process for energy production, and system for partial oxidation (pox) and system for energy producti

专利摘要:
abstract the present disclosure reports to a power production system that is adapted to achieve high efficiency power production with complete carbon capture when using a solid or liquid hydrocarbon or carbonaceous fuel. more particularly, the solid or liquid fuel first is partially oxidized in a partial oxidation reactor. the resulting partially oxidized stream that comprises a fuel gas is quenched, filtered, cooled, and then directed to a combustor of a power production system as the combustion fuel. the partially oxidized stream is combined with a compressed recycle co2 stream and oxygen. the combustion stream is expanded across a turbine to produce power and passed through a recuperator heat exchanger. the expanded and cooled exhaust stream is scrubbed to provide the recycle co2 stream, which is compressed and passed through the recuperator heat exchanger and the pox heat exchanger in a manner useful to provide increased efficiency to the combined systems. translation of the patent abstract summary of the invention: "partial oxidation reaction with closed cycle sudden cooling". the present invention relates to an energy production system that is adapted to produce high efficiency energy with complete carbon capture when a solid or liquid hydrocarbon or carbonaceous fuel is used. more particularly, the solid or liquid fuel is first partially oxidized in a partial oxidation reactor. the resulting partially oxidized stream comprising a combustible gas is abruptly cooled, filtered, cooled, and then directed to a combustion of an energy production system as a combustion fuel. the partially oxidized stream is combined with a stream of recycled co2 and compressed oxygen. the combustion current is expanded through a turbine to produce energy and passed through a stove heat exchanger. the expanded and cooled outlet stream is purified to obtain the recycled co2 stream, which is compressed and passed through the stove heat exchanger and the pox heat exchanger in a useful manner to provide greater efficiency to the combined systems.
公开号:BR112014019522B1
申请号:R112014019522
申请日:2013-02-11
公开日:2020-04-07
发明作者:Eron Fetvedt Jeremy；R Palmer Miles；John Allam Rodney
申请人:8 Rivers Capital Llc；Palmer Labs Llc；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for PROCESS FOR ENERGY PRODUCTION, AND SYSTEM FOR PARTIAL OXIDATION (POX) AND SYSTEM FOR COMBINED ENERGY PRODUCTION (PPS).
FIELD OF THE INVENTION [001] The present invention relates to systems and methods for the generation of energy, such as electricity, that use a partial oxidation reactor to obtain a high efficiency combustion of a solid fuel. In particular, the system and method can use coal as a solid fuel.
BACKGROUND [002] Conventional means of producing energy from the combustion of a fuel typically lack the ability to simultaneously provide generation and high efficiency energy and carbon capture and sequestration (CCS) simultaneously. This limitation is extended when solid fuels are used in the combustion reaction because of the solid and inert nitrogen gas contents that remain in the combustion product stream. Therefore, there is an increasing need in the state of the art for systems and methods for the generation of high efficiency energy that allows a reduction in CO2 emissions and / or a greater ease of sequestration of what is produced.
[003] A publication in the field of high-efficiency power generation with CCS, U.S. Patent Application Publication no. 2011/0179799, granted to Allam et al., Provides a solution whereby a solid fuel such as coal, lignite, purge coke or biomass is gassed by reacting with oxygen and optionally steam in an oxidation reactor operating at a pressure and temperature high enough to allow the substantially complete conversion of solid fuel to a
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2/52 gaseous fuel that mainly comprises carbon monoxide and hydrogen as combustible components along with impurities derived from combustion, such as H2S, CS2, COS, HCN and NH3. The partially oxidized pure gaseous product is cooled, the ash is separated, and is optionally compressed to allow it to be introduced as fuel into the combustion chamber of the system for power generation. The operating pressure of the system for partial oxidation and the system for power generation can be such that no compression of the combustible gas is required. The energy system's combustor operates with an excess of O2 present after combustion, which ensures that the fuel and impurities derived from combustion are converted from the reduced forms to their oxidized forms which predominantly comprise SO2 and NO. The partial oxidation reactor can be provided with transpirationally cooled walls with a high pressure recycling CO2 stream that cools the gas of the partial oxidation product before removing ash to a temperature level of about 800 ° C. Additional cooling of the partial oxidation gas to about 400 ° C is necessary to ensure that all fine ash particles together with the solidified volatile inorganic components are condensed and filtered to prevent solid deposition, corrosion and equipment blockage. downward current. The cooling of the partial oxidation gas from 800 ° C to 400 ° C should take place in a heat exchanger with tubes for the high pressure partial oxidation gas that are resistant to corrosion of the metal powder due to the carbon formation reaction of Boudouard and the high partial pressure of CO in the partial oxidation gas. This is shown below in Formula (1).
CO + CO = C + CO2 (1)
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3/52 [004] The tubes must be designed to allow periodic water washing to remove solid deposits derived from the condensation of volatile inorganic components present in solid fuels, such as coal and lignite.
[005] Despite the advances in the publication described above, the systems and methods described here still do not provide a more advantageous solution to the problems that arise when solid fuels are used as an energy-producing combustion fuel. Thus, there remains a need for other systems and methods for the high-efficiency combustion of solid fuels with CCS.
BRIEF SUMMARY OF THE INVENTION [006] The present invention provides systems and methods for the production of high efficiency energy using solid fuels and obtaining simultaneous carbon capture. In particular, the systems and methods presented can use a partial oxidation reactor (POX) in which the solid fuel is burned in order to produce a POX stream comprising partial oxidation products. The POX stream can be directed to a combustion in which at least some of the partial oxidation products are substantially completely oxidized to produce a combustion product stream. In certain embodiments, the POX reactor can be operated at a pressure that is lower than the pressure in the combustion.
[007] In specific modalities, the POX reactor can be adapted to use an abrupt cooling fluid. For example, the blast cooling fluid can be introduced to cool the POX stream from the POX reaction temperature to a sharply cooled POX stream temperature. In exemplifying modalities, the ratio of the POX reaction temperature to the temperature
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The temperature of the sharply cooled POX stream can be about 3.25 or more (for example, about 3.5: 1 or about 4: 1). As non-limiting examples, the temperature of the POX reaction can be about 1,300 ° C or more (for example, about 1,300 ° C to about 1,600 ° C), and the temperature of the POX stream cooled down sharply may be a temperature of about 200 ° C to about 400 ° C. Sudden cooling can be accomplished by mixing directly with the POX stream in the POX reactor or in a separate vessel.
[008] In other embodiments, the solids (such as solid ash particles) produced during the partial oxidation of the primary POX fuel can be removed by separating the gaseous fuel gas plus vaporized sudden cooling fluid. Alternatively, the blast cooling fluid can be present as an additional liquid phase as well as in the gas phase and act as a scrubbing fluid to remove the volume of ash particles. An abrupt cooling temperature of about 400 ° C or less can be useful to prevent the metal powder from slowing down the Boudouard reaction where solid carbon is formed from the reaction of CO molecules. It may also be preferable to operate the system for blast cooling so that a single-phase gaseous POX product with entrained ash particles can be passed through a cyclone and filter system to remove the ash particles.
[009] In other embodiments, the mixture of the POX stream and the steam of the sudden cooling fluid can be additionally cooled, such as up to a temperature of about 100 ° C or less to obtain a cooled POX stream. The sudden cooling and / or the cooling of the POX stream is preferably carried out in such a way that most of the useful heat present in the
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5/52 current of POX suddenly cooled to the temperature of the POX reaction is recovered. The recovered heat can, for example, be transferred to the system for energy production to provide heating of the low temperature which can maximize the efficiency of the system for energy production, which is also described here. In some embodiments, some or all of the sudden cooling fluid can be separated from the cooled POX stream. The recovered blast coolant can be recycled to the POX reactor.
[0010] The systems and methods presented may allow the commercially available POX reactors to be adapted for efficient integration with a system for energy production. In addition, the systems and methods presented can be adapted for the separation of gaseous products. For example, substantially pure H2, CO, or mixtures thereof, can be separated from the cooled POX stream. The systems and methods presented are also beneficial, since some or all of the fuel and impurities derived from POX present in the POX stream can be oxidized in the system's combustor for energy production. After that, such impurities can be removed (for example, as acids and salts), such as with a stream of condensed water.
[0011] In some embodiments, the invention refers to a process that comprises the partial oxidation of a carbonaceous or hydrocarbon fuel by combining it with oxygen in a POX reactor. The fuel can include at least sulfur compounds. The POX reaction can result in a fuel gas mixture that comprises at least H2, CO and H2S. The POX reaction can also result in a fuel gas mixture that comprises at least H2, CO, H2S, NH3 and HCN. The POX system can be coupled with an energy production system (PPS) in which the combustible gas can be burned with oxygen, and the energy
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6/52 thermal energy formed by combustion can be converted into energy. The methods that use the system for POX and PPS combined can be defined by several modalities. The exemplary modalities are provided below.
[0012] All impurities derived from carbonaceous or hydrocarbon fuel, from the POX process, and from oxygen derived from the oxygen plant (for example, an air separation unit) that are present in the POX fuel gas of the POX system after abrupt cooling, removal of solid ash, and cooling by heat exchange with recycled high pressure CO2 from PPS are burned in the PPS. Exemplary impurities can be impurities that are present in addition to H2, CO, CH4, CO2, H2O, N2 and Ar.
[0013] All oxidizable impurities present in the POX fuel gas can be oxidized by the combustion of PPS.
[0014] Sulfur compounds, such as H2S, COS and CS2, which are present in POX fuel gas, can be oxidized as SO2, SO3, H2O and CO2. Any NH3 and HCN present in the POX fuel gas can be oxidized as NO, NO2, H2O and CO2.
[0015] The POX process preferably operates at a pressure of about 2 MPa or more.
[0016] PPS can be defined by power generation when using a turbine with an inlet pressure of about 10 MPa or more.
[0017] PPS can be defined by power generation when using a turbine with a pressure ratio of about 12 or less (from inlet to outlet).
[0018] The POX reaction can be carried out at an adiabatic flame temperature of about 1,300 ° C to about 1,600 ° C.
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7/52 [0019] The POX reactor power can be transformed into a paste with powdered solid fuel in water, CO2, or a combination thereof.
[0020] The POX reactor supply can be defined as comprising a dragged stream of powdered solid fuel.
[0021] The POX reactor supply can be defined as comprising a liquid such as a heated bitumen stream.
[0022] The POX reactor can be adapted to include an internal heat transfer section that transfers the radiant heat to part of a high pressure recycling stream taken from the PPS at a temperature of about 250 ° C or more and returned to the PPS at a temperature below the outlet temperature of the high pressure recycle stream leaving the PPS stove heat exchanger.
[0023] The direct products of the POX reaction can be quenched by means of direct mixing with a recycled part of the POX combustible gas quenched, with a part of condensed liquid water from the POX combusted gas quenched, with recycled CO2 from PPS, or a combination of these three.
[0024] The ash that comes from the fuel used in the process
POX can be removed after the POX products have abruptly cooled and before the POX fuel gas is further cooled.
[0025] The temperature reached in the sudden cooling of the POX stream can be at or below a temperature of about 400 ° C or at a temperature where the speed of the BOUDOUARD reaction is low enough so that no deposition of carbon or Corrosion of metal dust occurs in any equipment downstream in the POX or PPS system.
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8/52 [0026] POX products after rough cooling and ash removal can be cooled to a temperature of around 100 ° C or less by using a high pressure recycling fluid stream taken from and returned to the PPS.
[0027] PPS can be defined by mixing combustion products in the PPS combustor with a pressurized recycling stream and by passing the total stream through at least one PPS turbine adapted for power generation.
[0028] The PPS can be defined by the operation of the turbine or turbines at a final discharge pressure of about 0.1 MPa or more or, in other modalities, of about 1 MPa or more.
[0029] PPS can be defined by the use of one or more heat exchangers that heat the high pressure recycling stream previously compressed against at least the total turbine exhaust current or current.
[0030] PPS can be defined by converting SO2 and SO3 into
H2SO4 by reaction with O2, liquid H2O, NO2 and NO.
[0031] PPS can be defined by converting NO, NO2 and liquid H2O to HNO3.
[0032] PPS acid conversions can be performed at an operating temperature that corresponds to the point at which water condenses, up to a temperature at which water and acids are separated from the cooled exhaust gas of the turbine at the cold end of the heat exchanger. heat from the stove.
[0033] The acids plus the soluble inorganic components formed by the reaction with the acids and optionally diluted with condensed water from the PPS combustor can be removed for further treatment.
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9/52 [0034] A stream or streams of high pressure CO2 recycling fluid can be used to cool the gas of the POX product cooled down sharply after ash removal.
[0035] The high pressure CO2 recycling fluid stream can optionally comprise more than one fluid stream drawn from the PPS at more than one temperature level.
[0036] More than one stream of CO2 recycling fluid can be returned to the PPS at more than one temperature level.
[0037] A fluid stream can be taken from the PPS and returned to the PPS as more than a current at more than one temperature level.
[0038] More than one fluid stream can be taken from the PPS and returned to the PPS as a single heated stream.
[0039] The cooled pure POX fuel gas product, after abruptly cooling and separation of the cooled POX recycling fluid, can be compressed from the pressure at which it exits the system to POX to a pressure substantially the same as the pressure of PPS combustor inlet.
[0040] A fluid stream taken from the PPS to be used to cool a gas from the POX product that has been cooled down sharply can be part of the pressurized recycling stream of the PPS.
[0041] The oxygen used in the POX system can have a purity of more than 90 mol%, preferably more than 95 mol%.
[0042] The partially oxidized gas can be cooled abruptly with water, producing a gas mixture that contains at least H2, CO, CO2, one or more sulfur compounds (for example, H2S) and H2O.
[0043] The cooling of the POX fuel gas which has been cooled down sharply can be carried out with two pressurized recycled gas streams from the PPS; the input temperature of the first stream
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10/52 of recycling entering the POX heat exchanger can be at the discharge temperature of the PPS recycling CO2 compressor; and the inlet temperature of the second recycling CO2 stream entering the POX heat exchanger can be within 20 ° C of the water dew point in the exhaust stream of the PPS turbine.
[0044] The POX stream comprising the fuel gas can be abruptly cooled with water in order to produce a POX gas saturated with water vapor that has an excess of liquid water present; and the two inlet streams of the PPS pressurized recycle gas can leave the POX heat exchanger as a single stream at a temperature within 20 ° C of the POX gas dew point temperature.
[0045] The POX stream can be abruptly cooled with water in order to produce a sharply cooled POX stream that is above its dew point temperature and below 400 ° C; the two input currents entering the POX heat exchanger can be heated and combined at the temperature point corresponding to the second temperature of the input current; a first heated outlet fluid stream can be removed at a temperature within 20 ° C of the dew point temperature of the POX stream, and the remaining stream can also be heated and leave the POX heat exchanger at a temperature of about 380 ° C to 399 ° C.
[0046] A portion of the POX fuel gas after sudden cooling can be removed and passed through a catalytic exchange reactor to convert CO and H2O into H2 and CO2.
[0047] The outlet gas from the exchange reactor can be cooled in the POX heat exchanger cooled down sharply against the recycle gas taken from and returned to the PPS.
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11/52 [0048] The exchanged gas can be mixed with a part of the unchanged gas and further processed to separate water, CO2, sulfur compounds, mercury, and other volatile inorganic components, leaving a mixture that comprises H2 and CO at a ratio of 0.8 to 1 to 2.5 to 1.
[0049] The gas exchanged alone can still be processed to produce a stream of pure H2 of more than 99 mol%.
[0050] The content of each of the sulfur compounds, NH3, HCN of water in the H2 or H2 and CO streams can be less than 1 molar ppm.
[0051] The separation device can be defined as a system for pressure exchange adsorption (PSA) of multiple beds.
[0052] The low pressure residual PSA gas comprising the products adsorbed from the system to PSA can be compressed to the pressure required by the PPS combustor and mixed into the total flow of POX combustible gas to the PPS combustor.
[0053] The oxygen used for the POX of the primary fuel can be heated in the POX heat exchanger to a temperature of up to 350 ° C.
[0054] The oxygen used in the PPS combustor can be heated in the POX heat exchanger to a temperature of up to 350 ° C.
[0055] In some embodiments, the present invention may relate to a process for producing energy by using a combination of a system for POX and a PPS, and the process may comprise the following steps:
[0056] combination of a solid or liquid fuel and oxygen in a POX reactor under conditions sufficient to partially oxidize the fuel and form a POX stream comprising a combustible gas;
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12/52 [0057] sudden cooling of the POX stream by combining with a sudden cooling fluid under conditions sufficient to form a POX stream cooled down sharply to a temperature of about 400 ° C or less and to solidify at least part of all the melting solids present in the POX stream;
[0058] treatment of the POX stream cooled down sharply to remove at least a part of all the solids present in it;
[0059] directing the POX stream abruptly cooled to a POX heat exchanger and withdrawing a quantity of heat from the POX stream abruptly cooling the POX stream abruptly cooling to a temperature of about 100 ° C or less against a cooling stream, and forming a POX combustible gas stream;
[0060] passage of the POX fuel gas stream through a separating vessel and separation of at least a part of any water present in the POX fuel gas stream;
[0061] compression of the POX fuel gas stream to a pressure of about 12 MPa or more;
[0062] combustion of the POX fuel gas in a PPS combustor to form a stream of the combustion product (optionally with a portion of excess oxygen) at a pressure of at least about 10 MPa and at a temperature of at least about 800 ° C; and [0063] expansion of the combustion product stream through a PPS turbine to generate energy and form an expanded stream of the PPS combustion product.
[0064] In specific modalities, the process for the production of energy can also be defined by a variety of characteristics that can be independently applied to a process such
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13/52 as noted above. For example, solid or liquid fuel can be carbonaceous fuel. The combined fuel in the POX reactor can be a current drawn from a powdered solid fuel. The carbonaceous fuel can be specifically coal. Coal can be made into a paste with water or CO2. The roughly cooled POX stream may comprise ash, slag, or a combination thereof, and the step of removing the solids may comprise the passage of the sharply cooled POX stream through a water scrubbing unit. The step of removing the solids may comprise the filtration of the abruptly cooled POX stream in order to reduce the dust load to about 4 mg or less per cubic meter of combustible gas in the abruptly cooled POX stream. The POX reactor can be operated at a POX temperature, and a ratio between the POX temperature and the temperature of the POX stream that has been rapidly cooled can be about 2: 1 or more. The POX temperature can be from about 1,300 ° C to about 1,600 ° C. The POX reactor can be operated at a pressure of about 2 MPa or more. Abrupt cooling may comprise mixing the POX stream with: a recycled portion of the cooled POX fuel gas stream exiting the heat exchanger; a portion of the water separated from the cooled POX fuel gas stream; CO2 recycled from PPS, water, or a combination thereof. The cooling stream in the heat exchanger may comprise a stream of high pressure recycling fluid taken from and returned to the PPS. The high pressure recycling fluid stream can be a recycling CO2 fluid stream. The stream of recycling CO2 fluid can comprise the CO2 formed in the combustion of the POX combustible gas in the PPS combustor. The POX reactor can include an internal heat transfer component. The internal heat transfer component can
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14/52 be adapted to transfer radiant heat to a part of a high pressure recycling stream taken from a PPS component at a temperature of about 250 ° C or more. The internal heat transfer component can be adapted to return the high pressure recycle stream to a PPS component. The PPS turbine can have an inlet pressure of about 10 MPa or more. The PPS turbine can have an outlet pressure that is defined as a ratio between the turbine inlet and the turbine outlet. In an exemplary embodiment, the ratio may be about 10 or less.
[0065] In other additional modalities, the process for the production of energy when using a combination of a system for POX and a PPS can also comprise:
[0066] the passage of the expanded PPS combustion product stream through a PPS stove heat exchanger and thereby withdrawing heat from the PPS combustion product stream and the formation of a combustion product stream from Cooled PPS;
[0067] optionally, the passage of the stream of PPS combustion product cooled through a water cooler;
[0068] the treatment of the PPS combustion product stream cooled in a PPS scrubber, separating at least one or H2SO4, HNO3, or Hg salts dissolved in water and the formation of a recycling CO2 stream; and [0069] the pressurization of the recycling CO2 stream in a PPS compressor and the formation of a compressed recycling CO2 stream.
[0070] In specific modalities, the separation step may include the separation of conversion products of H2SO4 and HNO3 formed by the reaction of SO2, SO3, NO, NO2, H2O and O2 more
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15/52 condensed water and dissolved Hg salts. The passage of the expanded PPS combustion product stream through the PPS stove heat exchanger can cool the PPS combustion product stream to a temperature below the water dew point. The fuel gas in the POX fuel gas stream entering the PPS combustor can comprise at least one fuel gas component selected from H2, CO and CH4. The stream of POX combustible gas entering the PPS combustor may comprise one or more impurities separated from the combustible gas and derived from solid or liquid fuel, its partial oxidation, and oxygen. One or more impurities can comprise at least one of a sulfur compound, NH3 and HCN. One or more impurities can expressly exclude N2 and argon. Substantially all impurities can still be present in the POX fuel gas stream and can be burned in the PPS combustor. All oxidizable impurities present in the POX combustible gas stream can be oxidized by combustion in the PPS combustor. The combustion product stream of the PPS combustion may comprise a mixture of combustion products and at least part of the compressed recycled CO2 stream. The heat taken from the PPS combustion product stream can heat at least part of the compressed recycle CO2 stream. The POX stream can be abruptly cooled with water. The POX stream cooled with water can comprise at least H2, CO, CO2, H2S and H2O. The cooling stream in the POX heat exchanger can comprise two compressed recycled CO2 streams. An inlet temperature of the first compressed recycle CO2 stream entering the POX heat exchanger can be substantially the same as a temperature of the compressed recycle CO2 stream discharged from the compressor.
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16/52
PPS. An inlet temperature of the second compressed recycle CO2 stream entering the POX heat exchanger can be within 20 ° C of the water dew point in the expanded stream of the PPS combustion product. The POX stream cooled down sharply with water can be saturated with water vapor in order to comprise excess liquid water. The two compressed recycling CO2 streams can combine in the POX heat exchanger to form a single stream. The single compressed recycle CO2 stream coming out of the POX heat exchanger can be at a temperature that is within about 20 ° C of the POX fuel gas dew point temperature. The POX stream cooled down sharply with water can have a temperature that is above its dew point temperature and below about 400 ° C. The two compressed recycle CO2 streams can be heated, and the point at which the two compressed recycle CO2 streams combine to form the single stream may be at a temperature that substantially corresponds to the inlet temperature of the second recycle CO2 stream compressed. The single stream can be divided into the following: a first compressed heated recycled CO2 stream from the outlet that leaves the POX heat exchanger at a temperature that is within about 20 ° C of the dew point temperature of the POX stream ; and a second compressed heated recycle CO2 stream leaving the POX heat exchanger at a temperature of about 380 ° C to about 399 ° C.
[0071] In additional modalities, a part of the POX stream cooled down sharply can be directed through a POX catalytic exchange reactor. The POX catalytic exchange reactor can be adapted to convert a mixture of CO and H2O into an outlet gas of the exchange reactor that comprises a mixture of H2 and CO2. The gas from
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17/52 exchange reactor outlet can be cooled in the POX heat exchanger against a recycle gas taken from and returned to the PPS. The outlet gas from the exchange reactor can be mixed with a portion of the POX stream cooled down sharply and can also be processed to separate water, CO2, sulfur compounds, Hg, and volatile inorganic compounds, to form a mixture comprising H2 and CO at a rate of about 0.8: 1 to about 2.5: 1. The outlet gas from the exchange reactor can also be processed to form a stream of pure H2 with a purity of 99 mol% or more. The POX stream processor can be a multi-bed pressure exchange adsorption (PSA) system. A low pressure residual gas from the PSA system comprising products adsorbed from the PSA system can be compressed to a PPS combustor pressure and mixed into the total combustible gas stream entering the PPS combustor. The oxygen used in the POX reactor can be heated in the POX heat exchanger to a temperature of up to about 350 ° C. The oxygen used in the PPS combustor can be heated in the POX heat exchanger to a temperature of around 350 ° C.
[0072] In other embodiments, the invention can provide a system for combined POX and PPS, and the combined system can be useful in order to produce energy, such as electricity, from a non-gaseous starting fuel. In some modalities, a system for POX and PPS can comprise the following elements:
[0073] a POX reactor adapted to partially oxidize a liquid or solid fuel in the presence of oxygen to form a POX stream comprising a combustible gas;
[0074] one or more components adapted to come into contact with the POX current with an abrupt cooling fluid;
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18/52 [0075] an optional POX scrubber adapted to separate any solids present in the POX stream cooled down sharply from the POX fuel gas;
[0076] a POX heat exchanger adapted to remove the heat from the POX combustible gas against a part of a compressed recycling CO2 stream and emit a cooled POX combustible gas;
[0077] an optional separator adapted to separate any liquid water from the POX fuel gas;
[0078] a compressor adapted to compress the cooled combustible gas of POX to a pressure of about 12 MPa or more;
[0079] a PPS combustor adapted to burn POX combustible gas in the presence of oxygen and a portion of the compressed recycling CO2 stream and form a stream of the PPS combustion product at a pressure of about 12 MPa or more;
[0080] a turbine adapted to expand the current of the PPS combustion product and generate energy in a connected generator;
[0081] a fireplace heat exchanger adapted to remove the heat from the expanded stream of the PPS combustion product and add the heat to the compressed recycling CO2 stream;
[0082] a PPS purification tower adapted to separate any oxidized impurities from the expanded stream of the PPS combustion product and emit a recycled CO2 stream;
[0083] a PPS compressor adapted to compress the CO2 recycling stream to a pressure of about 12 MPa or more and form the compressed recycling CO2 stream;
[0084] flow components adapted to direct part of the compressed recycling CO2 stream to the POX heat exchanger;
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19/52 [0085] flow components adapted to direct a part of the compressed recycling CO2 stream to the PPS fireplace heat exchanger; and [0086] flow components adapted to direct the flow of
Compressed recycling CO2 from the POX heat exchanger to the PPS fireplace heat exchanger.
BRIEF DESCRIPTION OF THE DRAWINGS [0087] Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and in which:
[0088] FIG. 1 is a flow sheet illustrating an exemplary embodiment of a combined POX and PPS system according to the present invention in which the PPS generates energy by using a combustible gas derived from the partial oxidation of a liquid or solid hydrocarbon or carbonaceous fuel in the system for POX;
[0089] FIG. 2 is a flow sheet illustrating a part of the combined system of FIG. 1, in which the illustrated part shows in particular elements of the combined system useful for the production of mixtures of H2 or H2 + CO for export;
[0090] FIG. 3 is a graph of the temperature versus the heat transferred in a combustible gas heat exchanger to a system according to an exemplary embodiment of the present invention when using a CO2 coal slurry with a POX reaction cooled down with water that operates with excess water so that the POX fuel gas cooled down sharply is at the dew point temperature of the water;
[0091] FIG. 4 is a graph of the temperature versus the heat transferred in a POX heat exchanger to a system according to an exemplary embodiment of the present invention when using a CO2 coal paste with a blast cooled POX reaction
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20/52 with water that operates at an abrupt cooling temperature of 400 ° C;
[0092] FIG. 5 shows the balance between mass and heat of an ASPEN simulation of an energy system that combines a system for POX and PPS according to an exemplary embodiment of the present invention, in which the simulation included the use of a coal paste / CO2 in the POX reactor and the use of water as an abrupt cooling fluid; and [0093] FIG. 6 shows the balance between mass and heat of an ASPEN simulation of an energy system that combines a system for POX and PPS according to an exemplary embodiment of the present invention, in which the simulation included the use of a coal paste / CO2 in the POX reactor and the use of CO2 as an abrupt cooling fluid.
DETAILED DESCRIPTION OF THE INVENTION [0094] The invention will now be described more widely by reference to various embodiments. These modalities are provided in such a way that this presentation is complete and complete, and will fully address the scope of the invention to elements skilled in the art. Certainly, the invention can be incorporated in many different forms and should not be interpreted as limited to the modalities presented here; instead, these modalities are provided so that this presentation meets the applicable legal requirements. As used in the specification and the appended claims, the singular forms one, one, o / a include plural referents unless the context clearly dictates otherwise.
[0095] The systems and methods of the present invention are adapted to obtain partial oxidation (POX) of a carbonaceous fuel, in particular a solid fuel and / or a liquid fuel 870190088382, of 06/09/2019, pg. 25/71
21/52 do. Non-limiting examples of fuels that can be used in accordance with the present invention include coal, lignite, petroleum coke, bitumen, biomass, algae, wood, graded combustible solid waste, asphalt, used tires, crude oil , other liquid fuels containing ash, and still others. [0096] In various embodiments, the systems and methods of the invention are adapted to partially oxidize the fuel using oxygen, preferably substantially pure O2, to produce a current that is useful as a combustible gas. Partial oxidation can be carried out in a POX reactor. In particular embodiments, an air separation unit or other oxygen plant can be used in the systems and methods of the present invention. The plant's oxygen can be directed to the POX reactor. In some embodiments, oxygen can first be passed through a heat exchanger to increase the temperature of the oxygen entering the POX reactor. The nitrogen from the air separation plant can also be incorporated into the systems and methods. For example, dry N2 can be passed through a crusher that is turning solid fuels into particles and thereby partially drying the particulate fuel. The particulate fuel can also be crushed in a second crusher to a particle size preferably about 500 microns or less, about 250 microns or less, or about 100 microns or less. The small particulate fuel can be directed to a mixer to be formed as a paste with a paste forming medium. The pulp medium may comprise CO2, which preferably has a pressure of about 3.5 MPa or more, about 5 MPa or more, or about 8.5 MPa or more. The CO2 in the middle of the CO2 slurry may preferably be at a temperature of about 5 ° C to about 40 ° C, from about 10 ° C to about 30 ° C from about 12 ° C to about 25 ° C. CO2 in
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22/52 CO2 slurry medium can have a density of about 500 kg / m ³ to about 1,000 kg / m ³ , from about 600 kg / m ³ to about 900 kg / m ³ , or about 700 kg / m ³ to about 800 kg / m ³ . The paste medium may alternatively comprise water or a combination of CO2 and water. A solid fuel slurry used in the POX reactor can comprise about 25% to about 75%, about 30% to about 70%, or about 40% to about 60% by weight of solid fuel. The particulate fuel slurry is then combined in the POX reactor with oxygen, which preferably comprises about 90 mol% or more, about 95 mol% or more, about 97 mol% or more of oxygen. The POX reactor preferably operates at a pressure of about 4.5 to about 8.5 MPa and a temperature of about 1,450 ° C; however, the temperature and pressure can be in any combination of temperature and pressure ranges as otherwise indicated herein with respect to the nature of the POX stream leaving the POX reactor.
[0097] The partial oxidation of carbonaceous fuel in the reactor
POX forms a POX chain, which can be defined in terms of its components. In particular, the POX stream may comprise a combustible gas and one or more impurities (oxidizable and non-oxidizable impurities). The fuel gas may comprise hydrogen, carbon monoxide, or a combination thereof. Exemplary impurities derived from the original POX fuel (solid or liquid hydrocarbons or carbonaceous material) or from partial oxidation reactions include, for example, H2S, COS, CS2, HCN, NH3 and Hg. The current comes from the POX reactor in which the POX current produced in the reactor can be cooled down sharply with a cooling fluid. This can result in partial vaporization of the cooling fluid to produce a combustible gas that comprises the vaporized cooling fluid mixed with the
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23/52 fuel gas. Excessive sudden cooling fluid can be used to obtain a mixture of liquid cooling fluid and vapor fuel gas plus vaporized cooling fluid as a product of the POX reactor. The cooled POX stream can be subjected to separation so that solids (for example, solid ash particles) can be removed. The solids in particular can be removed in a mixture with the liquid cooling fluid that is separated from the fuel gas mixture. Any remaining fine ash particles can be removed by a downstream cooling fluid wash column followed by a spark plug or the like. Alternatively, sudden cooling can result in a gaseous phase with entrained ash particles that are removed in a combination of cyclones and filters. The cooled POX stream can then be cooled in a heat exchanger to recover at least some of the useful heat that was present in the POX stream prior to the sudden cooling. In particular, the volume of the vaporized cooling fluid mixed with the combustible gas can be condensed, and the heat can be transferred mainly to a high pressure recycle stream to reduce the temperature difference at the hot end of a recoverable heat exchanger in the system for energy production. This can be particularly beneficial for increasing the total efficiency of the system for energy production alone or in combination with the system for POX. The POX stream (i.e., the combustible gas stream) can be produced at a pressure that is less than or equal to the pressure required for further combustion of the combustible gas in the combustor for energy production. For example, a combustor and an associated energy production cycle that can be combined with the systems and methods of the present invention are described in US 2011/0179, / 1799, the quote of which is incorporated herein.
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24/52 reference title in its entirety. Such combustion and associated energy production cycle can be referred to here as a SYSTEM for NET energy. The system process for LIQUID energy provides energy generation by predominantly using CO2 as a working fluid. In particular, the process uses a turbine with a high pressure / low pressure ratio that expands a mixture of a high pressure recycling CO2 stream and combustion products from combustion of the fuel. Pure oxygen can be used as an oxidant in the combustion process. The hot turbine exhaust is used to partially preheat the high pressure recycling CO2 stream. The system's recycling CO2 stream for LIQUID energy is also heated by using the heat derived from the compression energy of the air load of the O2 production plant. All fuel and impurities derived from combustion, such as sulfur compounds, NO, NO2, CO2, H2O, Hg and others are further separated for disposal without any emissions into the atmosphere.
[0098] The systems and methods of the present invention can be specifically characterized as being a combination of a system for POX and a system for energy production (PPS). The NET energy system is an example of a PPS that can be used in accordance with the present invention. In particular, a POX combustible gas stream can be introduced into the PPS combustor as a part or all of the fuel stream for the combustion. In a high-pressure combustion cycle, the fuel gas in the POX stream must generally be compressed to the high pressure required in the system's combustor for energy production. For example, the POX fuel gas stream can be compressed in a compressor to a pressure of about 10 MPa or more, about 15 MPa or more, about 20 MPa or more, or about
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25/52 of 25 MPa or more. In other embodiments, the pressure can be from about 8 MPa to about 50 MPa, from about 15 MPa to about 45 MPa, or from about 20 MPa to about 40 MPa.
[0099] The POX combustible gas stream that comes from the reaction of oxygen with a solid or liquid fuel can comprise varying amounts of solids and melting solids that must be removed before the introduction of the POX combustible gas stream into the PPS combustor. . Specifically, the POX fuel gas stream can be abruptly cooled and cooled as needed to a temperature at which ash and other solid materials can be removed. This is beneficial to prevent contamination downstream of the equipment in the POX and PPS system. The heat released during the cooling of the POX fuel gas stream can be transferred to the system for energy production to maximize the overall efficiency of the system for energy production. In particular, this heat can be used to partially heat at least a part of the CO2 recycling fluid that circulates in energy production after cooling the combustion product stream and before the recycling CO2 fluid enters the combustion of the system for energy production. In particular, heat can be added to the recycling CO2 fluid after compression of the recycling CO2 fluid. Optionally, the oxygen required for the POX reactor and / or the system combustion for energy production can also be heated against the cooling POX current in the same heat exchanger or in a different heat exchanger.
[00100] The POX reactor can be adapted to provide a stream of outgoing POX fuel gas that has a temperature that is about 1,200 ° C or more, about 1,300 ° C or more, or about 1,400 ° C or more. More particularly, the temperature can
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26/52 from about 1,000 ° C to about 2,000 ° C, from about 1,200 ° C to about 1800 ° C, or from about 1,300 ° C to about 1,600 ° C. In several embodiments, one or more steps can be used to cool the POX stream (and thus the combustible gas to enter an additional combustion), preferably up to almost room temperature.
[00101] In one step, the POX current that immediately leaves the POX reactor at a temperature as described above can be abruptly cooled to a lower temperature. Abrupt cooling preferably reduces the temperature to 400 ° C or less, which is a region where the speed of the BOUDOUARD reaction is so low that no carbon formation or metal powder corrosion will occur. Sudden cooling to a temperature of 400 ° C or less serves to condense volatile metal salts for subsequent removal. The blast cooling step can be adapted to reduce the temperature of the POX stream to a lower temperature that can be set for a reason in relation to the temperature of the POX reaction. In particular embodiments, the ratio between the temperature of the POX reaction and the temperature of the POX stream cooled down sharply can be about 3.25: 1 or more, about 3.5: 1 or more, or about 4: 1 or more. More particularly, the ratio of the temperature of the POX stream to the sharply cooled POX stream can be from about 3.25: 1 to about 6: 1, from about 3.75: 1 to about 5.5 : 1, or from about 4: 1 to about 5: 1. In particular embodiments, the temperature of the sharply cooled POX stream can be about 400 ° C or less, about 350 ° C or less, or about 300 ° C or less. In particular embodiments, the temperature can be from about 200 ° C to about 400 ° C, from about 225 ° C to about 375 ° C, or from about 250 ° C to about 350 ° C. Sudden cooling can be performed by mixing
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27/52 remove the POX current with one or more sudden cooling fluids. Non-limiting examples of rough cooling fluids that can be used in accordance with the present invention include a stream of recycled POX product (i.e., at least part of the POX product that has already been cooled to a temperature of the cooling fluid abrupt and then cooled in the POX gas heat exchanger followed by the separation of liquid water), water at a temperature of the sudden cooling fluid, liquid CO2, its mixtures, and others. A temperature of the useful blast coolant can be about 150 ° C or less, about 100 ° C or less, about 75 ° C or less, or about 60 ° C or less. The temperature of the sudden cooling fluid can be in particular from about 10 ° C to about 150 ° C, from about 15 ° C to about 100 ° C, or from about 20 ° C to about 75 ° C . Alternatively, the blast cooling fluid can be preheated against the POX gas cooled down sharply or by other means to a temperature approach typically of about 20 ° C below the POX blast cooling temperature. In the modalities that use a sudden cooling with water, a part of the water can be vaporized, thus resulting a mixture of combustible gas, steam, and a part of liquid water, which removes the volume of the ash particles by washing. The temperature of the liquid and the total vapor will be determined by the pressure used in the POX reactor and the amount of liquid water used for the sudden cooling.
[00102] An additional step can provide for the separation of any liquid water and the volume of any ash particles or other vapor solids from the sharply cooled POX stream. The removal of solids can be performed using any conventional separation means or filters. Non-limiting examples of appropriate solids removal components include cyclone filters,
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28/52 sedimentation tanks, candle filters, bag filters, liquid washing towers, and others. In some embodiments, a separator can be provided at the bottom of the POX reactor. The separated steam can generally be introduced at the base of a countercurrent water wash column to remove other traces of particulate ash. The clean POX fuel gas plus the steam stream can then optionally be passed through a gas filter, such as a spark plug, to ensure that there can be no particle deposition in the heat exchanger used to cool the fuel gas. or in the downstream PPS. In some embodiments, a stream of liquid CO2 can be used as an abrupt cooling fluid. In this case, the total current after sudden cooling may consist of a single vapor phase with entrained solid particles. The amount of liquid CO2 used for the sudden cooling can be such that the temperature of the abruptly cooled stream is about 200 ° C to about 400 ° C. The ash can be removed in a series of filters as indicated above. In other embodiments, a separate combustible gas stream cooled after water separation can be used as a part or all of the sudden cooling fluid. In several embodiments, a preferred method of sudden cooling can use water. The system can also use a mixture of water and CO2 in which the amount of water is sufficient to produce sufficient liquid water after rough cooling to wash off the volume of ash particles.
[00103] In yet another step, the POX stream cooled down sharply (preferably after filtering the solids) can be cooled to almost room temperature. Therefore, the systems and methods presented may include one or more components adapted for heat exchange. In particular, a
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29/52 heat can be adapted to transfer the heat from the cooled POX stream sharply to one or more parts of the high pressure recycling CO2 stream used in the system for energy production. For example, heat can be transferred to the high pressure recycling CO2 stream taken from the discharge of the CO2 recycling compressor and / or to one or more appropriate points on the stove heat exchanger that is used in the energy production cycle. . The choice of temperatures for heat injection into the PPS stove heat exchanger and the number and inlet temperature of the currents taken from the PPS stove heat exchanger to be heated in the blast chilled fuel gas cooler can be determined by change the heat recovery process to ensure that the heat recovery is at the maximum temperature level consistent with the economical sizes of the heat exchanger.
[00104] The solid fuel used in the POX reactor can be supplied in a variety of ways. In the embodiments indicated above, a solid fuel can be supplied in a particulate form, preferably in a finely pulverized state, and can be made into paste with a paste medium. In preferred embodiments, the pulp medium may comprise, for example, water, liquid CO2, and combinations thereof. Liquid CO2 can be formed, at least in part, from CO2 recycled from the system for energy production. The use of CO2 as a slurry can be particularly useful in reducing the heat required to raise the POX fuel feed temperature to the range of the POX reactor compared to the use of a different slurry medium such as water (for example, condensed water and separated from the system for energy production). Although CO2 may be a preferred paste-forming medium, other materials, including water,
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30/52 can still be used as desired and can lead to acceptable losses in efficiency under certain embodiments of the present invention. The carbonaceous fuel used in the POX reactor can be a liquid such as heated bitumen, in which case no paste-forming fluid may be required.
[00105] When CO2 or water is used as a slurry, the composition of the POX stream leaving the POX reactor can have a high concentration of carbon monoxide (CO) and a partial pressure. In such embodiments, it may be particularly desirable to ensure that the sudden cooling of the POX stream is adapted to cool the stream and thereby form a sharply cooled POX stream that has a temperature of less than 400 ° C. The provision of such a drop in temperature may in particular limit the kinetics of the BOUDOUARD reaction to a sufficiently low state such that no carbon can be deposited in the POX current heat exchanger and in such a way that no corrosion with metal dust may occur in the downstream equipment.
[00106] With respect to the particular modalities, the systems and methods of the invention can encompass at least the following four sets of operational conditions with respect to the combination of the POX fuel load and the POX heat exchange: the fuel paste of CO2 with sudden cooling with CO2; the CO2 fuel paste with sudden cooling with water; the fuel and water paste with sudden cooling with water; and the slurry of fuel and water with sudden cooling with CO2. However, it should be understood that other combinations may arise based on the use of an additional paste formation medium and / or other sudden cooling fluids. In addition, the fuel slurry can be a combination of water and CO2. Of
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31/52 likewise, the sudden cooling fluid can be a combination of water and the cooled POX stream.
[00107] The heat released by cooling the POX stream cooled down sharply in the heat exchanger after ash removal can be transferred to one or more parts of the high pressure CO2 recycling stream taken from the system for energy production. The blast cooling fluid can be recycled POX combustible gas coming out of the cool end of the POX heat exchanger after liquid water separation, or it can be condensed and separated water. It can also be a combination of fuel gas and water. In addition, it can be recycled CO2, or a combination of combustible gas, or water, or both with CO2. In some embodiments, the source of sudden cooling fluid may be particularly relevant. The modalities that use a CO2 slurry can result in a net production of water derived from hydrogen and water present in the solid fuel load (for example, coal). Liquid water separated in this way can be treated to separate the flammable components dissolved in the water. These separate flammable elements can be compressed and returned to the system's combustor for energy production. The clean water stream can then be recycled to the solid fuel slurry system or to the POX blast cooling system, and all excess water can be sent to the system for energy production where it can be used to dilute any H2SO4 / HNO3 acid produced in the water separation stage in the energy production system as described in US Patent Application Publication no. 2011/0179799. In the modalities in which the solid fuel is made into a paste with water, the water present in the high temperature POX stream can react with the CO produced by the partial oxidation of the carbon in the solid fuel to produce
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32/52 hydrogen gas and carbon monoxide. These can be present in a ratio of about 1: 1 between H2 and CO by volume.
[00108] This consumption of water in the exchange reaction can be indicative of a water deficiency, and the water produced in the system for energy production can then be returned to the system for POX in order to produce the solid fuel coal slurry and from that compensate for this consumption. The pure cooled POX stream (i.e., the fuel gas stream) can then be compressed to the pressure required for combustion in the energy-producing combustion. In various embodiments, the system and method of the present invention can be adapted to produce an internal blast cooling fluid for use with the high temperature POX stream that exits the POX reactor. This can result from the sequential steps of the POX reaction, the removal of solids, the cooling with heat exchange, and the separation of water. The net amount of the combustible gas in the POX stream can be compressed and passed to the system's combustor for energy production with a relatively high concentration of flammable gases (eg H2 and CO) and with a caloric value that ensures useful combustion conditions in the system's combustor for energy production.
[00109] In some embodiments, a POX reactor according to the invention can be adapted to operate at a pressure that is higher than the pressure in the combustion system for energy production. The combustion system for energy production in particular can use CO2 as a working fluid that is continuously recycled in the system. Preferably, the POX stream can be abruptly cooled and cooled through heat exchange as described here using the cooled POX stream or water as a brisk cooling medium, and the POX stream cooled (i.e., a fuel gas) can be used in the system for proPetition 870190088382, from 06/09/2019, pg. 37/71
33/52 energy output without the need for additional compression. The POX reactor can comprise any reactor adapted for the combustion of a carbonaceous fuel, in particular in which the fuel is only partially oxidized, and in particular in which the reactor is adapted to operate at a pressure that is higher than the pressure operation of a combustion system for energy production as described herein. In exemplary non-limiting modalities, a POX combustor can use perspiration cooling cools where a cooling fluid, such as CO2, is passed through a porous perspiration layer that surrounds the POX combustion chamber, which can be particularly useful for preventing ash collision and agglomeration. Exemplary transpiration cooling modalities that can be used with a POX reactor according to the present invention are described in U.S. Patent Application Publication no. 2010/0300063 granted to Palmer et al., In U.S. Patent Application Publication no. 2011/0083435 granted to Palmer et al. and in U.S. Patent Application Publication no. 2012/0073261 granted to Palmer et al., Whose citations are incorporated herein by reference in their entirety.
[00110] In other embodiments, a POX reactor according to the invention can be adapted to operate at a pressure that is below the pressure of the system's fuel for energy production. In such embodiments, a POX stream to be used as a fuel in the energy system's combustor can be compressed prior to switching to the energy system's combustor. The POX reactor can comprise any commercially available system. Non-limiting examples of the commercially available systems useful in accordance with the present invention include a charcoal flow entrained reactor
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34/52 dry powder from Shell, a blast cooling reactor from GE / Texaco, a blast cooling reactor from Siemens, or similar systems. Useful POX reactors can include internal heat transfer sections that absorb the radiant heat from the POX burner. In such embodiments, a portion of the high pressure recycled CO2 stream in the system for energy production can be heated and returned to a higher temperature in the system for PPS. For example, the recycled CO2 at a temperature of about 400 ° C or more can be heated to a temperature of about 450 ° C to about 600 ° C inside the POX reactor and returned to the heat exchanger in the system to energy production, where it can be remixed with an additional part of the high pressure recycling CO2 stream at a similar temperature.
[00111] The combination of a POX reactor with a system for producing energy according to the present invention can provide a variety of useful aspects. As an example, the combination can be defined since impurities (such as coal or another solid fuel and partial oxidation of the fuel) can be retained in the cooled high pressure POX stream that enters the system combustion to production of energy. Such impurities can comprise H2S, COS, CS2, HCN, NH3 and Hg. These and other impurities can be oxidized in the energy system's combustor to form, for example, SO2, CO2, N2, NO and Hg, which can then be removed from the system for energy production. For example, a stream of condensed water from the combustion outlet stream of the energy production system may be acidic, which comprises one or more of HNO3, H2SO4, and dissolved inorganic salts, as described in the US Patent Application Publication at the. 2011/0179799.
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35/52 [00112] The processing of solid fuel through the POX reactor instead of directly through a combustion system for energy production can be particularly useful in light of the ability to possibly remove products from the scale reaction. For example, a POX stream leaving the POX reactor can be cooled down sharply to a temperature of around 400 ° C or less or another useful temperature to ensure that coal-derived ash (or other molten impurities that come from the coal or other solid fuel) is in a solid form that can be removed. Preferably, the solid impurities can be removed to a very low concentration and a particle size small enough to substantially prevent blockage and / or corrosion of the system components for energy production, such as heat exchangers, turbines, compressors, and others.
[00113] In addition to the above, the sudden cooling of the POX current of the POX reactor can be adapted to provide a POX current which is cooled sharply below a temperature as defined herein and is low enough to ensure that the concentration of the the vapor of all inorganic components in the solid fuel is likewise low enough to substantially prevent deposition in one or more components of the system for energy production. For example, partial oxidation of coal can produce one or more alkali metal salts including NaCl, CaSO4 and KCl, which can be removed as discussed herein. The upper temperature limit of the sharply cooled POX stream can also be adapted to ensure that the BOUDOUARD reaction is slow enough to substantially prevent carbon deposition and / or corrosion by metal dust
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36/52 in any heat exchanger or other components in the system for energy production.
[00114] The systems and methods of the present invention can be adapted to provide recovery of substantially all of the heat released during the cooling of the POX stream, preferably cooling to near ambient temperature, and heat recovery in the stream of POX. High pressure CO2 recycled in the system for energy production. This additional heating can in particular be provided at the lowest temperature level in the system's heat exchanger for energy production. The addition of additional heat in this way can provide a significant positive effect on the overall efficiency of the energy production system. This effect is due to the much higher specific heat of the high pressure recycling CO2 stream in the lower temperature range of 50 ° C to 400 ° C compared to the higher temperature range of 400 ° C to 800 ° C and to the lower specific heat of the turbine exhaust current which is cooling in the system's heat exchanger for energy production. This marked difference means that significant extra extra heat is required in the stove heat exchanger in the temperature range of 50 ° C to 400 ° C to heat the recycle CO2 stream. The additional heat obtained from the POX stream cooled down sharply in the POX stream heat exchanger provides an effective amount of additional heat for the energy system's combustor that is substantially equivalent to the amount of heat released when the combustible gas itself is burned .
[00115] In several modalities, the POX reactor is abruptly cooled to saturation when using a recycling water stream, and the heat-release temperature curve for the cooling of the POX stream abruptly cooled to almost room temperature.
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37/52 ente exhibits a large initial heat release when the water vapor derived from the sudden cooling water vaporization begins to condense. This heat release per unit of temperature drop progressively decreases as the POX stream cools. The effect requires that two separate high-pressure recycling CO2 streams taken from the high-pressure recycling stream of the energy production system be used to recover the heat from the rapidly cooled POX stream. In some embodiments, the first high pressure recycling CO2 stream can be drawn from the CO2 recycling compressor discharge at a temperature of about 45 ° C to about 70 ° C. The second high pressure recycle CO2 can be taken from the high pressure recycle stream at a point in the stove heat exchanger where there is a small approximation of the temperature to the dew point of the turbine exhaust cooling stream. These two streams together can provide a large initial heat release from the POX stream that is cooled down sharply as its water content begins to condense, which can be efficiently transferred back to the high pressure recycling CO2 stream at the temperature level. highest possible (see FIG. 3). In the modalities in which the POX stream is abruptly cooled initially to about 400 ° C, there is a cooling range between about 400 ° C and the water dew point of the POX stream cooled down sharply, and this range may require a lower flow of high pressure recycling CO2 to efficiently remove this part of the available heat from the POX stream that has been chilled sharply compared to the temperature range below the dew point of the POX stream water. This can be accomplished by removing a portion of the high pressure heating recycling CO2 stream at a point near and / or below the dew point temperature of the stream water
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38/52 POX quenched while the remainder is removed at a temperature close to and / or below the quench temperature (for example, about 400 ° C) (see FIG. 4). The high pressure recycling CO2 stream can then be returned to the stove heat exchanger at a temperature point corresponding to the bulky flow of high pressure CO2 in the stove heat exchanger. In various embodiments, options for the two currents to combine in the POX cooling heat exchanger with a single return current can be provided. In some embodiments, more than two streams of high pressure recycling fluid can be used.
[00116] In some embodiments, the combustible gas taken from the POX reactor after rough cooling and ash removal can predominantly comprise H2, CO, CO2 and H2O at a temperature of about 250 ° C to about 400 ° C. A part of this fuel gas stream can be taken to produce pure H2, CO, or a combination of these with varying ratios between H2 and CO. Typical applications for large-scale production of H2 can be, for example, hydrodesulfurization and hydrocracking at refineries and potentially as a vehicle fuel. Typical applications for mixtures of H2 and CO can be, for example, the production of Fischer-Tropsch hydrocarbon liquids (for example, with a ratio of about 2.2 between H2 and CO) and the production of methanol ( for example, with a ratio of about 2.0 between H2 and CO). In each case, the ratio of H2 to CO should be increased from the ratio of about 1 or less in the POX fuel gas stream where the ratio depends on the use of CO2 or water as a slurry for the solid fuel. The water-based paste with more water in the results in the POX gaseous product results in a significant proportion of CO which being converted into H2 and CO2, results
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39/52 having a ratio of H2 to CO just below 1. CO2-based paste has a much lower ratio of H2 to CO. It may be useful to pass through at least a portion of the sharply cooled POX fuel gas stream through a catalytic exchange reactor to convert CO to H2 by the reaction with steam, as shown below in Formula (2).
CO + H2O = H2 + CO2 (2) [00117] This can be accomplished by using a portion of the combustible gas taken at a temperature of about 250 ° C to about 400 ° C after removing ash and using a catalyst sulfur-tolerant CO exchange, such as a cobalt-based catalyst in the exchange reactor. The part of the fuel gas that has been enriched in H2 can then be cooled in a separate passage through the POX heat exchanger. The heat released in the exothermic exchange reaction can be transferred to the PPS. The switched outlet gas can then be mixed with a portion of the remaining cooled POX stream and the combined stream can be passed through a multi-bed pressure exchange adsorber designed to separate H2 and CO at the ratio of H2 to CO required as a single, non-adsorbed component whereas the adsorbed components can contain all sulfur compounds, HCN, NH3, Hg CO2, H2O and most CH4. This non-adsorbed fraction may also contain N2 and Ar derived from coal (or another solid or liquid fuel) and the oxygen used in the POX reactor. These inert components are preferably at a total concentration below 5%, which is acceptable for the gas supply to both FischerTropsch and methanol reactors. If the production of pure H2 is required, only the cooled gas exchanged will be fed into the PSA. The residual gas at a pressure close to the atmospheric pressure of the PSA with all the coal and the impurities derived from POX in a reduced form will be compressed.
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40/52 wet and returned to the remaining POX fuel gas for PPS combustion.
[00118] An embodiment of a system for energy production with partial oxidation of a solid fuel is described with reference to FIG. 1, in which a solid fuel is provided in the form of the coal feed stream 21 to be partially oxidized in the POX reactor 4. The coal stream 21 is ground and partially dried in the large particle crusher 1 which is also fed by the stream of dry nitrogen comprising N2 at a temperature of about 82 ° C (180 ° F) taken from an air separation unit 6, which produces oxygen streams 32 and 60 and nitrogen stream 23 from the air stream air inlet 62. Preferably, the dry nitrogen stream 23 can be heated against a stream at a higher exhaust temperature from the CO2-rich turbine exiting the stove heat exchanger in the PPS. The coal is further crushed to a particle size preferably of about 250 microns or less in the small particle crusher 2 to provide the particulate coal stream 25, which is directed to a paste mixer 3. In the paste mixer 3, the particulate coal is mixed with the stream of the CO2 slurry 29, which preferably has a pressure of about 8.5 MPa or more. The CO2 in the stream of CO2 slurry 29 in this mode is at a temperature of about 17 ° C. The CO2 in the stream of the CO2 slurry 29 has a density of about 865 kg / m ³ . The pulverized coal is increased in pressure in a locking funnel system or by other means to a pressure of 8.5 MPa before being mixed with CO2. A carbon slurry / CO2 stream 26 exits the pulp mixer 23 and preferably comprises about 45% by weight of coal. Alternatively, the pulp medium can be a chain of
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41/52 water. The pulverized coal injection system can also be configured as a dry feeding system in which the pulverized pressurized coal is entrained in a stream of nitrogen and fed into the POX burner. The pulp stream 26 is then pumped into the POX reactor 4, where it is combined with the oxygen stream 56, which preferably comprises an oxygen concentration of 97 mol% or more. The POX 4 reactor preferably operates at a pressure of about 8.5 MPa and a temperature of about 1,400 ° C; however, the temperature and pressure may be in any combination of temperature and pressure ranges as indicated herein or with respect to the nature of the POX stream leaving the POX reactor. The conditions for the preparation of the coal paste can be adjusted accordingly.
[00119] The POX 4 reactor is adapted to partially oxidize the coal and form a POX stream, which can leave the POX reactor and enter a sudden cooling chamber (not shown) or can be cooled suddenly inside POX reactor, as illustrated in FIG. 1. The POX stream may comprise a combustible gas which may comprise one or more combustible (i.e., oxidizable) materials including, but not limited to, H2, CO, CH4, H2S, COS, CS2, HCN and NH3. In addition, the POX stream may comprise Hg and other impurities derived from coal (or another solid fuel) as well as inert materials (eg, N2 and Ar), such as derived from oxygen stream 56, plus other trace components . The POX stream can also comprise one or more non-combustible materials, such as ash or slag, which can be filtered from the POX stream as desired.
[00120] The POX current (both internal to the POX reactor and as a separate component) is abruptly cooled when mixed
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42/52 with a sudden cooling fluid (liquid water stream 57 in the present mode). As illustrated, the liquid water stream 57 enters the POX reactor near the base in a restriction nozzle. The addition of the brisk cooling stream cools the components of the POX stream preferably below the water saturation temperature of about 304 ° C (although higher temperatures are also included). The brisk cooling temperature may also preferably be at a temperature at which non-combustible elements, such as ash and slag, are in solid form. Excessive blast cooling water is collected with the slag and fine ash volume in the deposit of the POX reactor vessel (or a separate blast cooling vessel) where it is removed for further treatment. The sharply cooled POX stream 58 passes to the scrubber unit 5, which comprises a water scrubber tower followed by a fine cartridge filter adapted to reduce the dust load to about 4 mg / m ³ or less of the gas fuel, about 3 mg / m ³ or less of the combustible gas, or about 2 mg / m ³ or less of the combustible gas. The purification unit 5 can also include any equipment and pumps required to recycle the purification water and also to treat the ash stream 66 for disposal. An exemplary modality of a useful system for the treatment of ash from the POX reactor and gas cleaning is a POX system from GE / Texaco with a coal / water slurry burner that, alternatively, can be modified to accept a slurry of coal / CO2.
[00121] Clean fuel gas plus steam stream 55 is cooled in heat exchanger 7. Output stream 59 is also cooled against the cooling water in heat exchanger 9. Liquid water 46 is separated in the separation vessel 8 of inlet current 61 and pumped at pump 11 back to the brusch cooling reactor
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43/52 co of POX and a portion of the water in the stream addition composition 38 to produce the blast cooling water stream 57. The liquid combustible gas stream 47 is compressed in a multistage centrifugal compressor 10 to an appropriate pressure for the inlet as stream 48 to the combustion system for energy production 14. As an example, the stream of combustible gas 47 can be compressed to a pressure of about 30.5 MPa. The compressed combustible gas stream 48 is heated in the heat exchanger 12 of the stove to an appropriate temperature for entry into the combustion of the system for energy production 14. As an example, the compressed combustible gas stream 48 can be heated to a temperature about 746 ° C. The heated fuel gas stream 64 is burned in the system's energy producing combustion 14, where it is combined with oxygen and CO2. In the illustrated embodiment, the combined O2 / CO2 stream 51 comprises 30% O2 and 70% CO2 on a molar basis. The combined O2 / CO2 stream 51 was preferably heated to an appropriate temperature for the entry into the combustor of the energy production system 14. As an example, the combined O2 / CO2 stream 51 can be heated to a temperature of about 746 ° C in the heat exchanger 12 of the fireplace. A hot recycle CO2 stream 52 is directed from the heat exchanger 12 of the stove and is at an appropriate temperature for the combustion inlet of the energy production system 14. As an example, the hot recycle CO2 stream 52 can be heated to a temperature of about 746 ° C.
[00122] In the combustion of the energy production system, the combustion gases from the burning of the combustible gas are cooled with the hot recycling CO2 stream 52, producing a combined stream of combustion product 50 at a temperature of about
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44/52 of 1,150 ° C and a pressure of about 30 MPa in the illustrated embodiment. This is expanded to a pressure of about 3 MPa in turbine 13 coupled to an electrical generator 65, producing output power 63. The output current 49 of the turbine is cooled in the heat exchanger 12 of the stove and exits as the current of cooled product 53 to a temperature of about 64 ° C in the illustrated embodiment. The stream 53 is cooled to a temperature of about 17 ° C in the water cooler 16. The output stream of the cooler turbine 54 enters a purification tower 17, which has an output stream 40 which is largely recycled through from the circulation pump 18 to the liquid inlet 41 of the purification tower above the compacted section of the tower that receives the cooler turbine outlet current 54. A part of the chain 40 is separated as chain 39 for further treatment. As the exhaust gas from the turbine cools below the water dew point in the heat exchanger 12 of the stove, the following reactions occur.
NO + / O2 = NO (3)
NO2 + SO2 = SO3 + NO (4)
SO3 + H2O = H2SO4 (5) [00123] The above reactions will proceed in the presence of liquid water, nitrogen oxides, SO2 / SO3, and excess oxygen. The concentrations of SO2 / SO3 are reduced to very low levels, since the limiting reaction shown in Formula (3) proceeds quickly to 3 MPa, and the reactions of Formula (4) and Formula (5) are very fast. When all the sulfur oxides have been converted to sulfuric acid, the nitrogen oxides are converted at a conversion rate of about 95% per pass to nitric acid with the following reaction sequence.
2NO2 + H2O = HNO2 + HNO3 (6)
3HNO2 = HNO3 + 2NO + H2O (7)
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45/52
NO + _^1/2 O2 = NO 2 (8) [00124] In FIG. 1, the nitric acid present in the liquid acid product stream 39 will convert all the mercury present into mercuric chloride. The scrubber tower 17 is preferably provided with an additional acid mist washing and removing section that can act as an efficient dilute acid removal device, since virtually all of the above reactions will have occurred upstream of the scrubbing tower 17. The mixed acids are treated with the limestone paste stream 36 (or another suitable base) in the mixer 15 to produce the gypsum stream and calcium nitrate 37. Other trace metal salts can also be separated. The residual water stream 38 after the removal of calcium nitrate and dissolved salts can be used as a composition for a cooling tower or the system for sudden cooling of POX, or as purification water in the purification tower 17.
[00125] Predominantly, the CO2 stream 42 leaving the purification tower 17 at a pressure of about 2.9 MPa is compressed in a multi-stage intercooled compressor 19 followed by a dense fluid multi-stage pump at an appropriate pressure for entry into the combustion system for energy production, such as about 30.5 MPa. The compressed CO2 discharge stream 35 leaves the last stage of the pump 19 at a temperature of about 54 ° C, and part of this flow, the stream 70, is heated in the heat exchanger 12 of the stove to a temperature of about 746 ° C, coming out as a CO2 stream 52.
[00126] The air separation plant 6 in this modality produces a product stream of purity of 99.5 mol% of oxygen at a pressure of about 8.6 MPa that is divided into two separate streams. The oxygen stream 60 is heated in the heat exchanger 7 to a temperature of about 294 ° C, leaving as stream 56 to the
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46/52 use in the POX 4 reactor for partial oxidation of coal. The remaining oxygen stream 32 is mixed with CO2 at a pressure of about 8.6 MPa. Specifically, CO2 is taken from an intermediate stage of the compressor 19 as stream 30, and part of the stream 31 mixes with the stream of oxygen 32, forming a composition of about 30 mol% O2 and 70 mol% CO2. This diluted O2 stream 33 is compressed to a pressure of about 30.5 MPa in a multi-stage intercooled compressor 20 and the discharge stream 34 is heated in the heat exchanger 12 of the stove to a temperature of about 746 ° C. ° C and enters combustion 14 of the energy production system as current 51. Dilution of the pure O2 current 32 is beneficial to allow the oxygen required for combustion in combustion 14 of the energy production system to be heated to a high temperature without the need for oxidation-resistant materials. This ensures the safe operation of the system for energy production. The 30% O2 current is useful for moderating the adiabatic combustion temperature in the energy production system 14 to a value of about 2,400 ° C. The remainder of the CO2 stream 30 is the CO2 stream 29, which provides the CO2 for the pulverized coal paste formation and is directed to the paste mixer 3.
[00127] The cooling of the POX gas cooled down sharply in the heat exchanger 7 is useful to transfer the maximum amount of heat to the system for energy production to maximize total efficiency. The energy production system requires a significant amount of heat from an external source in the almost ambient temperature range up to about 400 ° C. This can be provided by using adiabatic air compressors in the air separation plant 6, and by transferring the heat from compression apart from the high pressure recycling CO2 stream. In this mode, the external heating load
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47/52 required is provided by abruptly cooling the cooled POX gas in the heat exchanger 7 and by heating two high pressure recycling CO2 streams. The high pressure recycle CO2 stream 28 at a temperature of about 54 ° C and the high pressure recycle CO2 stream 43 at a temperature of about 120 ° C taken from an intermediate temperature point in the heat exchanger 12 of the stove are heated to provide a combined heating outlet current 44 at a temperature of about 294 ° C, which is returned to the mixture with the main recycling CO2 stream at a corresponding temperature point in the heat exchanger 12 of the recuperator. Optionally, output current 67 can also be returned to the stove's heat exchanger at a corresponding temperature point to also mix with the recycling CO2 stream.
[00128] In FIG. 3 is a graph of temperature versus the percentage of heat release (diagrammatically) in the heat exchanger 7 of the stove of FIG. 1 to show the benefit of two separate high pressure recycling CO2 inlet streams to ensure efficient operation of the combined system. The 120 ° C temperature level of the current input 43 corresponds to an approximation of the temperature to the dew point of the water from the turbine exhaust stream in the heat exchanger 12 of the stove. The POX fuel gas cooled sharply enters the heat exchanger at a water saturation temperature of 304 ° C, and the total heated high pressure recycle stream exits at a temperature of 294 ° C.
[00129] It is shown in FIG. 4 an alternative method of operation in which the sudden cooling water stream reduces the temperature of the POX gas to about 400 ° C. There is an additional section of the heat exchanger where the fuel gas temperature of POX res
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48/52 chilled sharply drops to its dew point of around 300 ° C. To maximize the efficiency of the system for total energy production by minimizing the temperature difference in the heat exchanger 7, the heated high pressure CO2 stream is removed from the heat exchanger as two separate streams. Stream 44 is at a temperature of about 290 ° C and stream 67 is at a temperature of about 390 ° C. These currents are returned separately to the heat exchanger 12 of the fireplace where they meet with the main high pressure recycling CO2 stream at the appropriate corresponding temperatures.
[00130] In exemplary embodiments, the heat exchanger 7 can be a multi-channel unit welded to high pressure or connected by diffusion. The construction material is preferably resistant to corrosion in the presence of the impurities present in the POX gas plus liquid water. The heat exchanger 12 of the fireplace is preferably a multichannel unit connected by diffusion. This unit is preferably adapted for operation at temperatures up to about 800 ° C and to be resistant to acid corrosion at temperatures below about 200 ° C. A suitable example material is Specialty Metals 740 alloy. In some embodiments, the average temperature at the hot end of the heat exchanger 12 can be reduced to less than 750 ° C, in which case alloy 617 may be appropriate. Optionally, the intermediate section between 200 ° C and 540 ° C can be made of stainless steel. The section that is subject to potential acid corrosion below 200 ° C can be constructed to allow replacement at intervals.
[00131] In additional modalities, alternative arrangements of the elements can be used to process the POX current. In an exemplary embodiment, FIG. 2 shows an optional arrangement in which the POX product is used for the production of combustible gas
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49/52 speed for the energy production system and for the production of a separate and purified mixture of H2 and CO. A side stream 66 is taken from the sharply cooled POX gas stream 55 after ash removal and passed through a catalytic exchange converter 67 which has a sulfur-resistant cobalt-based exchange catalyst (or other suitable material) . The highest temperature outlet gas stream 70 is cooled in heat exchanger 7 to a temperature of about 60 ° C, flows out as stream 73, and is also cooled by the cooling water in heat exchanger 74 to a temperature of about 20 ° C as stream 75. Condensed water is separated into separator 77, and the cooled gas stream 76 enters a multi-bed pressure exchange absorber unit 79. Water separated in separator 77 is added to the stream liquid water 46. The pressure exchange adsorption unit (PSA) 79 is designed to separate the inlet gas stream 76 into a stream of pure H2 or pure H2 and CO 80 that exits the unit at a pressure of about 8 MPa and a residual gas stream 71 that contains all impurities (eg H2S, COS, CS2, HCN, NH3, Hg and other trace components) as well as some combination of H2, CO, CO2, CH4 and H2O . The separation of impurities is such that the concentration of these components in the product stream of H2 or H2 and CO 80 is below 1 ppm. This arrangement uses a stream 83 of the cooled POX gas which contains a high concentration of CO to mix with the exchanged cooled gas stream 76 so as to produce a stream 72 which, when passed through the PSA unit 79 produces the required flow and the ratio of H2 to CO required in the product stream 80 of 8 MPa. If pure H2 is required, current 83 is equal to zero. The residual gas stream 71 of PSA 79 at a pressure of 0.12 MPa is compressed in a multistage multi-stage compressor 81 at a pressure of about 8 MPa, and
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50/52 the discharge stream 82 is added to the fuel gas stream 47 of the system for energy production. The total fuel gas stream is compressed to a pressure of about 30.5 MPa in the compressor 10, and the resulting high pressure fuel gas stream 48 is sent to the system's combustion 14 for energy production through the heat exchanger 12 of the stove (with reference to FIG. 1). This arrangement ensures the transfer of all the coal and impurities derived from POX to the system for energy production, where they are oxidized in the combustion 14 of the system for energy production. In several embodiments, the consumption of additional water in the exchange reaction can proceed according to Formula (9) and may require a small flow of additional composition.
H2O + CO = CO2 + H2 (9) [00132] In the various modalities that incorporate elements of the systems and methods described here, the total efficiency of the systems and methods presented is less than 50% (based on the heating value ( LHV) with representative turbine and compressor efficiencies and differences in heat exchanger temperature and pressure drops). In addition, CCS is provided simultaneously with the substantially complete removal of all other fuel, POX, and impurities derived from combustion. The excess CO2 derived from the carbon in the fuel stream 21 is removed from the system for circulating CO2 as stream 71 at 30.5 MPa. This can be facilitated, as systems and methods can be adapted to deliver substantially all of the fuel-derived CO2 at a pressure of about 15 MPa or more, about 20 MPa or more, about 25 MPa or more, or about 30 MPa or more. This high efficiency can be advantageously achieved with a low cost system, such as when using commercially available POX reactor systems and a CO2 working fluid energy cycle
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51/52 high pressure, as described in U.S. Patent Application Publication no. 2011/0179799, which is hereby incorporated by reference in its entirety. As a comparative example, commercial coal-based combined gasification (IGCC) power generation systems with CO2 capture and compression up to pipe pressure have been shown to have efficiencies on a comparable basis of only 34% at 39% and have a much higher cost of capital.
[00133] EXPERIMENTAL PART [00134] The above described advantages of the methods and systems currently presented were verified through extensive ASPEN simulations under a variety of conditions with realistic estimates for the commercial performance of the equipment. Two sets of simulations were performed using Illinois # 6 coal as a solid fuel introduced into the POX combustor. In each case, the data are based on the use of CO2 as a means of coal paste. The simulations differed, since the first simulation (see FIG. 5) was based on the use of water as a sudden cooling fluid, and the second simulation (see FIG. 6) was based on the use of CO2 as a fluid of sudden cooling.
[00135] Details of the balance between mass and heat from the first simulation are provided in the table shown in FIG. 5. Under the conditions shown, a combustible gas was typically produced with a ratio of H2 to CO of 0.41 to 1. The efficiency calculated for this modality on the basis of the lowest heating value (LHV) was 51.44 %.
[00136] Details of the balance between mass and heat of the second simulation are provided in the table shown in FIG. 6. Under the conditions shown, a combustible gas was typically produced with a ratio of H2 to CO 0.17 to 1. In each case, the ratios
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52/52 of hydrogen can be increased with modes when using water exchange. The efficiency calculated for this modality on an LHV basis was 51.43%.
[00137] Many modifications and other modalities of the object presently presented will come to mind of the element versed in the technique to which this object belongs with the benefit of the teachings presented in the descriptions above and in the associated drawings. Therefore, it should be understood that the present invention should not be limited to the specific modalities described herein, and that modifications and other modalities should be included within the scope of the appended claims. Although specific terms are used here, they are used in a generic and descriptive sense only and not for purposes of limitation.

权利要求:
Claims (32)
[1]
1. Energy production process using a combination of a partial oxidation system (POX) and a system for energy production (PPS), characterized by the fact that it comprises:
combining a solid or liquid fuel and oxygen in a POX reactor (4) under conditions sufficient to partially oxidize the fuel and form a POX stream comprising a combustible gas;
briskly cool the POX stream by combining it with a brisk cooling fluid under conditions sufficient to form a briskly cooled POX stream to a temperature of about 400 ° C or less and to solidify at least part of any melting solids present in the POX chain;
abruptly treat the POX stream to remove at least a part of any solids present in it;
direct the cooled POX stream abruptly to a POX heat exchanger (7) and withdraw a quantity of heat from the cooled POX stream abruptly by cooling the cooled POX stream sharply to a temperature of 100 ° C or less against a current cooling, and form a POX fuel gas stream;
passing the POX fuel gas stream through a separating vessel (8) and separating at least part of any water present in the POX fuel gas stream;
compress the POX fuel gas stream to a pressure of 12 MPa or more;
burn POX fuel gas in a PPS combustion (14) to form a stream of combustion
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[2]
2/10 pressure of at least 10 MPa and a temperature of at least 800 ° C;
expanding the combustion product stream through a PPS turbine (13) to generate the energy and form an expanded PPS combustion product stream;
passing the expanded PPS combustion product stream through a PPS stove heat exchanger (12) and thereby removing heat from the PPS combustion product stream and forming a cooled PPS combustion product stream;
optionally, passing the cooled PPS combustion product stream through a water cooler;
treating the PPS combustion product stream cooled in a PPS scrubber (17), which separates at least H2SO4, HNO3 or Hg, and forming a recycling CO2 stream; and pressurizing the recycling CO2 stream in a PPS compressor (19) and forming a compressed recycling CO2 stream.
2. Process according to claim 1, characterized by the fact that the solid or liquid fuel is a carbonaceous fuel.
[3]
3. Process according to claim 2, characterized by the fact that the combined fuel in the POX reactor (4) is a entrained stream of solid powdered fuel.
[4]
4. Process according to claim 2, characterized by the fact that the carbonaceous fuel is coal.
[5]
5. Process, according to claim 4, characterized by the fact that one or more of the following conditions are met:
the coal is made into a paste with water or CO2.
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3/10 the POX stream cooled down sharply comprises ash, slag, or a combination thereof, and the step of removing the solids comprises the passage of the POX stream cooled down sharply through a water purification unit (5);
the step of removing the solids comprises filtering the cooled POX stream sharply in order to reduce the dust load to 4 mg or less per cubic meter of the combustible gas in the sharply cooled POX stream.
[6]
6. Process according to claim 1, characterized by the fact that the POX reactor (4) is operated at a POX temperature, and that a ratio between the POX temperature and the temperature of the POX current is suddenly cooled is 3.25 or more; optionally, the POX temperature is from 1,300 ° C to 1,600 ° C.
[7]
7. Process according to claim 1, characterized by the fact that the POX reactor (4) is operated at a pressure of 2 MPa or more; or with the sudden cooling comprising mixing the POX stream with: a recycled portion of the cooled POX combustible gas stream; a portion of the water separated from the cooled POX fuel gas stream; a part of a PPS CO2 recycling stream; or a combination of them.
[8]
8. Process, according to claim 1, characterized by the fact that one or more of the following conditions are met:
the cooling stream in the heat exchanger comprises a stream of high pressure recycling fluid taken from and returned to the PPS;
the oxygen used in the POX reactor (4) has a purity of 90 mol% or greater;
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4/10 the turbine (13) has an inlet pressure of 10 MPa or greater; optionally, the turbine (13) having an outlet pressure, which is defined as a ratio between the turbine inlet and the turbine outlet, and said ratio being 12 or less.
[9]
9. Process according to claim 8, characterized by the fact that the high pressure recycling fluid stream is a recycling CO2 fluid stream; optionally, the stream of recycling CO2 fluid comprises CO2 formed in the combustion of the POX combustible gas in the PPS combustor (14).
[10]
10. Process according to claim 1, characterized by the fact that the POX reactor (4) includes an internal heat transfer component.
[11]
11. Process according to claim 10, characterized in that the internal heat transfer component is adapted to transfer the radiant heat to a part of a high pressure recycling stream taken from a PPS component at a temperature 250 ° C or more; optionally, the internal heat transfer component being adapted to return the high pressure recycling stream to a PPS component.
[12]
12. Process according to claim 1, characterized by the fact that one or more of the following conditions are met:
passing the expanded PPS combustion product stream through the PPS stove heat exchanger (12) cools the PPS combustion product stream to a temperature below the water dew point;
the combustion product stream of the PPS combustion (14) comprises a mixture of combustion products and at least part of the compressed recycling CO2 stream.
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5/10 the heat taken from the PPS combustion product stream heats at least part of the compressed recycling CO2 stream;
the oxygen used in the POX reactor (4) is heated in the POX heat exchanger (7) to a temperature of 350 ° C;
the oxygen used in the PPS combustor (14) is heated in the POX heat exchanger (7) to a temperature of 350 ° C.
[13]
13. Process according to claim 12, characterized by the fact that the combustible gas in the POX combustible gas stream, which enters the PPS combustor (14), comprises at least one component of the combustible gas selected from H2, CO and CH4.
[14]
14. Process according to claim 13, characterized by the fact that the POX combustible gas stream, which enters the PPS combustor, comprises one or more impurities separated from the combustible gas and derived from the solid or liquid fuel, from its partial oxidation, and oxygen.
[15]
15. Process, according to claim 14, characterized by the fact that one or both of the following conditions are met:
one or more impurities comprise at least one of a sulfur compound, NH3 and HCN;
substantially all impurities are still present in the POX fuel gas stream and are burned in the PPS combustor (14).
[16]
16. Process, according to claim 12, characterized by the fact that the POX stream is abruptly cooled with water.
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6/10
[17]
17. Process according to claim 16, characterized by the fact that the POX stream cooled suddenly with water comprises at least H2, CO, CO2, H2S and H2O.
[18]
18. Process according to claim 17, characterized by the fact that the cooling stream in the POX heat exchanger (7) comprises two compressed recycling CO2 streams; optionally, an inlet temperature of the first compressed recycle CO2 stream entering the POX heat exchanger (7) is substantially the same as the temperature of the compressed recycle CO2 stream discharged from the PPS compressor (19 ).
[19]
19. Process according to claim 18, characterized by the fact that an inlet temperature of the second compressed recycled CO2 stream entering the POX heat exchanger (7) is within 20 ° C of the dew point of the water in the stream of the expanded PPS combustion process.
[20]
20. Process according to claim 19, characterized by the fact that the POX stream suddenly cooled with water is saturated with water vapor in order to comprise excess liquid water.
[21]
21. Process according to claim 20, characterized by the fact that the two compressed recycling CO2 streams combine in the POX heat exchanger (7) to form a single stream; optionally, the only compressed recycle CO2 stream exiting the POX heat exchanger (7) is at a temperature that is within 20 ° C of the POX fuel gas dew point temperature.
[22]
22. Process, according to claim 21, characterized by the fact that the POX stream suddenly cooled with
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7/10 water has a temperature that is above its dew point temperature and below 400 ° C.
[23]
23. Process according to claim 22, characterized by the fact that the two compressed recycling CO2 streams are heated, and the point at which the two compressed recycling CO2 streams combine to form the single stream is at a temperature that substantially corresponds to the inlet temperature of the second compressed recycling CO2 stream.
[24]
24. Process according to claim 23, characterized by the fact that the single chain is divided into:
a first heated and compressed recycling CO2 stream leaving the POX heat exchanger at a temperature that is within 20 ° C of the dew point temperature of the POX stream; and a second heated and compressed recycle CO2 stream from the outlet leaving the POX heat exchanger at a temperature of 380 ° C to 399 ° C.
[25]
25. Process according to claim 12, characterized by the fact that the POX stream is abruptly cooled with CO2 and optionally a part of the combustible gas.
[26]
26. Process according to claim 25, characterized by the fact that the POX stream suddenly cooled with CO2 comprises at least H2, CO, CO2, H2S and H2O.
[27]
27. Process according to claim 26, characterized by the fact that the cooling stream in the POX heat exchanger (7) comprises a compressed recycling CO2 stream; optionally, an inlet temperature of the compressed recycle CO2 stream entering the POX heat exchanger (7) is substantially the same as the current temperature
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8/10 te of compressed recycle CO2 discharged from the PPS compressor (19), and the only compressed recycle CO2 stream that exits the POX heat exchanger (7) is at a temperature that is within 20 ° C of POX fuel gas dew point temperature.
[28]
28. Process according to claim 12, characterized by the fact that at least part of the POX combustible gas cooled with water enters a catalytic exchange reactor adapted to convert a mixture of CO and H2O into an outlet gas of the exchange reactor, which comprises a mixture of H2 and CO2.
[29]
29. Process according to claim 28, characterized by the fact that the outlet gas from the exchange reactor is cooled in the POX heat exchanger (7) against a high pressure recycling CO2 gas taken from and returned to the PPS .
[30]
30. Process according to claim 29, characterized by the fact that the gas from the exchange reactor outlet is cooled in the POX heat exchanger (7) and mixed with a part of the POX stream that has been cooled down sharply which has been heat exchanger and is also processed to separate water, CO2, sulfur compounds, nitrogen compounds, and Hg, to form a mixture comprising H2 and CO at a ratio of 0.8: 1 to 2 , 5: 1.
[31]
31. Process according to claim 30, characterized by the fact that one or both of the following conditions are met:
the outlet gas from the cooled exchange reactor is further processed to form a pure H2 stream with a purity of 99 mol% or more;
the POX catalytic exchange reactor is a system for multi-bed pressure exchange adsorption (PSA); optionally,
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9/10 where a low pressure residual gas from the PSA system, which comprises products adsorbed from the PSA system, is compressed to a PPS combustor pressure and mixed into a total combustible gas stream that enters the PPS combustor ( 14).
[32]
32. System for partial oxidation (POX) and system for energy production (PPS) combined, characterized by the fact that they comprise:
a POX reactor (4) adapted to partially oxidize a liquid or solid fuel in the presence of oxygen to form a POX stream comprising a combustible gas;
one or more components adapted to bring the POX chain into contact with an abrupt cooling fluid;
an optional POX scrubber (5) adapted to separate all the solids present in the POX stream that has been sharply cooled from the POX fuel gas;
an optional filtration device adapted to separate solidified ash particles from a POX combustible gas stream cooled from one phase;
a POX heat exchanger (7) adapted to remove the heat from the POX combustible gas against a portion of a compressed recycling CO2 stream and emit a cooled POX combustible gas;
an optional separator (8) adapted to separate any liquid water from the POX fuel gas;
a compressor (10) adapted to compress the cooled POX fuel gas to a pressure of about 10 MPa or more;
a PPS combustor (14) adapted to burn POX fuel gas in the presence of oxygen and a part of the current
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10/10 of compressed recycling CO2 and forming a stream of the product of PPS combustion at a pressure of about 10 MPa or more;
a turbine (13) adapted to expand the current of the PPS combustion product and generate energy in a connected generator (65);
a stove heat exchanger (12) adapted to remove the heat from the expanded PPS combustion product stream and add the heat to the compressed recycle CO2 stream;
a PPS purification tower (17) adapted to separate one or more of H2SO4, HNO3 and Hg salts dissolved in water from the expanded PPS combustion product stream and emit a recycling CO2 stream;
a PPS compressor (19) adapted to compress the recycling CO2 stream to a pressure of about 10 MPa or more and forming the compressed recycling CO2 stream;
flow components adapted to direct a portion (28) of the compressed recycling CO2 stream to the POX heat exchanger (7);
flow components adapted to direct a portion (34) of the compressed recycling CO2 stream to the PPS stove heat exchanger (12); and flow components adapted to direct the compressed recycle CO2 stream (67) from the POX heat exchanger (7) to the PPS fireplace heat exchanger (12).

类似技术:

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公开号 | 公开日 | 专利标题

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JP6761022B2|2020-09-23|Partial oxidation reaction with closed cycle quenching

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同族专利:

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公开号 | 公开日

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JP6185936B2|2017-08-23|

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KR20140131332A|2014-11-12|

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AU2013216767B2|2017-05-18|

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TW201344038A|2013-11-01|

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AU2013216767A1|2014-09-18|

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MX2014009685A|2015-05-15|

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EA201400889A1|2015-01-30|

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PL2812417T3|2018-01-31|

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US9581082B2|2017-02-28|

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ZA201406310B|2016-03-30|

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JP2019090416A|2019-06-13|

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KR102101194B1|2020-04-16|

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CN107090317A|2017-08-25|

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MX358190B|2018-08-08|

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CN104302743B|2016-11-09|

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CA2864105C|2020-07-07|

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JP2017223232A|2017-12-21|

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JP2020097921A|2020-06-25|

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EP2812417B1|2017-06-14|

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WO2013120070A1|2013-08-15|

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CN104302743A|2015-01-21|

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EP2812417A1|2014-12-17|

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JP6761022B2|2020-09-23|

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HK1204000A1|2015-11-06|

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EA028822B1|2018-01-31|

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JP2015513028A|2015-04-30|

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CA2864105A1|2013-08-15|

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US20130205746A1|2013-08-15|

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US20140290263A1|2014-10-02|

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CN107090317B|2019-10-25|

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US8776532B2|2014-07-15|

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TWI620867B|2018-04-11|

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-02-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-04-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-12-07| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261597719P| true| 2012-02-11|2012-02-11|

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PCT/US2013/025563|WO2013120070A1|2012-02-11|2013-02-11|Partial oxidation reaction with closed cycle quench|

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