0.51 ppm to 3.50 ppm, from 1.00 ppm to 3.50 ppm, from 1.50 ppm to 3.50 ppm, from 2.00 ppm to 3.50 ppm, from 2.50 ppm to 3.50 ppm, from 3.00 ppm to 3.50 ppm, from 0.51 ppm to 3.00 ppm, from 1.00 ppm to 3.00 ppm, from 1.50 ppm to 3.00 ppm, from 2.00 ppm to 3.00 ppm, from 2.50 ppm to 3.00 ppm, from 0.51 ppm to 2.50 ppm, from 1.00 ppm to 2.50 ppm, from 1.50 ppm to 2.50 ppm, from 2.00 ppm to 2.50 ppm, from 0.51 ppm to 2.00 ppm, from 1.00 ppm to 2.00 ppm, from 1.50 ppm to 2.00 ppm, from 0.51 ppm to 1.50 ppm, from 1.00 ppm to 1.50 ppm, or from 0.51 ppm to 1.00 ppm metals.
The upgraded product 152 may have a viscosity at 50° C. of less than 100 centiStokes (cSt). In embodiments, the upgraded product 152 may have a viscosity at 50° C. from 25 to 100 cSt, from 30 to 100 cSt, from 40 to 100 cSt, from 50 to 100 cSt, from 60 to 100 cSt, from 70 to 100 cSt, from 75 to 100 cSt, from 80 to 100 cSt, from 90 to 100 cSt, from 25 to 90 cSt, from 30 to 90 cSt, from 40 to 90 cSt, from 50 to 90 cSt, from 60 to 90 cSt, from 70 to 90 cSt, from 75 to 90 cSt, from 80 to 90 cSt, from 25 to 80 cSt, from 30 to 80 cSt, from 40 to 80 cSt, from 50 to 80 cSt, from 60 to 80 cSt, from 70 to 80 cSt, from 75 to 80 cSt, from 25 to 75 cSt, from 30 to 75 cSt, from 40 to 75 cSt, from 50 to 75 cSt, from 60 to 75 cSt, from 70 to 75 cSt, from 25 to 70 cSt, from 30 to 70 cSt, from 40 to 70 cSt, from 50 to 70 cSt, from 60 to 70 cSt, from 25 to 60 cSt, from 30 to 60 cSt, from 40 to 60 cSt, from 50 to 60 cSt, from 25 to 50 cSt, from 30 to 50 cSt, from 40 to 50 cSt, from 25 to 40 cSt, from 30 to 40 cSt, or from 25 to 30 cSt.
The upgraded product 152 may then be cooled by cooler 154 to a temperature from 150° C. to 250° C., from 150° C. to 225° C., from 150° C. to 200° C., from 150° C. to 175° C., from 175° C. to 250° C., from 175° C. to 225° C., from 175° C. to 200° C., from 200° C. to 250° C., from 200° C. to 225° C., or from 225° C. to 250° C. to form a cooled, upgraded product 156. Various cooling devices are contem-plated for the cooler 154, such as a heat exchanger.
Referring again to
The depressurized, upgraded product 159 may then be passed to a gas/oil/water separator 160. The gas/oil/water separator 160 may separate the depressurized, upgraded product 159 into a first gas fraction 164, a liquid oil fraction 162, and a first water fraction 166. The gas/oil/water separator 160 may be any separator known in the industry. While the gas/oil/water separator 160 may separate the depressurized, upgraded product 159 into at least a first gas fraction 164 comprising CO, CO2, NH3, H2, H2S, C1, C2, C3, C4, C5, C6, or combinations thereof; a liquid oil fraction 162; and a first water fraction 166, it should be appreciated that additional fractions may also be produced.
In embodiments, the first gas fraction 164 may include from 0.5 wt. % to 3 wt. %, from 0.5 wt. % to 2 wt. %, from 0.5 wt. % to 1.5 wt. %, 0.5 wt. % to 1.2 wt. %, from 0.8 wt. % to 3 wt. %, from 0.8 wt. % to 2 wt. %, from 0.8 wt. % to 1.5 wt. %, from 0.8 wt. % to 1.2 wt. %, or approximately 1 wt. % H2 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 2 wt. % to 50 wt. %, from 2 wt. % to 25 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 13 wt. %, from 8 wt. % to 50 wt. %, from 8 wt. % to 25 wt. %, from 8 wt. % to 15 wt. %, from 8 wt. % to 13 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 15 wt. %, from 10 wt. % to 13 wt. %, from 11 wt. % to 50 wt. %, from 11 wt. % to 25 wt. %, from 11 wt. % to 15 wt. %, from 11 wt. % to 13 wt. %, or approximately 12 wt. % C1 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 2 wt. % to 50 wt. %, from 2 wt. % to 25 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %, from 8 wt. % to 15 wt. %, from 8 wt. % to 12 wt. %, from 10 wt. % to 15 wt. %, from 10 wt. % to 12 wt. %, or approximately 11 wt. % C2 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 2 wt. % to 50 wt. %, from 2 wt. % to 25 wt. %, from 2 wt. % to 15 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 13 wt. %, from 5 wt. % to 11 wt. %, from 7 wt. % to 15 wt. %, from 7 wt. % to 13 wt. %, from 7 wt. % to 11 wt. %, from 9 wt. % to 15 wt. %, from 9 wt. % to 13 wt. %, from 9 wt. % to 11 wt. %, or approximately 10 wt. % C3 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 1 wt. % to 50 wt. %, from 1 wt. % to 25 wt. %, from 3 wt. % to 15 wt. %, from 3 wt. % to 12 wt. %, from 3 wt. % to 10 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %, from 5 wt. % to 10 wt. %, from 8 wt. % to 15 wt. %, from 8 wt. % to 12 wt. %, from 8 wt. % to 10 wt. %, or approximately 9 wt. % C4 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 0 wt. % to 50 wt. %, from 0 wt. % to 25 wt. %, from 0 wt. % to 10 wt. %, from 0 wt. % to 5 wt. %, from 0 wt. % to 1 wt. %, from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 8 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 8 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %, from 5 wt. % to 10 wt. %, from 5 wt. % to 8 wt. %, from 6 wt. % to 10 wt. %, from 6 wt. % to 8 wt. %, or approximately 7 wt. % C5 by weight of the first gas fraction 164. The first gas fraction 164 may include from 0 wt. % to 25 wt. %, from 0 wt. % to 10 wt. %, from 0 wt. % to 1 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. % to 5 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt. %, from 3 wt. % to 5 wt. %, or approximately 4 wt. % C6 by weight of the first gas fraction 164.
In embodiments, the first gas fraction 164 may include from 0 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %, from 1 wt. % to 3 wt. %, or approximately 2 wt. % CO by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 0 wt. % to 25 wt. %, from 0 wt. % to 10 wt. %, from 0 wt. % to 1 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. % to 5 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt. %, from 3 wt. % to 5 wt. %, or approximately 4 wt. % CO2 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 1 wt. % to 50 wt. %, from 1 wt. % to 35 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 26 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 35 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 26 wt. %, from 15 wt. % to 50 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 26 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 35 wt. %, from 20 wt. % to 30 wt. %, from 20 wt. % to 26 wt. %, from 23 wt. % to 50 wt. %, from 23 wt. % to 35 wt. %, from 23 wt. % to 30 wt. %, from 23 wt. % to 26 wt. %, from 25 wt. % to 50 wt. %, from 25 wt. % to 35 wt. %, from 25 wt. % to 30 wt. %, from 25 wt. % to 26 wt. %, or approximately 25.6 wt. % H2S by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include from 1 wt. % to 50 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 20 wt. %, from 1 wt. % to 15 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 2 0 wt. %, from 10 wt. % to 15 wt. %, from 12 wt. % to 50 wt. %, from 12 wt. % to 25 wt. %, from 12 wt. % to 20 wt. %, from 12 wt. % to 15 wt. %, from 14 wt. % to 50 wt. %, from 14 wt. % to 25 wt. %, from 14 wt. % to 20 wt. %, from 14 wt. % to 15 wt. %, or approximately 14.6 wt. % NH3 by weight of the first gas fraction 164. In embodiments, the first gas fraction 164 may include no C5 or C6 components.
As shown in
In embodiments, the hydrotreated product 168 may have a T5 true boiling point (TBP) of less than 250° C., of less than 225° C., or of less than 200° C. In embodiments, the hydrotreated product 168 may have a T5 TBP of from 25° C. to 250° C. from 50° C. to 250° C. from 75° C. to 250° C., from 100° C. to 250° C., from 125° C. to 250° C., from 150° C. to 250° C., from 175° C. to 250° C., from 200° C. to 250° C. from 225° C. to 250° C., from 25° C. to 225° C., from 50° C. to 225° C., from 75° C. to 225° C. from 100° C. to 225° C. from 125° C. to 225° C., from 150° C. to 225° C., from 175° C. to 225° C., from 200° C. to 225° C. from 25° C. to 200° C., from 50° C. to 200° C., from 75° C. to 200° C., from 100° C. to 200° C. from 125° C. to 200° C. from 150° C. to 200° C., from 175° C. to 200° C., from 25° C. to 150° C., from 50° C. to 150° C., from 75° C. to 150° C., from 100° C. to 150° C. from 125° C. to 150° C., from 25° C. to 125° C., from 50° C. to 125° C., from 75° C. to 125° C., from 100° C. to 125° C., from 25° C. to 100° C., from 50° C. to 100° C., from 75° C. to 100° C., from 25° C. to 75° C., from 50° C. to 75° C., or from 25° C. to 50° C.
In embodiments, the hydrotreated product 168 may have a T90 TBP less than 500° C. such as from 200° C. to 500° C. from 250° C. to 500° C., from 300° C. to 500° C., from 350° C. to 500° C., from 400° C. to 500° C., from 450° C. to 500° C., from 200° C. to 450° C., from 250° C. to 450° C. from 300° C. to 450° C., from 350° C. to 450° C. from 400° C. to 450° C., from 200° C. to 400° C., from 250° C. to 400° C., from 300° C. to 400° C., from 350° C. to 400° C. from 200° C. to 350° C., from 250° C. to 350° C., from 300° C. to 350° C. from 200° C. to 300° C. from 250° C. to 300° C., or from 200° C. to 250° C. It should be understood that the T90 TBP is greater than the T5 TBP previously described.
In embodiments, the hydrotreated product 168 may have an API gravity from 25° to 30°, from 26° to 30°, from 27° to 30°, from 28° to 30°, from 29° to 30°, from 25° to 29°, from 26° to 29°, from 27° to 29°, from 28° to 29°, from 25° to 28°, from 26° to 28°, from 27° to 28°, from 25° to 27°, from 26° to 27°, or from 25° to 26°.
The hydrotreated product 168 may, in embodiments include less than 1.0 wt. %, less than 0.75 wt. %, less than 0.50 wt. %, or less than 0.30 wt. % total sulfur content by weight of the hydrotreated product 168. In embodiments, the hydrotreated product 168 may include from 0.1 wt. % to 1.0 wt. %, from 0.2 wt. % to 1.0 wt. %, from 0.3 wt. % to 1.0 wt. %, from 0.4 wt. % to 1.0 wt. %, from 0.5 wt. % to 1.0 wt. %, from 0.6 wt. % to 1.0 wt. %, from 0.7 wt. % to 1.0 wt. %, from 0.8 wt. % to 1.0 wt. %, from 0.9 wt. % to 1.0 wt. %, from 0.1 wt. % to 0.9 wt. %, from 0.2 wt. % to 0.9 wt. %, from 0.3 wt. % to 0.9 wt. %, from 0.4 wt. % to 0.9 wt. %, from 0.5 wt. % to 0.9 wt. %, from 0.6 wt. % to 0.9 wt. %, from 0.7 wt. % to 0.9 wt. %, from 0.8 wt. % to 0.9 wt. %, from 0.1 wt. % to 0.8 wt. %, from 0.2 wt. % to 0.8 wt. %, from 0.3 wt. % to 0.8 wt. %, from 0.4 wt. % to 0.8 wt. %, from 0.5 wt. % to 0.8 wt. %, from 0.6 wt. % to 0.8 wt. %, from 0.7 wt. % to 0.8 wt. %, from 0.1 wt. % to 0.7 wt. %, from 0.2 wt. % to 0.7 wt. %, from 0.3 wt. % to 0.7 wt. %, from 0.4 wt. % to 0.7 wt. %, from 0.5 wt. % to 0.7 wt. %, from 0.6 wt. % to 0.7 wt. %, from 0.1 wt. % to 0.6 wt. %, from 0.2 wt. % to 0.6 wt. %, from 0.3 wt. % to 0.6 wt. %, from 0.4 wt. % to 0.6 wt. %, from 0.5 wt. % to 0.6 wt. %, from 0.1 wt. % to 0.5 wt. %, from 0.2 wt. % to 0.5 wt. %, from 0.3 wt. % to 0.5 wt. %, from 0.4 wt. % to 0.5 wt. %, from 0.1 wt. % to 0.4 wt. %, from 0.2 wt. % to 0.4 wt. %, from 0.3 wt. % to 0.4 wt. %, from 0.1 wt. % to 0.3 wt. %, from 0.2 wt. % to 0.3 wt. %, or from 0.1 wt. % to 0.2 wt. % total sulfur content by weight of the hydrotreated product 168.
The hydrotreated product 168 may include less than 0.100 wt. % or less than 0.05 wt. % total nitrogen content by weight of the hydrotreated product 168. In embodiments, the hydrotreated product 168 may include from 0.01 wt. % to 0.10 wt. %, from 0.02 wt. % to 0.10 wt. %, from 0.03 wt. % to 0.10 wt. %, from 0.04 wt. % to 0.10 wt. %, from 0.05 wt. % to 0.10 wt. %, from 0.06 wt. % to 0.10 wt. %, from 0.07 wt. % to 0.10 wt. %, from 0.08 wt. % to 0.10 wt. %, from 0.09 wt. % to 0.10 wt. %, from 0.01 wt. % to 0.09 wt. %, from 0.02 wt. % to 0.09 wt. %, from 0.03 wt. % to 0.09 wt. %, from 0.04 wt. % to 0.09 wt. %, from 0.05 wt. % to 0.09 wt. %, from 0.06 wt. % to 0.09 wt. %, from 0.07 wt. % to 0.09 wt. %, from 0.08 wt. % to 0.09 wt. %, from 0.01 wt. % to 0.08 wt. %, from 0.02 wt. % to 0.08 wt. %, from 0.03 wt. % to 0.08 wt. %, from 0.04 wt. % to 0.08 wt. %, from 0.05 wt. % to 0.08 wt. %, from 0.06 wt. % to 0.08 wt. %, from 0.07 wt. % to 0.08 wt. %, from 0.01 wt. % to 0.07 wt. %, from 0.02 wt. % to 0.07 wt. %, from 0.03 wt. % to 0.07 wt. %, from 0.04 wt. % to 0.07 wt. %, from 0.05 wt. % to 0.07 wt. %, from 0.06 wt. % to 0.07 wt. %, from 0.01 wt. % to 0.06 wt. %, from 0.02 wt. % to 0.06 wt. %, from 0.03 wt. % to 0.06 wt. %, from 0.04 wt. % to 0.06 wt. %, from 0.05 wt. % to 0.06 wt. %, from 0.01 wt. % to 0.05 wt. %, from 0.02 wt. % to 0.05 wt. %, from 0.03 wt. % to 0.05 wt. %, from 0.04 wt. % to 0.05 wt. %, from 0.01 wt. % to 0.04 wt. %, from 0.02 wt. % to 0.04 wt. %, from 0.03 wt. % to 0.04 wt. %, from 0.01 wt. % to 0.03 wt. %, from 0.02 wt. % to 0.03 wt. %, or from 0.01 wt. % to 0.02 wt. % total nitrogen content by weight of the hydrotreated product 168.
The hydrotreated product 168 may include less than 0.20 wt. % or less than 0.15 wt. % asphaltene (heptane-insoluble) by weight of the hydrotreated product 168. In embodiments, the hydrotreated product 168 may include from 0.01 wt. % to 0.20 wt. %, from 0.05 wt. % to 0.20 wt. %, from 0.10 wt. % to 0.20 wt. %, from 0.15 wt. % to 0.20 wt. %, from 0.01 wt. % to 0.15 wt. %, from 0.05 wt. % to 0.15 wt. %, from 0.10 wt. % to 0.15 wt. %, from 0.01 wt. % to 0.10 wt. %, from 0.05 wt. % to 0.10 wt. %, or from 0.01 wt. % to 0.05 wt. % asphaltene (heptane insoluble) by weight of the hydrotreated product 168.
The hydrotreated product 168 may include less than 0.50 parts per million (ppm) or less than 0.50 ppm metals. In embodiments, the metals may be vanadium, nickel, or both. In embodiments, the hydrotreated product 168 may include from 0.01 ppm to 0.50 ppm, from 0.05 to 0.50 ppm, from 0.10 to 0.50 ppm, from 0.15 to 0.50 ppm, from 0.20 to 0.50 ppm, from 0.25 to 0.50 ppm, from 0.30 to 0.50 ppm, from 0.35 to 0.50 ppm, from 0.40 to 0.50 ppm, from 0.45 to 0.50 ppm, from 0.01 ppm to 0.45 ppm, from 0.05 to 0.45 ppm, from 0.10 to 0.45 ppm, from 0.15 to 0.45 ppm, from 0.20 to 0.45 ppm, from 0.25 to 0.45 ppm, from 0.30 to 0.45 ppm, from 0.35 to 0.45 ppm, from 0.40 to 0.45 ppm, from 0.01 ppm to 0.40 ppm, from 0.05 to 0.40 ppm, from 0.10 to 0.40 ppm, from 0.15 to 0.40 ppm, from 0.20 to 0.40 ppm, from 0.25 to 0.40 ppm, from 0.30 to 0.40 ppm, from 0.35 to 0.40 ppm, from 0.01 ppm to 0.35 ppm, from 0.05 to 0.35 ppm, from 0.10 to 0.35 ppm, from 0.15 to 0.35 ppm, from 0.20 to 0.35 ppm, from 0.25 to 0.35 ppm, from 0.30 to 0.35 ppm, from 0.01 ppm to 0.30 ppm, from 0.05 to 0.30 ppm, from 0.10 to 0.30 ppm, from 0.15 to 0.30 ppm, from 0.20 to 0.30 ppm, from 0.25 to 0.30 ppm, from 0.01 ppm to 0.25 ppm, from 0.05 to 0.25 ppm, from 0.10 to 0.25 ppm, from 0.15 to 0.25 ppm, from 0.20 to 0.25 ppm, from 0.01 ppm to 0.20 ppm, from 0.05 to 0.20 ppm, from 0.10 to 0.20 ppm, from 0.15 to 0.20 ppm, from 0.01 ppm to 0.15 ppm, from 0.05 to 0.15 ppm, from 0.10 to 0.15 ppm, from 0.01 ppm to 0.10 ppm, from 0.05 to 0.10 ppm, or from 0.01 ppm to 0.05 ppm metals.
The hydrotreated product 168 may have a viscosity at 50° C. of less than 20 centiStokes (cSt) or less than 15 cSt. In embodiments, the hydrotreated product 168 may have a viscosity at 50° C. from 5 cSt to 20 cSt, from 7 cSt to 20 cSt, from 10 cSt to 20 cSt, from 12 cSt to 20 cSt, from 15 cSt to 20 cSt, from 17 cSt to 20 cSt, from 5 cSt to 17 cSt, from 7 cSt to 17 cSt, from 10 cSt to 17 cSt, from 12 cSt to 17 cSt, from 15 cSt to 17 cSt, from 5 cSt to 15 cSt, from 7 cSt to 15 cSt, from 10 cSt to 15 cSt, from 12 cSt to 15 cSt, from 5 cSt to 12 cSt, from 7 cSt to 12 cSt, from 10 cSt to 12 cSt, from 5 cSt to 10 cSt, from 7 cSt to 10 cSt, or from 5 cSt to 7 cSt.
Aspect 1 is a process for upgrading a hydrocarbon-based composition comprising: combining a heated water stream, a hydrogen stream, and a hydrocarbon-based composition in a mixing device to create a combined feed stream; introducing the combined feed stream into a supercritical water hydrogenation reactor operating at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water; at least partially converting the combined feed stream to an upgraded product; passing the upgraded product stream to a gas/oil/water separator; separating the upgraded product stream to produce a gas fraction, a liquid oil fraction, and a water fraction; and introducing the liquid oil fraction to a mild hydrotreating unit to produce a hydrotreated product.
Aspect 2 is the process of aspect 1, further comprising passing the upgraded product stream to a cooling device prior to introducing the upgraded product stream to the gas/oil/water separator.
Aspect 3 is the process of any preceding aspect, further comprising passing the upgraded product stream to a depressurizer prior to introducing the upgraded product stream to the gas/oil/water separator.
Aspect 4 is the process of any preceding aspect, wherein the upgraded product stream is depressurized to less than 1 MPa in the depressurizer.
Aspect 5 is the process of any preceding aspect, wherein the pressurized, heated hydrocarbon-based composition has a temperature from 100° C. to 370° C.
Aspect 6 is the process of any preceding aspect, wherein the supercritical water hydrogenation reactor has a temperature of greater than 375° C. and less than 600° C. and a pressure greater than 22.1 MPa and less than 75 MPa.
Aspect 7 is the process of any preceding aspect, wherein the supercritical water hydrogenation reactor has a temperature of greater than 390° C. and less than 470° C. and a pressure greater than 24 MPa and less than 30 MPa.
Aspect 8 is the process of any preceding aspect, wherein the supercritical water hydrogenation reactor has a residence time of from 1 to 30 minutes.
Aspect 9 is the process of any preceding aspect, wherein the supercritical water hydrogenation reactor has a residence time of from 2 to 15 minutes.
Aspect 10 is the process of any preceding aspect, wherein the hydrocarbon-based composition has a T5 true boiling point from 351° C. to 500° C., and the hydrotreated product has a T5 true boiling point from 25° C. to 250° C.
Aspect 11 is the process of any preceding aspect, wherein the hydrocarbon-based composition has a T90 true boiling point from 601° C. to 750° C., and the hydrotreated product has a T90 true boiling point from 200° C. to 500° C.
Aspect 12 is the process of any preceding aspect, wherein the hydrocarbon-based composition has an API gravity from 5° to 11°, and the hydrotreated product has an API gravity from 25° to 30°.
Aspect 13 is the process of any preceding aspect, wherein the hydrocarbon-based composition has from 2.1 wt. % to 5 wt. % total sulfur content by weight of the hydrocarbon-based composition, and the hydrotreated product has from 0.1 wt. % to 1.0 wt. % total sulfur content by weight of the hydrotreated product.
Aspect 14 is the process of any preceding aspect, wherein the hydrocarbon-based composition has from 0.51 wt. % to 2.00 wt. % total nitrogen content by weight of the hydrocarbon-based composition, and the hydrotreated product has from 0.01 wt. % to 0.10 wt. % total nitrogen content by weight of the hydrotreated product.
Aspect 15 is the process of any preceding aspect, wherein the hydrocarbon-based composition has from 0.51 wt. % to 2.00 wt. % asphaltenes by weight of the hydrocarbon-based composition, and the hydrotreated product has from 0.01 wt. % to 0.20 wt. % asphaltenes by weight of the hydrotreated product.
Aspect 16 is the process of any preceding aspect, wherein the hydrocarbon-based composition has from 10 ppm to 100 ppm metals, and the hydrotreated product has 0.01 ppm to 0.50 ppm metals.
Aspect 17 is the process of any preceding aspect, wherein the hydrocarbon-based composition has a viscosity at 50° C. from 101 cSt to 700 cSt, and the hydrotreated product has a viscosity at 50° C. from 5 cSt to 20 cSt.
Aspect 18 is the process of any preceding aspect, wherein the hydrotreated product comprises: a T5 true boiling point from 25° C. to 250° C.; a T90 true boiling point from 200° C. to 500° C.; an API gravity from 25° to 30°; from 0.1 wt. % to 1.0 wt. % total sulfur content by weight of the hydrotreated product; from 0.01 wt. % to 0.10 wt. % total nitrogen content by weight of the hydrotreated product; from 0.01 wt. % to 0.20 wt. % asphaltenes by weight of the hydrotreated product; 0.01 ppm to 0.50 ppm metals; and a viscosity at 50° C. from 5 cSt to 20 cSt.
An example process for upgrading and desulfurizing a hydrocarbon-based composition according to embodiments described herein was run. The hydrocarbon-based composition had the properties shown below in Table 1. The properties of the hydrocarbon-based composition after the supercritical water hydrogenation step, as well as the resulting properties after the additional hydrotreating step are shown.
From the data in Table 1, it can be seen that the ScW reactor removed many impurities, including sulfur species from the feed hydrocarbon-based composition. Namely, it reduced the amount of sulfur in the feed by half. Once the feed was upgraded using the ScW reactor, it was then treated with a mild hydrotreating step. After the additional hydrotreating step, the amount of sulfur in the product was reduced even further, highlighting the unique synergy gained when combining the ScW process with a mild hydrotreating step.
Gas products of the gas stream were also evaluated and shown in Table 2.
From the above data, the deep desulfurization of a hydrocarbon-based composition was shown through the exploitation of the synergy attained by the high temperature and pressure effects of the supercritical water process, complemented by the hydrogen transfer facilitated via the catalytic effects of the hydrotreater (HT) step.
It should be apparent to those skilled in the art that various modifications and variations may be made to the embodiments described within without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described within provided such modifications and variations come within the scope of the appended claims and their equivalents.
As used throughout the disclosure, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” component includes aspects having two or more such components, unless the context clearly indicates otherwise.
Having described the subject matter of the present disclosure in detail and by reference to specific embodiments thereof, it is noted that the various details disclosed within should not be taken to imply that these details relate to elements that are essential components of the various embodiments described within, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Further, it should be apparent that modifications and variations are possible without departing from the scope of the present disclosure, including, but not limited to, embodiments defined in the appended claims. More specifically, although some aspects of the present disclosure are identified as particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.
