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    • 专利摘要:
    Self-cleaning adsorbents of toxic volatile organic compounds. The invention describes an adsorbent material comprising an active catalyst in hydrolytic degradation of pollutants based on zirconium hydroxide doped with lithium and/or magnesium compounds of a basic nature, which are neither toxic nor corrosive and have self-cleaning properties, being able to decontaminate air, water or surfaces contaminated with a chemical warfare agent or insecticide or an analogous compound. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2677143A1
    申请号:ES201631713
    申请日:2016-12-29
    公开日:2018-07-30
    发明作者:Jorge Andrés RODRIGUEZ NAVARRO；Elisa Barea Martínez；Elena LÓPEZ MAYA；Carmen RODRÍGUEZ MALDONADO；Rodrigo GIL SAN MILLÁN
    申请人:MINISTERIO DE DEFENSA；Mini De Defensa；Universidad de Granada；
    IPC主号:
    专利说明:

    SELF-CLEANING VOLATILE ORGANIC COMPOUND ADSORBENTS TOXIC
    SECTOR OF THE TECHNIQUE
    The present invention is framed in the field of chemical adsorbents, more specifically in that of adsorbents with detoxifying properties. The main field of application of the invention is the decontamination of air, water and surfaces contaminated with chemical compounds of high toxicity, including chemical warfare agents, industrial chemicals, insecticides and the like. STATE OF THE TECHNIQUE
    Volatile organic compounds (VOCs) One of the dangers our society faces is exposure to extremely toxic chemicals that pose a significant risk to health and the environment. One of the most harmful groups of pollutants are volatile organic compounds (VOCs). The European Union defines them as chemical substances with a vapor pressure greater than 10 Pa at 293 K and which can lead to important detrimental effects on health (carcinogenesis, teratogenesis and mutagenesis). VOCs are present in indoor and outdoor air, as well as in water and soil as a result of emissions from the chemical process, material construction, cosmetics, pesticides, detergents, etc. industries. On the other hand, although the 1997 Chemical Weapons Convention outlaws the production, storage and use of chemical warfare agents, unfortunately, these are still used and / or are susceptible to their use by terrorist agents. Situations like this show the need to develop technologies for purification of air, water and contaminated surfaces that are efficient against high toxicity compounds. Some of the most common chemical warfare agents are bis (2-chloroethyl) sulfide (HD, iperite or mustard gas), pinacolylmethylfluorophosphonate (GD
    or Somán), Tabún (GA), and O-ethyl-S- (2-diisopropylamino) ethylmethylphosphonothioate (VX) as well as analogs thereof. These are VOCs that are toxic both by inhalation and in contact with skin and mucous membranes. In the case of nerve agents, their activity is due to the lability of the P-X bonds (X = F, O, Cl, S) of the organophosphorus compounds. The behavior of X as a leaving group results in the irreversible anchoring of the organophosphorus residue to the active center, the enzyme acetylcholine esterase inhibiting its activity. Such inhibition results in the blockage of nerve impulse transmission causing death due to cardiorespiratory arrest.


    Some insecticides such as fenamiphos (ethyl-3-methyl-4- (methylthio) phenyl (1-methyl ethyl) phosphoramidate)) and malathion (2 - [(dimethoxyphosphorothioyl) sulfanyl] butanedioate) are also organophosphorus compounds that act at the enzyme level Acetylcholine esterase and can lead to permanent neurological disorders even at doses below fatal.
    Similarly, the activity of vesicant agents is related to the behavior of Cl atoms in C-Cl bonds as leaving groups which leads to irreversible alkylation of biomolecules, such as nucleic acids, leading to cell death. Other related compounds, of high toxicity, are phosgene (carbonyl dichloride) and cyanogen chloride and which are products of industrial interest.
    Therefore, it is important to protect both the airways, through individual (gas masks) or collective air filters, as well as the skin through protective clothing. It is also important to decontaminate both water or surfaces contaminated with these extremely toxic agents.
    Use of adsorbents for decontamination The use of adsorbents based on porous materials that can be incorporated into gas masks, collective air and / or water purification systems, or for surface decontamination, is of great social interest. Currently, the technology used for this purpose is based on the use of classic inorganic porous materials, such as activated carbons, zeolites and activated aluminas. However, although these adsorbents show good results in the capture of some of these toxic gases, they are not suitable for all of them and / or the operation of the protective equipment is limited by the excessive weight of the gas masks. and the poor comfort of protective fabrics. Another problem associated with current technology is that its action as a barrier is limited to a single exposure to toxic agents, so its destruction is necessary since there is a danger of them becoming secondary emitters of these toxic agents. Taking these considerations into account, it is of great interest to develop new technologies based on self-cleaning adsorbent materials that not only act as a barrier against these pollutants but are also capable of degrading them by transforming them into less toxic or harmless compounds.


    Elimination of chemical warfare agents Given the high toxicity of chemical warfare agents and related toxins, the use of lower toxicity analogues is desirable for testing materials.
    5 suitable for decontamination. Iperite (HD) simulants include 2-chloroethyl ethyl sulfide (CEES) and 2-chloroethylphenylsulfide (CEPS). Nerve gas simulants include dimethylmethylphosphonate (DMMP) and diisopropylfluorophosphate (DIFP).
    10 Regarding the background of materials with self-cleaning properties for these types of materials, there are some studies of catalytic systems capable of degrading nerve agent models. Thus, it has been shown that the oxohydroxozirconate clusters of metalorganic networks [J. E. Mondloch, M. J. Katz, W. C. Isley III,
    P. Ghosh, P. Liao, W. Bury, G. W. Wagner, M. G. Hall, J. B. De Coste, G. W. Peterson,
    15 R. Q. Snurr, C. J. Cramer, J. T. Hupp, O. K. Farha, Nature Mater. 2015, 14, 512-516 DOI: 10.1038 / NMAT4238] or zirconium hydroxide [T. J. Bandosz, M. Laskoski, J. Mahle, G. Mogilevsky, G. W. Peterson, J. A. Rossin, G. W. Wagner. J. of Phys. Chem. C, 2012, 116, 11606-11614] are able to mimic the hydrolytic activity of the phosphotriesterase enzyme with activity in the hydrolytic degradation of P-F, P-O bonds
    20 and P-S, typically found in high-toxic chemical warfare agents, called nerve gases, such as Sarin, Soman and VX [G. W. Peterson, et al, US 8,530,719 B1]. However, this system has poor activity against the degradation of C-Cl bonds found in vesicating agents (such as HD). In this regard, the authors of the present invention found that the doping of
    25 metal-organic networks of zirconium with lithium tertbutoxide improve the catalytic activity of these systems [López-Maya, C. Montoro, L. M. Rodríguez-Albelo, S. D. Aznar-Cervantes, A. A. Lozano-Pérez, J. L. Cenís, E. Barea, J. A. R. Navarro. Angew Chem. Int. Ed., 2015, 54, 6790-6794] to degrade both P-X bonds (being X = F, Cl, S, O or N, among others) typically found in nervous chemical warfare agents and
    30 industrial toxic compounds, such as C-Cl bonds found in vesicant agents (such as HD) and industrial toxic compounds (such as phosgene or cyanogen chloride).
    It is important to keep in mind that the degradation of toxic compounds may not be immediate, or that they are difficult to degrade compounds, so it is important to complement the catalytic activity with an adsorption process that extends


    the protection spectrum of the air and / or water filter or decontamination of a surface. The maximum exponent of this technology are adsorbents based on high porosity and hydrophobicity activated carbon (eg Saratech®) developed by Blücher [http://www.bluecher.com/en/brands/saratoga/military/ ] These types of systems can be found in the form of spheres, tissues or foams. They also have a high adsorption capacity with BET surfaces close to 2000 m2g-1, pore sizes in the range of micro and mesopores, pore volumes up to
    3.5 cm3g-1 and high hydrophobicity. These characteristics give rise to a broad spectrum of adsorption against volatile organic compounds that is not limited by moisture condensation in the porous structure (even in high relative humidity environments of 80%) and in aqueous solutions. However, the hydrophobicity of these systems prevents the hydrolytic degradation of toxic agents so that once they are confined in a pore with hydrophobic characteristics, they are protected from possible hydrolytic degradation by the action of environmental humidity. As a result, protective equipment must be destroyed in order to prevent them from becoming possible secondary emitters of these toxic substances. This inconvenience generates a series of problems such as the need for facilities for decontamination, the need for qualified personnel to perform these tasks, lack of recyclability, etc.
    Likewise, there are solutions for the decontamination of nerve agents and vesicants that are currently in use in the United States Army, such as the solution called DS2 that is composed of 2% NaOH, 28% ethylene glycol monomethyl ether and 70% diethylenetriamine [Richardson, GA “Development of a package decontamination system,” EACR-l 310-17, US Army EdgeWood Arsenal Contract Report (1972)]. However, these solutions have serious drawbacks as they are highly corrosive and the main component of the solution is toxic (diethylenetriamine), presenting teratogenic problems. In order to solve part of this problem, some of these amines have been incorporated into porous materials, for example alumina [R. S. Brown, et al, 2005, US 6,852,903 B1].
    In view of these results, porous materials have been sought that offer an integral solution: adsorption of the toxic followed by degradation of the same into non-toxic compounds. In this sense, porous metalorganic networks (MOFs) have proved to be a very promising solution as evidenced by the results of the inventors themselves and other authors previously cited. But nevertheless,


    Since degradation products generate products of an acidic nature, it is necessary to use a basic buffer that acts as a sacrificial cocatalyst
    [J.  E. Mondloch, M. J. Katz, W. C. Isley III, P. Ghosh, P. Liao, W. Bury, G. W. Wagner,
    M.  G. Hall, J. B. De Coste, G. W. Peterson, R. Q. Snurr, C. J. Cramer, J. T. Hupp, O. K. Farha, Nature Mater. 2015, 14, 512-516 DOI: 10.1038 / NMAT4238].
    Despite their good behavior, MOFs have problems in their practical implementation. These drawbacks are mainly related to the high cost of organic spacers, the difficulty of industrial scaling of their synthesis and their processing. OBJECT OF THE INVENTION
    As previously indicated, despite the good results of MOFs for the elimination of this type of contaminants, it is necessary to use a less expensive and simpler technical solution in which easily available and processable commercial products give rise to the degradation of PX, CY or As-Cl bonds better than those known to date.
    Thus, the main object of the present invention is an adsorbent material comprising an active catalyst in hydrolytic degradation of pollutants based on zirconium hydroxide doped with lithium and / or magnesium compounds of a basic nature, such as lithium alkoxides, lithium hydroxide , magnesium hydroxide, etc. In a preferred embodiment, this material is supported on a porous material (activated carbon, alumina, zeolite, porous silica, porous polymer) with a broad spectrum of adsorption of contaminating compounds.
    This material is not toxic or corrosive and has self-cleaning properties being able to decontaminate air, water or surfaces contaminated with a chemical or insecticide warfare agent or an analogous compound, where the decontaminant product is a self-cleaning adsorbent.
    Some background shows that zirconium hydroxide is capable of degrading nerve agents as a result of its hydrolytic action on PF bonds, but nevertheless the efficiency is low compared to other types of bonds such as C-Cl of vesicant agents and this is blocked by the presence of degradation products of toxic agents, such as methylphosphonic acid, hydrofluoric acid or hydrochloric acid, among others.

    DESCRIPTION OF THE FIGURES
    Figure 1.-Schematic representation of the mechanism for blocking the secondary emission of toxic substances in active carbon composites (SORBENT) -catalyst of zirconium hydroxide doped with lithium tertbutoxide (CAT).
    Figure 2.- Comparison of the activity of the catalyst (LiOtBu) 0.06 [Zr (OH) 4] with the separate components LiOtBu and Zr (OH) 4 in the 2.5 hidróL hydrolysis reaction of the diisopropylfluorophosphate nerve agent analog (DIFP) ) in an aqueous suspension
    (0.5  mL) without buffering the catalyst. In the case of lithium tertbutoxide, a 0.1 M aqueous solution is used.
    Figure 3.-Comparison of the activity of the catalyst (LiOtBu) 0.06 [Zr (OH) 4] with the separate components LiOtBu and Zr (OH) 4 in the 2.5 hidróL hydrolysis reaction of the vesicle agent analog 2-chloroethyl ethyl sulfide (CEES) in an aqueous suspension
    (0.5  mL) without buffering the catalyst. In the case of lithium tertbutoxide, a 0.1 M aqueous solution is used. DETAILED DESCRIPTION OF THE INVENTION
    Definitions
    "Basic compound", MA, means any compound comprising M = metallic ion and A = anion of a basic nature of the Brönsted or Lewis type. Particularly basic compounds are alkoxides, hydroxides, oxides, hydrides, alkylides, carbonates or metal carboxylates.
    The term "supported", referring to the relationship between an element or compound and a porous material, indicates that said element or compound is anchored on the surface of the porous material.
    The term "doped" refers to the addition of a minor compound or element to a majority compound or element. In this way, the majority compound would be doped with the minority compound.
    The term "activated" refers to the process that allows to fully reveal the adsorbent and / or catalytic properties of a material.


    In this context, the present invention is related to the complementarity of the catalytic activity of zirconium, an active catalyst in the hydrolytic degradation of phosphorus bonds with other chemical elements X, PX, preferably being X = F, Cl, O, They are; carbon with other chemical elements, C-Y, being preferably Y = Cl or Br; and / or arsenic-chlorine, As-Cl; with the broad spectrum of adsorption of porous materials (active carbons, alumina, porous silicas, porous metallurgical networks, etc.) (Figure 1).
    In particular, zirconium is active against the degradation of PX bonds, preferably X = F, Cl, O, S or N, typical of neurotoxic chemical warfare agents (Figure 2), C-Cl and / or bonds As-Cl of vesicant chemical warfare agents (Figure 3), as well as in the degradation of insecticides and analogs and industrial chemical compounds containing such links.
    The P-X and C-Y bonds are usually found in compounds used in nerve or neurotoxic chemical warfare agents such as Sarin, Tabun or Somán; or vesicants like Iperita; as well as in insecticides such as Parathion and industrial toxic compounds (TICs) of Toxic Industrial Compounds.
    Materials of the invention
    Thus, in a first aspect, the invention relates to materials, hereinafter "materials of the invention", for hydrolytic degradation of PX, CY and / or As-Cl bonds, comprising doped or activated zirconium hydroxide with a basic compound of lithium or magnesium.
    In a preferred embodiment the materials of the invention comprise zirconium hydroxide doped or activated with a basic compound and supported on porous adsorbent materials, preferably activated carbon, alumina, silica gel, zeolite, porous organic polymers or mixtures of said porous materials.
    In another preferred embodiment, the basic compound is selected from the group consisting of lithium tertbutoxide, lithium isopropoxide, lithium ethoxide, lithium methoxide, lithium hydride, butyllithium, or mixtures thereof, more preferably the basic compound is lithium tertbutoxide .


    In another preferred embodiment, the basic compound is selected from the group consisting of magnesium hydroxide, magnesium oxide, magnesium hydride, alkyl magnesium or mixtures thereof, more preferably the basic compound is magnesium hydroxide.
    The proposed formulation of this invention is based on commercial or easily accessible compounds.
    Method of preparation of the materials of the invention
    The object of this invention is also a process for preparing materials for hydrolytic degradation of PX, CY and / or As-Cl bonds, hereinafter "process for preparing materials of the invention", which comprises treating zirconium hydroxide with a solution of the basic compound of lithium or magnesium in an aprotic solvent and the subsequent incorporation of the zirconium hydroxide thus doped or activated into a porous adsorbent material.
    In a particular embodiment, the basic activating compound is selected from a basic lithium or magnesium compound, preferably a lithium or magnesium alkoxide being the preferred lithium tertbutoxide, followed by lithium isopropoxide, lithium ethoxide, lithium methoxide, hydride lithium, butyllithium, lithium hydroxide, magnesium hydroxide, magnesium oxide, magnesium hydride or alkyl magnesium.
    Thus, if the basic starting compound is lithium tertbutoxide, composites of formula (LiOtBu) m [Zr (OH) 4] are produced, where m can vary between 0.000001 and 1, preferably between 0.001 and 0.2, more preferably between 0.01 and 0.2, more preferably between 0.01 and 0.1, and even more preferably m = 0.06.
    After incorporating it into the porous material, its formula will be (LiOtBu) m [Zr (OH) 4] - [Porous material], where the ratio between catalyst and porous material can vary between 0.0001% to 99%.
    Alternatively, when magnesium hydroxide is used, the formula of the composites will be of the type [Mg (OH) 2] m [Zr (OH) 4] - [Porous material], where m can vary between 0.000001 and 1, preferably between 0.001 and 0.2, more preferably between 0.01 and 0.2, more preferably between 0.01 and 0.1, and even more preferably m = 0.06.
    After incorporating it into the porous material, its formula will be [Mg (OH) 2] m [Zr (OH) 4] - [Porous material], where the ratio between catalyst and the porous material can vary between 0.0001% to 99%.


    In a particular embodiment, the aprotic solvent is selected from the list consisting of tetrahydrofuran, ditertbutyl ether, diethyl ether, ethanol, methanol or mixtures thereof. Preferably, the aprotic solvent is tetrahydrofuran.
    Preferably, the porous adsorbent material is selected from the list consisting of active carbon, alumina, silica gel, zeolite, mesoporous silica and porous organic polymers or is a mixture of said materials.
    In a preferred embodiment, zirconium hydroxide is treated with a solution of lithium tertbutoxide in tetrahydrofuran to give a composite of formula (LiOtBu) 0.06 [Zr (OH) 4] once lithium alkoxide is incorporated into the hydroxide of Zirconium
    It has been observed that the catalytic activity of zirconium hydroxide is increased with this treatment.
    The zirconium hydroxide used is preferably in the form of a micrometric powder.
    or nanometric powder, materials that are easily acquired. Alternatively, zirconium hydroxide can be obtained by precipitation of soluble salts of zirconium (IV), for example, ZrOA2 (A = Cl, NO3, SO4), ZrCl4 by treatment with a base, such as metal hydroxide, amine or urea.
    The activating agent will be purchased from commercial sources and will preferably be a lithium or magnesium alkoxide with lithium tertbutoxide being preferred, followed by lithium isopropoxide, lithium ethoxide, lithium methoxide, lithium hydride, butyllithium, lithium hydroxide, hydroxide of magnesium, magnesium oxide, magnesium hydride or alkyl magnesium.
    Catalyst activation is accomplished by treating zirconium hydroxide with a solution of the basic lithium or magnesium compound in tetrahydrofuran at reflux for 12 hours in an inert atmosphere. Alternatively, doping with the activating substance can be done in other solvents such as ditertbutyl ether, diethyl ether, ethanol, methanol or mixtures. It can also be carried out at room temperature by milling assisted by a solvent.
    In a second stage the resulting zirconium catalyst dispersed in a solvent is mixed with the adsorbent.
    Alternatively, the zirconium catalyst can be prepared on the adsorbent by precipitation of a soluble zirconium salt, for example, ZrOA2 (A = Cl, NO3,


    SO4), ZrCl4, by treatment with a base, such as metal hydroxide, amine or urea, and then the activation process is carried out with a basic salt of lithium or magnesium.
    The adsorbent is preferably activated carbon, more preferably active carbon with a specific surface area greater than 1000 m2g-1 or alumina with a specific surface area greater than 100 m2g-1, or mixtures of both. Alternatively, porous organic compounds or mixtures of adsorbents can be used as adsorbent supports of the catalyst.
    The proportion of the catalyst in the adsorbent can vary between 0.001 and 99% by weight, preferably between 1 and 10%, more preferably 5%.
    The shape of the adsorbent can be in the form of powder, pellets, spheres, fibers, foams
    or derived forms.
    Adsorbent can be incorporated by physical mixing or by dispersing it in a solvent, preferably water or tetrahydrofuran, environmentally benign and non-toxic solvents.
    The compounds obtainable or obtained by the process of preparation of materials of the invention are also object of the present invention and shall be considered interchangeably materials of the invention.
    Pollutant removal procedure
    The object of the invention is also a decontamination process comprising chemical compounds with P-X, C-Y or As-Cl bonds, hereafter referred to as the "decontamination process of the invention", which comprises contacting the contaminant with the materials of the invention.
    Particularly, but not limited to, the contaminants that can be eliminated by this procedure are nervous or neurotoxic or vesicant chemical warfare agents, as well as insecticides and toxic industrial compounds (TICs) from Toxic Industrial Compounds.
    Examples of nerve or neurotoxic chemical warfare agents, also called nerve gases, which comprise chemical compounds with PX bonds are Sarin (GB), Tabun (GA), Soman (GD), Saarin cycle (GF), VX or VR, Novichok agents and other organophosphorus acetylcholinesterase inhibitor compounds.


    Examples of vesicant chemical warfare agents, liquid, solid or gaseous substances whose fundamental characteristic is their ability to produce blisters on the skin, which comprise chemical compounds with CY bonds are sulfur mustards (H), such as Iperite (HD or HS), Lewisite (L), Methyldichloroarsin (MD), Phosgene oxime (CX), Tear gas (Chloropicrin (Cl2CNO2)).
    Examples of insecticides comprising chemical compounds with P-X, C-Y bonds
    or As-Cl are organophosphorus pesticides such as Parathion, Methyl Parathion, Chlortion, Malathion or Gution.
    The process of the invention achieves adsorption of the contaminant by the adsorbent, followed by the transformation of the contaminant into harmless or less toxic products by hydrolysis reactions promoted by the catalyst.
    The active part of the catalyst is preferably zirconium hydroxide doped with lithium tertbutoxide by reaction of solid Zr (OH) 4 with a solution of LiOtBu in tetrahydrofuran.
    After contacting the disisopropylfluorophosphate (DIFP) nerve agent simulating compound with the material of the invention it has been observed that in less than 5 min the complete degradation of the P-F bond has occurred (Figure 2). The P-F bond present in a large number of nerve agents is the main source of toxicity since it facilitates the binding of the organophosphorus compound to the active center of the enzyme acetylcholine esterase. It is important to note that said catalytic activity is not affected by the presence of nerve agent degradation products such as methyl phosphonic acid.
    In the case of the C-Cl bonds found in the vesicle agent analogue (2-chloroethylene ethyl sulfide, CEES) the hydrolysis rate is also very fast with a half-life of degradation of only 8 minutes and complete degradation at 28 minutes (Figure 3). By way of comparison, the untreated Zr (OH) 4 has an activity similar to that of the control solution, only partial hydrolysis of the CEES being observed.
    Therefore, it is shown that the doped zirconium hydroxide catalyst with lithium alkoxides is active both in the degradation of PX bonds of nerve agents (such as Somán (GD) or VX Agent) and of C-Cl bonds of vesicating agents (such as Iperita (HD)).
    It is important to highlight that it is a solid catalyst, insoluble in water and other organic solvents and that its filtration and / or removal of the reaction medium results in


    that the progress of the catalyzed reaction stops, indicating that it is a heterogeneous catalyst.
    Toxicity tests against human lung cells (WI38 VA13 2RA) show that the catalyst is not toxic.
    Likewise, it is necessary to emphasize that the degradation may not be immediate or that the catalyst is not active as a result of the toxic not having hydrolysable bonds. Therefore, and in order to overcome these drawbacks, this invention makes use of a broad spectrum adsorbent as a second component. The typical adsorbent can be a classic amorphous inorganic adsorbent such as high surface active carbon, alumina or silica gel or a porous organic polymer. Said adsorbents are going to adsorb the toxic that has not degraded in contact with the catalyst and subsequently slowly degrade when the desorption equilibrium occurs and the toxic is brought into contact with the catalyst (Figure 1).
    Systems or devices for protection against pollutants
    In a final aspect, the invention relates to protection systems or devices against pollutants containing compounds with PX, CY or As-Cl bonds, hereinafter "protection systems against pollutants of the invention", which comprise the materials of the invention or allow the decontamination process of the invention to be carried out.
    In particular, filters comprising the materials of the invention are subject of the invention. More particularly, the filter cartridges for gas masks comprising the materials of the invention, the gas masks incorporating those cartridges, the filters of the air conditioning or ventilation systems comprising the materials of the invention, the filters for water purification or filtering systems and the systems that incorporate them.
    Also subject of the invention are fabrics or fabrics comprising or incorporating the materials of the invention. These fabrics can be used for the manufacture of protective garments.
    REALIZATION MODES


    Preparation of (LiOtBu) 0.06Zr (OH) 4
    The common preparation procedure consists of two stages. The first stage consisted in the preparation of a 0.75 M solution of LiOtBu in anhydrous tetrahydrofuran (THF) under an inert atmosphere of Ar. For this, 110g of LiOtBu were weighed and suspended in 3 liters of anhydrous THF. The resulting mixture was heated at 60 ° C for 30 minutes resulting in a clean solution. In a second stage 600 grams of Zr (OH) 4 was added to the 0.75 M solution of LiOtBu. The resulting suspension was heated at reflux with stirring for 16 hours. Finally, the solid was filtered, washed with abundant THF, and stored in an Ar atmosphere.
    Example 1. Catalytic activity of the catalyst against neurotoxics
    2.5 µL of the disisopropylfluorophosphate (DIFP) nerve gas simulant is added to 0.5 mL of an aqueous suspension containing 20 mg of zirconium (IV) hydroxide doped with lithium tertbutoxide, (LiOtBu) 0.06Zr (OH) 4. The reaction kinetics is followed by gas chromatography using dimethylsulfoxide as the internal standard. The results show that the complete degradation of the P-F bond of the neurotoxic agent model (DIFP) in less than 5 min (Figure 2). Also, the addition of the typical degradation product of the neurotoxic agents, methylphosphonic acid does not affect the degradation kinetics while in the case of untreated Zr (OH) 4 blocks its catalytic activity.
    Example 2. Catalytic activity of the catalyst against vesicant agents
    2.5 L of the 2-chloroethyl ethyl sulfide (CEES) vesicle gas simulant is added to 0.5 mL of a 1: 1 ethanol / water mixture containing 20 mg of zirconium (IV) hydroxide doped with lithium tertbutoxide, (LiOtBu) 0.06Zr ( OH) 4.
    The degradation of 50% of the C-Cl bonds of the simulant of the vesicant gas takes place at only 8 min, completing 100% after 28 min.
    Example 3. Block of the secondary emission of the adsorbent
    2.5 L of the disisopropylfluorophosphate nerve gas simulant or alternatively of the 2-chloroethyl ethyl sulfide bladder gas simulant in 200 mg of a mixture containing 90% by weight of active carbon and 10% by weight of catalyst


    of zirconium hydroxide doped with lithium tertbutoxide, in the presence of humidity at room temperature. The extraction of the adsorbed phase with 0.5 mL of dichloromethane and subsequent analysis by gas chromatography shows that complete degradation of the P-F bond of the neurotoxic and the C-Cl bond of the agent takes place
    5 vesicante. In the case of the control formed only by activated carbon, 100% of the toxic is recovered without degrading.
    It can therefore be concluded that the catalyst hydrolyzes a wide spectrum of P-X and C-Y bonds and that once incorporated into the porous material, it gives rise to an adsorbent material that has detoxifying properties avoiding problems
    10 related to the toxicity of contaminated adsorbents by blocking secondary emission processes.

    权利要求:
    Claims (25)
    [1]
    1. Material for hydrolytic degradation of P-X, C-Y or As-Cl bonds comprising zirconium hydroxide doped or activated with a basic compound of lithium or magnesium.
    [2]
    2. Material according to previous claim wherein the basic lithium compound is a lithium alkoxide.
    [3]
    3. Material according to any of the preceding claims wherein the lithium alkoxide is selected from the group consisting of lithium tertbutoxide, lithium isopropoxide, lithium ethoxide, lithium methoxide, lithium hydride or mixtures thereof, preferably lithium tertbutoxide.
    [4]
    4. Material according to the preceding claim, of formula (LiOtBu) mZr (OH) 4 where m can vary between 0.000001 and 1, preferably between 0.001 and 0.2, more preferably between
    [0]
    0.01 and 0.2, more preferably between 0.01 and 0.1, and even more preferably m = 0.06.
    [5]
    5. Material according to claim 1 wherein the basic magnesium compound is magnesium hydroxide, magnesium oxide, magnesium hydride, alkyl magnesium, preferably magnesium hydroxide.
    [6]
    6. Material according to the preceding claim, of the formula [Mg (OH) 2] m [Zr (OH) 4], where m can vary between 0.000001 and 1, preferably between 0.001 and 0.2, more preferably between 0.01 and 0.2, more preferably between 0.01 and 0.1, and even more preferably m = 0.06.
    [7]
    7. Material according to any of the preceding claims characterized in that the activated zirconium hydroxide is supported on porous adsorbent materials.
    [8]
    8.-Material, according to the preceding claim, characterized in that the porous adsorbent material is selected from the list consisting of activated carbon, alumina, zeolite, silica gel and porous organic polymers or is a mixture thereof.
    [9]
    9. Material according to the preceding claim, characterized in that the porous adsorbent material is activated carbon.
    [10]
    10. Process for the production of materials for the hydrolytic degradation of PX, CY or As-Cl bonds, according to claim 1, comprising the treatment of a zirconium hydroxide with a solution of the basic compound of lithium or magnesium in an aprotic solvent and the subsequent incorporation of the zirconium hydroxide thus doped or activated into a porous adsorbent material.

    [11]
    11. Process according to the preceding claim wherein the aprotic solvent is selected from the list consisting of tetrahydrofuran, ditertbutyl ether, diethyl ether, ethanol, methanol or mixtures thereof.
    [12]
    12. Method according to the preceding claim wherein the aprotic solvent is tetrahydrofuran.
    [13]
    13. Process according to any of claims 10 to 12 wherein the basic compound is a lithium alkoxide, preferably lithium tertbutoxide.
    [14]
    14. Method according to any of claims 10 to 13, characterized in that the proportion of the catalyst with respect to the porous material is between 0.001 and 99% w / w, preferably between 1 and 10%, more preferably 5%.
    [15]
    15.-Procedure for removing contaminants comprising chemical compounds with P-X, C-Y or As-Cl bonds comprising contacting the contaminant with the materials according to any of claims 1 to 8.
    [16]
    16.-Method according to previous claim characterized in that the contaminant is a nerve or neurotoxic chemical warfare agent, preferably Sarin, Tabún
    or Somán.
    [17]
    17. Method according to claim 15 characterized in that the contaminant is a vesicant, preferably Iperite.
    [18]
    18. Method according to claim 15 characterized in that the contaminant is an insecticide, preferably Parathion.
    [19]
    19.-Protection system against pollutants comprising compounds with P-X, C-Y or As-Cl bonds, comprising the materials according to claims 1 to 10 or allowing the process according to claims 15 to 18 to be carried out.
    [20]
    20.-Protection system according to previous claim characterized in that it is a filter.
    [21]
    21.-Gas mask comprising a filter according to previous claim.
    [22]
    22.-Ventilation or air conditioning system comprising a filter according to claim 20.
    [23]
    23.-Water purification system comprising a filter according to claim 20.

    [24]
    24.-Protection system according to claim 19 characterized in that it is a protective fabric.

    Figure 1
    Figure 2

    Figure 3
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    同族专利:
    公开号 | 公开日
    WO2018122440A1|2018-07-05|
    ES2677143B1|2019-05-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US10828873B1|2019-08-16|2020-11-10|Battelle Memorial Institute|Textile composite having sorptive and reactive properties against toxic agents|US6860924B2|2002-06-07|2005-03-01|Nanoscale Materials, Inc.|Air-stable metal oxide nanoparticles|
    GB0517342D0|2005-08-25|2005-10-05|Magnesium Elektron Ltd|Zirconate process|
    US8877677B1|2010-10-28|2014-11-04|The United States Of America As Represented By The Secretary Of The Army|Filtration media and process for the removal of hazardous materials from air streams|
    US9034289B1|2014-04-04|2015-05-19|The United States Of America As Represented By The Secretary Of The Army|Method and apparatus for prolonging the service life of a collective protection filter using a guard bed|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201631713A|ES2677143B1|2016-12-29|2016-12-29|SELF-CLEANING ADSORBENTS OF VOLATILE ORGANIC TOXIC COMPOUNDS|ES201631713A| ES2677143B1|2016-12-29|2016-12-29|SELF-CLEANING ADSORBENTS OF VOLATILE ORGANIC TOXIC COMPOUNDS|
    PCT/ES2017/070865| WO2018122440A1|2016-12-29|2017-12-29|Self-cleaning adsorbents of toxic volatile organic compounds|
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