Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F11/00—Treatment of sludge; Devices therefor
  • C02F11/06—Treatment of sludge; Devices therefor by oxidation
  • C02F11/08—Wet air oxidation
  • C02F11/086—Wet air oxidation in the supercritical state
• • 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
  • C10G7/00—Distillation of hydrocarbon oils
  • C10G7/10—Inhibiting corrosion during distillation
• • 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
  • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/326—Coal-water suspensions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
  • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L9/00—Treating solid fuels to improve their combustion
  • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
  • C10L9/086—Hydrothermal carbonization
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/005—Processes using a programmable logic controller [PLC]
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/02—Temperature
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2209/00—Controlling or monitoring parameters in water treatment
  • C02F2209/03—Pressure
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4012—Pressure
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

• Supercritical water gasification is an emerging technology with great potential to generate clean energy from sources that are typically considered waste, such as biowaste, or unclean fuel sources, including coal and other fossil fuels.
• sources that are typically considered waste, such as biowaste, or unclean fuel sources, including coal and other fossil fuels.
• water is heated to very high temperatures (for example, above about 647 Kelvin) under high pressure (for example, about 22 megapascals) that prevents the water from turning into steam.
• the high temperatures and high pressures during the supercritical water gasification generate a highly corrosive environment due to the presence of corrosive ions under the temperature and pressure conditions.
• a supercritical water gasification process may comprise providing a slurry having water to at least one of a plurality of system components.
• a temperature in at least one of the plurality of system components may be increased to a first temperature while a pressure in at least one of the plurality of system components is maintained at, or less than, a first pressure.
• the process may further comprise increasing the pressure in at least one of the plurality of system components to a second pressure at the first temperature, maintaining the first temperature and the second pressure for a first time period, increasing the temperature and pressure in at least one of the plurality of system components to a second temperature and a third pressure, respectively, and maintaining the second temperature and third pressure for a second time period.
• a reactor for supercritical water gasification may comprise a chamber configured to allow an increase in temperature while maintaining a pressure, and a salt collection chamber configured to collect salt precipitated during a process performed in the chamber.
• a supercritical water gasification process may comprise moving a slurry having corrosive ions disposed therein through a supercritical water gasification system to generate a fuel product.
• a temperature and a pressure of the slurry may be maintained such that the ionic product of water in the slurry does not increase above a corrosive ionic product value, thereby reducing corrosion of at least a portion of the supercritical water gasification system due to the corrosive ions.
• FIG. 1 depicts an illustrative supercritical water system according to some embodiments.
• FIG. 2A depicts a temperature and pressure path for a fluid during a supercritical water gasification process.
• FIG. 2B depicts a temperature and pressure path for a supercritical water gasification process according to some embodiments.
• FIG. 3 depicts a supercritical water gasification operation cycle according to some embodiments.
• FIG. 4 depicts a flow diagram for an illustrative method of reducing corrosion in a supercritical water gasification system.
• the present disclosure relates generally to a system and methods for reducing corrosion in supercritical water gasification systems (or supercritical water reactor systems) by decreasing the amount of corrosive ions formed during the supercritical water reaction process.
• system components include, without limitation, heaters, pre- heaters, pumps, reactor vessels (“reactors”), heat exchangers, and gas/liquid separators.
• the temperature and/or pressure of the fluid may be controlled such that the ionic product of the fluid is maintained below a certain value and/or within a certain range.
• the ionic product of the fluid may be controlled such that the ionic product of the fluid is maintained below a certain value and/or within a certain range.
• the concentration of corrosive ions in the fluid may be diminished or even eliminated, reducing corrosion of the inner surfaces of system components, thereby increasing the lifespan of system components and the overall efficiency of the system.
• FIG. 1 depicts an illustrative supercritical water gasification system according to some embodiments.
• a supercritical water gasification system 100 may include a feedstock inlet 130 for introducing a slurry 155 into the system.
• the slurry 155 may comprise a high pressure slurry feed.
• the feedstock may include any type of matter capable of undergoing supercritical water gasification, including, without limitation, biomass fluids (for example, micro algae fluids, bioresidues, biowastes, or the like), slurries of coal and other fossil fuels, and oxidizable wastes.
• the supercritical water gasification system 100 may be configured to operate as various gasification systems, including, without limitation, a coal gasification system, a biomass gasification system, a waste oxidation system, a hydroprocessing reactor system, and a pressurized water reactor system.
• the slurry 155, along with air 150 and fluid 135, may be fed into a heater 105, such as a gas-fired heater, with the flow controlled at least partially by a pressure pump 185.
• the fluid 135 may include water.
• the combination of the slurry 155 and the fluid 135 may be heated in the heater 105.
• the heater 105 may be used to heat the slurry 155 prior to the slurry entering the reactor vessel 110.
• the fluid 135 may be used to generate steam 140, for instance, in order to recover heat in certain flue gasses 145.
• the steam 140 may be used outside of the gasification process (for example, as a heat source).
• Certain gases, such as steam 140 and flue gas 145, may be exhausted from the heater.
• the heated slurry 155 may be fed into a reactor vessel 110.
• the slurry 155 may be heated by combining it with superheated steam or supercritical water before it is fed into a reactor vessel 110.
• the slurryl55 Prior to entering or within the reactor vessel 110, the slurryl55 may be heated under pressure to become a supercritical fluid.
• the pressurization of the slurry 155 may be delayed such that the slurry will be supercritical after it leaves the pressure pump 185.
• the temperatures and pressures for generating a supercritical fluid may depend on the type of fluid and the composition thereof (for example, the type and concentration of ions at different temperatures and pressures).
• the fluid 155 includes water
• the fluid may be heated to at least about 647 Kelvin at a pressure of at least about 22 megapascals to become a supercritical fluid.
• the slurry 155 may be heated to various other temperatures, including about 650 Kelvin, about 700 Kelvin, about 800 Kelvin, about 900 Kelvin, about 950 Kelvin, about 1200 Kelvin, about 1500 Kelvin, or ranges between any two of these values (including endpoints).
• the slurry 155 at supercritical temperatures may be at various pressures during the supercritical water gasification process, such as about 22 megapascals, about 23 megapascals, about 24 megapascals, about 25 megapascals, about 30 megapascals, about 35 megapascals, about 40 megapascals, or values between any two of these values (including endpoints).
• the slurry 155 may include corrosive ions such as the ions of various inorganic salts.
• the corrosive ions may be highly corrosive to the components of the supercritical water gasification system 100, such as the inside surface of system components, including the heater 105, the reactor vessel 110, and/or any pipes connecting the components together.
• the corrosive ions may include anions and/or cations.
• Non- limiting examples of anions include chloride ions, fluoride ions, sulfide ions, sulfate ions, sulfite ions, phosphate ions, nitrate ions, carbonate ions, bicarbonate ions, hydroxide ions, oxide ions, and cyanide ions.
• Non-limiting examples of cations include, without limitation, potassium cations, calcium cations, ammonium cations, magnesium cations, and sodium cations.
• the supercritical fluid in the slurry may react with the slurry 155 within the reactor vessel 110 to generate a reactor product 160.
• the fluid 155 may include one or more catalysts configured to facilitate the gasification reactions.
• the reactor product 160 may move through one or more heat exchangers, such as a heat recovery heat exchanger 115 and a cool-down heat exchanger 125.
• a gas/fluid separator 120 may be provided to separate the reactor product 160 into the desired fuel gas product 165 and waste products 170, such as fluid effluent, ash and char.
• the fuel gas product 165 may include any fuel capable of being generated from the feedstock slurry 155 responsive to reacting with the fluid 135 under supercritical conditions.
• Illustrative fuel gas products 165 include, but are not limited to, hydrogen-rich fuels, such as 3 ⁇ 4 and/or CH 4 .
• the fluid 135 may be heated to various temperatures under different pressures within the supercritical water gasification system 100 .
• the slurry 155 may be in a subcritical condition, wherein the slurry 155 is at a high temperature that is below the supercritical temperature or at a high pressure that is below the supercritical pressure.
• subcritical water may have a temperature of about 570 Kelvin, about 600 Kelvin, about 610 Kelvin, about 620 Kelvin, about 630 Kelvin, about 647 Kelvin, or in a range between any of these values (including endpoints).
• the pressure of the fluid at the subcritical temperature may be about 8 megapascals, about 12 megapascals, about 16 megapascals, about 20 megapascals, about 22 megapascals, about 25 megapascals, or in a range between any of these values (including endpoints).
• the slurry 155 may also include corrosive ions that are highly corrosive to the system components of the supercritical water gasification system 100, for example, in subcritical conditions.
• the presence of corrosive ions in the slurry 155 may depend on various factors, such as the pressure and/or temperature of the subcritical slurry. For instance, in a supercritical water gasification process in which the pressure of the slurry 155 is above the supercritical pressure while the temperature of the slurry is below the supercritical temperature, the slurry may be highly corrosive.
• the slurry 155 may be heated to supercritical temperatures while the pressure remains below supercritical pressure. For these embodiments, the slurry 155 may be much less corrosive to system components.
• the supercritical water reactor system 100 depicted in FIG. 1 is provided for illustrative purposes only and may include more or fewer components as required, such as one or more valves, pre-heaters, reactor vessels, pumps for pumping the fluid 135 through the system and other components known to those having ordinary skill in the art.
• the flow of the slurry 155 through the supercritical water reactor system 100 is not limited to the particular path depicted in FIG. 1, as this is provided for illustrative purposes only.
• the components of the supercritical water gasification system 100 may be fabricated from various materials, such as common corrosion resistant metals including, without limitation, nickel alloy, chrome-molybdenum alloy, nonmagnetic iron-based alloy, and/or certain ceramic materials.
• a sensor 175 may be configured to receive information associated with components of the supercritical water gasification system 100, such as the reactor vessel 110.
• the sensor 175 may be configured to measure various properties, including, without limitation, temperature, pressure and flow rate within a system component.
• a controller 180 may be in communication with the sensor 175.
• the controller 180 may generally include a processor, a non-transitory memory or other storage device for housing programming instructions, data or information regarding one or more applications, and other hardware, including, for example, a central processing unit (CPU), read only memory (ROM), random access memory, communication ports, controllers, and/or memory devices, non-transitory computer-readable media, and other components known to those having ordinary skill in the art.
• the controller 180 may be configured to receive information from the sensor 175. Certain operational aspects of the supercritical water gasification system 100 may be directed by the controller 180, such as heating elements, pumps, valves (for example, valves configured to vent pressure), or the like. In an embodiment, the controller 180 my execute control software configured to control operation of one or more components of the supercritical water gasification system 100 to carry out aspects of embodiments disclosed herein.
• the sensor 175 and the controller 180 depicted in FIG. 1 are non-limiting as they are provided for illustrative purposes only. Embodiments provide for various other configurations, including, without limitation, one or more sensors associated with a one or more system components, one or more controllers associated with one or more sensors and/or system components, or combinations thereof.
• embodiments are not so limited.
• embodiments may include any other type of supercritical water reaction system capable of operating according to some embodiments described herein, including supercritical water oxidation systems.
• FIG. 2A depicts a temperature and pressure path for a fluid during a supercritical water gasification process.
• a fluid undergoing a supercritical water gasification process may be controlled to various temperatures 210 and pressures 205 during the process.
• the fluid may include any fluid capable of generating a product fuel through the supercritical water gasification process, such as a coal slurry.
• the fluid and/or water in the fluid may have an ionic product 215 value or range of ionic product values, such as those depicted in FIG. 2A.
• the units depicted for the ionic product 215 represent the exponent "e" in the following form: 1 x 10 e .
• K ⁇ axm + x ⁇ ⁇ , where a m and ax " are the activities of X3 ⁇ 4 + and X ⁇ , respectively.
• the ionic product 215 of a fluid changes based on the temperature and/or pressure of the fluid.
• the ionic product 215 is not limited to the ionic product of pure water, as it may refer to one or more other fluids (e.g., feedstock slurries) and/or water contained therein.
• the fluid follows a temperature and pressure path 220 as it proceeds through the various stages of the process.
• the fluid may be at a temperature of less than about 500 Kelvin and a pressure of about 1 megapascal when entering the supercritical water gasification system.
• the fluid may then be heated in a heater to about 570 Kelvin at a pressure of about 23 megapascals before being fed into a reactor vessel where it may be heated to above 850 Kelvin at a pressure of about 35 megapascals.
• the path 220 depicted in FIG. 2A illustrates a temperature and pressure progression for fluid in a typical supercritical water gasification process.
• the critical point of water about 647 Kelvin and about 22 megapascals
• the solubility of inorganic salts decreases rapidly, causing the inorganic salts to precipitate and attach to the inner surfaces of system components, which may cause corrosion and/or clog piping connecting system components.
• the ionic product 215 of water increases rapidly from about 10 ⁇ 45 mol 2 /l 2 to about 10 ⁇ 12 mol 2 /l 2 , causing disassociation of ions, for example, of inorganic compounds.
• a coal slurry may contain a mix of hetero atoms including, chlorine, sulfur, potassium, and/or nitrogen which may become free ions during the supercritical water gasification process.
• the product of water remains very low, for example, about 10 " mol /l or below.
• Conventional supercritical water gasification operating cycles increase pressure 205 before and during the increase in temperature 210.
• the ionic product 215 is very high, for example, 10 "12 mol 2 /l 2 or above.
• the ionic product 215 falls such that at about 775 Kelvin and about 23 megapascals, the ionic product is about 10 "25 mol 2 /l 2 , more than 10 orders of magnitude lower than in the subcritical zone.
• FIG. 2B depicts a temperature and pressure path for a supercritical water gasification process according to some embodiments.
• embodiments modify the pressure 205 at different temperatures 210 during the supercritical water gasification process to generate a temperature and pressure path 225 such that the fluid does not have an ionic product 215 greater than about 10 "20 mol 2 /l 2 .
• embodiments provide for maintaining the pressure 205 below about 8 megapascals while raising the temperature 210 during the supercritical water gasification process. Accordingly, the fluid avoids high ionic product zones 230, 235 where the fluid is the most corrosive.
• FIG. 3 depicts a supercritical water gasification operation cycle according to some embodiments.
• a supercritical water gasification operation cycle may include multiple phases 380, 382, 384, 386, 388, 390 for processing a fluid 300 to generate a fuel product 375.
• a supercritical water gasification operation cycle may start with a fluid 300 at ambient temperature (for example, less than about 400 Kelvin) and at a pressure less than about 8.6 megapascals (for example, about 8 megapascals) being fed through a slurry inlet 305 to a heat exchanger 310 (for example, a heat recovery heat exchanger).
• ambient temperature for example, less than about 400 Kelvin
• a pressure less than about 8.6 megapascals for example, about 8 megapascals
• the fluid 300 enters a heating phase 380 in the heat exchanger 310 in which the pressure of the fluid 300 is maintained at less than about 8.6 megapascals, while the temperature of the slurry is raised to a temperature of about 674 Kelvin to about 775 Kelvin.
• the pressure of the fluid 300 during the heating phase 380 must be monitored and controlled because the increasing temperature of the fluid will operate to increase the pressure of the fluid.
• pressure may have to be vented or otherwise released in order to prevent the pressure of the fluid 300 from rising above 8 megapascals.
• the excess pressure may be captured for use when pressurization is required within the operation cycle, such as in the pressurization phase 382.
• the ionic product of the fluid 300 may be from about 10 " mol /l to about 10 " mol /l .
• the fluid 300 will enter a pressurization phase 382.
• the pressure of the fluid 300 will be raised to about 23 megapascals to about 28 megapascals, which is above the pressure of 23 megapascals at the critical point of fluid 300 (using water as an example).
• a pressure pump 315 may be used to pressurize the fluid 300.
• the ionic product of the fluid 300 may be from about 10 "28 mol 2 /! 2 to about 10 "23 mol 2 /l 2 .
• salts such as inorganic salts, will precipitate out of the fluid 300 under a suitable applied pressure during a salt precipitation phase as will be described below.
• a salt precipitation phase 384 may occur within a salt precipitator reactor 320.
• the inorganic salts in the fluid have a low solubility at about 775 Kelvin and at about 23 megapascals and will precipitate out of the fluid 300.
• Non-limiting examples of inorganic salts include sodium chloride, ammonium sulfate, ammonium phosphate, ammonium chloride, ammonium carbonate, and ammonium sulfite, potassium chloride, potassium sulphate, potassium phosphate, potassium nitrate, calcium chloride, calcium sulfate, and calcium nitrate.
• the inorganic salts may include corrosive ions such as chloride ions, fluoride ions, sulfide ions, sulfate ions, sulfite ions, phosphate ions, nitrate ions, carbonate ions, bicarbonate ions, hydroxide ions, and cyanide ions.
• corrosive ions such as chloride ions, fluoride ions, sulfide ions, sulfate ions, sulfite ions, phosphate ions, nitrate ions, carbonate ions, bicarbonate ions, hydroxide ions, and cyanide ions.
• corrosive ions such as chloride ions, fluoride ions, sulfide ions, sulfate ions, sulfite ions, phosphate ions, nitrate ions, carbonate ions, bicarbonate ions, hydroxide ions, and cyanide ions.
• the throughput of the fluid 300 through the salt precipitator reactor 320 in the salt precipitation phase 384 may be managed to ensure that the fluid is in this phase for a sufficient amount of time, such that all or substantially all of the inorganic salts precipitate out of the fluid.
• the flow of fluid 300 may be controlled so that the fluid is in the salt precipitator reactor 320 for a minimum residence time.
• the residence time may be about 30 seconds, about 1 minute, about 2 minutes, about 5 minutes, or ranges between any two of these values (including endpoints).
• the fluid 300 may flow from the salt precipitation reactor 320 to a heater 350.
• the heater 350 in addition to receiving and heating the fluid 300, may be configured to receive water 335 and air 330 and to vent out steam 340 and flue gas 345.
• the fluid 300 may enter a conversion phase 386 in which the temperature of the fluid may be increased to about 925 Kelvin to about 975 Kelvin, and the pressure of the fluid may be increased to about 25 megapascals to about 35 megapascals.
• the temperature of the fluid 300 will be at or above the critical temperature and critical pressure.
• the critical temperature of water is about 647 Kelvin and the critical pressure of water is about 22 megapascals.
• the temperature and pressure of the fluid 300 before entering the supercritical state may be maintained such that the water in the fluid is in a vapor state.
• the pressure of the fluid 300 may be raised, at least in part, by increasing the temperature of the fluid within the confined space of the heater and/or reactor. For instance, if the temperature of the fluid 300 is increased from about 700 Kelvin to about 925 Kelvin in a confined space (for example, a space that does not or substantially does not release pressure), the pressure of the fluid may increase from about 25 megapascals to about 33 megapascals. As such, very little, if any, additional pressurization may be required to obtain the desired pressure during the conversion phase 386.
• product of the fluid during the conversion phase may be about 10 " mol /l .
• conversion may occur rapidly within a reactor vessel 325, for instance, in less than 1 minute.
• embodiments provide for management of the throughput of the fluid 300 to ensure a fluid residence time at the conversion phase 386 temperature and pressure conditions sufficient for full conversion.
• the slurry portion of the fluid 300 will react with the supercritical water portion of the fluid within the reactor vessel 325 to generate one or more reactor products, such as hydrogen, carbon dioxide, methane and carbon monoxide and other lightweight hydrocarbons in small quantities.
• heat may be recovered during the conversion phase 386 for use during one or more other phases within the operation cycle.
• the ionic product in the reactor vessel 325 may be about 10 ⁇ 22 mol 2 /l 2 . This ionic product level is about 10 orders of magnitude lower than the ionic product reached during conventional supercritical water gasification process cycles.
• the fluid 300 has reached the conversion phase 386, most of the inorganic salts have been removed from the fluid, further diminishing a source of system component corrosion.
• a pressure letdown phase 388 the pressure of the fluid decreases as it flows out of the reactor vessel 325 and toward a second heat exchanger 360 (for example, a cooling heat exchanger).
• a second heat exchanger 360 for example, a cooling heat exchanger.
• the fluid is far less corrosive.
• the fluid may be maintained at a higher pressure during the pressure letdown phase as a higher fluid density is more conducive to efficient heat recovery and CO 2 recovery and sequestration may occur using more compact storage of product gases.
• the pressure during the pressure letdown phase 388 may be reduced to less than about 8 megapascals.
• the pressure may be recovered for other phases of the supercritical water gasification process, such as the pressurization phase. For example, steam which has been separated from inorganic salts, product gases and char waste may be recycled for other process phases.
• a pressure reservoir may be configured to recover and store released pressure.
• the ionic product of the fluid 300 reduces to less than about 10 ⁇ 40 mol 2 /l 2 .
• the fluid 300 may be cooled using a heat exchanger 355.
• a gas/liquid separator 360 may be used to collect product gases 375 from solution and to release certain waste products 370, such as ash and char effluent.
• Illustrative product gases include hydrogen (3 ⁇ 4), methane (CH 4 ), carbon monoxide (CO), and carbon dioxide (CO 2 ).
• heat may be recovered during the cooldown phase 390 for use during one or more other phases of the supercritical water gasification operation cycle, such as the heating phase 380.
• the ionic product of the fluid 300 does not go above 10 ⁇ 22 mol 2 /l 2 . Accordingly, the corrosiveness of the fluid 300 during the supercritical water gasification process may be diminished independent of other factors, such as system component design, system component materials, slurry concentration, or the like, that would otherwise have an influence on the corrosion rate.
• the supercritical water gasification process depicted in FIG. 3 is for illustrative purposes only and may include more or fewer phases 380, 382, 384, 386, 388, 390 in one or more different sequences.
• the temperatures and pressures described in relation to the phases 380, 382, 384, 386, 388, 390 are non-limiting, as any temperature, pressure and/or temperature-pressure combination may be used during any phase that is capable of operating according to the teachings herein.
• embodiments such as the process depicted in FIG. 3, are described as occurring within multiple system components (for example, salt precipitation reactor 320, a heater 350, and the like), embodiments are not so limited. More or less components, including more or less than depicted in FIG. 3, may be used according to embodiments.
• FIG. 4 depicts a flow diagram for an illustrative method of reducing corrosion in a supercritical water gasification system.
• a supercritical water gasification system may receive 405 a slurry including corrosive ions.
• the components of the supercritical water gasification system may be configured 410 to control the temperature and the pressure of the slurry as the slurry flows through the supercritical water gasification system.
• the components of the supercritical water gasification system may maintain 415 the temperature and the pressure of the slurry such that the ionic product of water in the slurry does not increase above a corrosive ionic product value.
• the ionic product of the fluid is maintained below about 10 ⁇ 22 mol 2 /l 2 .
• the supercritical water gasification system may operate to generate 420 synthesis gas from the slurry through a supercritical water gasification process.
• a supercritical water gasification system will be configured to generate an 3 ⁇ 4 synthesis gas from an aqueous biomass slurry formed from organic plant waste.
• the system will include a heat recovery heat exchanger, a salt precipitation vessel, a reactor vessel, a heater, and a cooldown heat exchanger connected in fluid communication in series.
• the system components will be formed from a nickel alloy material.
• a series of pumps will be used to force the biomass slurry through the system, which will enter at a temperature of about 350 Kelvin and a pressure of about 0.5 megapascals.
• the biomass slurry will enter a heating phase within the heat recovery heat exchanger.
• the biomass slurry will be heated to a temperature of about 720 Kelvin and the pressure will be capped at about 8 megapascals.
• a portion of the heat used for the heating phase will be from heat energy captured during a subsequent cool down phase.
• the pressure will be maintained at about 8 megapascals by venting pressure from the heat recovery heat exchanger that builds up during heating of the coal slurry.
• the biomass slurry will flow toward a pressure pump configured to pressurize the biomass slurry to a pressure of about 24 megapascals as the biomass slurry flows toward the salt precipitation vessel.
• the biomass slurry will reach a temperature of about 720 Kelvin at a pressure of about 24 megapascals.
• Inorganic salts such as sodium chloride, ammonium sulfate, ammonium phosphate, ammonium chloride, ammonium carbonate, and ammonium sulfite will precipitate out of the biomass slurry within the salt precipitation vessel.
• the flow of the biomass slurry through the salt precipitation vessel will be controlled such that the biomass slurry is resident in the salt precipitation vessel for sufficient time to remove precipitated salts from the slurry, about 2 minutes.
• the biomass slurry will flow through the heater and into the reactor vessel.
• the biomass slurry will be heated using indirect heating to a temperature of about 925 Kelvin.
• the pressure of the biomass slurry will increase to about 31 megapascals.
• the ionic product of the biomass slurry will be about 10 - " 22 mol 2 2
• the biomass slurry will react with the supercritical water to produce a reactor product and waste products, such as liquid effluent, ash and char.
• the reactor product and waste products will flow out of the reactor vessel during a pressure letdown phase in which the pressure of the fluid including the reactor product and waste products will be about 5 megapascals. Pressure released during the pressure letdown phase will be captured and used to pressurize the biomass slurry during the pressurization phase.
• the reactor product and waste products will enter a cooldown heat exchanger during a cooldown phase in which the fluid containing the reactor product and waste products will decrease to about 450 Kelvin.
• a gas/liquid separator will be used to separate the 3 ⁇ 4 fuel gas product and the liquid effluent, ash and char waste products.
• mol fl operates to diminish the number of corrosive ions in the fluid moving through the system.
• the nickel alloy material used to form the system components will corrode at a low rate compared to conventional systems, prolonging the lifespan of the system components and the efficiency of the supercritical water gasification process. Additionally, the system will have longer service intervals and require less cleaning and maintenance as compared to a conventional system.
• a supercritical water gasification system will be configured to generate a synthesis gas including 3 ⁇ 4, CO2, CH 4 , and CO from an aqueous liquid coal slurry.
• the system will include the following system components: a heat recovery heat exchanger, a heater and a cooldown heat exchanger formed from a nickel alloy material, a salt precipitation vessel and a reactor vessel formed from a nickel alloy material, a pressurization pump, and a depressurization component.
• the system components will be in fluid communication, connected in series with the coal slurry flowing through the system components in the following order: heat recovery heat exchanger, pressurization pump, salt precipitation vessel, heater, reactor vessel, depressurization component, and cooldown heat exchanger.
• Each of the system components will include a temperature sensor configured to measure the temperature of fluid flowing through the system component.
• Each temperature sensor will be configured to measure temperature in the range of about 600 Kelvin to about 1400 Kelvin.
• each system component will include a pressure sensor configured to measure the pressure within the system component.
• Each pressure sensor will be configured to measure pressure in the range of about 0.1 megapascals to about 45 megapascals.
• Each system component will also include a flow sensor configured to indicate whether a fluid is flowing through the system component.
• a central control device will be in communication with each of the temperature, pressure and flow sensors.
• the central control device will include a processor configured to execute control software adapted to receive information from each of the sensors.
• the control software will determine where the coal slurry is flowing within the system using the flow sensors and will determine the temperature and pressure of the coal slurry using the temperature and pressure sensors of the system component experiencing coal slurry flow.
• the control software will be configured to obtain the operational temperature and pressure for each system component during the phases of the supercritical water gasification process. Operational aspects of the system components will be controlled by the control software to maintain the operational temperature and pressure if they are not within a threshold variance from limits.
• the control software will control the heating and pressure elements of the heat recovery heat exchanger during a heating phase to ensure that the fluid is heated to about 720 Kelvin at a pressure below 8 megapascals.
• the control software will monitor the pressure of the fluid to ensure that the pressure of the fluid increases to about 25 megapascals.
• the control software will receive information from the flow sensor that the fluid is flowing through the salt precipitation vessel and that a salt precipitation phase has commenced.
• the control software will control the temperature and pressure elements of the salt precipitation vessel to ensure that the temperature of the fluid is about 720 Kelvin and that the pressure is about 25 megapascals.
• the flow of the fluid through the salt precipitation vessel will be controlled by the control software such that the residence time of the fluid within the salt precipitation vessel is sufficient to ensure all precipitated salts are removed from the fluid, about 1 minute.
• the control software will detect that the fluid is flowing through the heater and into the reactor vessel and that a conversion phase has commenced.
• the control software will control the heating and pressure elements of the heater and the reactor vessel such that the temperature of the fluid will reach about 920 Kelvin at a pressure of about 32 megapascals within the reactor vessel in order to generate the reactor product.
• the control software will detect that the fluid is flowing into a depressurization component and will monitor the pressure using the pressure sensor to ensure that the pressure of the fluid decreases to less than about 8 megapascals.
• the control software will monitor the temperature of the fluid to ensure that it is cooling down to a temperature below 570 Kelvin before entering a gas/liquid separator where the fuel gas product is separated from the fluid.
• the monitoring and control of the temperature, pressure and/or flow of the fluid during the phases of the supercritical water gasification process will ensure that the concentration of corrosive ions will be sufficiently diminished during the conversion phase.
• the diminished concentration of corrosive ions will reduce the corrosive effects during the reaction of the supercritical water with the coal slurry within the reactor vessel, thereby prolonging the lifespan of system components and the overall efficiency of operating the system. Additionally, the system will have longer service intervals and require less cleaning and maintenance as compared to a conventional system.
• a range includes each individual member.
• a group having 1-3 cells refers to groups having 1, 2, or 3 cells.
• a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.

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• 2013
  • 2013-04-30 CN CN201380074837.4A patent/CN105264048B/zh not_active Expired - Fee Related
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