• 专利附录
  • 专利说明
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    • 专利摘要:

    公开号:ES2765198T9
    申请号:ES13708739T
    申请日:2013-02-28
    公开日:2020-08-19
    发明作者:Stéphane Villalonga；Fabien Nony；Jean-Luc Yvernes；François Garonne
    申请人:Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] High pressure storage tank lined with fire protection material, processes for preparing it, and its uses
    [0002] Technical area
    [0003] The present invention relates to the technical field of high pressure storage tanks and, more particularly, to the field of fire protection of such tanks.
    [0004] In fact, the present description discloses a material for the protection against fires of a high pressure storage tank, said material being a thermosetting elastomeric resin matrix comprising endothermic fillers.
    [0005] The present invention relates to a high pressure storage tank lined with said material, a process for preparing the coated material or tank and its uses.
    [0006] Prior state of the art
    [0007] Although flame retardants do not offer absolute protection against fire, they have played and continue to play an important role in reducing the occurrence and intensity of fires.
    [0008] Flame retardants are an important family in the plastic additives and textile processing business, with over $ 4 billion in estimated sales for 2008. Flame retardants are the fastest growing family of plastic additives in the world ( de Amico, E., Chem. Week (2008) (13/20 October), p23). Today, there are many flame retardant products, such as fire retardant fillers, intumescent systems or inert materials, from many suppliers (for example, more than a hundred are mentioned in the book "Flame Retardants for plastics and textiles - Practical applications" by Edward D . Weil), as well as many applications.
    [0009] However, there is little work done for high pressure storage tanks subjected to several hundred bars. The state of the art has few means and processes implemented to protect against fires and fires of such tanks.
    [0010] However, the international application WO 99/03792 entitled "Methods of making high-temperature glass fiber and thermal protective structures" published on January 28, 1999 focuses on fire protection in storage tanks. The invention described herein relates to a glass fiber capable of withstanding temperatures in excess of 1900 ° F (ie, 1038 ° C), produced by treating a glass fiber with acids and then with an organometallic material. Other fire-resistant materials are based on the principle of bonding or incorporating into a substrate surface a pre-induced fabric of an active material (intumescent or sublimation). Patent US4405425 describes the production of a material by extrusion of a fire resistant silicone elastomer.
    [0011] International application WO 97/17570 proposes a storage tank whose structure comprises an internal bladder and a fiber-reinforced resin envelope, said resin being optionally a silicone resin. The tank is expected to be fire retardant through a suitable choice of the materials that constitute it or through the use of appropriate additives.
    [0012] Utility model AT 001849 describes a tank for pressurized gas at least partially covered with a protective non-porous polyurethane layer that may contain flame retardants.
    [0013] Therefore, there is a real need for a material and processes to protect high pressure storage tanks from fire, which is easy to implement and which takes into account the limitations related to this type of tanks, such as storage cycles and filling / emptying.
    [0014] Presentation of the invention
    [0015] The inventors have solved the above technical problem by formulating a fire protection material and its realization for fire protection of high pressure storage tanks, as well as a contribution to shock protection and better integration in a storage system.
    [0016] More particularly, the present disclosure describes a fire resistant material comprising a thermosetting elastomeric resin matrix in which endothermic fillers are incorporated. Advantageously, the fire-resistant material consists only of a thermosetting elastomeric resin matrix in which endothermic fillers are incorporated.
    [0017] With this material, the present invention not only allows to provide thermal protection to the high pressure storage tank in which the material is placed, but also to provide additional protection against impacts and offer great freedom in the external shape that can be used to optimize the integration of the block (tank and protection) in the storage object. Therefore, the formulation of the material used in the invention allows the latter to have a triple function, a main function of thermal protection and two complementary and implicit functions of protection against shock and adaptability to have the best possible integration of the tank in a system. storage.
    [0018] By "thermosetting elastomeric resin matrix" is meant the base portion of the material used in the invention that shapes the latter.
    [0019] The concept of "thermosetting elastomeric resin" refers to a property of the resin / polymer that is reversibly deformable and that does not suffer damage such as fractures, non-elastic deformations or ruptures, when deformed and when cross-linked, resulting in a material insoluble and infusible.
    [0020] In the context of the present invention, the thermosetting elastomer resin matrix used is a silicone resin.
    [0021] Advantageously, the thermosetting elastomeric resin matrix implemented in the invention has a thickness between 100 µm and 10 cm, in particular between 500 µm and 5 cm and, in particular, between 900 µm and 2 cm.
    [0022] The advantages of the material used in the invention that are the consequence of the realization of a silicone resin matrix are numerous. As examples of such advantages, the following may be mentioned:
    [0023] - a high charge rate to incorporate a controllable and adjustable amount of endothermic charges;
    [0024] - an adjustable protection thickness and external shape to select the resistance time of the material and the capacity of the tank to be manipulated and integrated with the storage systems;
    [0025] - a monobloc structure that does not require assembly or union;
    [0026] - a simple embodiment that allows to easily have any type of conformable geometries and industrial rates thanks to molding in a mold or injection at high pressure into a mold of the formulation according to the invention;
    [0027] - resistance to fatigue cycles of high pressure storage tanks due to its flexibility;
    [0028] - a facility to repair, remove, cut, re-paste, replace or replace.
    [0029] Furthermore, a silicone resin has the advantage of being non-combustible. Therefore, under the effect of heat, this resin degrades and turns into glass but does not burn.
    [0030] In the material used in the present invention, endothermic fillers are incorporated, introduced, dispersed, coated and / or encapsulated in the thermosetting elastomeric resin matrix as defined above. An endothermic filler is a compound that, under the effect of heat, reacts chemically, producing, more frequently, water and thus cooling the structure. The volatile products of this chemical reaction also slow combustion by reducing the amount of flammable mixtures. Such a charge is also known as a "flame retardant".
    [0031] Any endothermic filler known to those skilled in the art can be used in the context of the present invention. However, during the performance of the present invention, those skilled in the art will prefer to avoid flame retardants that emit toxic fumes.
    [0032] The endothermic fillers used in the context of the present invention, in particular, can be selected from aluminum trihydroxide (ATH), disodium tetraborate decahydrate (or borax), trisodium phosphate dodecahydrate, magnesium dihydroxide (or brucite), colemanite, a melamine monophosphate, a melamine pyrophosphate, melamine polyphosphate, zinc borate, hydromagnesite, tripolyphosphate (TPP), resorcinol bis (diphenylphosphate) (RDP), bisphenol-A bis (biphenylphosphate) (BPADP) and mixtures thereof.
    [0033] More in particular, the endothermic fillers used in the context of the present invention are aluminum trihydroxide (ATH).
    [0034] The user will define the amount of endothermic fillers in function, knowing that the use of a thermosetting elastomeric resin matrix makes it possible to use both low and large amounts of endothermic fillers. Advantageously, the amount of endothermic loads expressed by weight with respect to the total weight of the thermosetting elastomer resin material is between 10% and 90%, especially between 15% and 80% and, in particular, between 40%. and 70%.
    [0035] The present invention relates to a process for preparing a fire resistant material for a high pressure storage tank. This process as defined in claims 1 to 3 comprises the following steps:
    [0036] a) preparing a mixture comprising at least one thermosetting elastomeric resin precursor (ie, silicone resin precursor) and at least one endothermic filler;
    [0037] b) optionally degassing the mixture obtained in step (a);
    [0038] c) adding to the mixture obtained in step (a) or degassed mixture obtained in step (b), an agent to obtain from said precursor said thermosetting elastomeric resin;
    [0039] d) optionally degassing the mixture obtained in step (c);
    [0040] e) shaping the mixture obtained in step (c) or the degassed mixture obtained in step (d), whereby a material according to the present invention is obtained.
    [0041] During step (a) of the process according to the present invention, the skilled person will be able to determine which precursor or precursors to implement depending on the thermosetting elastomeric resin sought, the load or loads used, the loading speed and the envisaged shaping process, such as, by way of non-limiting examples, vacuum assisted casting, injection and transfer. Said precursor can be a monomer, a mixture of different monomers, an oligomer, a mixture of different oligomers, a prepolymer, a mixture of different prepolymers, a non-cross-linked polymer, a mixture of different non-cross-linked polymers or one of their mixtures.
    [0042] Furthermore, in the mixture prepared in step (a) of the process according to the invention, the endothermic fillers are advantageously added to the thermosetting elastomeric resin precursors. More particularly, they are progressively incorporated to obtain the most homogeneous dispersion possible.
    [0043] The precursors of the thermosetting elastomeric resin are advantageously used, in stage (a) of the process according to the invention, in liquid form. When several precursors of the various thermosetting elastomer resins are used, they can be mixed at once or they can be added one after the other or in groups, to form a first mixture in which the endothermic filler (s) are added.
    [0044] Similarly, the endothermic filler or fillers can be used during step (a) of the process according to the invention, in solid form or in liquid form.
    [0045] Mixing during step (a) is carried out with stirring using a mixer, and at room temperature (ie 23 ° C ± 5 ° C).
    [0046] The mixture obtained after step (a) can be in liquid or pasty form. Advantageously, the mixture obtained after step (a) is a liquid mixture.
    [0047] Optional degassing during step (b) allows to remove, if necessary, the air introduced during step (a) in the liquid mixture.
    [0048] Any technique known to those skilled in the art can be used to degas a solution during step (b) of the process according to the present invention. Advantageously, degassing during stage (b) of the process according to the present invention is selected from degassing under vacuum, in particular by putting the mixture from stage (a) under reduced pressure, stirring under reduced pressure and / or sonicating under reduced pressure; ultrasonic degassing of the mixture from step (a). More in particular, degassing during step (b) of the process according to the present invention is vacuum degassing.
    [0049] Everything that has been previously indicated for the degassing of step (b) of the process according to the invention applies mutatis mutandis to the degassing of step (d) of this same process.
    [0050] During step (c) of the process according to the present invention, a person skilled in the art will be able to determine which agent or agents to use depending on the desired thermosetting elastomer resin and the precursor or precursors used in step (a). Said agent can be a polymerization catalyst, a polymerization activator, a cross-linking agent or a mixture thereof.
    [0051] The agents used in step (c) of the process according to the present invention can be used, in liquid form or in solution in a suitable solvent. When several different agents are used, they can be mixed together before adding them to the mixture obtained in step (a) or step (b) or added one after the other or in groups to the mixture obtained in step (a) or step (b).
    [0052] Mixing during step (c) is carried out with stirring using a mixer or homogenizer, and at room temperature.
    [0053] The mixture obtained after step (c) or after step (d) is called in this document "formulation" and it differs from the material used in the present invention in that it is not shaped.
    [0054] Stage (e) of the process according to the present invention corresponds to this conformation. The latter is advantageously carried out by pouring into a mold the mixture obtained in step (c) or the degassed mixture obtained in step (d) or by injecting the mixture obtained in step (c) or the mixture under pressure into a mold. degassed obtained in step (d) or vacuum assisted transfer in a mold of the mixture obtained in step (c) or the degassed mixture obtained in step (d). The molds used may allow the entire tank to be covered with the formulation in a single stage (full mold) or only half the tank to be covered, requiring the repetition of stage (e) for the other half of the tank is covered. Despite the repetition of step (e), this variant offers the advantage of easy demoulding.
    [0055] These high pressure casting or injection techniques or vacuum assisted transfer are techniques known to those skilled in the art. Step (e) of the process makes it possible to give the material used in the invention the desired external shape. The latter is completely modular, for example a coating of substantially identical thickness and conforming to the external shape of the tank to be protected, or to locally protect sensitive areas with greater thicknesses or, alternatively, a parallelepiped adapted to fit tanks protected against one another and advantageously fill the free space by means of the formulation that in fact confers a greater resistance to fire, shocks and vibrations.
    [0056] Furthermore, high pressure casting or injection techniques or vacuum assisted transfer are cold (liquid channel) techniques without heating that allow the material used in the invention to be used in the form of an additional coating or coating that includes a tank and , in particular, a high pressure storage tank.
    [0057] The present disclosure describes the use of a material implemented in the present invention or capable of being prepared according to a process according to the invention to protect a fire resistant high pressure storage tank.
    [0058] For the purposes of the present invention, the term "high pressure storage tank" is intended to mean a tank containing a fluid under pressure and, in particular, a gas under pressure. Said tank is a type IV composite tank.
    [0059] "High pressure" means a fluid and in particular a gas at a pressure greater than atmospheric pressure, especially greater than 100 bar (10 MPa), preferably greater than or equal to 200 bar (20 MPa) and, in particular, between 200 and 2000 bar (20-200 MPa). The gas stored in the tank according to the invention is in particular natural gas, compressed air, a neutral or inert gas, nitrogen, argon, hydrogen gas, helium, oxygen or one of their mixtures.
    [0060] The term "protect from fire" or "protect against fire" means that the material used in the present invention makes it possible to protect the storage tank under high pressure during a fire to delay or even prevent its explosion.
    [0061] The present invention further relates to a high pressure storage tank of which only a part of the outer surface is covered with a fire resistant material as defined above or which can be prepared according to a process as defined above. . This storage tank is as defined in claims 4 to 7.
    [0062] In a first embodiment, it is not part of the invention, the entire external surface of the high pressure storage tank is covered or lined with a material used in the invention. By "material used in the invention" is meant both a fire resistant material as defined above and a material that can be prepared according to a process as defined above.
    [0063] In a second embodiment that forms part of the invention, only a part of the external surface of the high pressure storage tank is covered or lined with a material used in the invention.
    [0064] In this second embodiment, the area or areas not covered by the material used in the invention are left as is, that is, uncoated or covered with a different material from the material used in the invention, which is a fusible material. Therefore, in the context of the present invention, part of the external surface of the high pressure storage tank is covered with a fusible material.
    [0065] By "fusible material" is meant a material, also known as "hot-melt material", that is capable of liquefying, that is, of melting under the action of heat and / or that has a relatively low melting point. Said material is therefore unable to protect the wall of the high pressure storage tank from heat. Different fusible materials are known to those skilled in the art that can be used in the context of the present invention. Particular examples of such fusible materials include thermoplastics and low melting metal alloys or compounds. In particular, the fusible materials will be chosen from thermoplastic materials with a low melting point, such as polyolefins and, more in particular, polyethylene.
    [0066] On the surface of the high-pressure storage tank, the zones of fusible material may be arranged randomly or in the form of bands parallel to or intersecting on the axis or on the circumference of the tank. Figure 1 presents different possibilities regarding the arrangement of the fusible material on the surface of a tank according to the invention.
    [0067] This second embodiment offers the advantage, particularly in the case of storage tanks whose structure is made of one or more fusible materials, of increasing the protective effect of the material used in the invention by further preventing or delaying the bursting of the tank. In fact, in the event of a fire, the areas where the coating (or coating) is not protective (i.e. areas without coating or with a coating of fusible material) and most exposed to heat melt or degrade rapidly. Therefore, the tank wall can be locally attacked by fire, allowing it to degrade and / or melt locally and consequently the tank can leak faster through these areas while minimizing the risks of mechanical explosion. The rest of the coating material used in the invention is protective and makes it possible to delay the increase in pressure in the tank.
    [0068] Given that the material used in the invention covers part of the surface of the high pressure storage tank and that this surface also has areas of coating with a fusible material, the tank can be additionally covered with one or more additional protections, the latter being arranged over all or part of the material used in the invention and / or all or part of the fusible material.
    [0069] Therefore, all or part of the outer surface of the tank according to the present invention (that is, coated with the fire-resistant material used in the invention and eventually fusible material) is further covered with an intumescent product such as a paint. or an intumescent varnish. An intumescent product swells with heat at temperatures above 200 ° C. Thus, it makes it possible to protect the underlying layers, including the tank, from thermal radiation. The total protection time also depends on the thickness deposited and the thermal power received by the protection. There is a synergy between the use and the structuring of the charges used, that is, a synergy between the material used in the present invention and the intumescent product. By "intumescent product" is meant, in the context of the present invention, an intumescent varnish, paint or coating.
    [0070] Generally, an intumescent system consists of three ingredients which are (1) an acid source that promotes dehydration of the char; (2) a carbonizing agent, usually a macromolecule that has hydroxyl groups and (3) a blowing agent, which decomposes and releases a neutral gas, leading to the expansion of the polymer, the main component of the paint or varnish already the formation of a layer composed of many hollow cells.
    [0071] Any product known to those skilled in the art can be used in the context of the present invention. By way of illustrative and non-limiting examples, mention may be made of the products marketed by Artech, Chenguang, Clariant, Comus, Dahiachi, Thermal Science Inc., Innovative Fire Systems, Comus®, ITAC or Lurie.
    [0072] Also in the case of a tank covered with a material used in the present invention and an intumescent product, at least one zone of the intumescent product is replaced by a fusible material as defined above. Advantageously, at least one area of the fire-resistant material and at least one area of the intumescent product are replaced by an identical fusible material or by different fusible materials. In particular, at least one zone of the fire-resistant material replaced by a fusible material and at least one zone of the intumescent product replaced by a fusible material are superimposed. More particularly, all areas of the fire resistant material replaced by a fusible material and all areas of the intumescent product replaced by a fusible material overlap two by two.
    [0073] The presence of a fusible material together with a fire-resistant material eventually coated with an intumescent product provides greater protection for high-pressure storage tanks. This increased tank protection allows the thermal fuses in the storage system to significantly increase its reliability by providing a wider release range to depressurize the tank and prevent any explosion.
    [0074] Alternatively, all or part of the outer surface of the tank according to the present invention is further covered with an insulating and fire resistant material and, in particular, with a fabric or sock made of insulating material inert to fire. In fact, said material is not flammable, it is insulating and can be used over the material used in the present invention to maximize the fire protection of the tank. It can also be used in all or part of the tank in which at least part is coated with the material used in the present invention. The fire-inert insulation material layer can also be covered with an intumescent layer of product.
    [0075] As the insulating material inert to fire, basalt, mica, glass, carbon and silica can be mentioned. The insulating material inert to fire used in the context of the present invention is produced from fibers of said material, such as, for example, silica wool.
    [0076] A first alternative is to cover, with fabrics of fire-inert insulating material, the tank covered with the material used in the invention and, optionally, add an intumescent product to the fire-inert insulating material. Fabrics of fire-inert insulation material are cut to fit the shape of the tank and then wrapped around the tank. They can be sewn to stay around the tank or kept with rings.
    [0077] A second embodiment consists in producing a sock of insulating material inert to fire and, once manufactured, putting it around the tank. Using a sock allows you to completely cover the tank and stay in contact. In addition, it can be easily removed and / or changed.
    [0078] Any product based on the fire-inert insulation material known to those skilled in the art can be used in the context of the present invention. As illustrative and non-limiting examples, mention may be made of the products sold by Industries 3R Inc.
    [0079] Like the intumescent product, the fire-inert insulating material plays a synergistic role with the fire-resistant material, eventually combined with a fusible material in the fire protection of the high pressure storage tank.
    [0080] In summary, a storage tank according to the present invention can be:
    [0081] - a high pressure storage tank covered, in part, by a fire resistant material used in the present invention and the area or areas not covered by the fire resistant material used in the invention are covered by a fusible material as has defined above;
    [0082] - a high pressure storage tank covered, in part, by a fire resistant material used in the present invention and the area or areas not covered by the fire resistant material used in the invention are covered by a fusible material as has defined above; the tank thus lined is covered, totally or partially, by an intumescent product as defined above;
    [0083] - a high pressure storage tank covered, in part, by a fire resistant material used in the present invention and the area or areas not covered by the fire resistant material used in the invention are covered by a fusible material as has defined above; the tank thus covered is covered, totally or partially, with an insulating material inert to fire as defined above;
    [0084] - a high pressure storage tank covered, in part, by a fire resistant material used in the present invention and the area or areas not covered by the fire resistant material used in the invention are covered by a fusible material as has defined above; the tank thus covered is covered, totally or partially, with an insulating material inert to fire as defined above; the insulating material inert to fire is covered, totally or partially, by an intumescent product as defined above.
    [0085] The present invention provides the skilled person with an adjustable architecture according to the specifications of the tank with the use of the fire resistant material used in the invention and at least one other material selected from the intumescent product, the insulating material inert to fire and the material fuse as described. previously defined. The present invention also relates to a process for preparing a fire protected storage tank as defined above. This process according to claims 8 to 12 can be implemented in a high pressure storage tank empty or previously filled by the fluid and in particular the gas under pressure.
    [0086] Therefore, the process according to the present invention comprises a step of applying, on only a portion of the surface of the high pressure storage tank, a fire resistant material as defined above or prepared according to a process as defined above. The application of the fire resistant material advantageously corresponds to step (e) as defined above.
    [0087] The process according to the present invention may further comprise an additional step of applying, on all or part of the surface of the tank coated with the fire resistant material used in the present invention, an intumescent product as defined above. This application can be implemented by brush, roller, steamer or spray.
    [0088] The process according to the present invention may comprise an additional step of replacing at least one area of the fire resistant material optionally coated with intumescent material with a fusible material. Three different variants can be envisaged for this additional step.
    [0089] In a first embodiment, after the application of the fire-resistant material and, eventually, after the application of the intumescent product, the tank of which only a part of the surface is covered with a layer of fire-resistant material and, eventually, an additional layer of intumescent product can undergo a treatment to eliminate one or more areas of fire-resistant material possibly covered with an intumescent product and eventually replace them with a fusible product as defined above. Therefore, after the application of the fire-resistant material and eventually after the application of the intumescent product, at least a zone of the fire-resistant material optionally coated with the intumescent product is removed and eventually replaced by a fusible product. Given the nature of the fire resistant fusible material, removal during this stage is done simply by cutting the material eventually coated with an intumescent product.
    [0090] Those skilled in the art will know how to choose the fusible product application technique to replace the removed areas. By way of illustrative and non-limiting examples, mention may be made of a brush, roller, sprayer or the application of a fabric coated with a fusible material as defined above.
    [0091] In a second embodiment, before the application of fire-resistant material and, eventually, before the application of an intumescent product, the tank can be pre-treated to occupy one or more areas of its surface with a fusible product as defined above. .
    [0092] Given the nature of the fire resistant fusible material, the addition of the fusible material during this stage is done by simple pouring or by melting the fusible material. Those skilled in the art will know how to choose the technique of application of the fusible product in the selected areas. By way of illustrative and non-limiting examples, mention may be made of an embodiment of the fusible material by joining one or more cut pieces to the desired shape, melting, injecting or transferring the fusible material in a mold to the desired shape.
    [0093] Once the fusible material is placed, the areas of the tank not covered by the fusible material are covered with a layer of fire resistant material and, eventually, an additional layer of intumescent product.
    [0094] In a third embodiment, before applying the fire resistant material and eventually before applying the intumescent product, the tank can be pre-treated to occupy one or more areas of its surface by a product other than a fusible product. This product acts as a mask and is advantageously selected so that it does not have any affinity with the tank surface, which facilitates its subsequent removal. By way of example, said mask can be a piece or a strip of fabric.
    [0095] Once the mask is fitted, the areas of the tank not covered by this mask are covered with a layer of fire resistant material and, eventually, an additional layer of intumescent product. The mask is then removed by pulling or removing it, thus freeing an area which is then filled with fusible material as described above and as claimed in any of the techniques envisaged in the context of the first embodiment (i.e. cutting material eventually covered with intumescent product).
    [0096] The process according to the present invention may also comprise an additional stage consisting of covering the tank, of which only a part of the surface is covered with a fire resistant material and eventually with a fusible material with an insulating material inert to fire. as defined above. Techniques for lining the tank with fire-inert insulating material will depend on the way the latter is made, that is, fabric made of fire-inert insulating material or sock made of fire-inert insulating material or filament winding, and are as previously defined. Once the fire-inert insulation material is placed, it can be covered, totally or partially, with an intumescent product as defined above. Finally, in the process according to the present invention, before the application of the fire-resistant material and possibly the fusible material on the tank and / or before the application of the intumescent product on the fire-resistant material and eventually on the material. fuse or on the fire-inert insulating material, the tank, the fire-resistant material, the fusible material and / or the fire-inert insulating material can be subjected to a treatment that facilitates the fixing of the fire-resistant material, the fusible material and / or the intumescent product by adding an adhesion primer and / or by a suitable surface treatment. In other words, an adhesion primer and / or a suitable surface treatment is applied to all or part of the tank surface and / or all or part of the tank surface coated with the fire resistant material, with the fusible material or with the insulating material inert to fire.
    [0097] "Adhesion primer" means a coating that improves the bond, adhesion or adhesion of the fire resistant material, the fusible material and / or the intumescent product. There are different adhesion primers in the state of the art. The person skilled in the art will be able to choose which one to use according to the nature of the surface of the high pressure storage tank, depending on the nature of the fire resistant material and, in particular, based on the thermosetting elastomeric resin that constitutes it, depending on the fusible material and / or the intumescent product. You will also choose whether a suitable surface treatment is necessary. By way of illustrative and non-limiting examples, the following adhesion primers may be mentioned: WACKER G790, G783, FD, DOW-CORNING 12000S, 1205, P, GE SILICON SS4004, PRIMAIRE RHODIA RHODORSIL, PM820, Organosilanes, Organotitanates, Organophosphates, etc.
    [0098] Other features and advantages of the present invention will become apparent to those skilled in the art upon reading the examples below given for illustrative and non-limiting purposes, and with reference to the accompanying figures. Brief description of the drawings
    [0099] Figure 1 presents various ways of arranging on the surface of the high pressure storage tank a resistant non-fire resistant fusible liner (shaded area) allowing local leakage of the tank to minimize its maximum pressure at the beginning of the leak and minimize any explosion.
    [0100] Figure 2 is a photograph of a high pressure storage tank lined with a fire resistant material implemented in the invention.
    [0101] Detailed exposition of particular realizations
    [0102] I. Material
    [0103] The material used in the present invention was prepared from silicone which forms the thermosetting elastomeric resin matrix and ATH as endothermic filler.
    [0104] The ATH widely used in many applications for cost reasons acts by decomposing endothermically at temperatures between 80 and 200 ° C, which has the effect of lowering the temperature of the material and thus reducing its degradation rate. In addition, its decomposition releases water vapor that dilutes flammable mixtures and forms a screen for the penetration of oxygen on the surface of the material.
    [0105] The ATH and silicone used in the present embodiment are, respectively, ATH SH150 Rio Tinto Alcan and Elastosil RT601 resin from Wacker Chemie AG.
    [0106] II. Process for the preparation of the material used in the invention
    [0107] The formulation consists of carrying out the following stages:
    [0108] - the resin is weighed, 360 g, and then placed in a container in a mixer;
    [0109] - the loads are weighed, 600 g, and then gradually incorporated into the resin using the propeller of the mixer;
    [0110] This stage is quite important because it is necessary that the dispersion of the charges be as homogeneous as possible. The higher the loading rate, the more difficult the dispersion.
    [0111] - once the resin-filler mixture has been obtained, a first degassing may be necessary;
    [0112] In fact, during the addition of the charges, the propeller incorporates into the mixture an amount of air that must be removed from the mixture for its subsequent production.
    [0113] - once the mixture has degassed, it is necessary to weigh the correct amount of hardener, 40 g, and mix again so that the mixture is homogeneous.
    [0114] - a second degassing can make it possible to eliminate the air bubbles incorporated during the second mixing.
    [0115] Once this last stage is completed, a formulation is obtained, that is, a finished product that needs to be foundry molded.
    [0116] III. Shaping of the material used in the invention
    [0117] Carrying out in the tank consists of pouring the formulation obtained in point II into the bottom of a mold.
    [0118] The bottle-shaped high-pressure storage tank is placed and pushed into this formulation, and the material is then distributed over the middle of the tank. The material is then allowed to polymerize at room temperature or in an oven to have a half-surface protected tank.
    [0119] Then it is necessary to restart the process to have a protection in the whole tank. The two semi-protections are held together by the natural union of the silicone. Therefore, a high pressure storage tank lined with a silicone material is obtained in which ATH is incorporated (Figure 2).
    [0120] IV. Additional treatment of the tank lined with the material used in the invention
    [0121] Intumescent paint, such as Innovative Fire Systems Pacfire paint, can be put into the tank high pressure storage coated with the material of the present invention.
    [0122] This paint makes it possible to obtain a protective barrier by creating an expanded carbon layer, which has a very marked thermal barrier effect.
    [0123] The application of the paint is done with a simple brushing, being careful to first use the GE SILICON SS4004, a primer that promotes adhesion. This primer can also be helpful in maximizing the bond between the silicone and the tank compound.
    权利要求:
    Claims (12)
    [1]
    1. A process to prepare a fire resistant material for a high pressure storage tank, comprising a thermosetting elastomeric resin matrix in which endothermic fillers are incorporated, characterized in that it comprises the following stages of:
    a) preparing a mixture comprising at least one thermosetting elastomeric resin precursor and at least one endothermic filler, said step (a) being carried out at room temperature;
    b) optionally degassing the mixture obtained in step (a);
    c) adding, to the mixture obtained in step (a) or to the degassed mixture obtained in step (b), an agent that makes it possible to obtain said thermosetting elastomeric resin from said precursor, said step (c) being carried out at room temperature ;
    d) optionally degassing the mixture obtained in step (c);
    e) cold forming the mixture obtained in stage (c) or the degassed mixture obtained in stage (d) by molding, injection or vacuum assisted transfer in a mold in said tank,
    by which a fire resistant material is obtained comprising a thermosetting elastomeric resin matrix in which endothermic fillers are incorporated, said thermosetting elastomeric resin matrix being a silicone resin matrix.
    [2]
    2. Process according to claim 1, characterized in that said endothermic charges are selected from aluminum trihydroxide (ATH), disodium tetraborate decahydrate (or borax), trisodium phosphate dodecahydrate, magnesium dihydroxide (or Brucite), Colemanite, a melamine monophosphate, a melamine pyrophosphate, a melamine polyphosphate, zinc borate, hydromagnesite, a tripolyphosphate (TPP), resorcinol bis (diphenylphosphate) (RDP), bisphenol-A bis (diphenylphosphate) (BPADP) and their mixtures.
    [3]
    Process according to claims 1 or 2, characterized in that the amount of said endothermic loads expressed in weight with respect to the total weight of the thermosetting elastomeric resin material is between 10% and 90%, notably between 15% and 80% and, in particular, between 40% and 70%.
    [4]
    4. High pressure storage tank in which only a part of the external surface is covered with a fire resistant material comprising a thermosetting elastomeric resin matrix in which endothermic fillers are incorporated, said thermosetting elastomeric resin matrix being a silicone resin matrix that can be prepared according to a process as defined in claim 1,
    said tank which is a type IV tank and
    the area or areas of the external surface of the tank not covered by said fire-resistant material that remain as is or covered with a fusible material.
    [5]
    5. High pressure storage tank according to claim 4, characterized in that all or part of the external surface of said tank is further covered with an intumescent product.
    [6]
    6. High pressure storage tank according to claim 5, characterized in that at least one zone of the intumescent product is replaced by a fusible material.
    [7]
    High pressure storage tank according to claim 4, characterized in that all or part of the external surface of said tank is further covered with an insulating material inert to fire and in particular a fabric or sock of insulating material inert to fire. fire, said inert material being eventually covered with an intumescent product.
    [8]
    8. Process to protect a high pressure storage tank that comprises the steps of applying, only on a part of the surface of said tank, a fire-resistant material that comprises a thermosetting elastomeric resin matrix in which endothermic loads are incorporated. , said thermosetting elastomeric resin matrix being a silicone resin matrix, which can be prepared according to a process as defined in claim 1,
    said tank being a type IV tank.
    [9]
    Process according to claim 8, characterized in that said process further comprises an additional step of applying an intumescent product on all or part of the tank surface, only a part of which is covered by the fire resistant material.
    [10]
    10. Process according to claims 8 or 9, characterized in that it comprises an additional step of replacing at least one area of the fire-resistant material possibly covered with the intumescent product by a fusible material.
    [11]
    Process according to claims 8 or 10, characterized in that said process comprises an additional stage of coating the tank, in which only a part of the surface is covered with a material fire resistant and possibly a fusible material, with an insulating material inert to fire.
    [12]
    Process according to any of claims 8 to 11, characterized in that a suitable primary adhesion layer and / or surface treatment is applied to all or part of the tank surface and / or to all or part of the surface of the tank covered with the fire resistant material, the fusible material or the insulating material inert to the fire.
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    同族专利:
    公开号 | 公开日
    EP2820109A1|2015-01-07|
    WO2013127902A1|2013-09-06|
    US20150008227A1|2015-01-08|
    CA2865868A1|2013-09-06|
    EP2820109B1|2019-10-23|
    US10765897B2|2020-09-08|
    ES2765198T3|2020-06-08|
    FR2987367A1|2013-08-30|
    FR2987367B1|2015-03-06|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR1251797A|FR2987367B1|2012-02-28|2012-02-28|FIRE PROTECTIVE MATERIAL, HIGH PRESSURE STORAGE TANK COATED WITH SUCH MATERIAL, PROCESSES FOR THEIR PREPARATION AND USES THEREOF|
    PCT/EP2013/054000|WO2013127902A1|2012-02-28|2013-02-28|Fire protection material, high-pressure storage tank coated with said material, methods for preparing same, and uses thereof|
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