• 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:
    The present invention relates to a process by which inorganic fibers (glass, carbon, aramid, etc ...) are recovered in fiber-resin composite materials, with the significant advantage of working at room temperature. The process comprises the steps of solvent treatment and separation of the fiber from the degraded resin residues. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2604311A1
    申请号:ES201531174
    申请日:2015-08-06
    公开日:2017-03-06
    发明作者:Agustín BUENO LÓPEZ；Dolores LOZANO CASTELLÓ；Francisco PERUCHO SÁNCHEZ
    申请人:Universidad de Alicante；
    IPC主号:
    专利说明:

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    DESCRIPTION
    PROCEDURE FOR RECOVERY OF INORGANIC FIBERS AT ENVIRONMENTAL TEMPERATURE IN FIBER-RESIN COMPOSITE MATERIALS
    Inorganic fiber recovery procedure at room temperature in fiber-resin composite materials.
    FIELD OF THE INVENTION
    The present invention relates to a process by which inorganic fibers (glass, carbon, aramid, etc.) are recovered in fiber-resin composite materials.
    STATE OF THE PREVIOUS TECHNIQUE
    Cab cruises, yachts and various vessels are made of fiber-resin composite materials for the hull and superstructure. These composite materials are manufactured mainly with polyester and fiberglass, a combination that makes them light and strong at the same time. Fiberglass-resin composite materials are also being used to manufacture the blades of wind turbines that transform wind energy into electricity. Although fiberglass is the most commonly used inorganic fiber for economic reasons, other types of fibers such as aramid or carbon are sometimes used, either alone or as a reinforcement for glass.
    The aeronautical and automobile industries also use fiber-resin composite materials. Thus, for example, the structure of the Airbus A380 is made of 40% carbon fiber and BMW sold in 2013 the first car manufactured in series with carbon fiber.
    Other of the innumerable applications of fiber-resin composite materials that could be mentioned are the manufacture of sports equipment, warehouses, marine stairs, railings, structural parts, insulation, etc. In most applications, it is used that fiber-resin composite materials are lightweight, have good mechanical properties, are resistant to corrosion and require little maintenance. In the case of glass fibers, they are also cheap.
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    Currently in Europe, more than 120,000 tons of fiber-resin composite materials are sent to landfill annually, and much of this amount comes from its use as construction material for boats. In the case of carbon fibers, for example, world demand in 2008 amounted to about 35,000 tons, with an annual increase of 7-8%. This creates a great problem, since places of final colocation of these wastes must be enabled, once their useful life has ended. The storage of these wastes is a problem for the environment, and they even become harmful to health, which is mainly due to the degradation of the polymeric resin.
    An alternative to the accumulation of waste in the landfill is its recycling to eliminate the resin and recover the inorganic fibers (glass, carbon, aramid, etc.). Inorganic fibers could be reused, which would save a large amount of energy necessary for its manufacture and give added value to the recycling process.
    So far various methods have been developed to recycle fiber-resin composite materials. The publication "Recycling of Reinforced Plastics” (Appl Compos Mater (2014) 21: 263-284) collects the methods available for recycling glass-resin composite materials, and the publication "Recycling carbon fiber reinforced polymers for structural applications: Technology review and market outlook '(Waste Management 31 (2011) 378-392) available for carbon fiber-resin materials. These methods are summarized below.
    There are methods based on mechanical treatments of the waste, such as crushing the composite material. This method is applicable to all composite materials, regardless of the nature of the fiber and resin. Today this is the only option with commercial application. The great limitation of this procedure is that the fibers lose their mechanical properties when crushed. This limits its reuse to low added value applications in which such mechanical properties are not necessary, but the vast majority of the original fiber applications are discarded. US20080217811 and WO2013076601 are examples of this type of treatment in which the crushed composite is mixed with new resin and used to make insulation panels.
    The multinational Befesa has developed a recycling method that consists of incorporating
    Glass fiber-resin composite material waste to new polymer matrix
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    joining them chemically. Thus, the final product obtained, which is a mixture of fiberglass and plastic already recycled, can be reused in applications that do not require very demanding mechanical properties.
    There are also recycling methods based on the pyrolysis of the fiber-resin composite material, where the resin is removed by heat treatment in a non-oxidizing atmosphere at high temperature (450-650 ° C). A process of this type is shown in WO2005040057, which refers to the polymer matrix in which the fiber is found is removed by pyrolysis, gasification, incineration or combustion of the resin matrix. The great disadvantage of these procedures is that they are pollutants and that they partially degrade the fibers, which limits or prevents their reuse.
    Hydrolysis-based methods consist of treating the fiber-resin composite with water using an acidic or basic catalyst. These methods present the added problem that the fiber must be separated after the treatment and that the fibers also degrade, so they also do not allow reuse in applications that require good mechanical properties.
    Another option is the methods simply based on energy recovery, which consist of burning the resin (usually at temperatures close to 1000 ° C) to use the emitted energy. However, with these methods we also have the disadvantage that the fiber is not recovered, and therefore cannot be reused.
    Given this problem, the SINTEF company, together with a group of Norwegian companies and organizations, has developed a method to take advantage of the materials used in the vessels, through a chemical recycling process that allows the resin to be separated from the fiberglass for that both products can be reused ( www.sciencedaily.com/releases/2011/06/110609083228.htm). The inventors suggest that the process is effective, since it allows about 80% of the materials that make up the boats to be recycled. However, its industrial implementation has the disadvantage that it requires treating materials at high temperatures, close to 220 ° C for 2 hours, which makes its application considerably difficult.
    Therefore, so far there is no method of recycling fiber-resin composite materials that allows the reuse of recovered inorganic fibers that do not use
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    aggressive treatments that degrade the fibers, whether mechanical or chemical at high temperatures.
    EXPLANATION OF THE INVENTION
    It is necessary, in the light of the above, to seek a global solution to the problem of recycling fiber-resin composite materials by methods that can operate in mild temperature conditions and that are not chemically aggressive with inorganic fibers, so that Allow reuse.
    The main advantage of the procedure described here is that it allows the resin to be separated at room temperature from the fibers, recovering the fibers without being damaged and allowing their subsequent reuse. For this purpose, a halogenated organic solvent, preferably a chlorinated organic solvent, or any other halogenated solvent, must be used for the recovery of the inorganic fiber by chemically separating the fiber from the resin matrix.
    The present invention thus relates to a process by which inorganic fibers are separated from the resin in fiber-resin composite materials by a chemical treatment at room temperature, which allows the recovery of the inorganic fiber without damaging it.
    Thus, in a first aspect, the present invention relates to a process of recovering inorganic fibers from a fiber-resin composite material (hereinafter, the process of the present invention) which is carried out at room temperature and comprises The following stages:
    a) treatment of the fiber-resin composite with a halogenated organic solvent,
    b) separation of the resin fiber from the material dissolved in step a).
    In the present invention room temperature is understood at a temperature that does not exceed the boiling point of the solvent.
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    In a more particular embodiment, the process of the present invention comprises a stage prior to step a) of conditioning and cutting the fiber-resin starting material and elimination of other materials such as wood, metals, etc.
    In a particular embodiment of the present invention, inorganic fibers are selected from glass fibers, carbon fibers or aramid fibers.
    In a particular embodiment, the resin of the fiber-resin compound is a thermosetting resin or a hot melt with sufficient reactivity to be degraded by the solvent used.
    In a particular embodiment, the halogenated organic solvent is a chlorinated organic solvent. More particularly, the chlorinated organic solvent is selected from dichloromethane, chloroform, 1,2-dichloroethane, trichlorethylene, chlorobenzene.
    In a particular embodiment, step a) of treating the fiber-resin composite material is carried out in a reactor.
    In another particular embodiment, step a) of treating the fiber-resin composite material is performed under agitation.
    In another particular embodiment, step a) of treating the fiber-resin composite material is carried out for 15-180 minutes.
    In another particular embodiment, the halogenated organic solvent is recovered by a solvent extraction system and the residual organic solvent is removed. More particularly, the residual organic solvent is removed by applying a stream of a gas or immiscible liquid in the reactor or by applying a temperature above the boiling temperature of the solvent.
    In another particular embodiment of the present invention, step b) of separating the resin fiber from the material dissolved in step a) is performed by sieving.
    The procedure of the present invention is capable of being automated and scaled
    to be able to work at different scales. That is, it could be scaled at any time
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    to extend the performance and achieve a greater amount of recovered materials, or even modify the configuration respecting the steps defined in the procedure.
    All the materials used in the present invention described below (closing joints, pipes, reactors, etc.) must be compatible with the solvent used.
    The basic steps of the procedure are described below.
    Previous stage of conditioning of the fiber-resin composite material.
    This prior and optional stage consists in conditioning the fiber-resin composite material, eliminating other materials such as wood, metals, etc. and chop the fiber-resin composite into fragments of adequate dimensions to the dimensions of the installation.
    Stage a: treatment of the fiber-resin composite with a halogenated organic solvent.
    The first stage of the procedure consists in introducing the fiber-resin composite fragments into a reactor and treating them with a halogenated organic solvent to degrade the resin. When the solvent comes into contact with the chopped composite material, the resin degrades and the fiber begins to separate.
    Although it is not essential, it is recommended that the reactor has at least one agitation system to accelerate the degradation of the resin and the separation of the fibers.
    After the degradation of the resin, the solvent is removed from the reactor by taking it to its original tank, using a particulate filter so that the solvent comes out clean.
    Once most of the solvent has been removed from the reactor, the solvent that is impregnated with the mixture of fibers and degraded resin is removed. This can be done in several different ways or combinations thereof. One option is to introduce into the reactor an immiscible liquid (for example water) which, after washing the mixture of fibers and degraded resin, is removed from the reactor. Both liquids are subsequently separated by decantation, recovering the solvent. The mixture of fibers and degraded resin must finally be dried, either in the reactor itself (favoring it with temperature and circulating air, for example), or outside it.
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    Another alternative for removing the halogenated organic solvent that permeates the mixture of fibers and degraded resin is to heat the reactor above the boiling temperature of the solvent (for example, 40 ° C for dichloromethane, 61 ° C for chloroform, 84 ° C for 1,2-dichloroethane, etc.) and drag the evaporated solvent with a gas (for example air). The preheated entrained gas can also be introduced at the necessary temperature. To avoid solvent emissions, this can be subsequently recovered by condensation or by adsorption in an adsorbent solid (activated carbon, zeolites, silica gel, etc.). This alternative avoids the drying stage but requires additional energy to achieve a temperature higher than the boiling point of the solvent.
    Finally, we proceed to remove the mixture of fibers and degraded resin from the main reactor (if not done before) moving to stage b of the process.
    In a particular embodiment, it would be convenient for the entire stage a of the process to be carried out in a sealed room, for example inside a room with forced ventilation and a gas adsorption system, for example, activated carbon filter. For the correct operation of the procedure, it is necessary to ensure that the temperature of the room where it is carried out is lower than the boiling point of the solvent. Therefore, in the case of using a solvent with a boiling point close to room temperature (for example, 40 ° C for dichloromethane) an air conditioning system may be necessary.
    Stage b: separation of inorganic fibers from degraded resin residues.
    This step can be carried out by sieving, so that the fibers, larger in size, are separated from the small particles of degraded resin by subjecting them to a vibration system in a sieve that allows the degraded resin particles to pass through.
    BRIEF DESCRIPTION OF THE FIGURES
    FIGURE 1: Scheme of the experimental process that could be used to carry out the inorganic fiber recovery procedure. A solvent tank 1, a reactor 2, a pump 3 to transfer the solvent, a conduction to extract the solvent from the reactor 4 and a fluid inlet 5 are shown.
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    DETAILED EXHIBITION OF MODES OF EMBODIMENT
    The preferred embodiment of the process described in the present invention is described below. For a better understanding of it, Figure 1 is presented.
    To start the procedure, the solvent tank 1 is filled. This tank is used to store the halogenated organic solvent and has an airtight cap that prevents the solvent from evaporating outside.
    The solvent must be a halogenated organic solvent, selected from dichloromethane, chloroform, chlorobenzene or other solvents with similar characteristics. The choice of a solvent or another can be based on mainly economic criteria.
    The inorganic fibers are made of glass, carbon or aramid. Among these three, the type of fiber does not affect the procedure.
    The nature of the resin does matter, being usable with most resins except for some of a hot melt nature that, due to their chemical inertia, are not degraded by halogenated organic solvents.
    Preliminary stage: conditioning of the fiber-resin composite.
    This previous stage is optional and in it, the fiber-resin composite material is separated from other materials that may be present, such as wood or metal and cut into fragments according to the dimensions of reactor 2. Reactor 2 is the container where it is carried carry out the treatment of the fiber-resin composite with the solvent to recover the inorganic fibers. It has a lid that closes tightly and can be opened or closed to introduce the starting fiber-resin composite material and remove the recovered fiber after the procedure. Once the material is chopped, it is placed in reactor 2 to continue with the next steps of the procedure.
    The fragments will be of greater or lesser size according to the dimensions of the reactor used in step a. Although not essential, for guidance purposes the fragments may have a size around one tenth of the reactor diameter approximately.
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    Stage a: treatment of the fiber-resin composite with solvent.
    The solvent is then pumped from the solvent tank 1 to the reactor 2 where the fiber-resin composite material is chopped. For this, pump 3 is used.
    When the halogenated organic solvent (in this case a chlorinated organic solvent was used, in particular 1,2-dichloroethane) comes into contact with the chopped fiber-resin material, the resin and the fiber begin to separate. It is recommended to use an agitation system to keep the reactor contents moving during treatment. Once the fibers and the resin have been separated, the stirring system is stopped, if any.
    This chemical treatment should stop as soon as the resin begins to degrade, without waiting for the resin to dissolve completely. If this is done, the recovered solvent can then be reused in successive stages. The time required usually varies between 15 and 180 minutes, and its optimization depends on the type of resin treated, the solvent used and the design of the reactor.
    The solvent is then removed from the reactor 2 through conduction 4, bringing it back to the solvent tank 1. This extraction can be carried out by gravity, and the conduit 4 must be protected with a particulate filter to prevent the exit of the reactor 2 of the degraded resin particles together with the solvent.
    The solvent is then removed from the fibers by heating the reactor 2 above the boiling point of the solvent (for example, 40 ° C for dichloromethane, 61 ° C for chloroform, 84 ° C for 1,2-dichloroethane, etc. ), and air is introduced through the air inlet 5 to entrain the evaporated solvent. The solvent removed in the drying stage can be retained in the filter (for example activated carbon, zeolite, silica gel, etc.) before expelling the air flow to the outside, or it can be condensed to be reused. As already described in the general description, instead of air, water can also be introduced into the reactor, or another immiscible liquid with the halogenated organic solvent, subsequently separating the solvent and said liquid by decantation. In this case it would be necessary to proceed subsequently to dry the fibers.
    Stage b: separation of the fibers from the degraded resin residues.
    Finally, the fibers of the reactor 2 are extracted, which are mixed
    with a large amount of degraded resin particles. The mixture of fibers and particles
    of resin can be separated by sieving, subjecting them to vibration in a sieve of
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    a sufficient size so that the fibers do not pass through and the particles do. A fluidization system or any other system suitable for separating solids can also be used.
    The fibers obtained have chemical properties similar to the original, only partially losing the structural order in the case of fibers with a specific arrangement.
    This gives the possibility of reusing them in any application in which it is not necessary to have perfectly ordered fibers.
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    权利要求:
    Claims (12)
    [1]
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    1. Procedure for recovering inorganic fibers from a composite fiber-resin material characterized in that it is carried out at room temperature and comprises the following steps:
    a) treatment of the fiber-resin composite with a halogenated organic solvent
    b) separation of the resin fiber from the material dissolved in step a)
    [2]
    2. Method according to claim 1, which comprises a stage prior to step a) of conditioning and cutting the fiber-resin starting material.
    [3]
    3. Method according to any of claims 1-2, wherein the inorganic fibers are selected from among glass fibers, carbon fibers or aramid fibers.
    [4]
    4. Method according to any of the preceding claims, wherein the halogenated organic solvent is a chlorinated organic solvent.
    [5]
    5. Method according to claim 4, wherein the chlorinated organic solvent is selected from dichloromethane, chloroform, 1,2-dichloroethane, trichlorethylene, chlorobenzene.
    [6]
    6. Method according to any of the preceding claims, wherein step a) of treating the fiber-resin composite material is carried out in a reactor (2).
    [7]
    7. Method according to any of the preceding claims, wherein step a) of treating the fiber-resin composite material is carried out under stirring.
    [8]
    8. Method according to any of the preceding claims, wherein step a) of treating the fiber-resin composite material is carried out for 15-180 minutes.
    [9]
    9. Method according to any of the preceding claims, wherein the halogenated organic solvent is recovered by a solvent extraction system (4) and the residual organic solvent is removed.
    [10]
    10. Method according to claim 9, wherein the residual organic solvent is removed by applying a stream of a gas or immiscible liquid in the reactor (2).
    [11]
    11. Method according to claim 9, wherein the residual organic solvent is removed by applying a temperature above the boiling temperature of the solvent.
    [12]
    12. Method according to any of the preceding claims, wherein step b) of separation of the resin fiber from the material dissolved in step a) is carried out by sieving.
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    同族专利:
    公开号 | 公开日
    ES2604311B1|2017-12-18|
    US20180230285A1|2018-08-16|
    WO2017021574A1|2017-02-09|
    引用文献:
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    FR2811246B1|2000-07-06|2003-01-17|Electricite De France|PROCESS FOR RECOVERING COMPOSITE MATERIALS|
    WO2014179939A1|2013-05-08|2014-11-13|East China University Of Science And Technology|Methods for recovering carbon fiber from carbon-fiber-reinforced polymer composites|CN108219190B|2017-12-19|2020-07-03|清华大学|Method for preparing aramid pulp by using scrapped bulletproof helmet|
    EP3788452A4|2018-05-01|2021-11-10|Piaggio Fast Forward, Inc.|Method for determining self-driving vehicle behavior models, a self-driving vehicle, and a method of navigating a self-driving vehicle|
    CN112996685A|2018-10-22|2021-06-18|皮亚吉奥科技有限公司|Shifting assembly and mobile carrier comprising same|
    WO2021074446A1|2019-10-17|2021-04-22|Dsm Ip Assets B.V.|Method to enable recycling of a panel|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201531174A|ES2604311B1|2015-08-06|2015-08-06|PROCEDURE FOR RECOVERY OF INORGANIC FIBERS AT ENVIRONMENTAL TEMPERATURE IN FIBER-RESIN COMPOSITE MATERIALS|ES201531174A| ES2604311B1|2015-08-06|2015-08-06|PROCEDURE FOR RECOVERY OF INORGANIC FIBERS AT ENVIRONMENTAL TEMPERATURE IN FIBER-RESIN COMPOSITE MATERIALS|
    PCT/ES2016/070570| WO2017021574A1|2015-08-06|2016-07-27|Method for recovering inorganic fibres at room temperature in composite materials of fibre and resin|
    US15/750,475| US20180230285A1|2015-08-06|2016-07-27|Method for recovering inorganic fibres at room temperature in composite materials of fibre and resin|
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