Method and plant for producing ice, slurry ice / ice particles, snow, hydrates, cold water, or combinations or a mixture / suspension thereof, in a closed process

Abstract

The invention relates to a method and a plant for producing ice, slurry ice / ice particles, snow, hydrates, cold water, or combinations or a mixture / suspension thereof, wherein: at least one substance stream (2) in the form of ice, slurry ice / ice particles, snow, hydrates, cold water, or combinations or a mixture / suspension thereof, are brought together with a refrigerant of a substance stream (1) in an apparatus (3) and expand and cool in and / or upon emerging from the apparatus (3); the stream (1 / 2) emerging from the apparatus (3) and consisting of the substance streams (1) and (2) is fed to a vessel (4) that has a storage function; phase separation of the substance streams (1) and (2) is performed in the vessel (4); the first substance stream (1) comprising the refrigerant is extracted from the vessel (4); and a cooling function (K) is implemented using the second substance stream (2) in the form of ice, slurry ice / ice particles, snow, hydrates, cold water, or combinations or a mixture / suspension thereof, the temperature of which second substance stream has been reduced.

Description

[0001]Method and system for producing ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixtures / suspensions in a closed process. The invention relates to a method and a system for producing ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixtures / suspensions in a closed process according to the preamble of the 1st and 15th patent claims. The storage of cold water and water ice has many (theoretical) advantages (e.g., ecological storage material, pumpability of ice slush). However, ice slush systems have not been able to establish themselves for various reasons (e.g., excessively expensive plant technology,Too low coefficients of performance). Various technologies cannot be scaled to large capacities, or when scaled to large capacities, no cost reductions or efficiency improvements could be achieved. Therefore, a process-based production of ice slurry is required (e.g., injector technology). Furthermore, conventional refrigeration machines with (still) approved refrigerants (damage to the climate and the environment, flammability, risk of explosion, toxicity, etc.) are often used to generate cold. A method and device for producing ice slurry are known from the publication DE 102010018497 A1. In this solution, water is mixed with a subcooled refrigerant using a mixing nozzle. Upon contact, the water freezes, forming a so-called ice slurry. The pressure is also released in the mixing nozzle. The coolant and ice slurry are separated in a storage tank.so that the ice slurry is discharged through an outlet and can perform its cooling task. After use, it is returned to the tank via a return line, discharged from the storage tank together with the coolant, and separated into water and coolant by means of a pump and a separator. The coolant is returned to its original state, and the cycle is closed. A complex separation process (e.g., reverse osmosis, nanofiltration) is required to cool a partial flow in an evaporator (material separation of coolant and refrigerant) of a refrigeration system. The publication WO 2007 / 121603 A1 describes a device for producing ice slurry, specifically using carbon dioxide as the coolant. The carbon dioxide is injected into an aqueous solution via nozzle devices.to produce ice slush. Carbon dioxide can be injected in liquid and / or gaseous form into an aqueous solution using injector nozzles or, alternatively, by prior mixing in a nozzle. The refrigerant is also pressurized and has a temperature range around or below 0 degrees Celsius. The refrigerant circuit and the utilization circuit (with a cooling consumer) are separated into two material streams. The hydrate slush (possibly with ice particles) is created in the vessel either by cooling coils or by expansion. The coil can be positioned inside or outside and also serves to control the temperature in the vessel. Recooling of the refrigerant in the form of carbon dioxide is not planned and may not be absolutely necessary for the production of hydrates; however, it limits improved process control. Furthermore, the hydration heat is removed from the storage vessel.which can have a negative impact on temperatures. The heat exchanger arranged on the vessel does not allow for high performance. Ultimately, ice production takes place in a two-stage process via the dissolution of the hydrates. Overall, the described system is not energy-efficient and is not capable of providing high cooling capacities. A method and device for cooling are also described in EP 2667 116 A1. A coolant is mixed with liquid carbon dioxide at a pressure at which the mixture is in the liquid state. The mixture of carrier medium and liquid carbon dioxide is then expanded while cooling to a pressure at which at least a portion of the carbon dioxide evaporates. The expanded mixture is then fed to a separator in which the evaporated carbon dioxide is separated from the carrier medium.The separated carrier medium is pressurized again and recycled to be mixed with liquid carbon dioxide. The mixture, after expansion, and / or the carrier medium from the separator passes through a heat exchanger, where it is brought into thermal contact with a medium to be cooled. The gaseous carbon dioxide is discharged via the gas outlet 19 and used in a heat exchanger 20 to cool a medium or released into the atmosphere. This is therefore an open process. Disadvantageously, no storage of the coolant (carrier medium) takes place, but only a phase separation in the separator. Likewise, no ice slush production, etc., is realized. The medium is cooled in the temperature range -85...-56 °C. The heat exchanger 9 represents an additional expense,which is not required in the inventive solution and would not function. A pressure relief device is required after a mixing device for the liquid carbon dioxide and the carrier medium, which also represents additional expense. A refrigerant compressor for the liquid carbon dioxide is disadvantageously not provided. Furthermore, the control of the refrigerant and coolant flow (liquid carbon dioxide and carrier medium) is via a valve 8, which is disadvantageous. The pressure range is only between 10 bar and 20 bar, which means that only a limited operating range is available. Unfortunately, the cooling of the medium with the heat exchanger is described insufficiently comprehensible manner. Another solution is also described in the document DE 102019127488 A1.which is a closed process. The task of this solution is to provide a flexibly usable fluid circuit with a working medium circulating therein and a method for operating the fluid circuit to generate refrigeration capacity. The cold should be used at a temperature level or pressure level below the triple point of the working medium. The device should be reliable and safe, in particular without the risk of blockage by solid particles of the working medium, and should be able to be operated efficiently and easily controlled. A mixture of environmentally friendly, non-flammable fluids should be usable. There is no cold storage, no ice slush production, etc. The focus is rather on optimising the operation of a refrigeration machine (safety,Avoiding blockage). CO2 (R744) is used as the refrigerant, and R125 (also a refrigerant) or R410 (refrigerant mixture) is used as the coolant, although R410 is not environmentally friendly. A mixing device is provided for mixing a carrier fluid with the working medium, as well as a separator for separating the carrier fluid from a gaseous fluid flow. A compressor and a heat exchanger are arranged between the separator and the mixing device. Furthermore, another heat exchanger is arranged between the mixing device and the separator, which entails additional expenditure. In general, no refrigeration or ice-making plants or storage systems are known that are suitable for the large-scale utilization of surplus electricity, especially from renewable energy sources.are suitable. Furthermore, no solutions exist for the industrial provision of process cooling and process heat. The flexibilization of energy supply systems as well as a consistent ecological design of processes and plants are new in this context. The object of the invention is to develop a plant and a method for the production of ice, ice slurry / ice particles, snow, hydrates, cold water or combinations thereof or mixtures / suspensions for industrial or technical applications, with which high cooling capacities and high ice production can be achieved using an ecological refrigerant and coolant, whereby very high storage charging capacities, very high storage discharging capacities or system integration, if necessary direct application to e.g. foodstuffs or supply in pipelines (e.g. district cooling) can be achieved and only low operating and maintenance expenditure is required. It should be possible to produce ice, ice slurry / ice particles,To provide snow, hydrates, cold water or combinations thereof or mixtures / suspensions from 20 °C to -100 °C. This object is achieved with the features of patent claims 1 and 15. Advantageous embodiments arise from the subclaims. In the method for producing ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixtures / suspensions, in a closed process, according to the invention, a) at least one second material stream in the form of ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixtures / suspensions, b) and a first material stream with at least one refrigerant, c) are combined in an apparatus, wherein the material streams expand and cool in the apparatus and / or upon exiting the apparatus, d) wherein the stream exiting the apparatus from the first and second material streams is fed to at least one container with a storage function,e) a phase separation of the first and second material streams takes place in the vessel, and - the first material stream is withdrawn from the vessel with the refrigerant, and - the second material stream, with its reduced temperature, in the form of ice, ice slush / ice particles, snow, hydrates, cold water, or combinations or mixtures / suspensions thereof, performs a cooling function. After phase separation in the vessel, the first material stream is sucked out of the vessel, compressed in the refrigerant circuit, recooled, and returned to the apparatus. In a first variant, the second material stream is withdrawn from the vessel as a coolant circuit to perform the cooling task and fed into the coolant circuit of the vessel via a heat exchanger.where - the coolant circuit leads from a heat exchanger via the apparatus to the container or - the coolant circuit leads from the heat exchanger to the container and at least one further second material stream leads as a secondary circuit via the apparatus into the container and / or in a second variant, the cooling task is implemented with at least one heat exchanger assigned to the container and at least one further second material stream leads as a secondary circuit via the apparatus into the container. In this case, an indirect and / or direct heat transfer takes place between the first material stream and the second material stream in the apparatus and / or upstream of the apparatus, wherein it is also possible to heat and / or cool the material streams in the apparatus, in particular zone-wise, by means of at least one additional heating and / or at least one additional cooling. It is possible,that a first secondary circuit and a second secondary circuit of the coolant of the second material stream from the container under pressure via the device back into the container. Because the temperature at the outlet from the device is significantly reduced compared to the inlet into the device, the cooling task can be achieved with the coolant separated in the container. In the device, a mixing and / or a dispersion and / or a dissolution of the first material stream in the second material stream and / or a temporary hydrate formation and / or a reaction, for example to carbonic acid, can take place. The expansion takes place in and / or after the device to produce ice, ice slush / ice particles, snow, hydrates,Cold water or combinations thereof, or a mixture / suspension of the cooled second stream, utilizing individual or a combination of the following effects: o Change in the thermodynamic state of the first stream through evaporation at 10 to 300 kJ / kg or possibly even higher, o Degassing of the first stream due to physical solubility, o Dissolution of the hydrates of the first stream and the second stream, o Joule-Thompson effect and thus expansion of the refrigerant of the first stream. The pressure increase of the second stream before feeding to the apparatus is carried out in particular to a pressure of 1.1 bar to 200 bar, with the pressure increase being implemented in several stages if necessary. Furthermore, the first stream is fed into the apparatus at a pressure of preferably 1.1 bar to 200 bar, possibly in different phases and at a temperature of typically -40 °C to 50 °C.if necessary, depending on the realized recooling in the first heat exchanger and / or intermediate cooling or further cooling in an additional heat exchanger. The first material stream consists of or comprises at least one refrigerant, wherein the refrigerant is preferably insoluble or only slightly soluble in the coolant. The refrigerant consists in particular of or comprises carbon dioxide, propane, nitrous oxide (laughing gas), or gases or vapors with / without phase change, or combinations of the aforementioned substances or other suitable refrigerants. The coolant of the second material stream can consist of a mixture of water with at least one freezing-point-lowering substance for operation at storage temperatures well below 0 °C. It is possible to implement the following modifications to the first material stream individually or in any combination: a. transcritical or subcritical operation,b. Single- or multi-stage compression up to a maximum compression pressure of approximately 200 bar, with or without intake superheat c. Parallel connection of compressors, d. With and without intermediate cooling, particularly using internal and / or external heat exchangers e. If necessary, use of one or more ejectors f. If necessary, use of one or more refrigerant dryers g. If necessary, use of one or more oil separators. After phase separation, a coolant from the second material stream of the coolant circuit can be fed from the vessel to a second heat exchanger, and in the second heat exchanger, the coolant from the second material stream can take over the cooling task. In parallel or alternatively, at least one cooling task can be realized by the vessel with at least one heat exchanger combined with the vessel. Since the expansion of the material streams in the apparatus results in significant cooling,The apparatus can be heated to prevent ice formation or to dissolve ice. Furthermore, the invention comprises a system for producing ice, ice slush / ice particles, snow, hydrates, cold water, or combinations thereof or mixtures / suspensions, wherein the system according to the invention comprises at least one apparatus having at least one first inlet for a pressurized first material stream of a refrigerant of a refrigerant circuit and at least one second inlet for a pressurized second material stream of a coolant of a coolant circuit and / or at least one secondary material stream with / from a coolant in the form of ice, ice slush / ice particles, snow, hydrates, cold water, or combinations thereof or mixtures / suspensions, and the apparatus has at least one chamber in which the first and second material streams can be combined, expanded, and cooled.wherein a container with a storage function for phase separation of the first and second material streams is connected to the apparatus, wherein the container has at least one first outlet for the refrigerant and at least one further outlet for the coolant. The system for producing ice, ice slush / ice particles, snow, hydrates, cold water, or combinations or mixtures / suspensions thereof in a closed process for the realization of a cooling task is further characterized according to the invention in that, in a first variant, the second material stream is taken from the container as a coolant circuit for the realization of the cooling task and is fed into the coolant circuit of the container via a second heat exchanger.where a) the coolant circuit leads from the heat exchanger via the apparatus to the tank, or b) the coolant circuit leads from the heat exchanger to the tank and at least one further second material stream leads as a secondary circuit via the apparatus into the tank, and / or in a second variant, the cooling task is implemented with at least one heat exchanger assigned to the tank and at least one further second material stream leads as a secondary circuit via the apparatus into the tank. In the first variant, the system is equipped: - with at least one device for combining and subsequently expanding the first and second material streams to produce ice, ice slush / ice particles, snow, hydrates, cold water, or combinations thereof, or a mixture / suspension of the second material stream, - with the second heat exchanger for implementing heat transfer for the cooling task from the material to be cooled / cooling medium to the second material stream,- with a pump for conveying the second material stream and for realising a pressure increase to 1.1 bar to 200 bar upstream of the device, - with at least one first heat exchanger for realising a recooling of the refrigerant of the first material stream to a temperature between -40°C and 50°C upstream of the device, - with at least one compressor for compressing and conveying the first material stream and for realising a pressure of 1.1 bar to 200 bar upstream of the device,- with the tank for phase separation of the first and second material streams. The tank with storage function can have a tangential or substantially tangential feed for at least one stream supplied from the device. In the tank for phase separation of the first and second material streams, the refrigerant of the first material stream is separated in an upper area, and the coolant of the second material stream is separated in a lower area. The refrigerant is then fed from the upper area and the coolant from the lower area of ​​the tank, each under pressure, back into the tank via the device. Advantageously, areas of the system that are subject to icing or where there is a risk of icing can be provided with at least one additional heater and / or at least one heat exchanger.wherein several heating zones can be provided, and the heating can be effected, for example, by means of electrical resistance and / or microwaves and / or induction heating and / or a material flow. Furthermore, it is possible to provide the apparatus with additional cooling to dissipate the heat generated during hydrate formation and / or during reactions and / or dissolution processes. According to the invention, at least one further, second material flow can lead into the vessel via the apparatus as a secondary circuit. Advantageously, the at least one apparatus has at least one inlet for the first material flow and at least one or more inlets for the second material flow and, if appropriate, also for the secondary circuit(s). Means for generating a swirling flow can also be arranged in the apparatus.to achieve better contact between the material flows. These means can be designed with or without rigid or moving internals to influence the flow. A continuous or pulsating flow can pass through the apparatus. Furthermore, other flow effects such as turbulence, instability, boundary layer effects, subsonic and supersonic flow can be realized as required. The system and the method according to the invention can be used, for example, as a heat pump system and / or as a combined cooling and heating system. The invention is explained in more detail below with reference to exemplary embodiments and associated drawings. They show: Figure 1: a schematic representation of the closed process, feeding the second material flow 2 from the container via a heat exchanger and the apparatus into the container (cold storage). Figure 2: a schematic representation of the closed process.Feeding of the second material stream 2 from the container (cold storage) via the heat exchanger into the container and the first secondary material stream from the container (cold storage) and the apparatus into the container. Figure 3 shows, in addition to the variant according to Figure 2, another secondary material stream from the container (cold storage) via the apparatus into the container. Figure 4 shows, in addition to the variant according to Figure 2, two-stage compression and intermediate cooling as well as further cooling of the first material stream 1. Figure 5 shows, in addition to the variant according to Figure 4, expansion of the refrigerant with a turbine to generate mechanical power, arrangement of the turbine upstream of the apparatus. Figure 6 shows, in addition to the variant according to Figure 1, heat transfer from the container to a heat exchanger to realize the cooling function. Figure 7 shows a first variant of the apparatus with a feed for material stream 1 (refrigerant) and a feed for material stream 2 (coolant).Figure 8 shows a second variant of the apparatus with one feed for stream 1 (refrigerant) and two feeds for stream 2 (coolant). According to Figure 1, the system, in a closed process, has a first stream 1 containing at least one or consisting of at least one refrigerant, and a second stream 2 containing at least one or consisting of at least one coolant. The system is further equipped with an apparatus 3 and an adjoining tank 4 with a storage function. In the closed process, tank 4 is first filled with refrigerant (for stream 1) and coolant (for stream 2), with their phase separation occurring in tank 4. The first stream 1 leads in a refrigerant circuit A from tank 4, in which a phase separation of stream 1 and stream 2 occurs, via a compressor 5 into a first heat exchanger 1.1.of the first material stream 1, in which recooling R of the material stream 1 is realized and under pressure into the apparatus 3. The second material stream 2 leads in a coolant circuit B from the vessel 4, via a heat exchanger 2.1 of the material stream 2 for realizing a cooling task K via a pump 6, also under pressure into the apparatus 3. The pressure increase of the material stream 2 to a high pressure may also occur in several stages. In the apparatus 3, the first and second material streams 1, 2 are combined and expand and cool from temperatures T1 of the first material stream 1 and T2 of the second material stream 2 upstream of the apparatus 3 to a lower temperature T of the stream 1 / 2 exiting the apparatus. The stream 1 / 2, reduced to a temperature T, is fed from the apparatus 3 to the vessel 4, in which a phase separation of the two material streams 1 and 2 again takes place.wherein preferably the refrigerant of the material stream 1 is deposited / separated in the upper region and the coolant of the material stream 2 in the lower region of the container 4. As a result, very low temperatures of the coolant of down to -20 °C and even lower down to -100 °C can be achieved. In the apparatus 3, a direct or indirect heat transfer takes place between the first material stream 1 and the second material stream 2. According to an example not shown, a heat transfer / temperature equalization of the two material streams 1, 2 can also be realized in a device upstream of the apparatus 3 (e.g. heat exchanger). Furthermore, the material streams 1,2 can also be heated and / or cooled in the apparatus 3 by at least one additional heating means ZH and / or at least one additional cooling means ZK, in particular zone by zone. A continuous or pulsating flow preferably passes through the apparatus 3, and further flow effects such as turbulence, instability, boundary layer effects, subsonic and supersonic flow can be realized if required. The feed of the material stream 1 (e.g. carbon dioxide R744 or another refrigerant) into the apparatus 3 is preferably carried out at high pressure, in particular at 1.1 bar to 200 bar and possibly in different phases with a temperature of typically -40 °C to 50 °C depending on the recooling and / or intermediate cooling. The second material stream 2 is preferably fed at a pressure of 1.1 bar to 200 bar at a temperature of -40 °C to 50 °C. When both material streams 1 and 2 are combined in the apparatus 3, their complete and / or partial contact occurs, whereby, for example, bubbles or drops form. It is also possible that the two material streams mix with direct heat transfer. The following processes are possible when the two material streams 1 and 2 are combined in the apparatus 3: - possibly dissolution of material stream 1 in material stream 2, - possibly temporary hydrate formation (possibly limiting the process), - possibly reactions to form, for example, carbonic acid, - possibly downstream heat transfer with an external heat exchanger. The expansion taking place in the apparatus 3 and / or subsequent thereto to produce ice, ice slush / ice particles, snow, hydrates,Cold water or combinations thereof or a mixture / suspension of a cooled second material stream 2 is preferably carried out using the following individual effects or combinations thereof: - Change in the thermodynamic state of material stream 1 through the evaporation of material stream 1 / refrigerant (approx. 10 kJ / kg to 300 kJ / kg), - If necessary, degassing of the refrigerant (material 1) due to its physical solubility, - If necessary, dissolution of the hydrates (materials 1 and 2), - If necessary, Joule-Thompson effect during expansion of the refrigerant (material stream 1), - If necessary, evaporation of material stream 2. Furthermore, the phase separation of the material streams takes place in the container / storage unit 4 (preferably at -100 °C to 20 °C) and / or at least partially in the apparatus during the removal of the gaseous phase (material stream 1) and the collection of ice, ice slush, ice particles, snow, the hydrates,of the cold water or combinations, mixtures, or suspensions thereof (stream 2). The first stream 1 consists of inorganic or organic substances or mixtures or suspensions thereof, whereby in particular all gases and all vapors, as well as mixtures thereof with or without phase change, can be used as refrigerants, for example, carbon dioxide, propane, or nitrous oxide (laughing gas), or combinations thereof, are preferred as gases, and mixtures with, in particular, air are preferably used. Depending on the choice of refrigerant, the pressure may need to be changed or adjusted accordingly when feeding it into the apparatus 3. Stream 1 further preferably consists of or comprises a refrigerant that is insoluble or only slightly soluble in the refrigerant of stream 2, thereby promoting phase separation. The refrigerant is preferably insoluble or only slightly soluble in water (e.g., R290,Propane) and possibly in the subcritical range. Mixtures (e.g., water and freezing-point-lowering substances) and / or substances that promote phase changes, such as nucleating particles and / or droplets, can also be used as refrigerants for operation at storage temperatures significantly below 0 °C. The suitable pressure of material streams 1 and 2 upon feeding to apparatus 3 can be calculated or determined by experiment. Material stream 2 contains a coolant or consists of a coolant in the form of ice, ice slush / ice particles, snow, hydrates, cold water, or combinations thereof or a mixture / suspension. From the vessel 4, the material stream 1 (e.g., carbon dioxide, possibly with very low water vapor content) is now sucked in and compressed by compressor 5 in a closed circuit from the upper area of ​​the vessel 4.the recooling of material stream 1 via the first heat exchanger 1.1 of material stream 1 and the feeding into apparatus 3. The following modifications of the refrigerant circuit (material stream 1) can be carried out, whereby the measures can be implemented individually or in various combinations: - preferably transcritical operation (but also subcritical operation), - single- or multi-stage compression up to a maximum final compression pressure of approx. 200 bar, with or without intake superheat, - parallel connection of compressors, - with and without intermediate cooling, - if necessary, use of one or more ejectors, - if necessary, use of one or more refrigerant dryers, - if necessary, use of at least one oil separator. Furthermore, parallel to material stream 1, material stream 2 is taken from the lower area of ​​the vessel 4 in the form of ice, ice slush / ice particles, snow, hydrates,Cold water or combinations thereof or their mixture / suspension is taken and fed to the second heat exchanger 2.1 of the second material flow 2 to realize a cooling task K and from there pumped under pressure into the apparatus 3 by means of the pump 6. A direct or indirect discharge of the storage (container 4 with storage function) with regard to the second material flow 2 can take place. The system according to the invention serves to produce and / or store ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixture / suspension. The container 4 can be filled at the beginning / before the start of the process with coolant (preferably water) and the refrigerant (e.g. carbon dioxide), from / in which ice, ice slush / ice particles, snow, hydrates,Cold water or their combinations or mixtures / suspensions. Before initial use, the container 4 is preferably evacuated and then filled with the coolant 2 and refrigerant 1. It is possible to connect several devices 3 in parallel to increase the cooling capacity or ice production. Furthermore, it is possible to use higher-pressure pumps for the second material stream 2 in order to partially suck in the material stream 1, particularly in the area of ​​the device 3 (injector effect). This also makes it possible to lower the temperature of the material stream 1 or to reduce the temperature reduction for the material stream 1 and / or the compression capacity for the material stream 1 and / or to achieve better pre-cooling for the material stream 2. Further pre-cooling of the material stream 1 is possible internally (in the device) or externally.also by external cooling elements or those provided in apparatus 3. The process and the system can be used as a heat pump system and / or as a combined cooling and heating system. For this purpose, the heat obtained from the recooling of the refrigerant can be used for heating purposes. It is also possible to use the waste heat generated during the implementation of the process according to the invention, e.g., for heating purposes, for process heat provision, for charging thermal energy storage systems (heat storage systems) with warm water, hot water, steam, and other heat transfer media; but also for refrigeration with absorption chillers, adsorption chillers,Steam jet chillers or as a heat source system for at least one further heat pump. Heat can be extracted from the first material stream using at least one cooler and / or at least one recooler and used for heating purposes and / or storage charging in a temperature range from 40°C to 400°C. To recover the compression power of the compressor 5 of the first material stream 1, it is possible to integrate an expansion machine into the refrigerant circuit of the first material stream 1. This is preferably carried out upstream of the device 3. This also enables partial expansion of the material stream 1, and it cools down. The expansion machine can, for example, be a displacement machine and / or turbine T, with which, in particular, a generator G is driven to generate electricity (see Figure 5). Further embodiments of the system according to the invention are shown in Figures 2 to 6. In contrast to Figure 1, Figure 2 showsthat the material flow 2 of the coolant circuit B intended for the cooling task is returned from the heat exchanger 2.1 back to the tank 4. For this purpose, a pump 6 is located between the tank 4 and the heat exchanger 2.1. To reduce the temperature of the coolant, a first secondary material flow 2N1 from the tank 4 leads via a pump 6.2 at high pressure and a temperature T2 into the apparatus 3 (to which the first material flow is also fed) and from there, after expansion and cooling, back into the tank 4. The coolant returned to the tank 4 is significantly cooled,whereby the temperature of material stream 2 is also reduced to realize the cooling function. The first material stream 1 of the refrigerant circuit A is led from the tank 4 via the compressor 5 and the first heat exchanger 1.1 to the device 3, as in Figure 1. In the system according to Figure 3, in addition to the variant according to Figure 2, a second secondary stream 2N2 is present in the coolant circuit B, which is fed from the tank 4 via another pump 6.3 to the device 3 at a high pressure and a temperature T3. In the system according to Figure 4, the coolant circuit B is designed as in Figure 2. In addition to the variant according to Figure 2, the refrigerant circuit A has a two-stage compression and intermediate cooling as well as further cooling of the material 1. For this purpose, the first material stream 1 leads from the compressor 5, which realizes the first compression stage, via an intermediate tank 7 and another compressor 5.1,which realizes the second compression stage, to the first heat exchanger 1.1. Between the first heat exchanger 1.1 and the device 3, a further heat exchanger 1.2 is provided for further cooling of the first material stream 1. Furthermore, the further heat exchanger 1.2 is coupled to the further compressor 5.1 via the container 7. As a result, a partial flow of the refrigerant between the two heat exchangers 1.1 and 1.2 is expanded in the expansion device 1.3 and cools the remaining material stream (approximately 20% to 90% of the entire first material stream) and the material stream after compression with the compressor 5. The variant according to Figure 5 has essentially the same structure as in Figure 4, but additionally realizes an expansion of the refrigerant in the first material stream 1 upstream of the device 3 with an expansion machine, here a turbine T, to generate mechanical power.Here, the drive of a generator G for power generation is realized. In Figure 6, the refrigerant circuit A is designed as in Figures 1, 2, and 3. The cooling function of the coolant circuit B is realized here by means of heat transfer from the container 4 to a pipe system (heat exchanger 8) that surrounds the container or is integrated into the container, through which a coolant flows. The low temperatures in the container 4 are thereby transferred to the heat exchanger 8 and the coolant flowing through the heat exchanger 8, whereby the coolant of the heat exchanger 8 is cooled and the cooling function K is realized. According to embodiments not shown, it is also possiblein all variants, one or more secondary streams of the refrigerant of the refrigerant circuit A are to be provided. Furthermore, all described variants can operate with a multi-stage compression of the refrigerant circuit and be provided with a device for expanding the refrigerant upstream of the device 3, e.g. a turbine T for generating mechanical power,such as driving a generator G to generate electricity. Thus, the variants described in Figures 1 to 6 can be combined as required. Furthermore, several devices 3 can be used in one system, and then, if necessary, several containers 4 and a corresponding number of pumps and heat exchangers for the coolant circuit B, as well as compressors and heat exchangers for the refrigerant circuit A. Alternatively, several devices 3 can be coupled to only one container 4 (not shown). Figures 7 and 8 show two structural designs of devices 3. Figure 7 shows a variant of the device 3 with an inner hollow-cylindrical / tubular first shell 9.which has an inlet 9.1 and an outlet 9.2 and is provided with a funnel-shaped extension 9.3 towards the outlet 9.2. The first shell 9 is surrounded at a distance by another hollow cylindrical / tubular second shell 10, which is longer than the first shell 9 and projects beyond the outlet 9.2 of the first shell 9. The first and second shells 9,10 are arranged centrally to one another along a longitudinal axis A. A first annular space 3.1 is formed between the outer circumference of the first shell 9 and the inner contour of the second shell 10, and a first chamber 3.2 is formed after the outlet opening 9.2 of the first shell 9. The second shell 10 has a funnel-shaped diameter extension 10.3 after the cylindrical region towards the outlet 10.2 and a funnel-shaped diameter reduction 10.4 at the inlet 10.1. It is possible to feed the first material stream 1 via the inlet 9 and the second material stream 2 via the inlet 10 (as shown) or vice versa. The two material streams 1, 2, which are fed under high pressure,2 come into contact in the region of chamber 3.2 and exit the apparatus 3 at outlet 10.2 as stream 1 / 2 and are introduced into the container 4, not shown here. In the apparatus 3, the material flows expand and thereby cool down considerably. An indirect heat transfer takes place between the material flows in region 3.1 and a direct heat transfer takes place in region 3.2. Figure 8 shows a further variant of an apparatus 3 in which the first shell 9 and the second shell 10 are designed as in Figure 7, whereby they are additionally surrounded by a third hollow cylindrical shell 11. The third hollow cylindrical shell 11 likewise has an inlet 11.1 and an outlet 11.2 and is provided with a funnel-shaped extension 11.3 in the direction of the outlet 11.2. The second jacket 10 is surrounded at a distance by the hollow cylindrical / tubular third jacket 11, which is longer here,than the second shell 10 and thus projects beyond the outlet 10.2 of the second shell 10. The first, second and third shells 9, 10, 11 are also arranged centrally to one another along the longitudinal axis A. A second annular space 3.3 is formed between the outer circumference of the second shell 10 and the inner contour of the third shell 11, and a second chamber 3.4 is formed after the outlet opening 10.2 of the second shell 10. Here, too, it is possible to feed the first material stream 1 via the inlet 9.1 and the second material stream 2 via the inlet 10.1 (as shown) or vice versa. For example, one or both secondary streams 2N1, 2N2 can be introduced into the inlet 11.1. The two high-pressure feed streams 1, 2 come into contact in the area of ​​chamber 3.2 and enter the second chamber 3.4 at the outlet 10.2, where they come into contact with the feed stream of the secondary circuit(s) 2N1, 2N2, for example. The annular spaces 3.1,3.3, indirect heat transfer is realized, and in chambers 3.2, 3.4, direct heat transfer is realized. In apparatus 3 and / or downstream of apparatus 3, all material flows expand, thereby cooling significantly, and are introduced as flow 1 / 2 into the container 4 (not shown here). In both variants according to Figures 7 and 8, for example, the respective outer jacket (second jacket 10 or third jacket 11) is provided with an additional heater ZH and / or additional cooler ZK and / or a heat exchanger 3W, which can also be divided into zones. The additional heater ZH or the heat exchanger 3W can, for example, impede the function according to the invention,For example, prevent unwanted ice formation on the surfaces of apparatus 3. Additional cooling ZK is preferably used for hydrate formation. According to embodiments not shown, the streams 1 / 2 exiting the apparatus can also be introduced essentially tangentially into the vessel / storage tank 4. This achieves better separation of the coolant and the refrigerant. Alternatively, a different introduction of the material streams into apparatus 3 can be selected. For example, material stream 2 can be introduced via inlet 9.1 and material stream 1 via inlet 10.1. When a jacket is arranged in the form of the third jacket 11, for example, a secondary material stream 2N1, 2N2 can be introduced into apparatus 3 via inlet 11.1. The feed of the material streams can also be radial or oblique, according to examples not shown. The expansion, acceleration, and pressure reduction take place in apparatus 3.which is required for the production of ice, ice slush / ice particles, snow, hydrates, cold water, or combinations thereof, or mixtures / suspensions. When the material flows are combined, hydrates can form, or reactions can occur between the material flows, or possibly a physical dissolution of gases from the first material flow 1 in the liquid of the second material flow 2. The hydrates can also decompose toward the outlet 10.2 or 11.2 or downstream of the outlets; outgassing of the refrigerant, possibly also a Joule-Thompson effect, and possibly a reverse reaction can occur. Desired turbulence effects, boundary layer effects, and instability effects can occur in the apparatus 3 through the flow guidance and various known design modifications.to reduce the pressure and / or improve the heat transfer between the material flows or to avoid unfavorable operating conditions. With the method and the plant according to the invention, high cooling capacities and high ice production can be achieved, for example for industrial applications, using an ecological refrigerant (such as carbon dioxide) and a coolant (ice, ice slush / ice particles, snow, hydrates, cold water or combinations or mixtures / suspensions thereof), whereby coolant temperatures of 20 °C to -100 °C can be provided. With the plant and the method according to the invention, very high storage charging capacities (up to, for example, the megawatt range,Very high storage discharge capacities (up to, for example, the megawatt range) are possible. However, depending on the dimensions, the system can also provide lower capacities in the kilowatt range. Furthermore, district cooling can also be provided via pipelines, for example. Direct application to food products, for example, is also possible. Due to the relatively simple design of the system, only minimal operating and maintenance effort is required. Another advantage is that the system can also be used as a heat pump system and / or as a combined cooling and heating system.

Claims

AMENDED CLAIMS received by the International Bureau on 03 May 2024 (03.05.2024) 1. Process for producing ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixture / suspension in a 5 closed process, characterized in that a) at least one material stream (2) in the form of ice, ice slush / ice particles, snow, hydrates, cold water or combinations or mixtures / suspensions thereof b) is combined with a refrigerant of a material stream (1) c) in an apparatus (3) and in and / or upon exiting 10 the apparatus (3) relax and cool, d) the stream (1 / 2) emerging from the apparatus (3) from the material streams (1) and (2) is fed to a container (4) with storage function, e) in the container (4) a phase separation of the material streams (1) and (2) takes place and 15 - the first material flow (1) with the refrigerant is taken from the container (4) and - the second material flow (2) with reduced temperature in the form of ice, ice slush / ice particles, snow, hydrates, cold water or their combinations or mixture / suspension realises a cooling function, 20 wherein a pressure increase of the material flow (2) before feeding to the apparatus (3) takes place by means of at least one pump (6) to a pressure of 1.1 bar to 200 bar and wherein 25 a relaxation takes place in and / or after the apparatus (3) to produce ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixture / suspension using individual or a combination of the following effects: - Change in the thermodynamic state of the first material stream (1) 30 by evaporation at typically 10 to 300 kJ / kg, degassing of the first stream (1) due to physical solubility, - Dissolution of the hydrates of stream (1) and stream (2) Joule-Thompson effect and relaxation of the first stream (1). 35 2. Method according to claim 1, characterized in that after the phase separation of the first material stream (1) and the second material stream (2) in the container (4), a gaseous phase of the first material stream (1) is discharged, wherein in a refrigerant circuit (Ä) the first material stream (1) is sucked in and compressed and recooled and fed to the apparatus (3) 5 is fed back in, and a) the second material flow (2) is taken from the container (4) as a coolant circuit (B) for the realization of the cooling task (K) and fed into the coolant circuit (B) via a heat exchanger (2.1) to the 10 container (4) is fed back, whereby - the coolant circuit (B) leads from the heat exchanger (2.1) via the apparatus (3) to the container (4) or - the coolant circuit (B) leads from the heat exchanger (2.1) to the container 15 (4) and at least one further second material stream as a secondary circuit (2N1, 2N2) via the apparatus (3) into the container (4), and / or b) the cooling task is carried out with at least one container (4) assigned 20 heat exchanger (8) is realized, and at least one further second material flow as a secondary circuit (2N1, 2N2) leads via the apparatus (3) into the container (4).

3. Method according to claim 1 or 2, characterized in that a first 25 Secondary circuit (2N1) and a second secondary circuit (2N2) of the coolant of the material flow from the container (4) under pressure via the apparatus (3) into the container (4).

4. Method according to one of claims 1 to 3, characterized in that in 30 the apparatus (3) a mixing and / or dispersion and / or dissolution of the material stream (1) in the material stream (2) and / or a temporary hydrate formation and / or a reaction takes place.

5. Method according to one of claims 1 to 4, characterized in that the 35 Pressure increase is achieved in several stages using several pumps.

6. A process according to any one of claims 1 to 5, characterized in that the feed of the material stream (1) into the apparatus (3) is carried out at a pressure of 1.1 bar to 200 bar and, under certain circumstances, in different phases and at a temperature of, in particular, typically -40 °C to 50 °C, if necessary in 5 Dependence on a realized recooling in the heat exchanger (1.1) and / or an intermediate cooling or further cooling in an additional heat exchanger (1.2).

7. Method according to one of claims 1 to 6, characterized in that the 10 first material stream (1) consists of or comprises a refrigerant, wherein the refrigerant is not or only slightly soluble in the coolant and that all inorganic or organic substances or their mixtures or suspensions are used as refrigerants, wherein in particular 15 All gases and all vapors as well as their mixtures with or without phase change can be used as refrigerants, whereby, for example, carbon dioxide or propane or nitrous oxide or combinations thereof are preferably used as gases and mixtures with air in particular are preferably used. 20 8. Method according to one of claims 1 to 7, characterized in that the coolant for operation with storage temperatures significantly below 0 °C consists of a mixture of water with at least one freezing point lowering substance and / or substances which promote a phase change, such as nucleating particles 25 and / or drops.

9. Process according to one of the preceding claims 1 to 8, characterized in that the following modifications of the first material stream (1) are carried out individually or in any combination: 30 a) transcritical or subcritical operation, b) single- or multi-stage compression up to a maximum discharge pressure of approximately 200 bar, with or without intake superheat, c) parallel connection of compressors, d) with and without intermediate cooling, in particular using 35 internal and / or external heat exchangers, e) if necessary, use of one or more ejectors, f) use of one or more refrigerant dryers if required, g) use of at least one oil separator if required.

10. Method according to one of claims 1 to 9, characterized in that a 5 Heating of the apparatus (3) to prevent ice formation or to loosen ice.

11. Plant for carrying out the process according to claim 1, for producing ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof 10 or mixture / suspension, characterized in that it has at least one apparatus (3) which has at least one first feed for a pressurized first material stream (1) of a refrigerant of a refrigerant circuit (A) and at least one second feed for a pressurized second material stream (2) of a coolant of a 15 refrigerant circuit (B) and / or at least one secondary material stream (2N1, 2N2) with / from a refrigerant in the form of ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixture / suspension, that the apparatus (3) has at least one chamber in which the first and the second material stream (1, 2) can be combined, expanded and cooled and 20 that a container (4) with a storage function and for phase separation of the first and second material streams (1, 2) is connected to the apparatus (3), that the container (4) has a first outlet for the refrigerant and at least one further outlet for the coolant and that the system is equipped with: 25 - with at least one apparatus (3), - with the second heat exchanger (2.1) for realising a heat transfer from a cooling material / cooling medium (K) to the second material flow (2), - with a pump (6) for conveying the second material flow (2) and for 30 Implementation of a pressure increase to 1.1 bar to 200 bar upstream of the device (3), - with the first heat exchanger (1.1) for realising a recooling of the refrigerant of the first material flow (1) to a temperature between -40°C and 50°C upstream of the device (3), - with a compressor (5) for compressing and conveying the first material flow (1) and for realising a pressure of 1.1 bar to 200 bar upstream of the device (3), - with the device (3) for combining and subsequently 5 Relaxing the first and second material streams (1, 2) to produce ice, ice slush / ice particles, snow, hydrates, cold water or combinations thereof or mixture / suspension, - with the container (4) for phase separation of the first and second material streams (1, 2). 10 12. Plant according to claim 11, characterized in that a) the second material flow (2) is taken from the container as a coolant circuit (B) for realizing the cooling task (K) and is fed into the coolant circuit (B) via a heat exchanger (2.1) to the 15 container, whereby - the coolant circuit (B) leads from the heat exchanger via the apparatus to the container (4) or - the coolant circuit (B) leads from the heat exchanger to the container 20 (4) and / or - at least one further second material stream (2) as a secondary circuit (2N1 , 2N2) via the apparatus (3) into the container (4) and / or 25 b) the cooling task (K) is realized with at least one heat exchanger (8) assigned to the container (4), and at least one further second material flow leads as a secondary circuit (2N1, 2N2) via the apparatus (3) into the container (4). 30 13. Plant according to one of the preceding claims, characterized in that - the container (4) with storage function has a tangential or substantially tangential feed for at least one stream (1 / 2) and / or - that means for generating a flow with swirl are arranged in the apparatus (3) 35, wherein the means of the apparatus (3) for generating the flow with swirl with or are designed without rigid or moving components to influence the flow.

14. Installation according to one of the preceding claims, characterized in that 5 areas of the system which are subject to icing or where there is a risk of icing are provided with an additional heater (ZH) and / or heat exchanger (3W), wherein in particular the apparatus (3) has a heat exchanger (3W) and / or an additional heater (ZH) with in particular one or more heating areas and that the 10 Additional heating (ZH) is effected by means of electrical resistance and / or microwaves and / or induction heating and / or by a material flow and / or that the apparatus (3) has an additional cooling (ZK) for dissipating the heat which is generated during the hydrate formation and / or during reactions and / or dissolution processes 15 is created.

15. Plant according to one of the preceding claims, characterized in that at least one further material stream leads into the apparatus (3) as a secondary circuit (2N1, 2N2). 20 16. Plant according to one of the preceding claims, characterized in that a continuous or pulsating flow passes through the apparatus (3) and that, if required, further flow effects such as turbulence, instability, boundary layer effects, subsonic and supersonic flow can be realized. 25 17. Use of the method according to claim 1 and the plant according to claim 11 as a heat pump plant and / or as a combined cooling and heating plant, and / or as a heat source for at least one further heat pump, wherein the material flow (1) is provided with at least one cooler and / or at least one 30 heat exchangers are used to extract heat and use it for heating purposes and / or storage charging in a temperature range of 40°C to 400°C.

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