Electrically heated hybrid high temperature process

Abstract

The invention relates to a method for the continuous operation of one or more heat-consuming processes, characterized in that at least one heat-consuming process is electrically heated, the maximum temperature in the reaction zone of the heat-consuming process is greater than 500°C, at least 70% of the products of the at least one heat-consuming process are further continuously processed in downstream processes and / or fed to a local energy carrier network, and the electrical energy required for the at least one heat-consuming process is obtained from an external power grid and from at least one local energy source, wherein the at least one local energy source is supplied with at least 50% of its annual energy requirement from the at least one local energy carrier network and with at most 50% of its annual energy requirement from products of the heat-consuming process, wherein natural gas, naphtha, hydrogen, synthesis gas and / or steam are stored as energy carriers in the at least one local energy carrier network, wherein the at least one local energy carrier network is supplied with at least one further product and / or by-product from at least one further chemical process, and wherein the total capacity of the local energy carrier network is at least 5 GWh. The invention also relates to the use of the method as a minute reserve for a public power grid and to the use of a local energy carrier network of a chemical site for storing electrical energy.

Description

[0001] This invention relates to a method for continuously performing one or more heat-consuming processes, wherein at least one heat-consuming process is electrically heated, the highest temperature in the reaction zone of the heat-consuming process is greater than 500°C, at least 70% of the product of the at least one heat-consuming process is further continuously processed and / or supplied to a local energy carrier network in a downstream process, and the electrical energy required for the at least one heat-consuming process is obtained from an external power grid and from at least one local power source, wherein the at least one local power source is supplied from the at least one local energy carrier network to at least 50% of its annual energy demand, and the at least one local power source supplies the product from the heat-consuming process to no more than 50% of its annual energy demand, wherein natural gas, naphtha, hydrogen, syngas and / or steam are stored as energy carriers in the at least one local energy carrier network, wherein the at least one local energy carrier network supplies at least one other product and / or byproduct from at least one other chemical process, and wherein the total capacity of the local energy carrier network is at least 5 GWh. The present invention further relates to the use of the method as a minute reserve for a public power grid, and to the use of local energy carrier networks at chemical sites in storing electrical energy.

[0002] One of the biggest problems making renewable energy available is the lack of storage capacity to absorb ongoing changes due to significant dependence on weather effects.

[0003] Since the 1980s, the issue of storing renewable energy has been a topic of concern. Despite using renewable energy, energy suppliers have considered measures including the following to provide on-demand electricity to energy users (such as the chemical industry):

[0004] US 4,776,171 describes an energy generation and management system consisting of multiple renewable energy sources, multiple energy storage sources, and multiple control and distribution stations to meet industrial needs.

[0005] US 2011 / 0081586 describes a combination of renewable energy with an electrochemical or electrolytic cell, wherein the electrochemical or electrolytic cell balances the fluctuations in the renewable energy and thus makes it continuously usable.

[0006] US 2008 / 0303348 discloses a power plant that uses only renewable energy sources while still achieving demand-dependent control. US 2008 / 0303348 describes a combination of wind, solar, and energy derived from burning biomass. The power plant is said to be able to continuously and spontaneously switch between the three energy sources, thereby readily and cheaply meeting the corresponding industrial needs.

[0007] Despite using fluctuating renewable energy sources, the main focus of these initiatives is on providing electricity to users on demand. Therefore, users specify the amount of electricity generated, and the weather determines the portion of renewable power generation.

[0008] US 2012 / 0186252 describes a method for generating and establishing electricity that goes beyond simply matching the needs of external users. According to US 2012 / 0186252, conventional power plants operate using fossil and / or renewable fuels and supply the generated electricity to the public grid when there is demand. During periods of low electricity demand, the generated electricity is used internally to produce hydrogen, which is then reacted with carbon dioxide in the Sabatier process to produce the renewable fuel methane. The hydrogen generator can thus mitigate the slow power of local sources by varying the production pipeline. Furthermore, during periods of surplus electricity, electricity from the public grid is used to operate the internal hydrogen generator. The hydrogen generator operates accordingly to both electricity demand and supply; when demand is low, the generator draws power from local sources, while during periods of surplus electricity, power comes from the public grid. A disadvantage of this method is that, because the hydrogen generator is used to regulate the power output of the conventional power plant to the grid's demand, it operates as a heat-consuming process with varying output yields. The operating procedures required for integrated chemical industrial sites to ensure stable output from hydrogen generators have not been disclosed.

[0009] US 4,558,494 describes the direct use of solar energy to produce ammonia. The heat required for this endothermic method is provided by a heat transfer fluid, which is heated by solar energy if available, and heated by the combustion of the produced ammonia if no solar energy is available. Therefore, US 4,668,494 discloses the use of two different energy sources, solar energy and oxidation energy, in an endothermic chemical process; however, it does not describe the use of electrical energy.

[0010] In 2016, renewable energy accounted for 50% of installed capacity and 30% of electricity generation in Germany (date: February 26, 2017; “Energy for Germany, Facts, Perspectives and Positions in a Global Context”, Weltenergierat–Deutschland eV, 2017). This will increase significantly again in the coming years, due to the economic attractiveness of renewable energy-based power generation technologies, primarily due to rising costs for fossil fuel suppliers, and secondly due to market regulatory measures.

[0011] In the near future, as more and more renewable energy sources, such as solar, wind, and hydroelectric power, are supplied to the grid, there will be increasing power spikes that will not be fully acceptable to electricity consumers. These power spikes (known as excess power) must be absorbed through controlled startup processes to ensure grid stability.

[0012] Consumers provide what is known as negative control power. Control power is defined as secondary control power and minute reserve power, depending on the required start-up time. This capacity is provided as a control power source (called control power reserve) regardless of whether it is needed. In 2016, the average agreed-upon negative secondary control power and minute reserve power were each approximately 1900 MW. In 2016, Germany spent nearly €200 million on control power reserves for primary control power, secondary control power, and minute reserve power (from a 2017 monitoring report by the German Federal Grid Agency, Bundesnetzagentur).

[0013] The cost of using controlled power is determined by the balance energy price. The balance energy price in the electricity market may be significantly lower than its generation cost, or it may be supplied at a lower price than fossil fuels with the same calorific value, or even free (i.e., no payment), or at a negative price, based on its energy content. In 2016, the average balance energy price was -€14.12 / MWh. This means that consumers who accept surplus electricity receive additional credit notes. The total amount of credit notes in 2016 was approximately €10.78 million.

[0014] In Germany, the Renewable Energy Sources Act guarantees priority access to the grid from renewable energy producers. If, despite all grid optimization and development measures, a reduction in renewable energy generation is unavoidable due to overcapacity or insufficient transmission capacity, compensation must be provided by the grid operator responsible for the reduction. In 2016, these so-called supply management measures affected 3743.2 GWh, which had to be compensated at a cost of approximately €643 million (from the Bundesnetzagentur's 2017 monitoring report).

[0015] The cost pressure on thermal power plants used as baseload generators is increasing due to the significant reduction (18-20 GW) in the minimum surplus power load of conventional power plants caused by the supply of wind and solar power. On the other hand, technological constraints (minimum load and start-up time) and system stability requirements (providing system services) necessitate a minimum generation capacity from conventional power plants. Simplified estimates suggest that ensuring system stability currently requires a minimum generation capacity of 4-20 GW from conventional power plants. This requirement is to provide sufficient idle and active power reserves to respond to fluctuating wind and solar power supply. im Stromsektor [Status Report on Power Sector Flexibility Requirements]).

[0016] These issues place high demands on the usable load range and response time of power plants. Lignite and hard coal power plants have start-up times of several hours. Combined cycle power plants have a start-up time of approximately one hour. Only gas turbine power plants can start up within minutes. The plant efficiency of combined cycle power plants is 55% to 60%, hard coal power plants 42% to 47%, lignite power plants 38% to 43%, and gas turbine power plants 34% to 40%. The usable load range for all types of combined heat and power (CHP) plants is between 40% and 90% of maximum power, with the highest plant efficiency at full load. Given these characteristics, the challenge is to connect consumers with high continuous electricity demand to the grid, enabling baseload power plants to operate with maximum continuity under high load conditions.

[0017] Currently, short-term power fluctuations are compensated for by so-called high-power power plants, which absorb load spikes within the system service range of the grid operator. This is now primarily achieved through pumped and pressurized storage plants and gas and steam power plants. In the former case, Germany's installable capacity is largely exhausted. Gas and steam power plants used for peak load compensation are largely ignored by energy suppliers due to their excessively long amortization periods (because their annual operating time is too short). Furthermore, compressed air storage power plants are relatively inefficient, at around 40% to 50%.

[0018] In grid frequency control, control circuits with different speeds are used: primary control with a response time of less than 30 seconds, secondary control with a response time of less than 5 minutes, and finally tertiary control that allows for a longer response time. Primary control is automatically triggered and directly affects the operating status of the power plant. Secondary control is also automatically triggered and can be activated by standby mode to maintain reserve capacity. Tertiary control (or minute reserve) is typically activated through organizational measures. Secondary control and minute reserve can be positive (in cases of increased power demand) or negative (in cases of decreased power demand). Positive secondary control and minute reserve are typically activated by opening the reserve power plant. Negative minute reserve requires energy consumers. Based on existing technology and pumped storage power plants, this is also achieved through capacity variations in large power plants and combined heat and power plants with end consumers (e.g., light arc furnaces or cold storage warehouses). However, its capacity distribution is uneven across regions (see the IDOS report). Furthermore, the demand for negative minute reserve may increase due to the development of renewable energy. In 2016, the four German grid suppliers required approximately 710 GWh of negative secondary control capacity, while the total negative minute reserve was approximately 54 GWh (see monitoring report from Bundesnetzagentur, 2017, page 158).

[0019] Another device used to buffer the gap between electricity supply and demand is thermal storage. Thermal storage devices store energy in the form of heat. Heat sources can be, for example, flue gas from combustion processes, electric heaters, or solar collectors. Electrical energy can be generated from heat stored during thermoelectric processes. Therefore, the higher the temperature at which heat is generated, the more effective the thermal storage device. Thermal storage devices can be divided into three main categories. Sensible heat storage devices store heat in the form of an actual temperature rise; in latent heat storage devices, energy is stored in the phase change of the storage medium. Thermochemical and adsorption storage devices reversibly store thermal energy as heat of chemical reaction or heat of adsorption / absorption. As sensible heat storage devices, liquid or solid materials with high heat capacity are used. Standard liquids are water with a temperature range of 0°C to 100°C, heat transfer oil with a temperature range of 0°C to 400°C, nitrates with a temperature range of 250°C to 570°C, carbonates with a temperature range of 450°C to 850°C, and sodium with a temperature range of 100°C to 800°C. Standard solid thermal storage devices are moist gravel beds with a temperature range of 0°C to 100°C, concrete with a temperature range of 0°C to 500°C, gravel or sand, granite or ferroalloy with a temperature range of 0°C to 800°C, and brick with a temperature range of 0°C to 1000°C.

[0020] The latent heat storage device used is a material that changes its physical state between solid and liquid or between liquid and gas within its operating range.

[0021] The standard material is water, which is used as a solid-liquid latent heat storage device at 0°C and as a gas-liquid latent heat storage device in the temperature range of 100°C to 350°C. Other solid-liquid latent heat storage devices include crude paraffin at approximately 34°C, eicosane at approximately 37°C, lauric acid at approximately 44°C, myristic acid at approximately 54°C, stearic acid at approximately 70°C, sodium sulfate (Na₂SO₄·10H₂O) at approximately 32°C, pentahydrate (Na₂S₂O₃·5H₂O) at approximately 48°C, barium hydroxide octahydrate (Ba(OH)₂·8H₂O) at approximately 78°C, a eutectic sodium chloride / magnesium chloride mixture at approximately 450°C, or a eutectic sodium chloride / magnesium fluoride mixture at approximately 832°C. Thermochemical storage devices utilize reversible reactions. This reaction can be used for the dehydration of metal hydrides such as MgH2, Mg2NiH4, and Mg2FeH6; the dehydration of metal hydroxides such as Mg(OH)2, Ca(OH)2, and Ba(OH)2; the decarboxylation of metal carbonates such as MgCO3, PbCO3, CaCO3, and BaCO3; and the partial reduction of polyvalent metal oxides such as PbO2, Sb2O5, MnO2, Mn2O3, CuO, and Fe2O3. The adsorption storage device used is a salt hydrate, such as MgSO4·7H2O, MgCl2·6H2O, CaCl2·6H2O, CuSO4·5H2O, and CuSO4·H2O, or an ammonium chloride, such as CaCl2·8NH3, CaCl2·4NH3, and MnCl2·6NH3. Finally, endothermic high-temperature processes that provide hydrogen-rich products, such as steam reforming or natural gas pyrolysis, can be used as thermochemical storage devices. Hydrogen can be used physically or for energy purposes.

[0022] An important application of thermal storage media is in solar thermal power plants. Salt melt, hot oil, and concrete are used as storage media here. Furthermore, thermal storage media used in power plants improve load flexibility regarding minimum load and load variation rates. For example, steam storage media are used to provide controllable power.

[0023] In discussions about the energy revolution and reducing CO2 emissions to protect the climate, the electrification of chemical processes, particularly the use of highly endothermic chemical reactions as a secondary control mechanism and a minute's reserve of excess electricity, still doesn't make much sense.

[0024] If large heat flows must be introduced at very high temperature levels, electricity is currently primarily used as the energy source for non-catalytic gas / solid and solid-state reactions. A typical application is metallurgical furnaces [Ullmann: Metallurgical Furnaces]. The only relevant gas-phase process established on an industrial scale is the plasma process for the production of acetylene from methane [Baumann, Angewandte Chemie, issue B, Vol. 20 (1948), pp. 257-259, 1948] and the process for the production of reducing gases in the steel industry. The literature does include other descriptions of the use of electrical energy in gas-phase processes; however, it has not yet been possible to develop any applications from these that can be economically used on an industrial scale.

[0025] An electrically heated process for preparing hydrogen cyanide (HCN) from alkanes, particularly methane and ammonia, is described. US Patent Specification 2,958,584 discloses the preparation of HCN from propane and ammonia in a fluidized bed of electrically heated carbon particles, while US 6,096,173 describes the preparation of hydrogen cyanide from the gas-phase reaction of methane and ammonia using corona discharge.

[0026] US 7,288,690 describes a steam cracking method for hydrocarbons in which the cracking tube is electrically heated. The improvement achieved by this invention is essentially the integration of heat and power, thereby simultaneously generating heat and electricity from the combustion of fuel. The fuel is preferably burned in a gas turbine that drives a generator. The generated electrical energy is used to heat the cracking tube. The actual heat present in the combustion exhaust gas is used to preheat the feed mixture. A disadvantage of this solution is the coupling between the energy flow available for electric heating of the cracking tube and the energy flow available for preheating the feed mixture. This coupling forces one of the two process stages into a suboptimal operating state. Furthermore, the applicability of this invention is limited to non-thermally integrated processes.

[0027] DE 10 2013 209 883 describes an integrated apparatus for the electrochemical production of hydrogen cyanide in a batch operation, which can adapt its process output to an external power source with the aid of weather forecasts. Similarly, DE 10 2012 023832 describes an integrated dynamic apparatus for the electrochemical production of acetylene. Electrical energy is supplied to the respective reactors via an external power grid and via a local power source, where the local power source directly utilizes the hydrogen-rich waste gas stream from the production of hydrogen cyanide or acetylene without intermediate storage for power generation. The power source used can be a fuel cell and gas turbine power plant, or a combined cycle power plant. Hydrocarbons and hydrogen are stored; these storage units have hydrogen capacity, enabling the plant to produce hydrogen (approximately 5000 MWh) within 48 hours. Considering the Wobbe index, the storage units supply the hydrocarbons and hydrogen to a natural gas grid, or guide the hydrocarbons back to the reactors. There is no disclosure of using the stored gases to operate the local power source.

[0028] The dynamic operating mode results in drawbacks in operational reliability due to the need to store highly reactive substances such as acetylene and hydrogen cyanide that can be decomposed to compensate for fluctuating production volumes. Another drawback is that frequent start-ups and shutdowns cause significant temperature fluctuations in the reactor, adversely affecting its lifespan and operational reliability. Yet another drawback is the substantial additional mechanical and equipment costs required for introducing gas into the natural gas grid, which is unnecessary for this process. A further drawback is the excessively long planning intervals between process kinetics (particularly those in the separation stages) and weather forecasts, preventing the process from being used as a secondary or tertiary reserve.

[0029] In addition, there are descriptions of the preparation of syngas using plasma generators (37 L. Kerker, R. Müller: "Das Plasmareforming-Verfahren zur Erzeugung von Reduktionsgasen" [Plasma reforming process for producing reducing gases], Stahl Eisen 104, (1984), No. 22, 1137) and the decomposition of hydrocarbons using electric or electromagnetic processes ( P., Lohmüller, R. and Watson, AM 2000. Hydrogen, 2. Production. Ullmann's Encyclopedia of Industrial Chemistry).

[0030] However, many important high-temperature processes currently operate solely using energy fed via oxidation processes (by heat and / or allothermal heat). The drawbacks of these oxidation processes—namely, feedstock dependence and limited availability, and CO2 emissions associated with them—are well-known. On an industrial scale, these energy-intensive processes run continuously, thus requiring continuous heating. In Germany, the energy required for these processes is estimated at 300-600 TWh. This roughly equates to Germany's current net electricity generation. Therefore, endothermic high-temperature processes have a significant capacity to absorb excess electricity.

[0031] Some important heat-consuming processes are high-temperature processes, i.e., processes carried out at temperatures between 500 and 2500°C. Representative of these highly energy-intensive processes include steam reforming and dry reforming, dehydrogenation (e.g., from primary alcohols to aldehydes, from secondary alcohols to ketones, from alkanes to alkenes, and from cycloalkanes to cycloolefins), hydrogen cyanide production via formamide cracking or from methane and ammonia, nitric oxide production from air, steam cracking or pyrolysis of hydrocarbons, and pyrolysis of water. Steam reforming and dry reforming are processes used to produce a mixture of syngas, carbon monoxide, and hydrogen from carbon-containing energy carriers (e.g., natural gas, light gasoline, methanol, biogas or biomass, and water or carbon dioxide). Steam cracking of hydrocarbons is industrially recognized as a process for producing short-chain olefins (especially ethylene and propylene) and aromatic compounds from hydrocarbon-containing energy carriers (e.g., from shale gas, naphtha, and liquefied petroleum gas). This process is kinetically controlled and has a short reaction time. Pyrolysis is a process that converts hydrocarbons into their stable carbon and hydrogen end products. The process is carried out using a balanced control method, with a relatively long residence time.

[0032] According to existing technologies, endothermic high-temperature processes such as steam cracking or steam reforming require a heat input far exceeding the heat input required for the endothermic reaction. Typically, the excess heat output introduced is 80% to 200% based on the heat required for the endothermic reaction. In integrated chemical sites, this excess heat can be output to downstream stages, for example, to generate steam at different pressure levels. In this way, the thermal efficiency of the equipment can be increased to 90% or higher. However, a disadvantage of this process is that the primary energy demand and associated greenhouse gas emissions far exceed the actual requirements of the high-temperature reaction. Another disadvantage is the rigid energy coupling between different devices in the integrated site; these couplings mean that the operating points of each device can only be adjusted within strict limits.

[0033] To enable chemical production to be used in the energy revolution as a confluence point for surplus electricity from renewable energy sources, the concept of electric heating for energy-intensive chemical processes is needed. Since these processes are typically continuous operations, the energy supply must be designed to absorb fluctuations in the availability of surplus electricity. In addition to introducing surplus electricity, at least one other energy source is correspondingly required.

[0034] WO 2014 / 090914 discloses a method for supplying heat to a reactor in a hybrid manner, i.e., by fossil heating or an electric method. WO 2014 / 090914 gives the first indication of using a chemical process as a minute reserve for the use of excess electricity. A method for conducting a heat-consuming high-temperature process is described, wherein the total energy required on average per year comes from at least two different energy sources: at least one electrical energy source that provides 0% to 100% of the total energy required, particularly using excess electricity, and additional non-electrical energy sources that provide any excess energy required. The main challenge in this conceptual case is the stress on the equipment in the conversion between the two energy sources, and the dynamic conversion with minimal losses, i.e., without conversion and selectivity losses. Another disadvantage of this solution is that it may be necessary to install two separate devices for generating heat in the process area exposed to high temperatures. This increases the complexity of the process and the tendency to fail.

[0035] EP3249027 claims a process for reducing emissions in the production of olefins via steam cracking of hydrocarbons. In this process, the cracking tubes can be heated by the heat of combustion of fuel or by electric heating. The ratio of electric heating to combustion heat can be varied while maintaining a constant total output. It is also conceivable to connect cracking tubes heated only by electric heating or only by combustion heat in parallel. One disadvantage of this invention is that two different heat sources must be installed in the cracking furnace.

[0036] Therefore, one object of the present invention is to enable high-temperature chemical processes to be used in the energy revolution as a sink for excess electricity from renewable energy sources. Another object is to provide chemical processes as energy users within the power grid, with negative secondary control and / or minute reserves for frequency control. Yet another object is to make endothermic chemical processes more flexible, allowing them to select power sources based on wholesale electricity prices, thereby achieving economic optimization.

[0037] Another objective is to minimize the target power variation in the input endothermic process during power supply transitions, ensuring consistent production output. Another objective is to maximize the efficiency of the local power supply and minimize CO2 output.

[0038] Another objective is to integrate local power into the overall quality and thermal system of the endothermic process. If a local power source that can be quickly turned on or off is used, an energy carrier that can be turned on or off sufficiently quickly is required.

[0039] Another objective of this invention is to find a method that can increase flexibility in the storage and use of electrical energy compared to existing technologies.

[0040] Furthermore, although the present invention uses excess electricity, it still aims to homogenize the productivity of the heat-consuming process under discussion and minimize the stress on machinery and equipment.

[0041] Furthermore, this invention improves the planning of downstream processes by controlling the load of upstream heat-consuming processes, regardless of whether there is excess electricity, based on the demand of downstream processes.

[0042] The equipment and methods offer maximum efficiency. Furthermore, the method of the present invention utilizes conventional and widely available infrastructure. Moreover, the method should be carried out with a minimum number of steps, and these steps should be simple and reproducible.

[0043] Currently, in various industrial processes, a significant amount of thermal energy is wasted as waste gas and waste heat, polluting the environment. The recovery and utilization of this waste heat can significantly improve the energy and economic efficiency of many processing plants across different industrial sectors. In integrated sites within the chemical industry, the available energy carriers are fluid media distributed throughout the site (local energy carrier network) via associated piping networks and storage containers. These energy carriers can be feedstocks such as natural gas or liquefied petroleum gas, commodities such as hydrogen or syngas, and additives such as steam or compressed air. This local energy carrier network provides a sufficiently high capacity to store mechanical energy, heat, and / or combustible materials, and provides this energy without delay when needed for local power generation.

[0044] method:

[0045] The objective is achieved according to the invention by means of: a method for continuously performing one or more heat-consuming chemical processes, wherein at least one heat-consuming process is electrically heated, the highest temperature in the reaction zone of the heat-consuming process is greater than 500°C, at least 70% of the product of the at least one heat-consuming process is further continuously processed in downstream processes and / or supplied to a local energy carrier network, and the electrical energy required for the at least one heat-consuming process is obtained from an external power grid and from at least one local power source, wherein the at least one local power source is supplied from at least one local energy carrier network to at least 50% of its annual energy demand, and without intermediate storage, the at least one local power source supplies the product from the heat-consuming process to no more than 50% of its annual demand, wherein natural gas, naphtha, hydrogen, syngas and / or steam are stored as energy carriers in the at least one local energy carrier network, wherein the at least one local energy carrier network supplies at least one other product and / or byproduct from at least one other chemical process, and wherein the total capacity of the local energy carrier network is at least 5 GWh.

[0046] The present invention further relates to the use of at least one local energy carrier network in a chemical site for storing electrical energy, wherein the energy carrier used is natural gas, liquefied gas or naphtha, hydrogen, ammonia, syngas, ethylene, propylene, lean gas, compressed air and / or steam, and wherein the total capacity of the energy carrier network is at least 5 GWh.

[0047] Local energy carrier networks can be divided into networks / storage units for heat carriers (e.g., steam), networks / storage units for intermediates (e.g., hydrogen and syngas), and networks / storage units for feedstocks (e.g., natural gas and naphtha). It is preferable to use at least two local energy carrier networks.

[0048] Preferably, at least two different local energy carrier networks are used, selected from a group of energy carriers, preferably steam, intermediates, preferably hydrogen and / or syngas, especially hydrogen, and feedstock, preferably natural gas and naphtha, especially natural gas. A two-component combination of heat carrier and intermediate is preferred, or a three-component combination of heat carrier, intermediate and feedstock.

[0049] Advantageously, at least 50%, preferably 70%, and particularly 90% of the product of at least one heat-consuming process is further continuously processed and / or supplied to a local energy carrier network in a downstream process. Preferably, the percentage of the product range is 50% to 100%, preferably 70% to 100%, and particularly 90% to 100%. A downstream process should be understood to mean the downstream conversion of the product from the heat-consuming process into other products.

[0050] Advantageously, at least one local power source is supplied from the local energy carrier network to at least 50% of its annual energy demand; preferably at least 70%, more preferably at least 80%, and even more preferably at least 90%. Advantageously, the percentage ranges from 50 to 100%, preferably 70 to 100%, more preferably 80 to 100%, and particularly 90 to 100%. More preferably, at least one local power source is supplied solely by the local energy carrier network.

[0051] Advantageously, at least one local power source, together with the products directly from the heat-consuming process, is supplied to a level not exceeding 50% of its annual energy demand, preferably not exceeding 20%, more preferably not exceeding 10%. Advantageously, the percentage ranges from 50% to 0%, preferably from 20% to 0, and particularly from 10% to 0.

[0052] This means that the product (used to supply local power) is obtained directly from the heat-consuming process without intermediate storage and is directed to the local power source. More preferably, the product stream from the heat-consuming process is not directly directed to the local power source without intermediate storage.

[0053] Advantageously, at least one other product and / or byproduct is supplied to the local energy grid by at least one other chemical process. These other chemical processes are, for example, olefin processes, syngas processes, partial oxidation, hydrocarbon pyrolysis, water electrolysis, smelting processes, and / or hydrogenation.

[0054] For example, hydrogen energy carrier networks are supplied by processes such as steam cracking, steam reforming, methane pyrolysis, styrene synthesis, propane dehydrogenation, syngas production, and formaldehyde synthesis. Steam energy carrier networks are supplied by processes such as steam cracking, steam reforming, acetylene processes, syngas production, acrylic acid synthesis, phthalic anhydride synthesis, maleic anhydride synthesis, ethylene oxide synthesis, and formaldehyde synthesis. Hydrocarbon energy carrier networks are supplied by feedstocks such as naphtha, natural gas, and liquefied petroleum gas (LPG).

[0055] Endothermic processes, such as steam cracking, steam / dry reforming, styrene synthesis, propane dehydrogenation, butane dehydrogenation, hydrogen cyanide synthesis, and methane pyrolysis, are both energy sources and users; while exothermic processes, such as maleic anhydride, phthalic anhydride, acrolein and acrylic acid, ethylene oxide, formaldehyde, and TDI / MDI, are only energy sources.

[0056] power supply:

[0057] At any time of day, depending on the current power supply, the electrical energy required for a heat-consuming process can come from different sources. Three modes are possible: (i) solely from an external power source, particularly the public power grid; (ii) solely from at least one local power source; or (iii) jointly from one external power source and from at least one internal local power source.

[0058] Preferably, all three modes (i), (ii) and (iii) can at least temporarily provide all the energy required for at least one heat-consuming process.

[0059] Advantageously, the annual average amount of energy required obtained from an external power source is 10% to 90%, preferably 25% to 75%, and more preferably 50% to 75%.

[0060] Advantageously, the energy required for the heat-consuming process is supplied by electricity to at least 50%, preferably at least 75%, and more preferably at least 90%; in particular, the required energy is supplied solely by electricity. Advantageously, the percentage ranges from 50 to 100, preferably 75 to 100, and especially 90 to 100.

[0061] The continuous performance advantageously lasts for more than one day, preferably more than one week, more preferably more than one month, even more preferably more than two months, and especially more than six months, during which the process output variation based on the maximum process output does not exceed 50%, preferably not more than 30%, more preferably not more than 20%, and especially not more than 10%. Advantageously, the percentage range is 50 to 0, preferably 30 to 0, more preferably 20 to 0, and especially 10 to 0.

[0062] The process output of the present invention is advantageously matched with the reactant requirements of the downstream process, i.e., the downstream conversion of products from the heat-consuming process to other products.

[0063] The local energy carrier network advantageously has a total capacity of greater than 5 GWh, preferably greater than 10 GWh, more preferably greater than 20 GWh, and particularly greater than 50 GWh. Advantageously, the total capacity is in the range of 10 GWh to 1000 GWh, preferably 20 GWh to 500 GWh, and more preferably 50 GWh to 200 GWh.

[0064] External power supply:

[0065] External power sources refer to the power grid; this also includes integrated system power plants, especially integrated system power plants with a startup time of more than 15 minutes.

[0066] The term "electric grid" refers to all or a portion of transmission lines, substations, and local distribution networks that enable the transmission and regulation of electricity between different physical nodes of the grid and between different commercial, private, and large-scale consumers connected to the grid.

[0067] The difference between external power sources and local internal power sources is that the electricity generated by external power sources is supplied to the power grid, from which many users can obtain electricity. Local internal power sources are allocated only to a few chemically heat-consuming processes, preferably 1 to 10 processes, more preferably 1 to 5 processes, and particularly 1 to 3 processes. The power generated in the internal local power sources is transmitted via local power lines that operate independently of the public power grid in terms of frequency and voltage. Therefore, based on the total electrical energy generated in the internal power sources, the power generated in the internal local power sources is advantageously supplied to the public power grid at a level of less than 20%, preferably less than 10%. Advantageously, the percentage ranges from 20% to 0%, preferably from 10% to 0. More preferably, the power generated in the internal local power sources is not supplied to the public power grid.

[0068] When heat-consuming processes are underutilized and / or external power demands are high, local power sources can release power to the external power grid. For example, local power sources can be used additionally as positive secondary control power or minute-by-minute reserve power.

[0069] If a connection from local power to the general public power grid is not required, complex control equipment can be omitted. Furthermore, locally generated power does not need to meet grid specifications.

[0070] Local power supply:

[0071] Useful examples of at least one local power source advantageously include power generation based on gas turbines (GT) and / or steam turbines (ST) and / or fuel cells.

[0072] Gas turbines are known to those skilled in the art and are described, for example, in C. Lechner and J. Seume (editors): Gasturbinen (stationary gas turbines), Springer, Berlin 2003. Useful fuel for gas turbines advantageously includes combustible feedstock and / or exhaust gas streams in each integrated location, as well as process streams from heat-consuming processes, advantageously including reactants and / or products of the heat-consuming processes.

[0073] An integrated production site in the chemical industry is a production site with a closed quality and energy loop, where production operations, raw materials, chemical products, energy and waste streams, and material and waste streams are interconnected (www.basf.com / global / en / investors / calendar-and-publications / factbook / basf-group / verbund.html). Integrated production sites are characterized by cascaded production chains. Product diversity increases along this cascade. An integrated production site typically has three stages: the preparation of a commodity in the first stage, the preparation of intermediates in the second stage, and the preparation of a specialty or final product in the third stage. Each stage in this cascade may consist of one or more other stages. Integrated production sites require the introduction of small amounts of raw materials, such as LPG, naphtha, light gasoline, vacuum distillation residues, aromatics, sulfur, as well as water, air, and electricity, to produce thousands of different compounds and formulations prepared from them. The ratio of the product produced by an integrated production site to the raw materials used is greater than 10, preferably greater than 100, and more preferably greater than 500.

[0074] In combustible waste gas streams, hydrogen-rich waste gas streams are advantageous.

[0075] Examples include waste gas streams from steam cracking, steam reforming, ammonia synthesis, methanol synthesis, formaldehyde synthesis, styrene production, coke production, and steel production. These combustible waste gas streams have different compositions and, depending on their source, different names, such as blast furnace gas, coke oven gas, coupling gas, dehydrogenated gas, formalin gas, etc. (WO 2014 / 095661 A1). A common characteristic of these gases is that their calorific value is lower than that of common fuels such as natural gas. Based on their calorific value, the gas is referred to as lean gas (calorific value at most approximately 1200 kcal / Nm³). 3 ), weak gases (calorific value up to 3000 kcal / Nm³) 3 ) or rich gas (calorific value up to 6000 kcal / Nm³) 3 ) (G. Wagener. Gas-und Wasserfach 91, 73, 1950).

[0076] Fuel cells, for example, are described in Hoogers, G. (ed.). (2002). Fuel cell technology handbook. CRC press, such as polymer electrolyte membrane fuel cells (PEMFC), phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC), molten carbonate fuel cells (MCFC), or solid electrolyte fuel cells (SOFC).

[0077] Oxygen-fueled power plants that utilize oxygen-rich waste gas streams can also be used as local power sources.

[0078] As an alternative or additional source of local power, a useful source of local power is the generation of electricity from steam turbines.

[0079] If hydrogen is used as a source of local power generation, the following processes are particularly advantageous: gas turbines, SOFCs and / or MCFCs and / or PEMFCs and / or AFCs. Hydrogen-driven gas turbines advantageously operate at inlet temperatures up to 1500°C with efficiencies up to 41%. SOFCs advantageously operate at temperatures between 650°C and 1000°C with efficiencies up to 60%. MCFCs advantageously operate at temperatures between 650°C and 1000°C with efficiencies up to 60%. PEMFCs advantageously operate at temperatures between 50°C and 180°C with efficiencies up to 50%. AFCs advantageously operate between 20°C and 80°C with efficiencies up to 70%.

[0080] If hydrocarbons are used as a source of local power generation, the following processes are particularly advantageous: gas turbines and / or SOFCs and / or MCFCs. Natural gas-driven gas turbines advantageously have inlet temperatures up to 1230°C and efficiencies up to 39%. SOFCs advantageously operate at temperatures between 650°C and 1000°C and have efficiencies up to 60%. SOFCs advantageously operate at temperatures between 550°C and 700°C and have efficiencies up to 55%.

[0081] The following is a table summarizing the preferred local power sources:

[0082]

[0083]

[0084] gas turbine:

[0085] (1a): The start-up time from the off state to full power is advantageously 30 seconds to 30 minutes, preferably 60 seconds to 20 minutes, and more preferably 90 seconds to 10 minutes (e.g., for the SIEMENS SGT-A65 model, a cold start time of less than 7 minutes at full power is specified).

[0086] (1b): The power is advantageously 40% to 120% of the nominal power, preferably 50% to 110% of the nominal power, and more preferably 60% to 105% of the nominal power. (See: C. Lechner, J. Seume (edited)) Gasturbinen, page 190).

[0087] (1c), (5c), (6c): The exhaust gases produced by these generators are hot, allowing the energy present to be used to generate steam. The steam can drive a steam turbine and generate additional electrical energy. In this way, the efficiency of converting chemical energy into electrical energy can be significantly improved (up to 20%). In quasi-steady-state operation, the gas turbine outlet temperature is approximately 650°C (see: C. Lechner, J. Seume (edited)). Gasturbinen, page 124), SOFC outlet temperature is about 700°C and MCFC outlet temperature is about 550°C (see Wikipedia "Gas Turbine", : T(op)-100K).

[0088] Steam turbine:

[0089] (2a): The start-up time of the steam turbine from standby state is advantageously between 10 and 60 minutes. In standby state, the turbine is advantageously preheated to 300°C and rotated at a low speed (about 1 Hz) (see: Wikipedia "Dampfturbine").

[0090] (2b): The power is advantageously 10% to 120% of the nominal power, preferably 20% to 110% of the nominal power, and more preferably 40% to 105% of the nominal power (see: Statusbericht). (im Stromsektor [Status Report on Flexibility Requirements of the Power Sector], Chapter 4). The steam turbine can be stopped while adjusting its speed until it is completely idling, provided that a steam supply is ensured.

[0091] (2c): The steam turbine is advantageously separated from combustion, which provides energy for steam generation and superheating. In integrated locations, the steam turbine can advantageously be supplied from an existing steam network. With this configuration, steam can be generated using various fuels. The steam can be stored in a large steam network, for example, 10m³. 3 Up to 100,000m 3 Therefore, it can buffer changes in the availability of chemical energy.

[0092] (2d): The steam turbine generator can be advantageously coupled directly or indirectly to a generator type that produces hot exhaust gas, such as GT, SOFC, or MCFC. Direct coupling means that the exhaust gas flow from the upstream generator is used to generate steam in the steam turbine (e.g., in a combined cycle power plant). "Indirect" means that the exhaust gas flow generates steam from the upstream generator, which is then supplied to the steam network of the integrated site. The steam turbine can be supplied by this network.

[0093] Fuel cells:

[0094] (3a), (4a): The start-up time of PEMFC and AFC is advantageously 10 seconds to 15 minutes, preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes. The operating temperature of PEMFC and AFC is about 80°C. The kinetics of the electrode reaction at room temperature are sufficient to generate electrical energy. In the integrated location, waste heat flow can be advantageously used to allow the fuel cell to be maintained at the operating temperature without difficulty.

[0095] (3b) and (4b): CO2 emissions from PEMFC and AFC operations are less than 50 g CO2 / kW. el Preferably less than 20gCO2 / kW el More preferably less than 5g CO2 / kW el In particular, they do not emit CO2. PEMFCs and AFCs advantageously use hydrogen as fuel.

[0096] (3c), (4c), (5b), (6b): The usable power range of the fuel cell generator is advantageously 1% to 100% of the maximum power, preferably 5% to 90% of the maximum power, and more preferably 10% to 70% of the maximum power.

[0097] (3d), (4d), (5c), (6c): The electrical efficiency of a fuel cell generator depends advantageously on the cell voltage increasing in a strictly monotonic manner, and the load depends advantageously on the generated current increasing in a strictly monotonic manner. The cell voltage is highest at idle and decreases as power output increases. This means that the efficiency of a fuel cell under partial load is greater than its efficiency under full load. This characteristic is the opposite of that of a turbine generator, which has the highest efficiency under full load. Therefore, fuel cell generators have a wider usable power range and are suitable for continuous power control.

[0098] Starting and stopping the local power supply:

[0099] The start-up or shutdown time of the local power supply is advantageously shorter than the required response time of the minute reserve in the power grid (<15 minutes), preferably shorter than the required response time of the secondary control (<5 minutes), and more preferably shorter than the required response time of the primary control (<30 seconds).

[0100] Starting from a standstill, the following power sources will reach full load within a 15-minute startup time: gas turbine generator, PEMFC generator, and AFC generator. Additionally, starting from a standstill, the following power sources will reach full load within a 5-minute startup time: PEMFC and AFC.

[0101] Starting from partial load operation, all listed power sources can reach full load within a 15-minute transition period. Furthermore, starting from partial load operation, the following power sources will reach full load within a 5-minute transition period: GT, PEMFC, AFC, SOFC, and MCFC. In the case of steam turbine generators, the rate of power increase is limited by steam availability. If the steam turbine is directly powered from the steam network, the steam turbine generator will reach full load with a 5-minute transition time. Additionally, gas turbine generators or steam turbine generators advantageously operate at 80% load, preferably 85% load, more preferably 90% load and reach full load within 30 seconds. Furthermore, PEMFC generators or AFC generators start at 60% load, preferably 70% load, more preferably 80% load and reach full load within 30 seconds. Furthermore, SOFC generators or MCFC generators start at 70% load, preferably 80% load, more preferably 90% load and reach full load within 30 seconds.

[0102] Starting from any operating state, all listed power supplies are able to reduce power to zero within 30 seconds.

[0103] Energy carrier:

[0104] Energy carriers used for local power operation are advantageously media that can be stored in an integrated facility with sufficient capacity. These media are advantageously flammable liquid or gaseous feedstocks, flammable gaseous or liquid commodities available in the distribution network of the integrated facility, or non-reactive gaseous, liquid, or solid energy carriers that can store mechanical energy, tangible heat, or latent heat and can be distributed on-site. These media are preferably natural gas, liquefied petroleum gas or naphtha, hydrogen, ammonia, syngas, compressed air, steam, or renewable solid storage media. Natural gas, hydrogen, or steam is more preferred.

[0105] Solid or liquid products are advantageously stored at ambient pressure or at their spontaneous vapor pressure. This is because liquids are practically incompressible.

[0106] Unlike gases and vapors, these media are compressible, meaning that their density (and therefore energy density) increases with increasing pressure. Example:

[0107] 1. Natural gas is advantageously transported in pipelines at levels below 50 bar.

[0108] 2. Hydrogen is advantageously stored and distributed in the integrated system network at two pressure levels (40 bar and 325 bar). The reason for the high pressure is that the high reaction pressure promotes hydrogenation (as a reaction that reduces the molar number).

[0109] 3. Steam is advantageously stored at different pressure levels, thus utilizing the pressure dependence of boiling temperature / condensation temperature. Steam functions as a heat carrier within its boiling point range. Due to phase change, it can absorb (in the case of evaporation) or release (in the case of condensation) large amounts of heat very well without any temperature change. Therefore, steam is stored at different pressure levels. Each pressure level is assigned an effective temperature range:

[0110] 1.5 bar → 110°C

[0111] 4 bar → 140°C

[0112] 6 bar → 155°C

[0113] 11 bar → 180°C

[0114] 16 bar → 200°C

[0115] 24 bar → 220°C

[0116] 40 bar → 250°C

[0117] 100 bar → 310°C

[0118] 117 bar → 320°C

[0119] Depending on the energy carrier, the method of the present invention can be configured in different ways.

[0120] Steam as an energy carrier:

[0121] Advantageously, this configuration of the method of the invention has one or two local power sources. If the method of the invention has one local power source, it is advantageously a gas turbine generator, a steam turbine generator, a PEMFC generator, an AFC generator, an SOFC generator, or an MCFC generator. One power source is preferably a steam turbine generator, a PEMFC generator, or an AFC generator. More preferably, it is a steam turbine generator. When the method of the invention has two local power sources, the first power source is advantageously a gas turbine generator, a PEMFC generator, an AFC generator, an SOFC generator, or an MCFC generator, and the second power source is a steam turbine generator; preferably, the first power source is a gas turbine generator, an SOFC generator, or an MCFC generator, and the second power source is a steam turbine generator; more preferably, the first power source is a gas turbine generator, and the second power source is a steam turbine generator. For each power source, 1-10 units, preferably 1-5 units, and more preferably 1-2 units are allocated to the heat-consuming process.

[0122] In this configuration of the method of the invention, the steam turbine generator plays a special role. The steam turbine is advantageously supplied with steam from a local steam tank, steam pipes of local equipment, or a steam network. Preferably, the steam turbine draws its steam from the steam network of the integrated site. Thus, the steam driving the steam turbine is permanently available, and the power of the steam turbine generator (e.g., steam pipes of a steam boiler or evaporative condenser) is no longer limited. The steam network is advantageously supplied by a central steam generator or multiple steam generators distributed throughout the integrated site. Preferably, the steam network is supplied by at least two steam generators. More preferably, the steam network is supplied via steam generators distributed throughout the integrated site using local heat sources. The steam generators can be evaporative condensers or steam boilers of chemical reactors, which can be heated by fuel, combustible waste gas flow, or electricity. The pressure in the steam network is advantageously from 4 bar to 200 bar, preferably from 6 bar to 150 bar, more preferably from 8 bar to 130 bar. The temperature in the network is advantageously from 150°C to 700°C, preferably from 200°C to 650°C, more preferably from 250°C to 600°C.

[0123] The volume of the steam network is advantageously 1000 m³. 3 Up to 10,000,000m 3 5000m is preferred 3 Up to 5,000,000m 3 More preferably 10000m 3 Up to 2,000,000m 3The internal energy of the steam stored in the steam network is advantageously between 1 MWh and 150,000 MWh, preferably between 10 MWh and 75,000 MWh, and more preferably between 20 MWh and 50,000 MWh.

[0124] Hydrogen as an energy carrier:

[0125] Advantageously, this configuration of the method of the invention has one or two local power sources. If the method of the invention has one local power source, it is advantageously a gas turbine generator, a steam turbine generator, a PEMFC generator, an AFC generator, an SOFC generator, or an MCFC generator. One power source is preferably a PEMFC generator or an AFC generator. More preferably, an AFC generator. When the method of the invention has two power sources, the first power source is advantageously a gas turbine generator, a PEMFC generator, an AFC generator, an SOFC generator, or an MCFC generator, and the second power source is a PEMFC generator or an AFC generator; preferably, the first power source is a gas turbine generator, an SOFC generator, or an MCFC generator, and the second power source is a PEMFC generator or an AFC generator; more preferably, the first power source is a gas turbine generator, and the second power source is an AFC generator. For each power source, 1-10 units, preferably 1-5 units, and more preferably 1-2 units are allocated to the heat-consuming process.

[0126] In this configuration of the invention, the cryogenic fuel cell plays a special role. The fuel cell is advantageously supplied by a hydrogen network at the integration site. Hydrogen is produced industrially on a scale by means of: coal gasification, hydrocarbon cracking, partial oxidation of natural gas, liquefied gas, or naphtha, steam reforming or autothermal reforming, methanol reforming, dehydrogenation of organic compounds, water electrolysis, or chlor-alkali electrolysis. Advantageously, the hydrogen is purified by pressure swing adsorption or by membrane methods, compressed, and introduced into the hydrogen network. For example, BASF's integration site in Ludwigshafen has a 40 bar network and a 325 bar hydrogen network. With this network, hydrogen is distributed to approximately 80 operations, and even some outputs. The fuel cell, used as a local power source, can operate in two modes: in normal mode as a generator or in reverse mode as a hydrogen generator, in which case electrical energy is used to split water into hydrogen and oxygen.

[0127] The volume of the hydrogen network is advantageously 100 m³. 3 Up to 100,000m 3 200m is preferred 3 Up to 50000m 3 More preferably 500m 3 up to 20000m 3The thermal energy stored in the hydrogen network is advantageously between 250 MWh and 250,000 MWh, preferably between 500 MWh and 120,000 MWh, and more preferably between 1,000 MWh and 50,000 MWh.

[0128] Natural gas as an energy carrier:

[0129] Advantageously, this configuration of the method of the invention has one or two local power sources. If the method of the invention has one local power source, it is advantageously a gas turbine generator, a steam turbine generator, an SOFC generator, or an MCFC generator. A single power source is preferably a gas turbine generator or an SOFC generator. More preferably, the single power source is a gas turbine generator. If the method of the invention has two power sources, the first power source is advantageously a gas turbine generator, an SOFC generator, or an MCFC generator, and the second power source is an SOFC generator or an MCFC generator; preferably, the first power source is a gas turbine generator, and the second power source is an SOFC generator. For each power source, advantageously, 1-10 units, preferably 1-5 units, more preferably 1-2 units, are allocated to the heat-consuming process.

[0130] The volume of the natural gas network is advantageously 1000 m³. 3 Up to 1,000,000m 3 2000m is preferred 3 Up to 500,000m 3 More preferably 5000m 3 Up to 200,000m 3 The thermal energy stored in the natural gas network is advantageously between 500 MWh and 500,000 MWh, preferably between 1,000 MWh and 200,000 MWh, and more preferably between 2,000 MWh and 100,000 MWh.

[0131] Load switch:

[0132] The method of the present invention advantageously utilizes a load switch to control electrical energy, which controls the switching between local and external power sources, or increases or throttles one of the power sources. Advantageously, the power supply ratio can be adjusted discontinuously and / or continuously. Load switches are known to skilled electrical engineers.

[0133] Advantageously, the switching is performed in discontinuous steps, especially in cases where the local power supply is partially incompatible with the load. Alternatively, the switching is performed continuously, especially in cases where the local power supply is partially compatible with the load.

[0134] Advantageously, the control parameter used for load switching is the price of electricity. Preferably, the required energy is obtained from an external power source when external electricity is cheaper than locally produced electricity from a local power source: for example, during periods of so-called surplus electricity and / or nighttime electricity availability (nighttime electricity is defined as electricity supplied at night, for example, between 10 p.m. and 6 a.m., and at a low price).

[0135] According to a German parliamentary report, surplus electricity is defined as the difference between the electrical energy that can be produced at a given time given available capacity and the electrical energy that consumers are using. Surplus electricity in the electricity market is provided at prices far below its generation cost, or at prices lower than those of fossil fuels with the same calorific value (based on their energy content), or even free (i.e., free of charge), or even at negative prices.

[0136] Preferably, at least 25% of the electricity is supplied annually on average, more preferably at least 50%, by the public grid using surplus electricity and / or nighttime electricity, preferably surplus electricity.

[0137] Preferably, on average, 25% to 100% of the energy required by the external power source per year, more preferably 50% to 100%, is provided by surplus power and / or nighttime power. However, more preferably, all energy from the external power source is provided by surplus power and / or nighttime power, preferably surplus power.

[0138] Power supply changes:

[0139] Advantageously, the power source can be changed during heat-consuming processes. A change in power source should be understood as the switching on or off of one or more local power sources, or the switching on or off of an external power source, particularly the public power grid. Furthermore, a change in power source should be understood as an increase or throttling of one of the power sources.

[0140] Advantageously, during switching, the electrical energy supplied to the process is reduced or varied by a maximum of 10% of the total power, preferably a maximum of 5%, and particularly a maximum of 1%. Advantageously, the percentage range is 10 to 0, preferably 5 to 0, and particularly 1 to 0. Low fluctuations can be achieved by means of the fast response time of local power supply and load switching. This response time is advantageously less than 30 minutes, preferably less than 15 minutes, and more preferably less than 5 minutes.

[0141] Advantageously, according to the invention, the heat-consuming process maintains its operating state during the switching period: advantageously, the change in the conversion rate of the heat-consuming process during the transition time does not exceed 2%, preferably not more than 1%, more preferably not more than 0.5%, and particularly not more than 0.2%. Advantageously, the change in energy only slightly alters the by-product selectivity of the high-temperature process; preferably, the increase in by-product selectivity does not exceed 1%, preferably not more than 0.5%, and particularly not more than 0.2% (absolutely).

[0142] Reactor design:

[0143] The endothermic method of the present invention is advantageously carried out in packed reactors, tubular reactors or light electric arc reactors (see Henkel, KD (2000). Reactor types and their industrial applications. Ullmann's Encyclopedia of Industrial Chemistry).

[0144] heating:

[0145] There are a variety of solutions in the prior art for providing thermal energy to heat-consuming processes via electricity: such as inductive or resistive methods, plasma methods, heating with the aid of conductive heating components / contact surfaces, and / or microwaves.

[0146] Direct power supply can be achieved through induction or resistance. In both cases, the reactor walls or packing within the reactor space advantageously constitute the corresponding resistance. The resistance variant is particularly preferred because all electrical losses due to the termination of external power supply directly benefit the heating of the packing.

[0147] The packing material can be in the form of a fluidized bed, a moving bed, or a fixed bed.

[0148] In a preferred embodiment, two or more electrodes are mounted in the packing, between which the packing acts as a resistor and is heated due to conductivity losses as current flows. The current can be transverse to the flow direction of the packing or longitudinally.

[0149] In the case of indirect power supply, electric heating elements, such as heating rods or heating boxes, are arranged around the perimeter of the reactor wall or embedded in the packing. When current flows through these electric heating elements, they are heated and the heat is released to the reactor wall or the packing around it.

[0150] In addition to electrical energy, other non-power sources can also be considered, such as heat transfer fluids like flue gas, superheated steam, or melts. The actual and / or latent heat present in the heat transfer fluid can be transferred to the packing or fluid process flow via internal components such as heat transfer tubes or heat pipes.

[0151] Moving bed reactor:

[0152] The reactor used in the method of the present invention advantageously comprises a random packing of solid particles of conductive material. The packing can be homogeneous or structured in height. Homogeneous packing can advantageously form a fixed bed, a moving bed, or a fluidized bed. Structured packing, depending on its height, advantageously forms a fixed bed at the bottom and a fluidized bed at the top. Alternatively, structured packing advantageously forms a moving bed at the bottom and a fluidized bed at the top.

[0153] The reactor support material is advantageously thermally stable in the range of 500 to 2000°C, preferably 1000 to 1800°C, more preferably 1300 to 1800°C, more preferably 1500 to 1800°C, and particularly 1600 to 1800°C.

[0154] The carrier material is advantageously at 10 S / cm and 10 5 Conductive within the range of S / cm.

[0155] The carrier material advantageously possesses a strength of 300 to 5000 kJ / (m²). 3 K), preferably 500 to 3000 kJ / (m 3 The volumetric specific heat capacity of K).

[0156] Useful heat transfer materials, particularly for methane pyrolysis, are advantageously carbonaceous materials, such as coke, silicon carbide, and boron carbide. The support is optionally coated with a catalytic material. These heat transfer materials can have different expansion capacities relative to the carbon deposited on them.

[0157] The carrier material advantageously has a regular and / or irregular geometry. Regularly shaped particles are advantageously spherical or cylindrical.

[0158] The carrier material advantageously has a particle size of 0.05 to 100 mm, preferably 0.1 to 50 mm, more preferably 0.2 to 10 mm, and particularly 0.5 to 5 mm, which is the equivalent diameter that can be determined by sieving with a specific sieve mesh size.

[0159] Mobile bed mode:

[0160] The support material is advantageously supplied countercurrently to the reactant gas. For this purpose, the reaction space is rationally configured as a vertical axis or an axis that widens from top to bottom, causing movement of the moving bed under gravity. However, the support material can also be used as a fluidized bed to guide the flow through the reaction space. Both variations allow for continuous or quasi-continuous operation.

[0161] Advantageously, the heat transfer resistance in the heat exchange between the gas and solid packing in the heat transfer zone has a length of 0.01 to 5 m, preferably 0.02 to 3 m, more preferably 0.05 to 2 m, and particularly 0.1 to 1 m of heat transfer unit length or height-of-transfer unit (HTU). The definition of HTU is taken from page 74 of http: / / elib.uni-stuttgart.de / bitstream / 11682 / 2350 / 1 / docu_FU.pdf.

[0162] The heat capacity flow rate is the product of the mass flow rate of the material flow and the specific heat capacity. Advantageously, the ratio of the heat capacity flow rate is 0.5 to 2, preferably 0.75 to 1.5, more preferably 0.85 to 1.2, and particularly 0.9 to 1.1. The ratio of the heat capacity flow rate is adjusted via the feed flow and optionally via side feed or side take-off of a branch.

[0163] When using a moving bed or fluidized bed, the temperature of the carrier entering the reactor is advantageously from 0 to 300°C, preferably from 10 to 150°C, and particularly from 50 to 100°C. The temperature of the reactant gas entering the reactor is advantageously from 0 to 100°C, preferably from 10 to 50°C.

[0164] In this operating mode, the product gas formed in the high-temperature region can be cooled very quickly, preferably at a speed of >200 K / s, more preferably >300 K / s, more preferably >500 K / s, and especially >1000 K / s.

[0165] Reactor:

[0166] Advantageously, for the method of the invention, an electrically heated, pressure-rated filling device is used, wherein the device is advantageously divided into upper, middle, and lower device sections. In the middle section, advantageously, at least one pair of electrodes is mounted in a vertical arrangement, and all electrodes are advantageously disposed within the conductive solid filler. The specific conductivity of the upper and lower device sections is advantageously 10. 5 S / m to 10 8 S / m. The intermediate equipment section is advantageously electrically insulated from the solid filler. The upper and lower equipment sections are advantageously electrically insulated from the intermediate equipment section. The upper electrode is advantageously connected via the upper equipment section, and the lower electrode is advantageously connected via the lower equipment section, or the electrodes are connected respectively via one or more connecting components that are in electrical contact with these sections.

[0167] The ratio of the cross-sectional area of ​​the upper and lower electrodes to the cross-sectional area of ​​the corresponding current-conducting connection assembly, or, without using the connection assembly, the ratio of the cross-sectional area of ​​the upper and lower electrodes to the cross-sectional area of ​​the corresponding current-conducting device portion, is advantageously 0.1 to 10, preferably 0.3 to 3, and particularly 0.5 to 2.

[0168] Advantageously, the cross-sectional area of ​​the electrode (e.g., the cross-sectional area of ​​all electrode pads in a mesh-type electrode) is 0.1 cm². 2 Up to 10000cm 2 1cm is preferred 2 Up to 5000cm 2 Especially at 10cm 2 Up to 1000cm 2 Within a certain range. Advantageously, the cross-sectional area of ​​the conductive connection component is within 0.1 cm². 2 Up to 10000cm 21cm is preferred 2 Up to 5000cm 2 Especially 10cm 2 Up to 1000cm 2 Within the range.

[0169] Without the use of connecting components (between the electrode and the upper or lower part of the device), the ratio of the cross-sectional area of ​​the upper and / or lower electrode (preferably the upper and lower electrodes) to the cross-sectional area of ​​the corresponding current-conducting device portion is advantageously 0.1 to 10, preferably 0.3 to 3, and particularly 0.5 to 2. Advantageously, the cross-sectional area of ​​the electrode is 0.1 cm². 2 Up to 10000cm 2 1cm is preferred 2 Up to 5000cm 2 Especially 10cm 2 Up to 1000cm 2 Within this range. Advantageously, the cross-sectional area of ​​the upper and / or lower equipment portions is within 0.1 cm². 2 Up to 10000cm 2 1cm is preferred 2 Up to 5000cm 2 Especially at 10cm 2 Up to 1000cm 2 Within the range.

[0170] The reactor packing is advantageously a moving bed. Accordingly, the reactor is advantageously divided into multiple zones. The bottom-up arrangement is advantageously as follows: an outlet for the carrier, a gas inlet, a lower heat transfer zone, a lower electrode, a heating zone, an upper electrode optionally with side-exit, an upper heat transfer zone, an outlet for the gaseous product stream, and a feed for the carrier stream.

[0171] The lower heat transfer zone is the vertical distance between the upper edge of the air inlet and the upper edge of the lower electrode.

[0172] The upper heat transfer zone is the vertical distance between the lower end of the upper electrode and the upper end of the solid filler.

[0173] The heating zone at each point in the reactor cross-section is defined as the vertical distance between the lower end of the upper electrode and the upper end of the lower electrode.

[0174] Advantageously, the lower side of the upper electrode and the upper side of the lower electrode are horizontal across the entire reactor cross-section. Therefore, the length of the heating zone, and particularly the distance between the electrodes, is advantageously uniform across the entire reactor cross-section. The heated reactor cross-section is advantageously 0.005 m. 2 Up to 200m 2 0.05m is preferred 2 Up to 100m 2 More preferably 0.2m 2up to 50m 2 Especially 1m 2 up to 20m 2 The length of the heating zone is advantageously between 0.1m and 100m, preferably between 0.2m and 50m, more preferably between 0.5m and 20m, and particularly between 1m and 10m. The ratio of the length to the equivalent diameter of the heating zone is advantageously between 0.01 and 100, preferably between 0.05 and 20, more preferably between 0.1 and 10, and most preferably between 0.2 and 5.

[0175] The electrodes are advantageously located within the solid packing (see...) Figure 1 and Figure 2 The vertical distance between the upper edge of the solid filler (the lowest point in the case of an incline) and the upper edge of the electrode plate, or, when the electrode plate is not used, the vertical distance between the lower edges of the electrode pads at the upper electrode, is advantageously 10 mm to 5000 mm, preferably 100 mm to 3000 mm, and more preferably 200 mm to 2000 mm. This portion is advantageously 1% to 50% of the total height of the solid filler, preferably 2% to 20%, and more preferably 5% to 30%.

[0176] Electrodes can take all forms known to those skilled in the art. For example, electrodes can be in the form of mesh or rods. Electrodes are preferably in the form of mesh. For mesh forms, various configuration variations are of interest: for example, a honeycomb mesh composed of advantageous regular polygons, a rectangular mesh formed by parallel grooves and ridges, a spoke mesh, or a mesh composed of concentric rings. A spoke mesh is particularly preferred, which advantageously has 2 to 30 grooves and ridges arranged in a star shape and a mesh composed of concentric rings.

[0177] The cross-sectional blockage of the electrode is advantageously between 1% and 50%, preferably between 1% and 40%, more preferably between 1% and 30%, and particularly between 1% and 20%.

[0178] Particularly preferred are electrodes in the form of a mesh, which are fixedly mounted inside the upper or lower device portion, such as a cover, or fixed to a connecting assembly, such as a skirt fixed to the device portion.

[0179] A fixed support should be understood as the connection between a rigid body and its environment, which prevents relative movement between the rigid body and its environment in all directions.

[0180] In the case of star-shaped and fractal scale meshes, the electrode pads are advantageously connected at their outer ends to the reactor shroud or the skirt of the reactor shroud.

[0181] The contact area between the electrode and the reactor shroud or skirt is advantageously 0.1 cm². 2 Up to 10000cm 2 Between, preferably within 1cm2 Up to 5000cm 2 Between, especially at 10cm 2 Up to 1000cm 2 between.

[0182] The ratio of the cross-sectional area of ​​the skirt of the conductive reactor cover to the cross-sectional area of ​​the solid packing is advantageously 0.1% to 20%, preferably 0.2% to 10%, and more preferably 0.5% to 5%.

[0183] In a shrouded electrode unit, advantageously, less than 5%, preferably less than 2%, more preferably less than 1%, and particularly less than 0.1% of the total electrical energy introduced is dissipated. Preferably, the range of dissipated energy is 0% to 5%, preferably 0% to 2%, and particularly 0% to 1%. Thus, the electrical energy can be practically used almost entirely for heating the filling material between the electrodes.

[0184] The electrode materials, i.e., the pads and electrode plates, are advantageously iron, cast iron or steel alloys, copper or copper-based alloys, nickel or nickel-based alloys, refractory metals or refractory metal-based alloys, and / or conductive ceramics. More specifically, the pads are made of, for example, steel alloys according to DIN EN 10027-2 (issued: July 2015) with material numbers 1.0401, 1.4541, 1.4571, 1.4841, 1.4852, 1.4876; nickel-based alloys, for example, with material numbers 2.4816, 2.4642; and especially titanium with material numbers 3.7025, 3.7035, 3.7164, 3.7165, 3.7194, 3.7235. Among refractory metals, Zr, Hf, V, Nb, Ta, Cr, Mo, W, or alloys thereof are particularly advantageous; Mo, W, and / or Nb, or alloys thereof, are preferred, especially molybdenum and tungsten, or alloys thereof. Furthermore, the pads may comprise ceramics such as silicon carbide and / or carbon such as graphite, wherein the ceramics may be monolithic or fiber-reinforced composites (e.g., ceramic matrix compounds CMC, such as carbon fiber composites CFC).

[0185] Heat absorption process:

[0186] According to the present invention, the heat-consuming process is advantageously an endothermic high-temperature process, preferably wherein the energy consumption in the reaction zone is greater than 0.5 MW / m². 3 More preferably greater than 1 Mw / m 3 Especially those greater than 2MW / m 3 The process involves energy consumption, for example, between 0.5 and 10 MW / m². 3 between.

[0187] The heat-consuming process is advantageously carried out at an oxygen concentration of less than 5% by volume, especially less than 2% by volume, particularly in an anaerobic manner.

[0188] The highest temperature in the reaction zone is advantageously greater than 500°C, preferably greater than 800°C. For example, in the case of a dehydrogenation reaction, the temperature in the reaction zone is in the range of 500 to 2500°C, preferably 700 to 1800°C, for example, in the range of 500 to 800°C; in the case of a reforming reaction, the temperature in the reaction zone is in the range of 700 to 1000°C; in the case of a steam cracking reaction, the temperature in the reaction zone is in the range of 800 to 1100°C; in the case of a pyrolysis reaction, the temperature in the reaction zone is in the range of 800 to 1500°C; in the case of a carbon gasification reaction, the temperature in the reaction zone is in the range of 800 to 1200°C.

[0189] Useful heat-consuming processes advantageously include the following: the preparation of syngas, hydrogen, styrene, olefins (especially ethylene, propylene, and butene), propylene, benzene, acetylene, naphthalene, carbon monoxide, hydrogen cyanide, nitric oxide, hydrogen cyanide, and / or pyrolytic carbon, and the calcination of aluminum hydroxide. Preferred methods include: steam reforming and dry reforming, steam cracking or dry pyrolysis of hydrocarbons, especially the pyrolysis of methane, ethane, propane, and / or butane, the pyrolysis of water, the dehydrogenation of ethylbenzene to styrene, the dehydrogenation of propane to propylene, the dehydrogenation of butane to butene, and / or the dehydrogenation of cyclohexane to benzene, the pyrolysis of acetylene, the preparation of benzene from methane, the reduction of carbon dioxide to carbon monoxide, the preparation of hydrogen cyanide from natural gas and nitrogen, the preparation of hydrogen cyanide from methane and ammonia, and the preparation of nitric oxide from nitrogen and oxygen.

[0190] The following high-temperature reactions are preferably carried out, and more preferably in a moving bed reactor:

[0191] Syngas is produced by reforming hydrocarbons with steam and / or carbon dioxide, and hydrogen and pyrolytic carbon are generated together by the pyrolysis of hydrocarbons. Suitable support materials are particularly carbonaceous particles, silicon carbide particles, and nickel-containing metal particles.

[0192] Hydrogen cyanide is prepared from methane and ammonia or from propane and ammonia. Suitable support materials, especially carbonaceous particles, are required.

[0193] - Preparation of olefins via steam cracking of hydrocarbons. Suitable support materials, especially carbonaceous particles and silicon carbide-containing particles.

[0194] Methane couples to produce ethylene, acetylene, and benzene.

[0195] - Preparation of olefins via catalytic dehydrogenation of alkanes, such as the production of propylene from propane or butene from butane. Suitable support materials are, in particular, silicon carbide particles or iron-containing molded bodies coated with a dehydrogenation catalyst.

[0196] - Styrene is prepared by catalytic dehydrogenation of ethylbenzene. Suitable support materials are, in particular, silicon carbide particles coated with a dehydrogenation catalyst or iron-containing molded bodies.

[0197] - Preparation of dienes by catalytic dehydrogenation of alkanes or alkenes, such as the preparation of butadiene from butene or butane. Suitable support materials are, in particular, silicon carbide particles or iron-containing molded bodies coated with a dehydrogenation catalyst.

[0198] - Aldehydes are obtained by catalytic dehydrogenation of alcohols, for example, anhydrous formaldehyde from methanol. Suitable support materials are, in particular, silver-containing particles or silicon carbide-containing particles coated with a dehydrogenation catalyst, or iron-containing molded bodies. - CO is prepared from CO2 and carbon via the Boudouard reaction. Suitable support materials are, in particular, carbonaceous particles.

[0199] - Hydrogen and oxygen are produced by catalytic hydrothermal decomposition on a catalyst. Suitable support materials are, in particular, silicon carbide or iron-containing particles coated with, for example, ferrite-based cracking catalysts.

[0200] Syngas is advantageously used in downstream processes such as methanol synthesis, ammonia synthesis, carbonyl synthesis, and Fischer-Tropsch synthesis (“Synthesegas” [synthesis gas] page, in Wikipedia, last edited Free Encyclopedia: March 10, 2020, 17:41 UTC. URL https: / / de.wikipedia.org / w / index.php?title=Synthesegas&oldid=197642178).

[0201] Hydrogen is advantageously used in downstream processes such as coal hydrogenation, ammonia synthesis, aliphatic hydrogenation, selective hydrogenation of alkynes, and hydrogenation of nitro groups to amines (“Wasserstoff” [hydrogen] page, in Wikipedia, last edited by the Free Encyclopedia: March 15, 2020, 16:31 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Wasserstoff&oldid=197790800).

[0202] The most important olefins in industry include ethylene, propylene, and butene. Ethylene is advantageously converted into conversion products such as polyethylene, dichloroethane, ethylene oxide, and ethylbenzene in downstream processes (“Ethen” [ethylene] page, in Wikipedia, last edited by the Free Encyclopedia: April 23, 2020, 09:31 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Ethen&oldid=199192096).

[0203] Propylene is advantageously converted into conversion products such as acetone, acrolein, acrylonitrile, acrylic acid, allyl compounds, butyraldehyde, 1-butanol, polypropylene, propylene oxide, propane-1,2-diol, propane-1,3-diol, and thymol (“Propen” [propylene] page, in Wikipedia, last edited Free Encyclopedia: 1 October 2019, 18:51 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Propen&oldid=192770628).

[0204] Butene is advantageously converted into conversion products such as 2-butanol, 2-butanone, butadiene, methyl tert-butyl ether, or ethyl tert-butyl ether in downstream processes (“Butene” page, in Wikipedia, last edited Free Encyclopedia: 2019 Sep 3, 07:11 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Butene&oldid=191929887).

[0205] Butadiene is converted into conversion products such as synthetic rubber, acrylic acid-butadiene-styrene copolymer, and adiponitrile (“1,3-Butadien” [1,3-butadiene] page, in Wikipedia, last edited by the Free Encyclopedia: May 2, 2020, 13:49 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=1,3-Butadien&oldid=199535563).

[0206] Hydrogen is advantageously converted in downstream processes, such as…( P., Lohmüller, R. and Watson, AM 2000. Hydrogen, 2. Production. Ullmann's Encyclopedia of Industrial Chemistry).

[0207] Benzene is converted into conversion products such as ethylbenzene, cumene, cyclohexane, and nitrobenzene in downstream processes ("Benzol" [benzene] page, in Wikipedia, last edited by the Free Encyclopedia: April 20, 2020, 18:09 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Benzol&oldid=199100597).

[0208] Styrene is advantageously converted into conversion products such as polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-styrene-acrylate copolymer, and polyester resin (“Styrol” [styrene] page, in Wikipedia, last edited Free Encyclopedia: April 21, 2020, 09:59 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Styrol&oldid=199119904).

[0209] Hydrogen cyanide is advantageously converted into conversion products such as adiponitrile, acetone cyanohydrin, and cyanuric trichloride in downstream processes (“Cyanwasserstoff” [hydrogen cyanide] page, in Wikipedia, last edited Free Encyclopedia: April 23, 2020, 13:21 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Cyanwasserstoff&oldid=199198613).

[0210] Carbon monoxide is advantageously converted into conversion products such as phosgene, formic acid, methyl formate, acetic acid, and acetic anhydride in downstream processes. Furthermore, carbon monoxide is a component of syngas ("Kohlenstoffmonoxid" [carbon monoxide] page, in Wikipedia, last edited Free Encyclopedia: April 19, 2020, 06:01 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Kohlenstoffmonoxid&oldid=199031788).

[0211] Formaldehyde is advantageously converted into conversion products such as 1,4-butanediol, methylene diphenyl diisocyanate, polyoxymethylene, phenolic resins, and amino resins in downstream processes (“Formaldehyd” [formaldehyde] page, in Wikipedia, last edited by the Free Encyclopedia: May 3, 2020, 12:08 UTC. URL: https: / / de.wikipedia.org / w / index.php?title=Formaldehyd&oldid=199572039).

[0212] For preferred variations of the method of the present invention, the range of the maximum temperature target value is summarized in tabular form:

[0213]

[0214] High-temperature processes are preferred for heat-intensive processes, especially high-temperature processes in packed reactors with direct electric heating, which are particularly suitable for the use of electricity because electrical energy can be converted into heat with high heat release efficiency. It is part of the system's internal energy and can be converted into mechanical energy without increasing entropy. Typically, the conversion of electrical energy into heat energy destroys a certain proportion of the system's internal energy. This ratio decreases as the temperature of the radiator increases, and in the current case, it decreases as the temperature of the high-temperature heat absorption process increases.

[0215] The products of heat-consuming processes, particularly hydrogen, syngas, and / or olefins, can be advantageously supplied into the integrated site's supply network.

[0216] Sub-regulations and minute reserves:

[0217] This invention also relates to the use of the methods of this invention as load shedding capacity for secondary control and / or minute reserves for the public power grid. The methods of this invention allow the use of high-temperature methods as load shedding capacity for secondary control and / or as minute reserves in grid frequency control operations. With the methods of this invention, the high-temperature methods can be started up quickly and can also accept large amounts of energy, from 300 to 600 TWh. When operating in continuous mode, these methods can be permanently used to provide excess power, such as nighttime power.

[0218] advantage:

[0219] This invention utilizes a continuously operating, electrically heated, heat-consuming process to sustainably receive excess electricity. Therefore, large-scale chemical methods can be used as load shedding capacity and / or minute reserves for secondary control. This improves grid stability and significantly increases the use of renewable energy. Furthermore, the profitability is improved due to the load shedding capacity of the heat-consuming process, which facilitates grid regulation.

[0220] Furthermore, this invention enables load use for demand control in heat-consuming processes, regardless of the availability of excess power in the public grid. This improves the production planning of downstream processes and minimizes the need to store high-value, highly reactive, and therefore harmful intermediates. In addition, the security of the internal power supply is improved by utilizing energy carriers from a high-capacity integrated system network to supply internal power and offset interference from individual processes.

[0221] Directly electrically heated moving bed reactors are used as ohmic loads with high heat capacity. Consequently, they can also be supplied by sources that do not meet the specifications for supplying to the public power grid. More specifically, excess electricity can be used for heat-consuming processes without intermediate storage (i.e., in a virtually lossless manner), with an efficiency advantageously greater than 90%, preferably greater than 95%, particularly greater than 98%, i.e., advantageously in the range of 95% to 100%, preferably 98% to 100%, and thus without significant limitations in utilizing its cost advantages.

[0222] Because of the high temperature level provided by the heating output, the method of the present invention is implemented... The loss is preferably less than 60% of the introduced electrical energy, more preferably less than 50%, particularly preferably less than 40%, and especially less than 25%.

[0223] Therefore, this invention can serve as a technological platform for transitioning to electro-driven chemical processes (an energy revolution). This provides a foundation for the economically attractive use of surplus electricity and the provision of minute-by-minute reserves, thereby reducing energy costs.

[0224] The integrated site has a basic structure to store large quantities of energy carriers such as natural gas, light gasoline, hydrogen, or steam, and can use them without delay to drive a suitable power source.

[0225] Hydrogen's advantage lies in its versatility as both a commercial and chemical energy storage medium. It is suitable for driving turbine generators and fuel cell generators. The energy produced from hydrogen produces no CO2 emissions.

[0226] Energy can be stored in hydrogen for extended periods without loss. Compressed hydrogen at 40 bar has a high energy density of approximately 57 kWh / m³. 3 The energy density of steam at 500°C and 100 bar is approximately 11 kWh / m³. 3 .

[0227] Steam has the advantage of being used simultaneously as an energy storage medium and a driving medium for steam turbines. Furthermore, steam at various pressure levels is used to supply chemical engineering processes. BASF's Ludwigshafen plant consumes 2,000 tons of steam per hour. This is equivalent to 1,300 MW of power, approximately twice the average on-site electricity demand. To generate steam, all fuels can be used: combustible feedstocks, combustible products, combustible waste gas streams, heat generated by solar collectors, and heat generated by electricity. The pressure level grading in the steam network allows for the efficient conversion of introduced heat into steam. In particular, when electricity is supplied from the grid and local power is shut off, heat gained from combustible gas streams can be stored in the steam network as steam.

[0228] Using parallel-connected power sources, one being a steam turbine directly supplied with fuel and the other a steam turbine supplied by a steam grid, provides very good efficiency comparable to that of a combined cycle power plant.

[0229] The steam turbine is supplied with steam directly from the integrated site's steam network, which enables the power source to respond very quickly to changing electricity demands.

[0230] Attached image:

[0231] Figure 1 A schematic diagram of a variant of the method of the present invention is shown, comprising a fluidized bed reactor with direct resistance heating, a fixed bed reactor with induction heating, and a fixed bed reactor with indirect resistance heating in an integrated location. Each process is supplied with electrical energy from both the public power grid and a corresponding local power source.

[0232] Figure 2 A scheme based on a comparative process according to existing technology is shown. The internal power source is a combined cycle power plant with steam output, which is the most efficient among conventional power plants. The steam turbine is directly connected to the waste heat tank of the gas turbine generator. The response behavior of the steam turbine is determined by the inertia of the gas turbine waste heat tank.

[0233] Figure 3 The process flow of the present invention is illustrated. The internal power source (same as in a combined cycle power plant) consists of a gas turbine generator and a steam turbine generator. The steam turbine is not directly connected to the waste heat tank of the gas turbine, but rather directly connected to the steam network of the integrated facility. Therefore, the steam turbine can respond to changing loads virtually without delay.

[0234] Figure 4 The present invention illustrates a process scheme. The heat-consuming process is supplied by both the public power grid and local power. Local power is supplied by energy carriers from an integrated system network. The integrated system network stores energy carriers generated in the heat-consuming process and / or other processes within the integrated system. The main products of the heat-consuming process are supplied to downstream processes within the integrated system.

[0235] Figure 5 The process flow of the present invention is illustrated. The heat-consuming process is supplied by both the public power grid and local power. Steam is supplied to the local power source by an integrated system network. Hydrogen, a byproduct of the heat-consuming process, is stored in the integrated system network. The local power source is driven by a steam turbine generator. Hydrogen is extracted from the integrated system network for this purpose. The main product of the heat-consuming process is supplied to downstream processes within the integrated system.

[0236] legend

[0237] 1: Electric heating heat consumption process

[0238] 2: Separation devices for removing major products and by-products from heat-consuming processes.

[0239] 3: Steam integration site network

[0240] 4: Hydrogen Integration Site Network

[0241] 5: Natural Gas Integration Site Network

[0242] 6: Poverty Alleviation Integration Site Network

[0243] 7: Pipelines containing hydrogen gas flow

[0244] 8: Steam pipes

[0245] 10a: Pipes used to supply steam for internal power.

[0246] 10b: Piping used to supply hydrogen to the internal power source

[0247] 10c: Pipelines used to supply natural gas for internal power generation

[0248] 10d: A conduit used to supply lean gas to the internal power supply.

[0249] 11a: Internal power source driven by steam

[0250] 11b: Internal power source powered by hydrogen

[0251] 11c: Internal power source powered by natural gas

[0252] 11d: Internal power source driven by lean gas

[0253] 12a: Power lines from steam-driven power sources to heat-consuming processes.

[0254] 12b: Power line from hydrogen-powered power source to heat-consuming process.

[0255] 12c: Power lines from natural gas-powered power sources to heat-consuming processes.

[0256] 12d: Power line from a lean gas-driven power source to a heat-consuming process.

[0257] 16: Public power grid

[0258] 17: Product pipelines used to transport the main product from a heat-consuming process to a downstream process.

[0259] 20: Power lines used to supply electricity from the public power grid to heat-consuming processes.

[0260] 21: Busbars used to supply electrical energy from internal power sources to heat-consuming processes.

[0261] 31: Integrate other processes within the system

[0262] 32: Separation equipment in other processes within the integrated system removes energy carriers and introduces them into the integrated system network.

[0263] 36: Piping for hydrogen-containing gas streams from other processes within the integrated system.

[0264] 37: Steam pipes from other processes within the integrated system

[0265] 51: Downstream processes of heat-consuming processes within the integrated system

[0266] Example

[0267] Comparison Process 1: Combined Cycle Power Plant

[0268] Combined cycle: CH4 + 2O2 → CO2 + 2H2O + 481kJ el / mol (1)

[0269] This process allows for the generation of electricity from natural gas (a feedstock at the integrated site) using local power sources as needed. For every 1 mol of methane used, the combined cycle generator produces 481 kJ of electricity, while simultaneously emitting 1 mol of CO2. However, this process is not suitable for storing excess electricity from the grid. Compare this to process 2: a renewable energy source that electrolyzes hydrogen in a fuel cell and then converts it back into electricity.

[0270] ReGen+EL:H2O (l) +(1 / 75%*286)kJ el / mol→H2+ 1 / 2O2 (2)

[0271] AFC:H2+ 1 / 2O2→H2O (l) +(70%*237)kJ el / mol (3)

[0272] ReGen+EL+AFC:381kJ el / mol→166kJ el / mol(4)

[0273] This process allows electricity from the grid to be used to produce hydrogen. The hydrogen can then be supplied to the integrated site's pipeline network. The hydrogen can be used physically or, if needed, converted back into electricity in a local fuel cell. Approximately 0.44 kJ of electricity is recovered for every kJ of electricity supplied to this process. This electricity contains no CO2 emissions.

[0274] Comparative Process 3: Combination of Combined Cycle and Electrolysis / Fuel Cell

[0275] ReGen+EL+AFC+CCPP:CH4+2O2+92kJ el / mol→CO2+2H2O+521.5kJ el / mol (5)

[0276] The process of this invention combines methane pyrolysis with a hydrogen-driven power source.

[0277] ReGen+MePy:CH4+(74.8 / 81.3%)kJ el / mol→C (s) +2H2 (6)

[0278] AFC: 2H₂ + O₂ → 2H₂O (l) +(70%*474)kJ el / mol (7)

[0279] GT+ST:2H2+O2→2H2O(g)+(60%*484)kJ el / mol (8)

[0280] ReGen+MePy+AFC:CH4+O2+(74,8 / 81,3%)kJ el / mol→C (s) +H2O (l) +332kJ el / mol(9)

[0281] ReGen+MePy+(GT+ST):CH4+O2+(74,8 / 81,3%)kJ el / mol→C (s) +H2O (g) +290kJ el / mol(10)

[0282] COPP:C (s) +O2→CO2+(45%*393)kJ el / mol(11)

[0283] ReGen+MePy+AFC+COPP:CH4+2O2+(74,8 / 81,3%)kJ el / mol→CO2+2H2O+509kJ el / mol(12)

[0284] ReGen+MePy+(GT+ST)+COPP:CH4+2O2+92kJel / mol→CO2+2H2O+467kJ el / mol (13)

[0285] Excess energy from renewable resources available from the external power grid is used for the operation of the methane pyrolysis plant (Equation 6). The thermal efficiency of the pyrolysis, based on standard enthalpy of reaction, is 81.3%. The produced hydrogen is supplied to the integrated site's power grid. It can be used physically or energetically therein. The produced carbon is highly pure, inert, and free-flowing. For example, it can be transported and used physically, or stored in landfills. Hydrogen can be used, simultaneously or at different times during its production, to generate electricity in an AFC with a voltage efficiency of 70% (Equation 7), or to generate electricity in a combined gas turbine and steam turbine generator with a thermal efficiency of 60% (Equation 8), depending on local power sources. Each kilojoule of electricity from the external power grid (which is supplied to the methane pyrolysis) can be converted into approximately 3.1 kJ to 3.6 kJ of electrical energy due to the conversion of the produced hydrogen into electricity (Equations 9, 10), with virtually no CO2 emissions. Compared to the electrical energy storage in an electrolytic fuel cell circuit according to the prior art, the method of the present invention generates 6-8 times more electrical energy with zero CO2 emissions by using methane.

[0286] Some of the chemical energy present in methane is still stored in carbon byproducts and can be converted into electricity in conventional power plants, accompanied by CO2 emissions (Equation 11). If the use of carbon for energy purposes is permitted, the amount of electricity generated by the process consisting of methane pyrolysis and the conversion of external excess energy, as well as the resulting hydrogen and carbon into energy, is approximately 97% to 106% of the electricity generated by a combined cycle power plant according to the prior art at the same methane conversion rate (Equations 1, 12, 13). The possible excess in the method of the present invention is due to the use of electricity from an external power grid in the methane pyrolysis.

[0287] Considering the total input of mass and energy, the amount of electrical energy generated by the method of the present invention is about 90% to 98% of the electrical energy generated by the method consisting of an electrolysis / fuel cell circuit and a combined cycle power plant (Equations 5, 12, 13).

[0288] The basic advantage of this invention is that it can utilize input electrical energy to generate various types of electrical energy with no CO2 emissions using an internal power source.

[0289]

[0290] (1): The mass and energy in Equations 2, 3 and 4 are adjusted proportionally so that the electrical energy input in the comparative process and the process of the present invention is the same. Therefore, these values ​​can be directly compared with each other.

[0291] (2a): The electrical energy used is represented based on the energy of 1 mol of methane input into the integrated system from an external power grid.

[0292] (2b): The amount of electrical energy generated is expressed based on the energy of 1 mol of methane, which can be generated in the local power grid by the methane used and the electrical energy used in advance or by the products generated therefrom.

[0293] (2c): The storable electrical energy is represented by the energy of 1 mol of methane, which can be generated in the local power grid from the products of electrical energy produced in the integrated system.

[0294] legend

[0295] AFC: Alkaline fuel cell

[0296] CC: Combustion Chamber

[0297] ST: Steam turbine

[0298] EL: Electrolysis

[0299] G: Generator

[0300] GT: Gas Turbine

[0301] CCPP: Combined Cycle Power Plant

[0302] HP steam: High-pressure steam

[0303] COPP: Coal-fired thermal power plant

[0304] MePy: Methane Pyrolysis

[0305] LP steam: low-pressure steam

[0306] ReGen: Electricity from renewable energy sources

[0307] TPP: Thermal Power Plant

[0308] CM: Compressor

[0309] DM water: Feedwater used in waste heat boilers for gas turbines

Claims

1. A method for continuously performing an electrically heated pyrochemical process (1) of one or more chemical sites for obtaining hydrogen, wherein at least one pyrochemical process is electrically heated, the highest temperature in the reaction zone of said pyrochemical process is greater than 500°C, at least 50% of the hydrogen from said at least one pyrochemical process is further continuously processed in a downstream process (51) via a product pipeline (7) and supplied via a pipeline (7) to a local hydrogen network (4), and the electrical energy required for said at least one pyrochemical process is obtained from an external power grid (16) and from at least one local power source (11), wherein... At least one local power source (11) is supplied from a local hydrogen network (4) to at least 50% of its annual energy demand, and the at least one local power source supplies hydrogen directly from the heat-consuming process to no more than 50% of its annual energy demand, wherein hydrogen from the electrically heated heat-consuming chemical process (1) is stored as an energy carrier in the local hydrogen network (4), wherein the local hydrogen network (4) is supplied via a pipeline (36) with hydrogen (36) from at least one other chemical process (31), and wherein the total capacity of the local hydrogen network is at least 5 GWh.

2. The method of claim 1, wherein at least two different local energy carrier networks are used, wherein natural gas, naphtha, syngas or steam are stored as energy carriers in at least a second local energy carrier network.

3. The method of claim 1, wherein hydrogen from the heat-consuming process (7) serving as an energy carrier in the local hydrogen network (4) is distributed via an associated pipeline network and storage containers.

4. The method of claim 2, wherein hydrogen from the heat-consuming process (7) serving as an energy carrier in the local hydrogen network (4) is distributed via an associated pipeline network and storage containers.

5. The method of claim 1, wherein the total capacity of the local hydrogen network is at least 20 GWh.

6. The method of claim 3, wherein the total capacity of the local hydrogen network is at least 20 GWh.

7. The method according to any one of claims 1-6, wherein the local hydrogen network (4) is supplied by process steam cracking, steam reforming, methane pyrolysis, styrene synthesis, propane dehydrogenation, syngas production, and formaldehyde synthesis.

8. The method according to any one of claims 1-4, wherein the local power source used is at least one gas turbine (GT) and / or steam turbine (ST) and / or fuel cell.

9. The method of claim 7, wherein the local power source used is at least one gas turbine (GT) and / or steam turbine (ST) and / or fuel cell.

10. The method according to any one of claims 1-6, wherein the energy required for the heat-consuming process is provided by electrical energy to a extent that at least 90% is supplied.

11. The method of claim 9, wherein the energy required for the heat-consuming process is provided by electrical energy to a degree of at least 90%.

12. The method according to any one of claims 1-6, wherein the heat-consuming process is performed in an integrated location.

13. The method of claim 11, wherein the heat-consuming process is performed in an integrated location.

14. The method according to any one of claims 1-6, wherein the startup time of the local power supply is less than 15 minutes.

15. The method of claim 13, wherein the startup time of the local power supply is less than 15 minutes.

16. The method according to any one of claims 1-6, wherein the reactor for the heat-consuming process comprises a random packing of conductive material solid particles.

17. The method of claim 15, wherein the reactor for the heat-consuming process comprises a random packing of conductive solid particles.

18. The method of claim 16, wherein the heat-consuming process is carried out in a moving bed with countercurrent flow of solid-state flow and airflow, and the volumetric specific heat capacity of the moving bed is 300 kJ / (m³). 3 K) to 5000 kJ / (m 3 K).

19. The method of claim 17, wherein the heat-consuming process is carried out in a moving bed with countercurrent flow of solid-state flow and airflow, and the volumetric specific heat capacity of the moving bed is 300 kJ / (m³). 3 K) to 5000 kJ / (m 3 K).

20. The method of any one of claims 1-6, wherein the tapping from the external power grid and the connection and disconnection of the local power supply are controlled depending on the electricity cost.

21. The method of any one of claims 17-19, wherein the tapping from the external power grid and the connection and disconnection of the local power supply are controlled depending on the electricity cost.

22. The method according to any one of claims 1-6, wherein the heat-consuming process is steam reforming, dry reforming, pyrolysis of water, pyrolysis of hydrocarbons, and / or cracking.

23. The method of claim 21, wherein the heat-consuming process is steam reforming, dry reforming, pyrolysis of water, pyrolysis of hydrocarbons, and / or cracking.

24. Use of a local hydrogen network (4) at a chemical site in storing electrical energy, wherein hydrogen from a continuously operating, directly electrically heated, heat-consuming process (7) is supplied and stored in the local hydrogen network (4) and other hydrogen (36) from at least one other chemical process (31) is supplied and stored in the local hydrogen network (4), wherein the network distributes hydrogen at the chemical site, and wherein the total capacity of the local hydrogen network is at least 5 GWh.

25. The use according to claim 24, wherein the local hydrogen network supplies local power.

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