WO2024056893A1 - Procédé de transfert de chaleur entre deux processus indépendants - Google Patents

Procédé de transfert de chaleur entre deux processus indépendants Download PDF

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Publication number
WO2024056893A1
WO2024056893A1 PCT/EP2023/075516 EP2023075516W WO2024056893A1 WO 2024056893 A1 WO2024056893 A1 WO 2024056893A1 EP 2023075516 W EP2023075516 W EP 2023075516W WO 2024056893 A1 WO2024056893 A1 WO 2024056893A1
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Prior art keywords
stream
heat
range
heated
temperature
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PCT/EP2023/075516
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English (en)
Inventor
Lukas Mayr
Alexander Schroeder
Julian Meyer-Kirschner
FRANK Huetten
Jonas Matthias MAIRHOFER
Johannes Felix Haus
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Basf Se
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Publication of WO2024056893A1 publication Critical patent/WO2024056893A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • F01K25/12—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being metallic, e.g. mercury

Definitions

  • the present invention relates to a method for transferring heat between two independent process, in particular for transferring heat from a chemical conversion process, from a physicochemical process, from ambient heat, or from a combination of two or more thereof, to a target process in a chemical production plant.
  • thermal energy for endothermic processes is currently done by burning fossil fuels or by direct electric heating.
  • Fossil fuels are often preferred to direct electric heating because of lower efficiency and hence lower costs.
  • heat pumps have been used and designed to provide heat at a maximum temperature of about 150 °C.
  • Many technically relevant processes require large amounts of heat at temperatures significantly above this value. Examples include the melting of metals, distillation processes and endothermic chemical reactions. For thermodynamic reasons, endothermic chemical reactions typically take place at high temperatures.
  • DE 2951188 A1 relates to a method for utilizing waste heat from endothermic processes wherein heat is initially supplied from an external heat source at a high temperature level and residual heat from the reaction is obtained at a low temperature level, wherein the low temperature residual heat is recycled to the endothermic reaction with the aid of a heat pump.
  • a theoretical COP of 1 .95 can thus still be achieved, and thus theoretically almost twice as much heat can be provided for the reaction than if the electric power used for operating the heat pump were used directly for heating.
  • the COP is significantly lower at 1 .5, but the use of heat pumps can still be considered, e.g. if steam is no longer available for a process due to the temperature and pressure level, or is only available with extreme difficulty.
  • the object of the present invention to provide a method in which the utilization of heat such as with the aid of heat pumps is not restricted to the optimization of individual heat consuming processes such as endothermic reactions, or to the increased valorization of primary energy sources and in particular of sustainable energy sources or nuclear power.
  • heat sources at low temperature e.g. 20 to 80 °C
  • COP coefficient of performance
  • upgrading of heat sources is possible to directly supply heat to processes at temperatures of equal to or greater than 350 °C, preferably greater than 350 °C, more preferably 375 to 1 ,275 °C, e.g. by superheated saturated steam, to provide the necessary temperatures in a target process.
  • high temperature heat pumps allows electrification of processes where electrical heating is difficult to realize, and especially with a better electrical efficiency COP reai of greater than 1 .
  • the inventive method is particularly advantageous if, within a production plant, there is an exothermic heat source at low temperature and an endothermic heat sink at higher temperature.
  • the compressor/compressor cascades and heat transfer media used are accordingly adapted to the high temperatures.
  • tetraphenyl-compounds are also a possible heat transfer medium for realizing the inventive results.
  • some metals are suitable as a heat transfer medium for applications above 1 ,000 °C at the maximum temperatures.
  • the use of heat pumps can also be considered if the reaction temperature is too high to achieve a real COP > 1.
  • the compressors used in a heat pump can be operated at medium or high voltage, thus avoiding the electrical infrastructure, transformation losses and high currents.
  • the conventional use of electric heaters at very high temperatures often requires the concept of indirect heating, where heat is transferred from the electric heater to the process via radiation. This often leads to inhomogeneous temperature profiles and also increased equipment requirements.
  • the inventive method is not limited to endothermic reactions. Often, exothermic reactions are followed by energy-intensive separation steps/distillations, which in turn can benefit from the inventive method, even when using the waste heat from the preceding reaction as a heat source. In these cases, the high-temperature heat pump may also act as a high-temperature heat reservoir.
  • the present invention relates to a method for transferring heat to a target process in a chemical production plant, the method comprising:
  • the term tugdifferent“ with regard to the chemical conversion process and/or the physicochemical process in (ii) being different from the target process indicates that the inventive method does not recycle heat to a chemical conversion process and/or to a physicochemical process.
  • the chemical conversion process and/or the physicochemical process in (ii) may be the same as the target process, they are not identical in the sense that heat stemming from a specific chemical conversion process and/or physicochemical process may be recycled to the same chemical conversion process and/or physicochemical process in a different process, but not to the chemical conversion process and/or physicochemical process from which it stems.
  • the target process is a chemical conversion process and/or a physicochemical process
  • the chemical conversion process and/or the physicochemical process in (ii) is not the same chemical conversion process and/or physicochemical process of the target process.
  • heat is transferred in (ii) from a chemical conversion process and/or from a physicochemical process, and wherein the heat which is transferred according to (ii) is obtained from an exothermic reaction or wherein the heat which is transferred according to (ii) is excess heat of the heat employed for performing an autothermal reaction or an endothermic reaction.
  • the exothermic reaction comprises one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes and alkynes, preferably selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid.
  • the endothermic reaction comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming , styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.
  • the autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) processes of hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (C1-C10)alkanes, more preferably (C1-C8)alkanes, more preferably (C1- C7)alkanes.
  • the physicochemical process comprises, preferably consists of, one or more of a vapor-compression evaporation, and a chemisorption process.
  • the ambient heat which is transferred according to (ii) is heat from the environment, preferably heat from one or more or air, water, and solar radiation, including combinations of two or more thereof.
  • the heat transferred according to (ii) does not comprise energy from nuclear fission, solar thermal energy, geothermal energy, hydro energy, and wind energy.
  • the process according to the present invention does not relate to an optimization of a single process with respect to its energy-efficiency.
  • the present invention does not relate to a process wherein energy is recycled therein, especially for optimizing the energy conversion efficiency.
  • the process of the present invention does not relate to a process wherein the energy for transferring heat originates from a pure energy source.
  • transferring heat in (ii) comprises use of a heat pump, wherein the heat pump is selected from the group consisting of a compression heat pump, an absorption heat pump, and a chemisorption heat pump.
  • transferring heat in (ii) comprises use of a heat pump, wherein the heat pump is selected from the group consisting of a compression heat pump, an absorption heat pump, and a chemisorption heat pump
  • the absorption heat pump is a conventional heat pump (type I heat pump), a heat transformer heat pump (type II heat pump), or an adsorption heat pump, wherein the absorption heat pump is preferably a conventional heat pump.
  • the adsorption heat pump comprises and adsorbent, wherein the adsorbent comprises, preferably consists of, one or more of activated carbon, zeolites, and mixtures thereof.
  • the target process comprises, preferably consists of, the heating of one or more compounds, wherein preferably the target process comprises, preferably consists of, a chemical conversion process and/or a thermal separation of compounds, wherein more preferably the target process comprises one or more of a chemical reaction, an evaporation, a preheating step, and a crystallization process, including combinations of two or more thereof, wherein more preferably the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction, wherein the target process preferably comprises, preferably consists of, an endothermic reaction.
  • the target process comprises, preferably consists of, the heating of one or more compounds
  • the target process comprises, preferably consists of, a chemical conversion process and/or a thermal separation of compounds
  • the thermal separation of compounds comprises, preferably consists of, the isolation of isobutene from a mixture comprising n-butene, 2-butene and isobutene, preferably by distillation.
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the endothermic reaction comprises, preferably consists of, one or more of cracking, preferably catalytic cracking, dehydrogenation, styrene production, reverse water- gas shift, dehydration, thermal decomposition, dimerization, oligomerization, gamma-butyrolac- tone synthesis, and reforming, wherein cracking more preferably comprises cracking of one or more of steam, hydrocarbons, aliphatics, alkenes, preferably one or more of ethylene, propylene, and butylenes, dienes, preferably butadiene, acetylenes, cycloaliphatics, naphtha, polymers, plastics, biomass, oleaginous liquids, bitumen, tar ureas, carbamates, preferably carbamates to ole
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the endothermic reaction comprises, preferably consists of, dehydration of ethanol
  • the chemical process from which heat is transferred in (ii) comprises production of ethylene oxide, preferably from ethylene.
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the endothermic reaction comprises, preferably consists of, steam methane reforming, wherein steam methane reforming is preferably performed at 700 to 1100 °C, more preferably steam methane reforming to syngas comprising CO and hydrogen.
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the endothermic reaction comprises, preferably consists of, steam cracking, wherein steam cracking is preferably performed at about 850 to about 900 °C, more preferably steam cracking of naphtha to olefins, methane, and hydrogen.
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the exothermic reaction comprises, preferably consists of, one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes and alkynes, preferably selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid.
  • the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction
  • the autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) processes of hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (Ci-Cio)alkanes, more preferably (Ci-Cs)alkanes, more preferably (Ci-Cy)alkanes.
  • T1 is in the range of from 20 to 1 ,150 °C, more preferably in the range of from 80 to 1 ,100 °C, more preferably in the range of from 200 to 1 ,000 °C, more preferably in the range of from 400 to 800 °C, more preferably in the range of from 500 to 600 °C.
  • T2 is in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the first process stream provided in (i) has a pressure in the range of from 1 to 300 bar(abs), more preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • the first process stream provided in (i) has a weight hourly space velocity in the range of from 200 to 20,000 IT 1 , more preferably in the range of from 400 to 15,000 IT 1 , more preferably from 600 to 10,000 IT 1 , more preferably from 1 ,000 to 5,000 IT 1 .
  • transferring heat in (ii) comprises:
  • the heat provided in (ii.a) is obtained from a process stream from a chemical conversion process and/or from a physicochemical process, wherein the process stream from a chemical conversion process and/or from a physicochemical process preferably comprises one or more of steam, flue gas, more preferably flue gas from a steam generation process.
  • the method comprises (ii.a) and (ii.b)
  • transferring of heat according to (ii.b) is conducted using a heat exchanger (2)
  • the heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger, wherein the heat exchanger is preferably a reactor containing the first process stream provided in (i), more preferably the wall of a reactor containing the first process stream provided in (i).
  • the target process comprises NH3 reforming, and wherein transferring heat according to (ii.b) comprises at least partially converting NH3 to H2 and N2.
  • the heated first process stream obtained in (ii.b) has a temperature T2, wherein T2 is more preferably in the range of from 350 to 1 ,225 °C, more preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the heated first process stream obtained in (ii.b) has a pressure in the range of from 0.01 to 300 bar(abs), more preferably in the range of from 1 to 275 bar(abs), more preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • transferring heat in (ii) comprises:
  • the heat transfer medium is selected from the group consisting of mercury, cesium, rubidium, potassium, sodium, chlorofluorocarbons, hydrochlorofluorocarbons, preferably hydrochlorofluoroolefins, more preferably one or more of (Z)-1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropro- pene, hydrofluorocarbons, preferably hydrofluoroolefins, more preferably one or more of (Z)-1- Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropro- pene, hydrofluorocarbons, preferably hydrofluoroolefins, more preferably one or more of (Z)-1- Chloro-2,3,3,3-tetrafluoropropene and trans
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the stream provided in (ii.2) has a temperature equal to or greater than 300 °C, more preferably in the range of from 300 °C to 1000 °C, more preferably in the range of from 350 °C to 850°C.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the stream provided in (ii.2) has a pressure in the range of from 0.1 bar(abs) to 50 bar(abs), more preferably in the range of from 0.5 bar(abs) to 30 bar(abs), more preferably in the range of from 1 bar(abs) to 20 bar(abs).
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heat transfer medium in the stream provided in (ii.2) is in the liquid state.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heat transfer medium in the stream provided in (ii.2) is a two-phase fluid with a vapor phase and a liquid phase.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heat transfer medium in the stream provided in (ii.2) is in the supercritical state.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • transferring the heat in (ii.3) is conducted using a heat exchanger (5), wherein the heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger, wherein the heat exchanger is preferably a reactor containing the first process stream provided in (i), more preferably the wall of a reactor containing the first process stream provided in (i).
  • thermoelectric material in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heat provided in (ii.1 ) is obtained from a process stream from a chemical conversion process and/or from a physicochemical process, wherein the process stream from a chemical conversion process and/or from a physicochemical process preferably comprises one or more of steam, flue gas, preferably flue gas from a steam generation process.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heated stream obtained in (ii.3) has a temperature in the range of from 200 °C to 700 °C, preferably in the range of from 250 °C to 650 °C, more preferably in the range of from 350 °C to 550 °C.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heated stream obtained in (ii.3) is in the superheated vapor state.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the heated stream obtained in (ii.3) is in the supercritical state.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • increasing the pressure of the stream according to (ii.4) is conducted using a compressor (12).
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • increasing the pressure of the stream according to (ii.4) is conducted using a multi-stage compressor (12), the multi-stage compressor preferably comprising one or more working media, preferably one or two working media, wherein the two working media are chemically and/or physically different from each other.
  • the multi-stage compressor comprises one or more stages, wherein independently from one another each stage comprises a temperature elevation in the range of from 20 to 500 °C, more preferably in the range of from 50 to 200 °C.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • increasing the pressure of the stream according to (ii.4) is conducted adiabatically.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • a heat exchanger (2) wherein the heat exchanger more preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger, wherein the heat exchanger is preferably a reactor containing the first process stream provided in (i), more preferably the wall of a reactor containing the first process stream provided in (i).
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the target process comprises NHs reforming
  • transferring heat according to (ii.5) comprises at least partially converting NH3 to H2 and N2.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • a compressed stream is obtained having a temperature in the range of from 375 °C to 1 ,400 °C, more preferably in the range of from 475 °C to 1 ,100 °C, more preferably in the range of from 550 to 1 ,000 °C.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), preferably (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • a compressed stream is obtained having a pressure in the range of from 1 to 300 bar(abs), more preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • the heated first process stream obtained in (ii.5) has a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the heated first process stream obtained in (ii.5) has a pressure in the range of from 0.01 to 300 bar(abs), more preferably in the range of from 1 to 275 bar(abs), more preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • transferring heat in (ii) comprises (ii.1), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • expanding according to (ii.6) is conducted using a thermal expansion valve (9) or an expansion turbine (9).
  • expanding according to (ii.6) is conducted using an expansion turbine (9)
  • increasing the pressure of the stream according to (ii.4) is conducted using a compressor (12), wherein expanding is conducted using an expansion turbine, wherein the energy obtained from the expansion turbine, wherein the energy is more preferably obtained as electricity, is used to operate the compressor, or wherein the energy obtained from the expansion turbine is used to operate the compressor mechanically, more preferably via a shaft for directly transmitting the energy.
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • the expanded stream obtained in (ii.6) has the same pressure and temperature as the stream comprising a heat transfer medium provided in (ii.2).
  • transferring heat in (ii) comprises (ii.1 ), (ii.2), (ii.3), (ii.4), (ii.5), (ii.6), and (ii.7)
  • steps (ii.2) to (ii.7) are conducted in a closed system in which the stream comprising a heat transfer medium is circulated.
  • the method wherein the method preferably further comprises (ii.1), (ii.2), (ii.3), (ii.4), (ii.5), further comprises (iii) feeding the heated first process stream obtained in (ii.5) or (ii.b) into a first reactor, for obtaining a first product stream.
  • the method further comprises (iii) feeding the heated first process stream obtained in (ii.5) or (ii.b) into a first reactor, for obtaining a first product stream
  • the heated first process stream obtained in (ii.5) is fed into the first reactor having a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the method further comprises (iii) feeding the heated first process stream obtained in (ii.5) or (ii.b) into a first reactor, for obtaining a first product stream
  • the heated first process stream obtained in (ii.5) is fed into the first reactor having a gas hourly space velocity in the range of from 10 h’ 1 to 50.000 IT 1 , more preferably in the range of from 100 h’ 1 to 20,000 IT 1 , more preferably in the range of from 1 ,000 h’ 1 to 10,000 IT 1 .
  • the method further comprises (iii) feeding the heated first process stream obtained in (ii.5) or (ii.b) into a first reactor, for obtaining a first product stream
  • the method further comprises (iv) heating the first product stream obtained in (iii) to a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C, and feeding the heated first product stream into a second reactor for obtaining a second product stream.
  • heating the first product stream according to (iv) comprises transferring heat from the compressed stream obtained in (ii.4) to the first product stream obtained in (iii), for obtaining a heated first product stream, and a compressed stream having a temperature in the range of from 375 °C to 1 ,400 °C.
  • the method further comprises (iv), it is preferred that the first and second reactor independently from one another is an adiabatic reactor, an isothermal reactor, or a combination thereof.
  • an adiabatic or isothermal change of state is to be understood as a change of state effected close to the theoretical adiabatic or isothermal process.
  • the method further comprises (iv), it is preferred that the first and second reactor independently from one another is a tubular reactor.
  • transferring heat in (ii) comprises:
  • first heat transfer medium in (ii.2’) and the second heat transfer medium in (ii.5’) are independently from one another selected from the group consisting of mercury, cesium, rubidium, potassium, sodium, chlorofluorocarbons, hydrochlorofluorocarbons, preferably hydrochlorofluoroolefins, more preferably one or more of (Z)- 1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene, hydrofluorocarbons, preferably hydrofluoroole
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • the stream (10a) provided in (ii.2’) has a temperature equal to or greater than 300 °C, more preferably in the range of from 300 °C to 1000 °C, more preferably in the range of from 350 °C to 850°C.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • a heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger.
  • the heated stream obtained in (ii.3’) has a temperature in the range of from 350 °C to 950 °C, more preferably in the range of from 400 °C to 600 °C, more preferably in the range of from 450 °C to 550 °C.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • it is preferred increasing the pressure of the heated stream (11a) is conducted using a compressor (12a).
  • the stream (10b) provided in (ii.5’) has a temperature equal to or greater than 325 °C, more preferably in the range of from 325 to 1 ,000 °C, more preferably in the range of from 375 to 850 °C, more preferably in the range of from 450 to 650 °C, more preferably in the range of from 500 to 600 °C.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • a heat exchanger 13
  • the heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • a compressed stream (8a) is obtained having a temperature in the range of from 355 °C to 1 ,400 °C, more preferably in the range of from 455 °C to 655 °C, more preferably in the range of from 505 to 605 °C.
  • the heated stream (11 b) obtained in (ii.6’) has a temperature in the range of from 350 °C to 1150 °C, more preferably in the range of from 450 °C to 650 °C, more preferably in the range of from 500 °C to 600 °C.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • it is preferred increasing the pressure of the heated stream (11 b) is conducted using a compressor (12b).
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • a heat exchanger (2) wherein the heat exchanger more preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger.
  • the heated first process stream obtained in (ii.1 O’) has a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • it is preferred expanding according to (ii.7’) and (ii.11 ’) are independently from one another conducted using a thermal expansion valve (9a and/or 9b) or an expansion turbine (9a and/or 9b).
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • the heated first process stream obtained in (ii) is used as feed or co-feed for an endothermic reaction, preferably for a high temperature endothermic reaction.
  • transferring heat in (ii) comprises (ii.1 ’), (ii.2’), (ii.3’), (ii.4’), (ii.5’), (ii.6’), (ii.7’), (ii.8’), (ii.9’), (ii.1 O’), (ii.11 ’), and (ii.12’)
  • the heated first process stream obtained in (ii) is used as feed stream for a NH3 reforming process.
  • the unit bar(abs) refers to an absolute pressure wherein 1 bar equals 10 5 Pa.
  • a method for transferring heat to a target process in a chemical production plant comprising:
  • the endothermic reaction comprises one or more of steam cracking, ethane dehydrogenation, propane dehydrogenation, butane dehydrogenation, steam reforming, dry reforming , styrene production, methanol reforming, dimethyl ether reforming, reverse water-gas shift, alcohol dehydration, and NH3 reforming.
  • the autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) processes of hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (C1-C10)alkanes, more preferably (C1-C8)alkanes, more preferably (C1-C7)alkanes.
  • POx partial oxidation
  • transferring heat in (ii) comprises use of a heat pump, wherein the heat pump is selected from the group consisting of a compression heat pump, an absorption heat pump, and a chemisorption heat pump.
  • the absorption heat pump is a conventional heat pump (type I heat pump), a heat transformer heat pump (type II heat pump), or an adsorption heat pump, wherein the absorption heat pump is preferably a conventional heat pump.
  • the adsorption heat pump comprises and adsorbent, wherein the adsorbent comprises, preferably consists of, one or more of activated carbon, zeolites, and mixtures thereof.
  • the target process comprises, preferably consists of, the heating of one or more compounds, wherein preferably the target process comprises, preferably consists of, a chemical conversion process and/or a thermal separation of compounds, wherein more preferably the target process comprises one or more of a chemical reaction, an evaporation, a pre-heating step, and a crystallization process, including combinations of two or more thereof, wherein more preferably the target process comprises, preferably consists of, a distillation, preferably a column distillation, an endothermic reaction, an exothermic reaction, or an autothermal reaction, wherein the target process preferably comprises, preferably consists of, an endothermic reaction.
  • thermal separation of compounds comprises, preferably consists of, the isolation of isobutene from a mixture comprising n-butene, 2- butene and isobutene, preferably by distillation.
  • the endothermic reaction comprises, preferably consists of, one or more of cracking, preferably catalytic cracking, dehydrogenation, styrene production, reverse water-gas shift, dehydration, thermal decomposition, dimerization, oligomerization, gamma-butyrolactone synthesis, and reforming, wherein cracking more preferably comprises cracking of one or more of steam, hydrocarbons, aliphatics, alkenes, preferably one or more of ethylene, propylene, and butylenes, dienes, preferably butadiene, acetylenes, cycloaliphatics, naphtha, polymers, plastics, biomass, oleaginous liquids, bitumen, tar ureas, carbamates, preferably carbamates to olefins, aromatics, fuels, isocyanates, melamine, and diamines, wherein dehydrogenation more preferably comprises dehydrogenation of one or more of hydrocarbon
  • the endothermic reaction comprises, preferably consists of, dehydration of ethanol, and wherein the chemical process from which heat is transferred in (ii) comprises production of ethylene oxide, preferably from ethylene.
  • the endothermic reaction comprises, preferably consists of, steam methane reforming, wherein steam methane reforming is preferably performed at 700 to 1100 °C, more preferably steam methane reforming to syngas comprising CO and hydrogen.
  • the endothermic reaction comprises, preferably consists of, steam cracking, wherein steam cracking is preferably performed at about 850 to about 900 °C, more preferably steam cracking of naphtha to olefins, methane, and hydrogen.
  • the exothermic reaction comprises, preferably consists of, one or more of methanol production, dimethyl ether production, NH3 production, ethylene epoxidation, sulfuric acid production, and selective oxidation of one or more of alkanes, alkenes and alkynes, preferably selective oxidation of one or more of alkanes, alkenes and alkynes to acrolein or acrylic acid.
  • the autothermal reaction is selected from the group consisting of autothermal reforming of natural gas and hydrocarbons, including partial oxidation (POx) processes of hydrocarbons, wherein the hydrocarbons are selected from the group consisting of (Ci-C )alkanes, more preferably (Ci-Cs)alkanes, more preferably (Ci-Cy)alkanes.
  • POx partial oxidation
  • T1 is in the range of from 20 to 1 ,150 °C, preferably in the range of from 80 to 1 ,100 °C, more preferably in the range of from 200 to 1 ,000 °C, more preferably in the range of from 400 to 800 °C, more preferably in the range of from 500 to 600 °C.
  • T2 is in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, more preferably in the range of from 450 to 1175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the method of any one of embodiments 1 to 21 wherein the first process stream provided in (i) has a pressure in the range of from 1 to 300 bar(abs), preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • the method of any one of embodiments 1 to 23, wherein transferring heat in (ii) comprises:
  • T2 is preferably in the range of from 350 to 1 ,225 °C, more preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, preferably in the range of from 450 to
  • (ii.1 ) providing heat (4) from a chemical conversion process, from a physicochemical process, or providing ambient heat, or providing a combination of two or more thereof, having a temperature T3, wherein T3 is in the range of from 255 °C to 700 °C; (11.2) providing a stream (10) comprising a heat transfer medium, wherein the stream (10) has a pressure in the range of from 0.001 to 100 bar(abs) and a temperature equal to or greater than 250 °C;
  • thermofluorocarbons preferably hydrochlorofluoroolefins, more preferably one or more of (Z)-1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropro- pene, hydrofluorocarbons, preferably hydrofluoroolefins, more preferably one or more of (Z)-1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene, hydrocarbons, preferably one or more of butane, pentane, and hexane, ammonia, water, carbon dioxide, nitrogen, oxygen, air, noble gases, preferably one or more of helium, neon, argon, krypton
  • thermoelectric transferring the heat in (ii.3) is conducted using a heat exchanger (5), wherein the heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger, wherein the heat exchanger is preferably a reactor containing the first process stream provided in (i), more preferably the wall of a reactor containing the first process stream provided in (i).
  • the multi-stage compressor comprises one or more stages, wherein independently from one another each stage comprises a temperature elevation in the range of from 20 to 500 °C, preferably in the range of from 50 to 200 °C. 47.
  • thermoelectric heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger, wherein the heat exchanger is preferably a reactor containing the first process stream provided in (i), more preferably the wall of a reactor containing the first process stream provided in (i).
  • a compressed stream is obtained having a pressure in the range of from 1 to 300 bar(abs), preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • the heated first process stream obtained in (ii.5) has a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • the heated first process stream obtained in (ii.5) has a pressure in the range of from 0.01 to 300 bar(abs), preferably in the range of from 1 to 275 bar(abs), more preferably in the range of from 5 to 250 bar(abs), more preferably from 10 to 200 bar(abs), more preferably from 20 to 150 bar(abs), more preferably from 50 to 100 bar(abs).
  • steps (ii.2) to (ii.7) are conducted in a closed system in which the stream comprising a heat transfer medium is circulated.
  • the heated first process stream obtained in (ii.5) or (ii.b) is fed into the first reactor having a gas hourly space velocity in the range of from 10 h’ 1 to 50.000 h’ 1 , preferably in the range of from 100 IT 1 to 20,000 IT 1 , more preferably in the range of from 1 ,000 IT 1 to 10,000 IT 1 .
  • heating the first product stream according to (iv) comprises transferring heat from the compressed stream obtained in (ii.4) to the first product stream obtained in (iii), for obtaining a heated first product stream, and a compressed stream having a temperature in the range of from 375 °C to 1 ,400 °C.
  • first heat transfer medium in (ii .2’) and the second heat transfer medium in (ii.5’) are independently from one another selected from the group consisting of mercury, cesium, rubidium, potassium, sodium, chlorofluorocarbons, hydrochlorofluorocarbons, preferably hydrochlorofluoroolefins, more preferably one or more of (Z)-1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropro- pene, hydrofluorocarbons, preferably hydrofluoroolefins, more preferably one or more of (Z)-1-Chloro-2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene, hydrocarbons, preferably one or more of butane, pentane, and hexane, ammonia, water, carbon dioxide, nitrogen,
  • thermoelectric transferring the heat provided in (ii.1’) is conducted using a heat exchanger (5), wherein the heat exchanger preferably comprises one or more of an internal or external coil, a jacket heater, a double wall heat exchanger, an internal pipe heater, and a shell and tube heat exchanger.
  • the heated first process stream obtained in (ii.1 O’) has a temperature in the range of from 350 to 1 ,225 °C, preferably in the range of from greater than 350 °C to 1 ,225 °C, more preferably in the range of from 375 °C to 1 ,225 °C, preferably in the range of from 450 to 1 ,175 °C, more preferably in the range of from 550 to 1 ,075 °C.
  • a cycle is shown in Figure 1 schematically for the heat transfer medium mercury. This method concept is particularly interesting when an exothermic heat source at low temperature and an endothermic heat sink at higher temperature are present within a production plant.
  • the COP was 4.27, and the volumetric heating capacity (VHC) was 8337 kJ/m 3 .
  • Heat is transferred to Hg at the heat source, and heat is transferred from Hg at the heat sink to a stream of a target process.
  • Figure 1 shows a process scheme wherein mercury is used as heat transfer medium.
  • Figure 2 shows a method scheme for a thermodynamic cycle or heat pump process as closed loop process.
  • Figure 3 shows a method scheme for a two-stage thermodynamic cycle or two-stage heat pump process, wherein each stage comprises a closed loop process.

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  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
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  • General Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de transfert de chaleur vers un processus cible dans une installation de production chimique, le procédé comprenant les étapes suivantes : (i) fournir un premier flux de traitement (1) ayant une température T1 ; (ii) transférer de la chaleur d'un processus de conversion chimique, d'un processus physico-chimique, de la chaleur ambiante, ou d'une combinaison d'au moins deux de ceux-ci, au premier flux de traitement fourni de l'étape (i), pour obtenir un premier flux de traitement chauffé (3) ayant une température T2, où T2 > T1 ; (iii) conduire le processus cible avec le premier flux de traitement chauffé obtenu à l'étape (ii) ; le processus cible étant différent du processus de conversion chimique, du processus physico-chimique, ou de la combinaison du processus de conversion chimique et du processus physico-chimique à partir duquel de la chaleur est transférée selon l'étape (ii). Selon le procédé de la présente invention, un coefficient de performance supérieur à 1 peut être obtenu.
PCT/EP2023/075516 2022-09-16 2023-09-15 Procédé de transfert de chaleur entre deux processus indépendants WO2024056893A1 (fr)

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