KR100306706B1 - Improved method and apparatus for achieving high reaction rate - Google Patents

Abstract

The chemisorption reaction process of the present invention is performed under conditions in which volume expansion of the complex reaction product is limited, and with a half-cycle reaction cycle of less than 30 minutes each, and / or a maximum average mass diffusion path length of less than about 15 mm, And / or in a reaction chamber having a maximum heat diffusion path length of less than about 1.5 mm.

Description

Improved method and apparatus for obtaining high reaction rate

In technical terms, the adsorption / desorption reactions between certain metal salts and polar gases, termed "absorption" or "chemisorption", include cooling, heat storage, heat pump systems and high energy. Calculate the complex compounds that underlie power systems with density.

However, energy density, which is a measure of the amount of polar gas adsorbed on a salt, converting it into an amount of work or energy that can be stored in a given amount of complex, designes a commercial system. Is the only variable considered.

If nothing is more important, the reaction rates between the gas and the complex are important, which determines the time to adsorb or desorb a given amount of gas into the complex.

When the reaction rate is increased or maximized, the power that can be delivered by the system is increased or improved, i.e. more energy is transferred over a period of time, which further increases the heating and / or refrigeration or power capability of the system. Convert greatly.

As described in US Pat. No. 5,298,231 (WO 90/10491), complexes formed by adsorption of polar gases and metal salts have the properties of significant and usually substantial volumetric expansion during the adsorption reaction. If the adsorption reaction proceeds without limiting volume expansion to control the reaction product density, the final reaction product does not become the desired coherent, self supporting mass. Instead, the product is amorphous and powdery and the product mass will not retain its shape or structure.

Moreover, once the complex is so formed, the physical properties of the desired product are substantially irreversible unless they are subsequently desorbed and adsorbed without limiting expansion, and the complex is desorbed according to the invention, and then If it is charged into a limited heat exchanger (reaction chamber) cavity and does not react, the desired structure is not achieved by subsequent adsorption and desorption.

In addition, such volume-restricted complex reaction products, when heat and mass transfer are considered, are substantially comparable to reaction products where volume expansion is limited and the density of the reaction product is controlled during sorption reaction processes. This decreases the adsorption / desorption reaction rate.

In US Patent No. 5,298,231, a method of increasing the reaction rate of a chemical sorption process is disclosed by alternately adsorbing and desorbing polar gas reactants to a complex compound obtained by adsorbing a polar gas to a metal salt. The method includes limiting volume expansion and controlling the density of complexes produced during the reaction.

For many complexes, the adsorption and desorption kinetics are achieved by carrying out at least an initial adsorption reaction under conditions for obtaining a complex that is different from the unreacted salt and is at least partially coherent, cohesive, and self-supporting mass. Increases.

This reaction product is obtained by optimizing the density of the complex by limiting the volume expansion of the complex formed during the initial adsorption reaction.

The rate of reaction depends on the thermal conductivity of the solid and its gas diffusivity. In order to optimize or maximize the reaction rate, an optimum balance must be made between thermal conductivity and porosity (gas transport) to provide balanced high energy or heat transfer by proper mass transfer or diffusion of gas through the solid. .

Metal salts consisting of alkali metals, alkaline earth metals, transition metals, zinc, cadmium, tin, aluminum halides, nitrates, nitrites, oxalates, perchlorates, sulfates or sulfites, sodium borofluoride or double metal chlorides In a chemical sorption reaction process in which a polar gas is repeatedly adsorbed and desorbed on a complex compound formed by adsorbing a polar gas, a method and apparatus for obtaining a high reaction rate are provided.

1 is a diagram showing a reactor core having a plurality of fixed volume reaction chambers,

2 is a side cross-sectional view of the reactor core shown in FIG.

3 is a perspective view showing another embodiment of the reactor,

4 shows a multiple tube fin plate reactor core,

FIG. 5 shows a reactor design using a breathable material layer such as a fire brick sandwiched between multiple tube fin reactor cores.

FIG. 6 shows a multiple fin reactor core with slots for inserting breathable material along the reactor plate over the fins,

FIG. 7 illustrates a reactor core design including breathable discs spaced between adsorbent layers between reactor fins, and FIG.

8 is a sectional view showing another reactor core design.

It is an object of the present invention to further describe and limit the criteria for obtaining improved reaction rates as disclosed in the aforementioned U.S. Patent 5,298,231. It has been found that an important criterion for obtaining improved reaction rates is the design and use of sorption reactors having heat and material diffusion path lengths within certain limits. Specific reaction variables and characteristics and components of the device to obtain the above results will be described below.

After the initial adsorption reaction is carried out in a reaction vessel to be used or in some other reaction environment under appropriate conditions, the reactants can be delivered to a final reaction vessel with limited volume expansion means for subsequent reactions.

In one embodiment of the present invention, a method for improving the reaction rate between a polar gas reactant and an inorganic metal salt comprises the independent parameters of the thermal diffusion and material diffusion paths for the gas reactant passing through the metal salt in a given reactor or reaction chamber. Determining, determining the economically optimized reaction rate between the gas and the salt in the reaction chamber, determining the density of the complex required to obtain the optimum reaction rate, and Carrying out the reaction under conditions required to maintain the physical properties of the complex.

According to the invention, the solid-gas sorption reaction, ie adsorption and desorption of gas to solids, is carried out in a state and in an apparatus configured to produce a high power density. Such a reaction is preferably capable of obtaining a maximum power density per adsorbent mass, a maximum power density per reactor mass, and a maximum power density per desired or required reactor volume.

Half-cycle times, ie adsorption or desorption reaction times of reactions having improved reaction rates according to the invention, are less than 30 minutes, preferably less than about 20 minutes, usually from about 3 to about 15 minutes. Between. Not all applications require the same time for adsorption and desorption, and in some cases one or both reactions may be as short as about 2 minutes, while in other cases one of the reactions may be several minutes longer than 20 minutes. It may be extended.

Moreover, while in part load state, if the plant is not expected to generate its full cooling performance, freezing, heating or power, the reaction time limits inherent process cycling and prevents unnecessary heat loss. It may be extended to make.

It will also be appreciated that full cycle or full cycle time periods require a time period to adjust or change the pressure between adsorption and desorption half-cycles. Therefore, a full cycle time period is made up of the sum of the half cycle time and the two pressure-temperature adjustment times, which in the latter case usually range from a few seconds to several minutes each.

The optimum reaction rate depends on several independent variables including adsorption density, material diffusion path length, heat or thermal diffusion path length and thermodynamic operating conditions. The latter case is the overall process state, i.e. the specific temperature and pressure state at which the process is carried out, the pressure deviation or ΔP, i.e. the deviation between the operating or system pressure and the equilibrium pressure of the complex, and an approach of 8 ° K greater than the first adsorption reaction. Temperature (approach temperature) or ΔT.

Finally, the specific salts and the variables of the complexes formed between the salts and the specific selected polar gases must be taken into account, the properties of the salts and the final complexes comprising their equilibrium pressures to optimize the reaction state and have the maximum reaction rate. It is understood that it is an important determinant in balancing the aforementioned variables to obtain a system.

The term "optimized reaction product" or "optimized complex", as is sometimes used herein, refers to the sorption of polar gas to metal salts under process conditions such that the complex reaction product with the aforementioned characteristics is economically optimal. Refers to the complex being carried out.

Each reaction chamber or reactor module has dimensions that provide the basis for measuring or determining the heat diffusion path length (heat transfer) and the material diffusion path length (mass transfer), respectively. The thermal path length is the distance from the thermally conductive surface to the center of the mass of the complex. Heat conductive fins are an example of a thermally conductive surface. In this example, the thermal diffusion inside a given reactor is primarily a function of the pin count, ie the number of fins per unit length (height) of the reactor module. The larger the number of fins per unit of reactor length, the better the thermal diffusion and the smaller the heat diffusion path length.

In Figures 1 and 2, a simplified two-dimensional view of the reactor module is shown, in which a reaction chamber is provided between the plates 12, 14 extending radially from the heat transfer conduit 10. . The heat transfer path is the path from the furthest particle of the complex to the nearest thermally conductive surface. Therefore, for the reaction chamber between the thermally conductive fins or plates 12, 14, the simplified thermal path length is one half of the distance A between the two fins 12, 14.

According to the invention, the heat transfer path length is less than 4.5 mm, preferably about 4 mm or less, most preferably about 3 mm or less. When using the preferred group of salts disclosed herein, the most preferred heat transfer path length is 0.6 to 3.2 mm. In addition, this is equivalent to a pin count of at least 4 pins per 25 mm, preferably about 9 to 25 pins (thermal path length of 1.4 mm to 0.5 mm) per 25 mm for optimal power density requirements, which is greater than this in actual production. Can be.

The preferred range of thermal path lengths for some specific salts is shown in Table 1 below. Although the tube face is also a contributing factor to the heat path, it will be appreciated that the tube wall is not considered as such a simplified path length determinant. Usually, a suitable and practical pin thickness will vary from about 0.07 mm to about 2 mm. Small fin thicknesses are generally preferred when the heat diffusion path length is relatively short.

Fin thickness is typically set such that the temperature drop or rise in the fin is small compared to the desorption or adsorption approach temperature. The measurement or determination of the thermal path length can be readily determined for any three dimensional reaction chamber. The reactor cores shown in FIGS. 1 and 2 are for illustration only and other reactors shown and described in US Pat. No. 5,298,231 are examples of useful designs.

The size and shape of the fin or heat exchanger or heat conduction surface is based on general heat transfer calculations known to those skilled in the art. For example, referring to FIG. 3, the illustrated heat exchanger includes a plurality of heat exchange surfaces or fins extending vertically along the heat exchange fluid conduit 30.

The distance between the plates is varied due to the different reaction chambers in the wedge shape between adjacent non-parallel plates. However, the average distance between two adjacent plates 36, 38 will be measured at the midpoint between the inner and outer edges of each plate. In reactors with very low or small fin heights or small fin count designs, the proximity of salt or complex molecules to major heat transfer surfaces such as tubes or plates will be important in determining the thermal path length.

The measurement and determination of the heat path length may be performed irrespective of the shape or size of the adjacent solid fin or reaction chamber walls extending from the heat exchange conduit or conduit extending through the reactor and in heat transfer relationship therewith. In addition, such heat exchange surfaces, walls or fins usually comprise a non-breathing reactor module wall that forms or defines a reaction chamber or chambers within the reactor.

Another example of a suitable reactor core design is shown in FIGS. 4-7. The reactor core of FIG. 4 is a tube fin using multiple tubes 10 to transfer heat transfer fluid through a reactor in thermal contact with an adsorption layer formed between fins or plates 12, 14 and the breathable wall 16. Reactor.

In FIG. 5 a layer 24 of breathable material, such as a firebrick, is interposed between the reactor cores 25, 27. The reactor consists of as many reactor cores and multiple layers of breathable material as desired. The refractory brick may extend along the circumference of the reactor pin or plate 12 to cover the entire reactor core.

6 and 7 show a reactor core representing another embodiment of gas distribution means. Referring to FIG. 6, a reactor plate 12 is installed in order to install breathable materials such as refractory bricks, pumice, slabs or sheets of permeable ceramic, permeable cement, open cell plastic foam, and the like. Multiple elongated slots 18 are formed. Referring to FIG. 7, the fin material 22 is provided with the breathable material spaced apart in the layer 20 of the adsorbent salt. In the above two embodiments, the gas distribution through the mass of the salt or complex is enhanced, and the reaction rate is improved as the material diffusion path length, in particular the average material distribution path length, is reduced or optimized, as described in detail below.

The reactor core design shown in FIG. 8 includes an inner core that houses a layer 44 of adsorbent salt between the fill plates 42. The reactor core center contains a member 46 of breathable material (such as refractory brick), all contained within the reactor wall 48 with a plurality of radial heat exchange fins 50 extending radially. This reactor design is particularly suitable for air cooled reactor systems. Other heat transfer fin plate designs and shapes, such as tapered or spiral fins, can also be used in reactor core construction.

As explained above, although the length of the thermal diffusion path is a very important factor, the length of the material diffusion path, ie the path length of the refrigerant molecules to or from the adsorption factors or molecules, also depends on the volume expansion of the reaction product mass by limiting volume expansion in accordance with the present invention. This is extremely important in reactors or reactor chambers where the density is controlled.

In order to achieve high reaction rates in accordance with the present invention, the reactor or reactor must be designed to be able to move a significant amount of refrigerant in the adsorbent mass within a relatively short time period. Therefore, the material diffusion path length of the reactor is most important. The material diffusion path length is determined by measuring the distance between the point or face of gas introduction into the adsorbent mass (reaction chamber or module) from the opposite end or wall of the chamber to the molecules or particles of the complex during the adsorption and desorption cycle. And the maximum distance from which the gas must travel.

For example, referring to FIG. 2, which is a simplified illustration of a two-dimensional reactor, a breathable wall 16 through which gas flows into and out of the reaction chamber extends around the outer edge of the heat exchange fins. The distance from the breathable wall along the conduit 10 to the opposite inner side of the reaction chamber is dimension “B”, which can be easily measured and determined. Also, referring to FIG. 3, the maximum material diffusion path length dimension will be the distance between each outer edge of the reactor fin and the inner fin edge extending along the conduit 30. And the dimensions are easily determined for any reactor chamber size and shape. However, an important consideration in determining the expected desired or optimal material diffusion path length is that the gas is transferred to and from the adsorbent mass in the reaction chamber, ie the adsorbent for the gas distribution means, ie ports, vents, etc. The total mass of the particles must be taken into account.

The flow of refrigerant through and from the sorbent mass to and from the adsorption site is not merely dependent on gas permeability or penetration through the porous medium, but only gas permeation through the dense product mass contained in the limited volume. Nor is it. Instead, in the chemical sorption reaction process, the complex adsorbent changes its properties over the process by coordinating and adsorbing gas molecules. Since the coordination is usually a polar gas adsorbed to the complex in one or more coordination zones, the sorption rate is dependent on the shielding position due to the coordination site coverage and the accumulation of coordinated polar gas molecules towards the polar gas molecules introduced during the adsorption. Are affected. Thus, the material flow path length or average material diffusion path is extremely important and crucial for obtaining high reaction rates and power densities according to the present invention. Therefore, in addition to the maximum mass transfer distance to the adsorbent particles in any reactor, the average or mean distance of the gas that must travel to and from all particles of the mass must also be considered.

In this specification, the term material diffusion path length or distance is an algebraic mean for all particles of the shortest distance from all particles to a breathing surface, gas distribution inlet, outlet or other gas distribution means, contacting the compound. Is defined.

Where d _i is the shortest distance from the i th particle to the breathable plane and n is the number of particles.

According to the present invention, the average mass diffusion in rapid adsorption and desorption reactions that sorb a significant amount of refrigerant coordination theoretically obtainable in less than about 30 minutes, preferably less than 20 minutes, for each adsorption and desorption cycle. The path length is less than 15 mm, preferably less than about 13 mm, more preferably less than 8 mm. In order to meet this critical requirement, the reactor or reaction chamber of the device in which the adsorbent is present and the gas distribution components, such as tubes, reactor walls, channels, inlets, ports, vents, etc., are employed in such reactors. As defined above, the average material diffusion path is preferably designed to be 15 mm or less. For the preferred group of salts disclosed herein, the most preferred average material diffusion path length is 3-7 mm. Specific preferred average material diffusion path length ranges for some specific salts are shown in Table 1 below.

From the above, it will be apparent that the heat and material diffusion path lengths can be altered or varied by the choice or design of reactors having reaction chambers (modules) with dimensions of the desired fin depth and reaction chamber height. Increasing the pin count, or the number of fins per reactor unit length, will increase the thermal conductivity of the system and reduce the length of the thermal path.

Similarly, the material diffusion path length is also chosen by selecting or designing a reactor with a greater or smaller distance between the breathable means through which the gaseous reactants pass and the opposite inner end of the reaction chamber during the alternate adsorption and desorption reaction steps. Can be. For example, additional slots, gas tubing or breathable materials such as refractory bricks, porous cements, sintered metals or ceramics, etc. may be used to increase gas inlet and outlet exposure to reduce material diffusion path lengths. May be used in design.

In the design or selection of the reactor or reaction chamber shape, the above two parameters can be considered and selected to provide a reactor having a reaction chamber with a desired thermal diffusion and mass diffusion path length that confers an optimum or desired reaction rate. have. Thus, in accordance with the present invention, an optimal reactor capable of obtaining the desired reaction rate and power density will have both thermal (thermal) and mass diffusion path lengths as set forth above.

In the design of reactor cores for optimizing reactor module or reaction chamber dimensions in accordance with the present invention, a relatively short gas diffusion path is preferred in terms of reaction rate, but the weight ratio of the heat exchanger device to the adsorbent may be prohibited. To balance the above characteristics, the following principles can be applied.

The heat transfer surface extensions can be made of heat conductive and breathable materials with less gas flow resistance than in the case of complex compounds. To achieve this advantage, the reactor core fin plate itself can be designed to conduct gas directly through the fin or plate face to the layer of adsorbent on or in contact with each side of the fin plate.

Examples of suitable pin plate materials may include sintered and powder sintered metals, metal foams, or highly conductive nonmetal ceramics or other porous materials. Using such a fin plate for both heat transfer and gas distribution, since the dimension “A” is considered as both heat and mass transfer path distance with respect to the fins or plates 12, 14 including the mass distribution face, For example, the mass transfer distance no longer applies, especially with respect to distance “B” in FIG. 2.

Second, if it is not desirable to use a breathable reactor pin plate for both heat and mass transport, as shown in FIG. 7, a breathable disc with spaces between the reactor pin plates can be used. Breathable disc materials suitable for these solid reactants and gaseous refrigerants provide low gas resistance and enhance and contribute to gas distribution through the solid adsorbent.

A third means for increasing gas diffusion through the complex is to use a breathable or porous material that is added to the salt with the mixture and then flows into the reactor core. Of particular interest are materials that can be mixed with adsorbent salts and have geometries that provide a directional flow of gas through the salts and complex masses. Such materials are referred to herein as gas directional flow mixture components or gas distribution mixture compositions.

Such materials can be used to enhance the total gas or refrigerant delivery to or from the sorption sites of complexes or mixtures containing complexes and are breathable and adsorption and / or lower gas transport resistance than complex adsorbents during adsorption and / or desorption. A component having an elongated or expanded microporous surface, such as micro-tubes or other suitable shaped material. Examples of such materials include open cell metals, plastic or ceramic foams, porous cements, ceramics, sintered and sintered metals (ferrous or nonferrous), perforated metals or tubing, wire woven tubing, and the like. These are all breathable.

Representative suppliers of sintered and sintered metals and perforated tubing are Pacific Sintered Metals and Perforated Tubes, Inc. to be. The supplier of reinforcement tubing is Tylinter. Zircar Fibrous Ceramics is a manufacturer of ceramics such as zirconia, alumina, alumina-silica, Y ₂ O ₃ , Ta ₂ O ₅ , HfO ₂ and CeO ₂ .

Powder sintered and sintered members are available in the form of steels, stainless steels and other alloys such as nickel, chromium, molybdenum, tungsten, etc. Perforated metal tubing is available in aluminum, steel, stainless steel, monel and many other alloys. Available in form. Wire reinforcement materials, including tubing or porous sticks, are available in almost all forms of metals, plastics, ceramics, and the like. The particular metal or composition material selected for powder sintering, sintering or reinforcing micro-tubes is not particularly critical as long as it can be combined with gases and adsorbents under process conditions. In some cases, materials with high thermal conductivity are preferred if such components are also intended to increase thermal conductivity.

Although the particular material used for the gas directional flow mixture component is not critically important, for some materials the size of the hole or pore irrespective of its shape, e.g. tube, disk, wire, plate or sheet. Is an important requirement. Because of the particle size of the adsorbent and the migration of solids into the gas distribution pores, the preferred gas distribution pores or openings are less than 100 microns, more preferably less than 50 microns, and a thin face cover is preferred for the gas for solids migration. In no case should it be larger than to prevent the solid migration and occlusion or plugging of the pore unless the bulk of the dispensing component is protected.

Typical dimensions for the aforementioned disk, tube and wire components are a minimum diameter or about 0.1 mm and preferably a greater disk thickness. For mechanical reasons the disk thickness should be at least as above. The maximum thickness limit need not be technically limited, but for practical reasons thicknesses greater than 4 mm for tubes and wires, 5 mm for disks and sheets, and 10 mm for plates are often of no benefit.

Such gas directional flow mixture components can be introduced into and mixed with the adsorbent salt composition, for example in effective amounts of up to a minor percentage and up to about 30%, efficiently delivering gas to the most preferred and farthest adsorbent particles in the reactor core. It may have a direction to. By placing these components in contact with or at least relatively close to the atmosphere of the reactor (refrigerant) atmosphere to prevent overdelivery through the complex before gas reaches the gas distribution mixture components, the gas distribution or mass diffusion interface can be In practice, it is also desirable to provide an interface or boundary between the gas distribution mixture component and the complex compound.

It is to be understood and appreciated that the “optimal” reactor module or reaction chamber dimensions and the fin height and / or count or sorbent density will vary due to the process variables in which the device should be used. For example, where the device is to be used in a heat pump, the optimum reaction chamber dimensions and / or shapes, including pin count, fin height, etc., are very different from those used in thermal energy storage or low temperature freezer environments. Can be.

For heat pumps, when the reaction cycle time is relatively short, ΔP is typically about 1 bar or more, and the near temperature ΔT is typically between about 10 ° and 30 ° K or more, optimization of both heat and mass transfer Is very important. On the other hand, for thermal energy storage systems where ΔP is often less than 1 bar, typically between about 0.15 and about 0.6 bar, and ΔT is often between 4 ° and 8 ° K, the material diffusion path length (mass transfer) The criterion is of significantly greater importance than heat transfer.

Similarly, to achieve a cooling temperature in the sub-70 ° F. range in a low temperature freezer device, the pressure approach (ΔP) is typically very low, about 0.1 bar, and the material diffusion path length compared to the heat transfer characteristics of the device. Much more important.

Therefore, in such systems it is necessary or desirable to design devices with relatively short mass transfer pathways and / or low compound densities to optimize mass transfer or mass diffusion pathways. Thus, it will be apparent to those skilled in the art that the optimization of the reactor module or reaction chamber should take into account the purpose of use of the equipment in view of the aforementioned variables.

Another variable to be determined is the mass of salts per unit volume of the reaction chamber cavity, or the loading density and complex of solid particulate metal salts entering the reactor, and the optimum or desired reaction rate for adsorbing and desorbing gaseous reactants therefrom. The optimum density of the final complex reaction product to obtain.

In order to obtain the desired or optimal density of the complex in a fixed volume reactor, the amount or volume of unreacted salt flowing into the reaction chamber is such that the newly formed complex structure has a desired density when the complex reactant structure is produced during the sorption process reaction. It should be sufficient to cause volume expansion in each reaction chamber or module filled with the composition.

In general, the density of the resulting complex will be lower than that of the salt prior to the initial reaction, with the density of the fully adsorbed complex often being high. In addition, the density of the complex will vary depending on the operating conditions, ie pressure and volume. Each salt and complex will react somewhat differently at different temperatures and pressures. Therefore, these operating conditions must be taken into account together with the equilibrium pressure and the approach pressure of the complex. Therefore, the optimum density for each complex under these operating conditions must also be determined independently.

According to the invention, the loading density of the adsorbent salt reacting with ammonia in the heat exchange cavity is preferably between 0.2 and 1.0 g / cc, more preferably between 0.3 and 0.8 g / cc, but with a high bulk and injection density With respect to the adsorbent having a relatively high molecular weight), the adsorbent may exceed 1 g / cc.

However, according to the present invention, this density range should also take into account the heat and mass transfer variables disclosed above. Therefore, selection of salt densities that fall within the aforementioned limits should be used for reactors or reaction chambers having a thermal diffusion path length and / or a material diffusion path length presented and described herein.

Preferred load density ranges for some specific adsorbent salts used in the ammonia refrigerant system are also shown in Table 1 below. And it should be understood that the density is not intended to be absolute or independent for use in reactors having heat and / or material diffusion path lengths outside the scope of the aforementioned parameters.

The values shown in the table are the adsorbent densities of uncomplexed salts for the ammonia complex over a given range of NH ₃ coordination steps. The pressure given is the one normally used or encountered by the system evaporator, or corresponds to the pressure of the desorption reactor for another system reactor or for a condenser or other adsorption reactor. Density values are given in grams / cc and mean mass diffusion length and thermal path length values are given in millimeters.

If the salt loading density exceeds a value that results in insufficient volume for complete gas uptake, the actual gas uptake may be less than the coordination step.

Multimetal chloride salts with at least one metal of Cr, Cu, Zn, Sn, Al, Na, K, Sr, Ca, Co, Fe, Ba, Mn, Mg, Li, Ni and CuCl, CuCl ₂ , SnCl ₂ , AlCl ₃ NaCl, KCl, FeCl ₂ , Ammonia Complex:

Bromine, Iodide, Sulfate, Nitrate, Perchlorate of Cr, Cu, Sn, Zn, Al, Na, K, Fe, Cr, Cu, Zn, Sn, Al, Na, K, Sr, Ca, Co, A multimetal adsorbent having at least one metal of Fe, Ba, Mn, Mg, Li, Ni, and polyanionic salts:

At a given pressure and temperature, it was found that salts with low molecular weight tend to be optimized at low loading densities and salts with high molecular weight.

In addition, for some salts having a molecular weight of greater than about 200 and more importantly greater than about 1 kilogram per liter, for example some bromide, iodide, oxalate, sulfate, the system is 2.75 to 3.0 bar (40 to If the salt must be operated in a range larger than 45 psia), an appropriate loading density of from about 1.0 g / cc to 1.8 to 1.9 g / cc may be used since the salt is dense enough to continue to expand at limited expansion volumes. .

In addition, for the salt and for use at the high pressure, the mass diffusion path length may be increased by 2 or 3 mm. Moreover, in the case of low pressure refrigerants such as water, alcohols (methanol, ethanol, propanol) and amines (metalamines, ethylamines, diamines), the optimum density and / or diffusion paths are typically lower than for ammonia.

Those skilled in the art who are familiar with the measurement and determination of the expansion properties of the complexes to be produced, the operating conditions to be used and the independent gas diffusion and thermal diffusion path dimensions of the reaction chamber or chambers, depending on the selected salt and polar gas, The amount of initiating, unreacted particulate metal salt to be introduced into the reaction chamber to determine the density may also be determined.

Due to the complex nature of the combined mass diffusion and heat transfer processes, and given the other variables described above to achieve desirable system properties, the optimization of the system is generally approach temperature as well as the absolute temperature of the reaction, the compound density and the shape of the reactor module. And / or by varying the pressure and measuring the corresponding sorption rate and extent.

Substantial improvement is achieved due to the special improvement of the reaction rate by the optimization of thermal diffusion and material diffusion path length and complex density, which increases the economics of the reactor. Such an improvement substantially affects the efficiency of the complex and the amount of energy that can be provided by the system or apparatus during a given reaction cycle period.

For example, in some applications, a reaction rate of approximately 10 to 15 moles / mol-hr may result in a half cycle cycle of about 10 to 12 minutes, i.e., 10 to absorb and desorb the desired amount of gaseous ligand from the complex. Mean time in minutes. In comparison, a reaction rate of 25 to 30 moles / mol-hr means a half cycle period of about 5 to 7 minutes, thereby approximately doubling the energy available from the system for a given operating time period.

The high reaction rates obtained using the optimized reactor as described above can be maintained beyond a period of up to 20 minutes, as well as for short cycle periods. Therefore, a reaction rate of about 6 moles / mol-hr or more, typically 10-20 moles / mol-hr, may be maintained for at least 6 minutes, typically 12-15 minutes, and for some reactions up to 20-30 minutes. .

The numerical values of the reaction rates described above are average, based on the average of the reaction rates up to the time when the reaction is completed or otherwise terminated. The improvement is a directly increased cooling and / or heating or power capacity for any given size reactor system. Therefore, by decreasing the cycle time with increasing reaction rate, the tonnage of cooling capacity for a given amount or mass of complex used in the system or apparatus is correspondingly increased.

Such an improvement allows substantially greater cooling and / or heating or power capacity of the heat pump or similar refrigeration or power device utilizing the improvement or substantially more in generating a given amount of cooling and / or heating capacity. Enables small and light heat pumps or other devices.

According to the invention, the sorption reaction process is carried out under conditions that limit the volume expansion of the reaction product and can produce complexed solids having a different physical mass than the unreacted salt. Unreacted salts are typically powdered granular or granular materials, generally injectable and freely flowing in dry and uncoordinated form, which easily adapts to the internal shape of the reaction chamber being introduced.

When complexes are produced under sorption reaction conditions that are controlled and optimized by limiting the volume expansion of the reaction product according to the present invention, the complex reaction product is often at least partially immobilized and self-supporting with substantially different structures and Have physical properties

For several salts, following a single adsorption cycle with controlled volume expansion, substantially the entire complex reaction product is repeated after the adsorption / desorption cycle is repeated, even after the gaseous reactants are substantially completely desorbed, and then in the volume-limited reaction chamber. It is also a stiffened, cohesive, adhesive, self-supporting mass that retains its shape.

For other complexes, some of the reaction products have the properties described above. Moreover, the complex reaction product mass will retain the new structure without collapse or powder if maintained at a limited volume throughout the sorption process, unless subjected to substantial physical misuse or degradation.

In particular, SrCl ₂ , SrBr ₂ , CaCl ₂ , CaBr ₂ , CaI ₂ , CoCl ₂ , CoBr ₂ , BaBr ₂ , MgCl ₂ , MgBr ₂ , FeCl ₂ , FeBr ₂ , NiCl ₂ , ZnCl ₂ , MnCl ₂ , MnBr ₂ , The ammonia complexes of CrCl ₂ , SnCl ₂ , SnBr ₂ and LiCl are stabilized or fixed in the form of a stiff, structurally and physically very self-supporting uniform mass when reacted under volume-limited conditions in accordance with the present invention. Found.

Depending on the loading density, the structure of the CaBr ₂ .2-6 (NH ₃ ) ammonia complex is one example of a complex that may not always be fully or completely immobilized, adhesive or uniform.

The high reaction rates of the improved complexes formed according to the invention do not depend on the specific physical properties of the different reaction products. Thus, the improved kinetics can be achieved in volume during the sorption process with the proper heat and mass diffusion pathways, regardless of whether the final product is highly coherent, self-supporting and physically uniform, or only partially coherent and self-supporting. Expansion is inherently essential in the reaction product produced by control and limitation.

In addition, because the reaction product formed during the sorption reaction described above generally expands with respect to the reaction chamber surface, the reaction product provides improved heat transfer due to the degree of physical contact with the heat transfer surface of the reactor.

The complexes mentioned above are obtained without the use of other binders, additives, mechanical sintering, baking, etc., but typically undergo an initial adsorption reaction under density retention conditions and appropriate volume expansion restrictions, with air removed from the sorption chamber prior to sorption. Is achieved substantially and exclusively.

As already mentioned, the initial adsorption reaction or series of sorption reactions can be carried out with limited volume expansion in the reactor or reactor module or other reactors used in the system. Therefore, the sorption reaction can first be carried out in a separate vessel under conditions of preventing or limiting the loading and volume expansion of the appropriate salts in order to obtain a mass that is desirable physical self-supporting, adhesive and consistent. The mass obtained is then removed from the initial reactor vessel and placed in the final reactor with volume expansion limiting means.

Since these preformed complex reaction products are formed under the reaction conditions according to the invention, the complex reactants may act as if they were initially formed in different reactors and yielded the same improved power density performance results. will be.

Complexes in which improved reaction rates are obtained according to the present invention include chemical sorption reaction products of metal salts in the form of solid particulate reactants to which polar gas reactants are adsorbed which can form coordinating bonds with salts.

The preferred expression of the reaction is “adsorption,” but sometimes the reaction is also referred to as absorption or chemisorption reaction or product. Preferred complexes are disclosed in US Pat. No. 4,848,994. The preferred polar gaseous reactants are ammonia, water, sulfur dioxide, low alkanols (C1-C _5), alkylamines, polyamines and phosphine. Preferred metal salts include nitrates, nitrites, perchlorates, oxalates, as well as zinc, cadmium, tin and aluminum, as well as alkali metals, alkaline earth metals, transition metals, especially metals such as chromium, manganese, iron, cobalt, nickel, copper, tantalum and rhenium, Sulfates, sulfites and halides, especially chlorides, bromide and iodide. Also useful are bimetal chloride salts wherein at least one of the metals is an alkali or alkaline earth metal, aluminum, chromium, copper, zinc, tin, manganese, iron, nickel or cobalt. In particular, other salts which interest is NaBF ₄ to form a complex compound with ammonia _{NaBF 4 · 0.5-2.5 (NH 3)} . Other complexes are disclosed in US 5,186,020 and US 5,263,330.

Preferred complexes used in the reaction of the present invention include adsorption / desorption compositions comprising at least one of those set forth below or as components thereof.

As pointed out above, the actual adsorption and / or desorption reaction cycle or semi-cycle cycle is approximately 2 minutes or even shorter for explosive devices and extends to 20-25 minutes under certain load conditions or special design process conditions. Will be. However, the above-described advantages of the present invention, that is, the reaction rate, is rapidly reduced if the half-cycle continues for about 35 minutes.

During any particular adsorption or desorption reaction, using a reactor equipped with an improved heat and mass transfer gas diffusion path length and a preferred heat path length under the above-described conditions of the invention, the sorption is moisture, typically at least about 6-12. Minutes, sometimes 15-20 minutes, allow for a relatively rapid rate of progression of the reaction or a reaction showing a complete reaction.

It should be noted that the theoretical completion of the sorption process for any given complex as indicated above depends on the actual coordination range available under particular treatment temperature and pressure conditions, which is often less than the theoretical value of each complex (Table 2). . Moreover, it should be recognized that the design of the reactor according to the present invention is directed to higher reaction rates and / or close access pressures and temperatures rather than completion of the reaction.

However, in the sorption treatment performed under the volume expansion limitation according to the present invention in a reactor having the above-described heat and mass diffusion path length and salt loading density, the reaction of the refrigerant on the salt or complex is 15 minutes under the process temperature and pressure conditions. It is possible to proceed to at least 50% of the actual effective coordination sorption capacity within the following time.

Some salts and complexes, such as CaCl ₂ · 4-8 (NH ₃ ) and SrCl ₂ · 1-8 (NH ₃ ), may have at least 40% mass of dry salt material refrigerant, At least 20% of the dry salt weight can be adsorbed within at least 15 minutes. In addition, other salts, such as CaBr ₂ .2-6 (NH ₃ ) and MgBr ₂ .2-6 (NH ₃ ), may have 25% to 40% of the dry matter, and at least 15 within 12 minutes. % Of dry salt can be adsorbed. Other salts, such as FeBr ₂ .2-6 (NH ₃ ), can adsorb ammonia equivalent to at least about 10% dry salt weight during a sorption process within 10 minutes.

The reactor of the present invention in which the volume expansion of the complex is restricted during the adsorption treatment reaction can absorb, i.e. adsorb and desorb, at least 20 milligrams of NH ₃ per 1 cc of expanded adsorbent for 1 minute for up to 30 minutes of reaction time. have. Moreover, when the reaction time is limited to 30 minutes or less, this reactor can adsorb / desorption of 10 milligrams of NH ₃ per minute and 1 cc of total reactor internal volume. In other words, if saturation is achieved within 30 minutes in the entire volume inside the pressurized reactor, the early completion of the sorption is possible, so this progress can be limited.

The rate of reaction usually depends on the degree of completeness of the reaction. The state equation below is used to describe the progress of the reaction over time.

ΔN = ΔN _max (1-e ^-kt )

Where ΔN = reaction degree (moles / mole)

ΔN _max = maximum response (moles / mole)

t = time (sec)

k = response kinetic value (sec ^-1 )

Where k is the reaction constant

The equations are given in terms and units useful for the complex sorption reactions of the present invention. The reaction constant k represents the time dependence of the reaction progression at any time. The reaction rate is obtained by expressing the equation including k and time:

As shown herein, another convenient unit for the sorption reaction is included. As an example using this equation, SrCl ₂ NH ₃ can complex up to 7 moles of ammonia in steps 1 to 8, so that ΔN _max is 7. For a k value of 6 minutes (360 seconds) and 0.004 sec ⁻¹ , ΔΝ is 5.3 moles of ammonia per mole of salt. Reactions after 6 minutes require an average rate of 53 moles / mole-hr for 6 minutes. A reaction constant of 0.0004 yields an average reaction rate of ΔΝ or 9.4 moles / mole-hr of 0.94 within 6 minutes. Given the reaction constant (k) for any adsorbent constituent with any salt, the degree of reaction completion and rate of reaction at any time can be readily calculated. The actual amount and speed of the adsorbed refrigerant depends on the size ΔN _max of the sorption step. The sorption rate achievable by the present invention leads to the following minimum values for the reaction constants.

These reaction results are useful for adsorption and / or desorption periods of up to 30 minutes.

The following examples are provided to illustrate the improvements and parameters used to optimize the reactor system according to the present invention using the above formula. Where ΔN _max is the maximum amount of refrigerant that can be adsorbed, and ΔN is the amount adsorbed during time t. In the examples below, the k value is for ΔΝ given as time t in minutes and mole of refrigerant per mole of salt.

[Number of pins]

Adsorption rate experiments for CaBr ₂ · 2-6NH ₃ were performed under salt maintained at 108 ° C. and ammonia pressure of 3.93 bar. The heat exchanger was equipped with 18 mm (0.7 inch) high fins, and the salt was loaded with 0.7 g of non-ammonia salted salt per cm ³ of salt retention volume on the heat exchanger. For the number of 7, 12 and 14 pins per 25 mm (1 inch) the following results were obtained.

With the same heat exchanger parameters, the 12 fins provide the maximum sorption rate at these temperature and pressure conditions.

[Pin height]

Adsorption rate experiments for CaBr ₂ · 2-6 NH ₃ were carried out with a salt and ammonia maintained at 35 ° C. at a pressure of 0.272 bar and a temperature of 57 ° C. (−70 ° F.). All heat exchangers were equipped with five fins per 25 mm (1 inch) and the salts had a density of 0.6 grams of non-ammonia salts per cc. Pin height 8.8 mm (0.35 ″), 9.5 mm (0.375 ″) and 10 mm (0.40 ″) were tested.

Under these temperature and pressure conditions, although the minimum system cost (cost per unit cooling capacity obtained at -57 ° C (-70 ° F)) is obtained at a fin height of 10 mm (0.40 inch) as the cost of heat exchangers and vessels decreases. The optimum response rate is derived from a pin height of 9.5 mm (0.375 ″).

[Salt Load Density]

Adsorption rate experiments for CaBr ₂ .2-6 NH ₃ at 3.93 bar with salts maintained at 108 ° C. were performed. All heat exchangers have seven fins per 25 mm (1 inch) and the fins are 10 mm (0.40 inch) high. A loading density of 0.5 grams, 0.6 grams and 0.7 grams salt per cm ³ of salt retention volume on the heat exchanger was performed.

The maximum speed (max k) is obtained at a load density of 0.6 g / cc. The minimum system cost is obtained at a loading density of 0.7 because more salt is included in a given heat exchanger and vessel volume.

The reactivity of the salt can be further enhanced by initially adsorbing some gaseous ligands dropped into the salt, which is different from the gaseous reactants to be used in the complex. Any of the foregoing polar gas reactants can be used, with preference being given to water, ammonia, low aliphatic alcohols, amines or phosphines. The amount of additives should preferably be between about 0.05% and about 10% per salt weight. The use of hydrated salts which contain a small but effective amount of water adsorbed onto the salt can fulfill this purpose.

For some adsorption / desorption cycle systems, it is advantageous to use a mixture of bivariant adsorbents, which, together with the aforementioned monoovarant complexes, are essentially not expanded during the adsorption period of the polar refrigerant. In particular, in a bivariant system using zeolite, activated carbon, activated alumina, or silica gel as an adsorbent, which is a material that does not greatly expand in volume in the adsorption of polar refrigerant, the complex compound is used to adsorb the polar gas. The reaction product mass can be significantly improved by compounding with metal salts which produce complexes during the process.

This embodiment is particularly useful for water or ammonia refrigerant systems. The advantage of mixing metal salts and bimodal adsorbents is that the final adsorbent mass is highly desirable properties of the complex masses described above, namely controlled density and desirable heat and desirable material diffusion, good contact with the heat exchange surface, as well as increased heat. Conductivity and often a physical mass of an adherent, tacky, self-supporting structure with the improved reaction rates described above.

Although salts that result in the specific complexes described above are preferred, any of the salts described above may be used to mix with the bimodal material. The amount of salt used in the mixture may be in any proportion by weight depending on the particular salt as well as the above variables, including reactor design material diffusion path length, temperature or thermal diffusion path length, and loading density, all depending on the operating conditions. Preferably between 5% and about 25%. In order to obtain the desired improved results of using a mixture of bimodal and monomodal adsorbents, the monomodal adsorbents which expand sufficiently during the initial adsorption reaction with polar gases may undergo volume expansion of the combined adsorbent mixture during the sorption reaction process as described above. It should be understood that it is necessary to limit the density of the adsorbent mass.

Mixtures of bimodal and unimodal adsorbents are also advantageously used in nonpolar gas refrigerant systems. Such non-polar refrigerant groups are C ₁ -C ₆ natural gas lower alkanes, that is, methane, ethane, propane, butane, pentane and hexane, helium, argon and hydrogen, which are cold refrigerants, and oxygen, nitrogen, hydrogen, NO _x , which are atmospheric gases. , CO ₂ and CO, and fluorocarbon refrigerants of CFCs, HCFCs and HFCs.

For example, in a system in which methane is adsorbed on zeolite, the metal salt is mixed with zeolite and the polar gas is charged to a solid mixture adsorbed to form a complex, including a univariate salt, thereby reacting the product with the improved properties. You gain mass. The amount of salt used in these applications is as low as several percent of the mass below the main amount.

Following the initial adsorption, desorbed from the polar gas and is withdrawn from the reactor. The system is then charged with a nonpolar gas and the desired adsorption and desorption reactions are carried out. If the solid univariate and bimodal adsorbent mixtures are first filled with polar gas reactants to produce a mixture comprising complexes with the desired physical enhancements, this advantage is that any of the bimodal adsorbents in combination with the desired nonpolar gas or refrigerant system Can be used for.

Likewise, the above-described improvement involves mixing the metal salt with the metal hydrate, filling the mixture with ammonia or other polar gas to form a complex, desorbing the complex compound from the reactor to expel the ammonia or other polar gas, and then Can be used in metal hydrate adsorption systems by charging hydrogen into the system to effect hydrogen adsorption and desorption on the metal hydrates. Accordingly, the present invention is widely used to improve systems and processes using non-expandable solid adsorption reactants and alternately polar or nonpolar gases that are adsorbed and desorbed.

According to the present invention, an appropriate amount of solids which adsorbs these unexpanded adsorbents and gaseous reactants to expand and volumetrically, and the limitations and controls for this expansion result in adsorption reaction products having the above-described improved physical and / or mathematical properties. By mixing the reactants, improved system reaction rates can be achieved.

Because of the large improvement in the reaction rate provided by the aforementioned complex compounds, one of the salts mentioned above is outside the scope of any other adsorption reactants, ie the salts and complex compounds described above, or does not achieve an improved reaction rate as described herein. It is advantageous to mix with what is not.

It is also advantageous to use mixtures of two or more of the foregoing metal salts, for example one salt which yields a relatively high volumetric expansion complex and another salt with a low volumetric expansion complex. For example, by using a mixture or compound of salts such as strontium chloride and calcium chloride or magnesium chloride, or calcium bromide and calcium chloride, the resulting complex can provide improved reaction rates resulting from one of the two salts when used alone. Will have

According to another embodiment of the present invention, the aforementioned reaction rate improvement achieved by optimizing the density and independent variables of the heat transfer and mass transfer path lengths, as generally disclosed in US Pat. No. 5,298,231, is the volume during adsorption. It may be applied to a gas adsorption reaction product that does not expand.

Therefore, the reaction rate of the reaction product formed in the aforementioned gaseous reactants adsorbed on the zeolite, activated carbon, activated alumina and silica gel as well as the metal hydrate determines the reaction process parameters and reaction conditions to be used as described above, and the specific solid to be used. And selecting a gas, determining the desired adsorption reaction rate at which the system is used, determining the heat and material diffusion path lengths that will yield the desired reaction rate, respectively, and providing a reactor with the desired reactor cavity dimensions, This can be improved by charging the solid reactants into the reactor and following the previously described method of maintaining the desired density throughout the reaction process. This is achievable in a fixed volume reactor or in a reactor with one or more mobile surfaces to maintain the required compaction for the reactants during the adsorption reaction by loading the solids at the desired density into the reactor and using the necessary compression. .

Further, in another embodiment of the present invention, as shown in FIGS. 3 and 4, the illustrated reactor is equipped with multiple heat transfer fluid passages. In particular, in FIG. 3, four heat transfer conduits 22, 24, 26, 28 show the top of the reactor fin or plate 25 passing through. These different tubes are used to guide the heat exchange fluid at different times during the reaction cycle, to provide different passages for different heat exchange fluids, or to provide different uses of time and temperature for one or more fluids.

For example, during desorption, two passages are used as passages of the heating fluid, while the other two passages are not used during desorption. During adsorption, two different passages are used for the passage of the cooling fluid, while no heating fluid passage is used. Different passages are used for phase change heat exchange fluids that change between gas phase and liquid phase during heat transfer, or to direct different heat exchange fluids to different passages at different times during the reaction cycle. Branching headers or manifolds are used at the end of the reactor to which different tubes are connected or else outside of the reactor.

Another means of providing a different fluid path is shown in the reactor structure shown in FIG. The divider 34 here extends along the conduit 30 with different fluid flow paths 32 and 33. Again, as with the embodiments described above, such devices provide dual paths for different heat exchange fluids of the same or different phases.

In designing a system using the improved reaction products described herein, the determination of technical parameters to optimize material diffusion path length, thermal diffusion path length and loading density to maximize sorption rate, although important, is a practical parameter. It should be recognized that they should also be considered.

As mentioned above, optimization is performed to meet the specific operating requirements and application objectives for the device. Practical parameters include not only the heat exchange requirements of the system, but also the volume of the device and the amount of adsorbent used. Therefore, the size of the heat exchange component to achieve the lowest device volume, size and weight of a system using relatively small amounts of adsorbent is an important consideration in reaching the ultimate plant and system design.

As another example, also consider the practicality that the pin count and pin thickness are not so thin that they can be easily deformed during salt loading, or that the excess reactor mass and cost are not too thick or too large to be added unnecessarily and impractically to the system. Should be. While the lowest system cost is important for domestic heat pump sobers, the minimum system mass is needed for devices placed in orbit for use in other systems, for example space programs.

In addition, in other systems, such as some consumer goods, relatively small absorber volumes are required. Manufacturing tolerances in producing reactors with the above mentioned heat and mass transfer path dimensions should also be considered. While high power performance products often require adherence to strict standards, tolerances of ± 5 to ± 7% are allowed in other products. These factors should be considered in adapting or adjusting the optimum technical parameters independently determined in accordance with the invention.

The methods and apparatus of the present invention are useful in designing devices or systems that require or direct improved or optimized fin adsorption and desorption rates. For example, such reactors are particularly useful in systems such as those disclosed in US Pat. No. 5,161,389, which includes applications for rapid sorption cooling or freezing where the improved power density achieved according to the invention is highly desirable. The present system design and method of achieving high power density is particularly useful for the cooling systems and devices disclosed in US Pat. No. 5,271,239. Enhancements of the present invention can be used to achieve highly desirable reactor performance in air cooled reactors as disclosed in US Pat. No. 5,186,020. In addition to the systems and reactors described above, the process of the present invention can be used to achieve improved and optimized reaction rates in staged reaction systems as disclosed in US Pat. Nos. 5,025,635 and 5,079,928.

In particular, US Pat. No. 5,025,635 discloses a continuous isostatic step of a solid-steam chemisorption reaction in which a number of different complexes are placed in a reactor containing respective complexes having different evaporation pressures and are substantially independent of the concentration of the gaseous reactants. It is. The complexes are arranged in each reactor in succession in vapor pressure order, and the heat transfer fluid passes through each reactor for continuous heat exchange with the continuously arranged complexes. Thus, the adsorbent is introduced into each reactor using the above density, which has the heat and material diffusion path lengths disclosed herein, wherein the volume expansion of the complex formed during the sorption reaction process of the polar refrigerant with the metal salt It is limited according to the invention.

Likewise, systems in which the reactors and methods of the present invention have been used include the devices disclosed in US Pat. No. 5,079,928, wherein at least two reactors are used, each reactor having a vapor pressure that is substantially independent of the concentration of the gaseous reactants. It contains different complex compounds with The reaction is staged so that the heat transfer fluid used to heat and cool the reactant directs heat from the exothermic adsorption reaction to the endothermic desorption reaction to drive the endothermic desorption reaction. Here, at least three different compounds are used in different reactors, the reactors are arranged in succession in the order of the vapor pressures of the complexes, and the heat transfer fluid is continuously passed through the reactors continuously arranged in the order of the complex vapor pressures, as indicated above. By directing the reaction is carried out in stages.

The heat and material diffusion path lengths disclosed herein are intended to be used without any additives, to avoid the addition of inert materials. However, if suitable thermal conductivity enhancement or material diffusion / porosity enhancement additives are used, the heat and material diffusion paths may extend from about 10% to about 30%. Preferred as additives are metal or other materials having relatively high thermal conductivity or, in some cases, bimodal adsorbents such as carbon which exhibit suitable thermal conductivity in at least the selected direction.

Other additives include metal wool, highly conductive ceramic sintered metal, carbides, and the like, which are well known to those skilled in the art. However, high additive mass ratios of 20% to 30% or more need to be chosen carefully because of the negative effects on material and volume requirements and overall power density. The method of the present invention can be advantageously used in the design or production of a substantial number of useful goods and devices. Items for special types and examples of devices and equipment are:

Such as small or portable or personal freezers, refrigerators or refrigerator / freezer combinations, refrigerators, freezers or combinations and recreational units for recreational cars, boats, cars or trucks, such as refrigerators, freezers or combinations for small bars. Consumer leisure facilities;

Kitchen equipment such as quick freezers, used alone or in combination with microwaves and / or standard refrigerator / freezer units, cold / coffee makers, ice makers, ice cream makers, freeze dryers and beverage or water coolers;

Equipment and apparatus for exhibition and vending machines such as chillers, freezers and ice makers;

Durable consumer materials such as home refrigerators and freezers with or without quick freezing and commercial refrigerators and freezers, dehumidifiers and clothes dryers;

Building air conditioning units including household split air conditioners and heat pumps, light commercial split air conditioners and heat pumps, indoor air conditioners, household dehumidifiers, mixed air conditioners and refrigeration cycle units;

Air conditioners and chillers for cars, vans or trucks, or air conditioners and chillers for buses, trains, aircraft, or recreational or commercial boats and ships, including vehicular AC systems, vehicular heat storage and vehicular seat or bench cooling systems;

Air conditioners for electronic and electronic system boxes for electronics and chip cooling;

Single HVAC products and HVAC products within 20RT overcapacity, medical and laboratory equipment, environmental and military supplies, including combat, flight and space use clothing, industrial and commercial heat pumps, boilers, heat energy storage Other appliances and equipment such as equipment, gas turbine air conditioners, commercial dehumidifiers, spacecraft cooling refrigeration equipment, and the like;

The above items are not intended to characterize the invention, but rather are intended to provide representative examples of a particular type that include the apparatus and method of the invention. These as well as other systems are intended to incorporate the advantages and components of the present invention.

Polarity to metal salts consisting of halides, nitrates, nitrites, oxalates, perchlorates, sulfates or sulfites, sodium borofluoride or double metal chlorides of alkali metals, alkaline earth metals, transition metals, zinc, cadmium and tin aluminum In the chemical sorption reaction process in which polar gas is alternately repeatedly adsorbed and desorbed on a complex formed by adsorbing gas, the present invention relates to a method and apparatus for obtaining a high reaction rate.

Claims (51)

Halides, nitrates, nitrites, oxalates, perchlorates, sulfates of alkali metals, alkaline earth metals, transition metals, zinc, cadmium, tin, aluminum, to form physically coherent and cohesive, even partially Alternately adsorbing and desorbing polar gases to complex compounds formed by adsorbing polar gases to metal salts consisting of sulfite, sodium borofluoride or double metal chlorides, and one or more reactions having a maximum average material diffusion path length of less than 15 mm. And performing a reaction process in a reactor having a chamber, and limiting the volume expansion of said complex compound during a chemical sorption reaction. The process of claim 1 further comprising the step of introducing said metal salt into said reactor such that at least 60% of said salt material is within 25 mm of the gas distribution means in said reactor. 2. The improved chemisorption reaction process of Claim 1, wherein said reaction process is performed in a reactor having a maximum heat diffusion path length of less than 1.5 mm. The method of claim 1, further comprising: determining a chemical sorption process variable and a reaction condition to which the chemical sorption reaction process is to be performed, selecting a metal salt and a polar gas to be used in the chemical sorption reaction process, Determining a predetermined chemical sorption reaction rate for the polar gas, and a thermal diffusion comprising a material diffusion path length consisting of a first reactor dimension for the polar gas from which the predetermined chemical sorption reaction rate is to be obtained and a second reactor dimension. Determining a path length, providing a reactor with the one or more reaction chambers having the first and second dimensions, and a chemisorption reaction relative to a complex having a second density and formed without controlling volume expansion. During the initial sorption reaction to produce a reaction product that can be increased in speed. Performing the chemical sorption reaction in the reactor while controlling the swelling, and performing the reaction process using the complex compound having the second density at the increased reaction rate. Chemical sorption reaction process. The method of claim 1, wherein the zeolite, activated carbon, activated alumina or silica gel, alkali metal, alkaline earth metal, transition metal, zinc, cadmium, tin, halides, nitrates, nitrites, oxalates, perchlorates, sulfates of aluminum Or mixing with a metal salt consisting of sulfite, sodium borofluoride or double metal chloride, injecting a compound of said zeolite, activated carbon, activated alumina or silica gel and said metal salt into a reaction chamber, and the complex compound The polar gas is adsorbed to the mixture while limiting the volume expansion of the reaction product during the reaction process to produce a reaction product which can increase the chemisorption reaction rate compared to the mixture formed without control, and at the increased reaction rate Using the mixture containing the reaction product An improved chemical sorption reaction process further comprising the step of performing the reaction process. The method of claim 1, wherein the zeolite, activated carbon, activated alumina, silica gel or metal chloride is used in the alkali metal, alkaline earth metal, transition metal, zinc, cadmium, tin, aluminum halide, nitrate, nitrite, oxalate, sulfate Or mixing with a metal salt consisting of sulfite, sodium borofluoride or double metal chloride, charging the mixture into the reaction chamber and increasing the reaction rate compared to the complex formed without limiting volume expansion. Adsorbing and desorbing a polar gas to the mixture and forming a complex of the polar gas and the metal salt while limiting the volume expansion of the complex during the reaction process to produce a reaction product, desorbing the polar gas from the complex and Remove polar gas from the reaction chamber; (Purging); and an improved chemical sorption reaction processes charged to the non-polar gas into said reaction chamber and further comprising the step of performing the sorption reactions using said non-polar gas. The chemical sorption reaction process of claim 1, comprising performing the process in a reactor having one or more reaction chambers having a maximum thermal diffusion path length of less than 4.5 mm. 8. The process of claim 7, wherein said metal salt is charged to said at least one reaction chamber at a density between about 0.2 and 1.0 g / cc of reaction chamber volume. The method of claim 8, wherein the complex is SrCl ₂ -1-8 (NH ₃ ), the density is 0.4 to 0.8g / cc, the average material diffusion path length is between 2.5 and 7mm, the thermal path length is Chemical sorption reaction process, characterized in that 0.6 to 2.5mm. The method of claim 8, wherein the complex is CaBr ₂ -2-6 (NH ₃ ), the density is 0.4 to 0.8g / cc, the average material diffusion path length is 3 to 6mm, the thermal path length is 0.6 Chemical sorption reaction process, characterized in that from 3.0 to 3.0mm. The method of claim 8, wherein the complex is CaCl ₂ · 2-4, 4-8 (NH ₃ ), the density is 0.2 to 0.6g / cc, the average material diffusion path length is 2.5 to 6mm, the heat Chemical sorption reaction process characterized in that the path length is 0.6 to 3mm. The method of claim 8, wherein the complex is CaCl ₂ · 0-1, 1-2 (NH ₃ ), the density is 0.2 to 0.7g / cc, the average material diffusion path length is 3 to 6mm, the heat Chemical sorption reaction process characterized in that the path length is 0.6 to 3mm. The method of claim 8, wherein the complex is CoCl ₂ · 2-6 (NH ₃ ), the density is 0.2 to 0.8g / cc, the average material diffusion path length is 2.5 to 6mm, the thermal path length is 0.6 To 3 mm. The method of claim 8, wherein the complex is NiCl ₂ · 2-6 (NH ₃ ), the density is 0.2 to 0,7g / cc, the average material diffusion path length is 3 to 6mm, the thermal path length is Chemical sorption reaction process, characterized in that 0.6 to 3mm. The method of claim 8, wherein the complex is BaCl ₂ 0-8 (NH ₃ ), the density is 0.4 to 0.9g / cc, the average material diffusion path length is 3 to 6mm, the thermal path length is 0.6 Chemical sorption reaction process characterized in that from 3mm. The method of claim 8, wherein the complex is CoCl ₂ · 0-1, 1-2 (NH ₃ ), the density is 0.3 to 0.8g / cc, the average material diffusion path length is 2.5 to 6mm, the heat Chemical sorption reaction process characterized in that the path length is 0.6 to 3mm. The method of claim 8, wherein the complex is LiCl. 0-3 (NH ₃ ), the density is 0.2 to 0.5g / cc, the average material diffusion path length is 2.5 to 6mm, the thermal path length is 0.6 to Chemical sorption reaction process, characterized in that 3mn. The method of claim 8, wherein the complex is SrBr ₂ · 2-8 (NH ₃ ), the density is 0.4 to 0.8g / cc, the average material diffusion path length is between 2.5 and 6mm, the thermal path length is Chemical sorption reaction process, characterized in that 0.6 to 3mm. The method of claim 8, wherein the complex is MnCl ₂ · 2-6 (NH ₃ ), the density is 0.3 to 0.8g / cc, the average material diffusion path length is 2.5 to 6mm, the thermal path length is Chemical sorption reaction process, characterized in that 0.6 to 3mm. The method of claim 8, wherein the complex is CaI ₂ · 2-6 (NH ₃ ), the density is 0.3 to 0.9 g / cc, the average material diffusion path length is 3 to 6mm, the thermal path length is 0.6 Chemical sorption reaction process characterized in that from 3mm. The method of claim 8, wherein the complex is MgCl ₂ · 2-6 (NH ₃ ), the density is 0.3 to 0.8 g / cc, the average material diffusion path length is 2.5 to 6mm, the thermal path length is 0.6 Chemical sorption reaction process characterized in that from 3mm. The method of claim 8, wherein the complex compound is FeBr ₂ · 2-6 (NH ₃ ), the density is 0.4 to 0.8g / cc, the average material diffusion path length is 3 to 6mm, the thermal path length is 0.6 Chemical sorption reaction process characterized in that from 3mm. The method of claim 7, wherein the complex is SrBr ₂ -2-8 (NH ₃ ), the pressure in the reactor during the process is at least 45psia (310 Knm ^-2 ), the density is 0.5 to 1.8g / cc, The average material diffusion path length is 2.5 to 6mm, the thermal path length is chemical sorption reaction process, characterized in that 0.6 to 3mm. The chemical sorption reaction process of claim 1, wherein the reaction is performed in a reactor having a maximum thermal diffusion path length of less than 3 mm. The chemical sorption reaction process of claim 1, wherein the polar gas is ammonia. The chemical sorption reaction process of claim 1, wherein the metal salt is a mixture of two or more of the metal salts. The process of claim 1 wherein the polar gas is ammonia and the reaction process is carried out in a reactor having at least one reaction chamber having a maximum thermal diffusion path length between 0.6 and 3 mm and a maximum material diffusion path length between 2.5 and 7 mm. And the salt is charged into the reaction chamber at an input density of between 0.2 and 0.8 g / cc of the reaction chamber volume. 28. The chemical sorption reaction process of claim 27, wherein the reaction time of each adsorption and desorption cycle is between 3 and 20 minutes each. The chemical sorption reaction process of claim 1, wherein the reaction process is performed at an average reaction rate higher than 6 mole / mol-hr for at least 6 minutes. The method of claim 1, wherein the polar gas is ammonia, and the metal salt is SrCl ₂ , SrBr ₂ , CaCl ₂ , CaBr ₂ , CaI ₂ , CoCl ₂ , CoBr ₂ , BaCl ₂ , BaBr ₂ , MgCl ₂ , MgBr ₂ , FeCl ₂ , FeBr ₂ , NiCl ₂ , ZnCl ₂ , SnCl ₂ , SnBr ₂ , MnCl ₂ , MnBr ₂ , CrCl ₂ , LiCl, or a mixture thereof. The process of claim 1 wherein said polar gas is ammonia and said complex compound adsorbs and / or desorbs at least 20 mg / cc / minute of ammonia during the adsorption or desorption cycle, respectively. The chemical sorption reaction process according to claim 1, wherein the polar gas is ammonia and the complex compound adsorbs and / or desorbs at least 10 mg / cc / minute of ammonia per total reaction chamber volume. The method of claim 1, wherein the polar gas is ammonia, the reaction rate is the following formula: ΔN = ΔN _max (1-e ^-kt ) {In the above formula, ΔN = reaction (moles / mole) ΔN _max = maximum reaction (moles / mole) t = time (sec) k = reaction kinetics (kinetics) value (sec ^-1 )} The reaction is carried out to the reaction degree up to 4.5 moles / mole, the minimum value of k is 0.0004 characterized in that the chemical sorption reaction process. The method of claim 1, wherein the polar gas is ammonia, the reaction rate is the following formula: ΔN = ΔN _max (1-e ^-kt ) {In the above formula, ΔN = reaction (moles / mole) ΔN _max = maximum reaction (moles / mole) t = time (sec) k = reaction kinetics (kinetics) value (sec ^-1 )} The reaction is carried out to the reaction degree between 4.5 and 6 moles / mole, the minimum value of k is 0.0003, characterized in that the chemical sorption reaction process. The method of claim 1, wherein the polar gas is ammonia, the reaction rate is the following formula: ΔN = ΔN _max (1-e ^-kt ) {In the above formula, ΔN = reaction (moles / mole) ΔN _max = maximum reaction (moles / mole) t = time (sec) k = reaction kinetics (kinetics) value (sec ^-1 )} Wherein, the reaction is carried out to a reaction degree higher than 6 moles / mole, the minimum value of k is 0.0002. The process of claim 1 comprising performing the process in a reactor having at least one breathable heat exchange face and distributing the polar gas along a portion of the heat exchange face. The process of claim 1 having at least one breathable heat exchange face in contact with said salt and said complex, said process being carried out in a reactor for distributing said polar gas to said salt and said complex along a portion of said breathable face. Chemical sorption reaction process comprising the step. The method of claim 1, further comprising mixing the metal salt and the breathable mixture composition having a microporous surface, and performing the adsorption and desorption reaction using the mixture, thereby allowing the breathable mixture composition to pass the polar gas to the complex material. Chemical sorption reaction process comprising the step of dispensing. 7. The chemical sorption reaction process of claim 6, wherein the nonpolar gas comprises hydrogen and the adsorbent comprises a metal hydride. The nonpolar gas of claim 6, wherein the nonpolar gas comprises a C ₁ to C ₆ low cost alkane or mixture thereof, helium, argon, hydrogen, oxygen, carbon dioxide, carbon monoxide, NO _x or fluorocarbon refrigerant, and the adsorbent is zeolite, Chemical sorption reaction process comprising activated carbon, activated alumina or silica gel. Adsorption of polar gas to metal salts consisting of alkali metals, alkaline earth metals, transition metals, zinc, cadmium, tin, aluminum halides, nitrates, nitrites, oxalates, perchlorates, sulfates or sulfites, sodium borofluoride or double metal chlorides And at least one reaction chamber having alternating adsorption and desorption of the polar gas to the complex formed by the compound, and having at least a maximum average material diffusion path length of less than 15 mm. And a means for limiting the volume expansion of the complex. 42. The method of claim 41, wherein the reaction chamber has a maximum thermal diffusion path length between 0.6 and 3 mm and a maximum average material diffusion path length between 2.5 and 7 mm, wherein the salt or complex is 0.2 to 0.8 g / Reactor having a density between cc. 42. The reactor of Claim 41 comprising a plurality of heat exchange fins extending along said reactor and in heat transfer relationship with said metal salt, wherein the distance between said fins is no greater than 2.8 mm. 42. The reactor of claim 41 wherein the reaction chamber has a maximum thermal diffusion path length of less than 4.5 mm. 42. The reactor of claim 41 wherein the complex compound or the metal salt has a density between 0.2 and 1.0 g / cc relative to the reaction chamber volume in the reactor. 42. The method of claim 41, comprising gas distribution means for transferring polar gas to and from the metal salt or complex in the one or more reaction chambers, wherein at least 60% by weight of the metal salt or complex is less than 25 mm of the gas distribution means. Reactor characterized in that the range. 42. The reactor of Claim 41 comprising at least one heat exchange surface in thermal contact with said metal salt and said complex compound and comprising a breathable material. 42. The reactor of claim 41, comprising at least one breathable face, wherein the breathable face extends into the reaction chamber in contact with the metal salt and the complex along at least a portion of the breathable face. 42. The reactor of Claim 41 wherein said metal salt and said complex compound comprise a mixture of them and a breathable mixture composition having a microporous surface that each dispenses said polar gas into said mixture. 42. The reactor of claim 41 wherein the reaction chamber has a maximum thermal diffusion path length of less than 1.5 mm. 41. The improved chemisorption reaction process according to any one of claims 1 to 40, wherein the reaction process is carried out with a cycle of adsorption and desorption reactions of up to 30 minutes each.