• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method of manufacturing a dry electrolyte comprising a step of adding conductive liquid to a set of porous particles of resin or ion exchange polymer, preferably by immersing the particles in an excess of conductive liquid. Preferably, the method comprises a step of mixing at least one second liquid with the conductive liquid to be added to the particles, prior or simultaneous to the step of adding liquid to the particles. Preferably, the method comprises a step of cleaning the particles or prior to the step of adding conductive liquid. Preferably, the method comprises a stage of drying or solvent removal prior to or after the addition of conductive liquid, for example by a temperature increase or a flow of air through the particles or the use of a fluidized bed or the use or an absorbent agent. Dry electrolyte that has been produced according to the manufacturing method described. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2734416A1
    申请号:ES201930188
    申请日:2019-02-28
    公开日:2019-12-05
    发明作者:Gimpera Marc Sarsanedas；Hernández Marc Soto
    申请人:Drylyte SL；
    IPC主号:
    专利说明:

    [0001] Method of manufacturing a dry electrolyte and dry electrolyte.
    [0002]
    [0003] Field of the Invention
    [0004]
    [0005] The field of the present invention are the sectors of the industry that require conductive liquids and which with this invention can be replaced by dry electrolytes. As examples and without limitation, electric accumulators and batteries, electrolytic processes, the industrial sector of electro-polishing of metal surfaces among many others.
    [0006]
    [0007] Object of the invention
    [0008]
    [0009] The object of this invention relates to a method for manufacturing a dry electrolyte based on porous particles preferably manufactured by polymers or resins, and also the dry electrolyte produced by this method.
    [0010]
    [0011] Background of the invention
    [0012]
    [0013] In many applications and industry sectors the use of conductive liquids or liquid electrolytes is required. Liquid electrolytes are found in applications as diverse as electric accumulators and batteries, electrolytic processes, and in the electro-polishing sector among many others.
    [0014]
    [0015] Liquid electrolytes are aqueous solutions or other solvents that contain dissolved substances that provide electrical conductivity. In many applications, liquid electrolytes are corrosive, harmful and / or toxic, which poses a danger either by the characteristics of the liquid directly or by the emanation of gases such as for example in liquid electrolytes containing sulfuric acid and hydrochloric acid. This presents serious inconveniences in the handling of these liquid electrolytes, since it poses serious safety problems, both in their preparation and in their use. Similarly, post-life treatment requires special and expensive processes.
    [0016] One of the uses of liquid electrolytes is in the field of electro-polishing of metals. Current electro-polishing technologies warn up to 50% reduction in initial roughness. This implies that parts with high initial roughness must be pretreated with another polishing method to achieve acceptable results, which increases time and overall costs.
    [0017]
    [0018] The same applicant developed a technology to overcome these limitations in the electro-polishing sector. The ES201630542 patent presents a process for smoothing and polishing metals by ionic transport by free solid bodies. Said free solid bodies are described so that they can have a variable shape and dimension and have porosity and affinity to retain a certain amount of liquid.
    [0019]
    [0020] An ion exchange resin or polymer is an insoluble matrix of resin or polymer that has functional groups that allow to trap and release ions from a liquid medium. Its main uses are water softening, water purification, catalysis in organic reactions and in drug preparation.
    [0021]
    [0022] Description of the invention
    [0023]
    [0024] A dry electrolyte comprises a set of porous particles with the ability to retain a certain amount of liquid, and an electrically conductive liquid retained in said particles.
    [0025]
    [0026] The present invention is a method of manufacturing a dry electrolyte characterized in that it comprises a step of adding a conductive liquid to porous particles, that is, with the capacity to retain a certain amount of liquid, made of ion exchange resins or polymers, as well as the dry electrolyte manufactured by said method.
    [0027] An ion exchange resin or polymer is an insoluble matrix of resin or polymer that has functional groups that allow to trap and release ions from a liquid medium.
    [0028]
    [0029] In the usual uses of ion exchange resins such as in water softening, water purification, catalysis in organic reactions or in drug preparation, the resin particles are in a liquid medium.
    [0030] Although ion exchange resins and polymers are widely known and used in various fields, ion exchange resins or polymers have never been used to retain electrically conductive liquids in order to make an electrolyte. The applicant has not found any reference or indication in the state of the art of the use of ion exchange resins and polymers as the basis for producing a dry electrolyte.
    [0031]
    [0032] In addition, a great advantage of the use of ion exchange resins or polymers is the fact that they can be recycled and reused. With the appropriate process it is possible to extract, effluent or remove the contaminating elements from the particles. Recycled particles can be reused, which has the advantage of reducing waste and the environmental impact of its use.
    [0033]
    [0034] The use of ion exchange resins or polymers to retain electrically conductive liquids and produce a dry electrolyte useful for polishing parts in a gaseous medium is new and inventive.
    [0035]
    [0036] Preferably, these ion exchange resins or polymers are derivatives of sulfonated polystyrene or polystyrene-divinylbenzene. On the one hand, the ion exchange resins based on sulfonated polystyrene-divinylbenzene have a high porosity that allows a high retention of liquids inside, which increases the capacity of the dry electrolyte. On the other hand, the ion exchange resins based on sulfonated polystyrene-divinylbenzene by presenting sulfonic functional groups with ionic properties contribute to increasing the conductivity of the retained liquid. Finally, when the dry electrolyte made of ion exchange resins based on sulfonated polystyrene-divinylbenzene is used for electro-polishing, these functional groups retain the metal ions generated in the various processes.
    [0037] In other preferred embodiments, said particles may be based on polymers with carboxylic acid, amino, or ammonium functional groups, among others. These functional groups are capable of retaining generated ions and are active in ion exchange processes.
    [0038]
    [0039] Preferably, the porous particles have a spherical shape. The fact that they are spherical allows a rolling movement of the particle above the surfaces, which results in more contact points and more electrical activity. It is also the geometry that allows to retain more liquid with less external surface.
    [0040]
    [0041] Preferably the spherical porous particles have a size in a range of 0.1 to 1 mm in diameter. In electro-polishing processes, the particle size determines, in part, the level of final polishing. Particles of a larger size are easier to roll, but less penetration into the cavities and occlusions of the pieces to be polished. Particles smaller than a have more penetration, but do not eliminate macro roughness efficiently. Empirically, particles in a range of 0.1 to 1 mm in diameter have the optimal ability to roll on the surface, sufficient penetration in most cases and good effectiveness to eliminate macro and mirco-roughness.
    [0042]
    [0043] The liquid retained in the particles must be electrically conductive. The conductive liquid may be composed of one or more solvents and one or more solutes, dissociated or not.
    [0044]
    [0045] The solvent is preferably a polar solvent, such as without limitation, water, alcohols, DMSO, acetonitrile. Among polar solvents, water is one of the preferred solvents due to its polarity and electrical conductivity.
    [0046]
    [0047] The use of acids as part of the conductive liquid favors the process by increasing conductivity. The proton or hydronium ion (H + or H 3 O +) is the ion with a higher ionic mobility in water and other solvents. Therefore, conductive liquids with the presence of acids, which increase the amount of protons in the medium, have the effect of increasing the electrical conductivity. Among the acids, it is preferably the use of strong acids (pAa <2) since they are more dissociated, so they have a higher electrical conductivity.
    [0048] The amount of conductive liquid needed to prepare the dry electrolyte has to be within a range. The minimum amount of conductive liquid is that which allows a measurable electrical conductivity through the dry electrolyte. The maximum amount of conductive liquid must be below the saturation point of the resin.
    [0049]
    [0050] The saturation point of the ion exchange resin is defined as the point at which the resin does not admit more liquid. Above this point, adding more liquid would generate the presence of free liquid, that is, not retained by the resin, and therefore, would not be a "dry" electrolyte. Having the conductive liquid retained in the particles, and therefore having no free liquid, significantly increases the safety of dry electrolytes versus conventional liquid electrolytes. In this case the risks of spillage and chemical burns are reduced. For example, dry electrolytes containing sulfuric acid do not produce negative effects on the skin in short periods of contact. Furthermore, it has been empirically proven that the emanation of gases is reduced in comparison to a liquid electrolyte, since in the case of the present invention the liquid is retained within the particles and their pores. For example, no detectable gas emanates from dry electrolytes containing hydrochloric acid.
    [0051]
    [0052] Preferably the amount of conductive liquid is close, but below the saturation point.
    [0053]
    [0054] The amount of liquid depends on each case, the liquid used, the type of resin, the temperature, etc., so it must be determined empirically in each formulation. For example, the optimum amount of conductive liquid in relation to an AMBERLITE 252RFH ion exchange resin is between 40 and 50%.
    [0055]
    [0056] The method of manufacturing a dry electrolyte includes a step of adding the conductive liquid in the ion exchange resin or polymer. This process of addition can occur in one stage or in several, depending on the liquid.
    [0057]
    [0058] For example, when the conductive liquid is hydrochloric acid, it is added quickly and therefore can be carried out in a single stage. On the contrary, when the conductive liquid is methanesulfonic acid, the addition of the conductive liquid must be carried out in several stages to ensure rapid addition since in case If the liquid is added in a single stage, the surfaces of the resin or polymer particles become saturated and delay the impregnation of the interior of the particular.
    [0059] In a preferred embodiment there is a stage of mixing different liquids (at least one is electrically conductive) prior to the step of adding the liquid to the ion exchange resin or polymer particle. On certain occasions when the conductive liquid to be added to the particle causes a slow addition (for example, an acid), it is interesting to add a liquid (for example, water) to improve the rapidity of the addition of the conductive liquid. The mixing stage may be prior or simultaneous to the step of adding the conductive liquid to the particle.
    [0060] In a preferred embodiment, the step of adding the conductive liquid in the ion exchange resin or polymer is carried out by immersion of the ion exchange particles with a certain amount of conductive liquid, so that the particles are immersed in an excess of free liquid.
    [0061]
    [0062] The ion exchange mixture with the conductive liquid, preferably, is allowed sufficient equilibrium time so that the free liquid and the retained liquid have the same composition. During the equilibrium time the mixture is preferably stirred to favor the equilibration of the liquids. During the equilibrium time, the mixture should preferably be at a temperature above room temperature, for example at 60 ° C, in order to increase the exchange of liquids with the gel phase of the resin.
    [0063]
    [0064] The final composition of the mixture can be calculated considering the amount of liquid retained in the particles initially and the amount and composition of the conductive liquid.
    [0065] This process ensures a complete and homogeneous impregnation of the particles, which results in greater homogeneity in their conductivity.
    [0066]
    [0067] The manufacturing method also preferably comprises a step of cleaning the ion exchange resin or polymer prior to the step of adding the conductive liquid.
    [0068]
    [0069] During the production process of ion exchange resins or polymers, the formation of oligomers that are not part of the resin or polymer is inevitable. Commercially available are ion exchange resins or polymers containing these oligomers. These oligomers can have negative effects on processes in which dry electrolytes are used, so a resin cleaning step is preferred.
    [0070]
    [0071] The process of preparing a dry electrolyte can include a first step of cleaning the resin. This cleaning process can be a solid-liquid extraction process, in which a solvent removes soluble elements from the resin. Although other solvents can be used, preferably, the solvent to be used is water. The water or solvent used can be in neutral, acidic or basic conditions, at room temperature or at high temperature to increase the solubility of the impurities and thus drag the different types of impurities more easily.
    [0072]
    [0073] The manufacturing method preferably comprises a stage of drying or removing the excess solvent before or after the step of adding the conductive liquid.
    [0074]
    [0075] The dry electrolyte preparation process may include one or more drying steps to reduce the amount of water or solvent present in the ion exchange resin and thus prevent the particles from getting caught.
    [0076]
    [0077] The drying stage or stages may occur before and / or after the conductive liquid addition stage.
    [0078]
    [0079] This drying process can be carried out, for example, mechanically by filtration, centrifugation, thermally, by conduction, by a stream of air or gas, with a fluidized bed, using vacuum, among many other solvent removal methods. It is also possible to use a combination of the above methods, either simultaneously or sequentially. In the event that the conductive liquid contains a volatile or gas-generating compound, if there is a drying process, it will preferably take place prior to the addition of the conductive liquid. For example, if the liquid is hydrochloric acid, subsequent drying eliminates hydrochloric acid before water.
    [0080]
    [0081] Drying prior to the liquid addition stage is to empty the resin or polymer particle from the liquid that it could contain and thus enable subsequent filling of the particle with conductive liquid.
    [0082]
    [0083] Drying after the liquid addition stage is to remove excess liquid and leave the electrolyte at the appropriate point of humidification and rheology. That is to say, a point where the particles have no surface wetting. To achieve this purpose, a suitable method is to contact the particles with excess liquid electrolyte with an absorbent agent, a certain contact drying time and a separation of the particles from the absorbent agent. Said absorbent agent may be particles, powders, granules, tissues, gels, among others.
    [0084]
    [0085] In a preferred embodiment, said absorbent agent is dry or partially dried absorbent particles of a size significantly different from the size of the particles to be dried. Thus, the process of separating electrolyte charged particles from the absorbent agent can be a separation by size.
    [0086] In a preferred embodiment said absorbent agent is dry or partially dry ion exchange particles. Preferably, the minimum necessary of dry or partially dry ion exchange particles is used to remove excess liquid, in this way it is possible to ignore the step of separating the absorbent agent.
    [0087] If the dry electrolyte manufacturing method comprises a cleaning stage, a drying stage and an addition stage of the conductive liquid in this order and also the conductive liquid to be added to the particle contains the same solvent used in the process For cleaning, the amount of solvent to be removed from the particle in the drying stage can be adjusted with the amount of solvent to be added to the particle in the addition stage. For example, less solvent could be removed and a more concentrated solution added thus reducing the preparation time and energy of the dry electrolyte.
    [0088]
    [0089] As explained in this description, dry electrolytes based on ion exchange resins, as well as the method for their preparation, are non-obvious inventions that imply an improvement on the current state of the art and have a wide range of applications.
    [0090]
    [0091] Example of embodiment of the invention
    [0092]
    [0093] Example of a step of cleaning the ion exchange resin
    [0094] 3 L of distilled water are added to 3 kg of AMBERLITE 252RFH ion exchange resin. The temperature of the mixture is raised to 100 ° C and maintained for 20 minutes. The resin is filtered and the process is repeated another three times.
    [0095]
    [0096] Example of a stage of drying or solvent removal of the ion exchange resin prior to the step of adding the conductive liquid.
    [0097]
    [0098] 12.1 kg of ion exchange resin above its saturation point after being cleaned using distilled water are placed in a heated vessel provided with a stream of hot air with rotational movement and temperature control of the resin. When the temperature of the resin reaches 100 ° C, the resin is removed from the system, it is allowed to cool and 7.2 kg of ion exchange resin is obtained, which is equivalent to a removal of 4.9 kg of water.
    [0099]
    [0100] Example of the step of adding the conductive liquid to the ion exchange resin
    [0101] 60 kg of clean and partially dry ion exchange resin are placed in a container with mechanical agitation. To the resin is added in a single quick addition 19.6 L of 35% methanesulfonic acid in water. After a period of intense homogenization 81 kg of dry electrolyte are obtained.
    [0102]
    [0103] Example of the step of adding the conductive liquid by immersion and drying stage with particle of different size
    [0104]
    [0105] 4.3 kg of 0.7 mm medium diameter exchange resin washed with distilled water and partially dried are placed in a vessel equipped with mechanical stirring and heated to 60 ° C. To the resin is added 3.6 kg of 70% methanesulfonic acid in water. This results in a resin mixture impregnated with an excess of liquid solution. This mixture is kept under stirring at 60 ° C for 6 h so that a balance is produced between the liquid retained inside and the solution of the surrounding medium. After this time the resin is filtered and left under an air flow to remove the liquid. At this point the resin is slightly above the saturation point. Final drying is achieved by mixing this resin with a resin of Dry ion exchange of medium diameter 0.2 mm in a container provided with vigorous vibration to favor contacts between the two resins and that the dry resin absorbs the excess surface liquid of the impregnated resin. After 30 minutes of vibration, the resins of two different sizes are separated by sieve. After this procedure the impregnated resin is just below the saturation point. With this procedure a homogeneously impregnated resin is obtained both inside and in the part closest to the surface and at an optimum wetting point, that is, close but below the saturation point.
    [0106]
    [0107] Example of the step of adding the conductive liquid by immersion and drying stage with ion exchange particle
    [0108]
    [0109] 4.1 kg of 0.7 mm medium diameter exchange resin washed with distilled water are placed in a vessel equipped with mechanical stirring and heated to 60 ° C. The resin is added with 3.9 kg of 70% methanesulfonic acid in water. This results in a resin mixture impregnated with an excess of liquid solution. This mixture is kept under stirring at 60 ° C for 4 h so that a balance occurs between the liquid retained inside and the solution of the surrounding medium. After this time the resin is filtered and left under an air flow to remove excess liquid. At this point the resin is slightly above the saturation point. To this resin is added 720 g of dry ion exchange resin, mixed and stirred. After 12 h a dry electrolyte is obtained at an optimum wetting point.
    权利要求:
    Claims (12)
    [1]
    1. Method of manufacturing a dry electrolyte characterized in that it comprises a step of adding conductive liquid to a set of porous particles of resin or ion exchange polymer.
    [2]
    2. Method of manufacturing a dry electrolyte according to claim 1 characterized in that during the step of adding conductive liquid the porous particles are immersed in an excess of conductive liquid.
    [3]
    3. Method of manufacturing a dry electrolyte according to any of the preceding claims, characterized in that it comprises a stage of mixing at least one second liquid with the conductive liquid to be added to the particles, prior or simultaneous to the step of adding the conductive liquid to the set of ion exchange resin or polymer particles.
    [4]
    4. Method of manufacturing a dry electrolyte according to any of the preceding claims, characterized in that it comprises a step of cleaning the particles of the ion exchange resin or polymer prior to the step of adding the conductive liquid.
    [5]
    5. Method of manufacturing a dry electrolyte according to claim 4 characterized in that the step of cleaning the ion exchange resin or polymer includes a solids extraction by means of a liquid.
    [6]
    6. Method of manufacturing a dry electrolyte according to any of the preceding claims, characterized in that it comprises a drying or solvent removal stage before or after the addition of conductive liquid.
    [7]
    7. Method of manufacturing a dry electrolyte according to claim 6 characterized in that the step of drying or solvent removal includes an increase in temperature.
    [8]
    8. Method of manufacturing a dry electrolyte according to any one of claims 6 to 7, characterized in that the step of drying or solvent removal includes a flow of air through the particles.
    [9]
    9. Method of manufacturing an electrolyte according to any of claims 6 to 8, characterized in that the drying or solvent removal process includes the use of a fluidized bed.
    [10]
    10. Method of manufacturing an electrolyte according to any of claims 6 to 9, characterized in that the drying or solvent removal process includes the use of an absorbent agent.
    [11]
    11. Method of manufacturing an electrolyte according to claim 10 characterized in that the absorbent agent is totally or partially dry ion exchange particles.
    [12]
    12. Dry electrolyte characterized in that it has been produced according to any of the preceding claims.
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    同族专利:
    公开号 | 公开日
    ES2734416B2|2020-09-16|
    WO2020174112A1|2020-09-03|
    TW202033279A|2020-09-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3015681A|1958-11-06|1962-01-02|Hamilton Watch Co|Primary cell|
    US20110300778A1|2009-02-16|2011-12-08|Hitachi Chemical Company, Ltd.|Abrading agent and abrading method|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201930188A|ES2734416B2|2019-02-28|2019-02-28|METHOD OF MANUFACTURING A DRY ELECTROLYTE AND DRY ELECTROLYTE|ES201930188A| ES2734416B2|2019-02-28|2019-02-28|METHOD OF MANUFACTURING A DRY ELECTROLYTE AND DRY ELECTROLYTE|
    PCT/ES2020/070134| WO2020174112A1|2019-02-28|2020-02-25|Method for producing a dry electrolyte and dry electrolyte|
    TW109106149A| TW202033279A|2019-02-28|2020-02-26|Method for producing a dry electrolyte and dry electrolyte|
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