Patent Publication Number: US-2022212048-A1

Title: Fire suppression compositions

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a division of U.S. application Ser. No. 17/073,515 filed Oct. 19, 2020, which is incorporated herein by reference in its entirety. 
    
    
     TECHNICAL FIELD 
     The present disclosure relates to fire suppression compositions comprising CF 3 I and CO 2 . 
     BACKGROUND 
     Halon 1301 has frequently been employed as a fire suppression agent. However, production of this agent was banned in 1994 due to its high ozone depleting potential. There is therefore a desire to replace Halon 1301 with more environmentally friendly fire suppression agents. A promising alternative to Halon 1301, CF 3 I (trifluoroiodomethane), failed a key MPS test, the bulk load test, and can be subject to decomposition during use. A solution must be found that will improve the stability of the alternative fire suppression agents. 
     SUMMARY 
     This disclosure relates to fire suppression compositions comprising blends of CF 3 I and CO 2 . The CF 3 I is present in an amount of from 23 mol. % to 80 mol. %, based on the total amount of CF 3 I and CO 2  present in the fire suppression composition. 
     In one aspect, the present disclosure provides a fire suppression composition comprising CF 3 I and CO 2 , wherein said CF 3 I is present in an amount of between 23 mol. % and 40 mol. %, e.g. from 23 mol. % to 39%, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 24 mol. % to 38 mol. %, e.g. from 25 mol. % to 37 mol. %, from 26 mol. % to 36 mol. %, from 27 mol. % to 35 mol. %, or from 28 mol. % to 34 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may present in an amount greater than 29 mol. % based on the total moles of CF 3 I and CO 2  present in the fire suppression composition, e.g. from 29 to 39 mol. %, 29 to 38 mol. %, 30 to 37 mol. %, 31 to 36 mol. %, 32 to 35 mol. %, or from 33 to 34 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 23 mol. % to 39.9 mol. %, for example from 24.5 mol. % to 39.5 mol. %, from 25.5 mol. % to 39 mol. %, or from 30 mol. % to 38 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of 22.5 mol. %, 23.5 mol. %, 25.3 mol. %, 25.5 mol. %, 30.4 mol. %, 30.5 mol. %, 32.4 mol. %, 32.5 mol. %, 35.1 mol. %, 35.5 mol. %, 39.9 mol. % or any ranges between any of these values, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. The CF 3 I may be present in an amount of 30 to 35 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     In a further aspect of the present disclosure, there is provided a fire suppression composition comprising CF 3 I and CO 2 , wherein said CF 3 I is present in an amount greater than 53 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 53 mol. % to 85 mol. %, e.g. 53 mol. % to 75 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount from 53 to 84 mol. %, 54 mol. % to 80 mol. %, 55 mol. % to 79 mol. %, 56 to 78 mol. %, 58 to 76 mol. %, 59 to 75 mol. %, 60 to 72 mol. %, 62 to 70 mol. %, 63 to 69 mol. %, 64 to 68 mol. %, or 65 to 67 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of 67.2, 67.5, 75.5, 75.7, 80.1, 80.5, 83.3, 83.5 mol. % or any ranges between any of these values, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. The CF 3 I may be present in an amount of 67 to 80 mol. %, based on the total moles of CF 3 I and CO 2  present in the fire suppression composition. 
     The amount of CF 3 I, expressed as a percentage of the total amount of CF 3 I and CO 2  in the fire suppression composition, may also be expressed in weight %. 
     Thus, in a further aspect of the present disclosure, there is provided a fire suppression composition comprising CF 3 I and CO 2 , wherein said CF 3 I is present in an amount of between 57 weight % and 75 weight %, e.g. from 57 weight % to 74 weight %, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 57 weight % to 74 weight %, for example from 58 to 73 weight %, from 60 to 72 weight %, from 61 to 71 weight %, from 62 to 70 weight %, or from 63 to 69 weight %, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of greater than 65 weight %, e.g. 65 to 74 weight %, from 65 to 73 weight %, 66 to 72 weight %, 67 to 71 weight %, from 68 to 70 weight %, or from 69 to 70 weight %, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 57 weight % to 74.7 weight %, for example from 59 weight % to 74.4 weight %, from 60.3 weight % to 74 weight %, or from 65 weight % to 73 weight %, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of 56.4 weight %, 57.8 weight %, 60.1 weight %, 60.3 weight %, 66 weight %, 66.1 weight %, 68.1 weight %, 68.2 weight %, 70.7 weight %, 71 weight %, 74.7 weight % or any ranges between any of these values, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     In a further aspect of the present disclosure, there is provided a fire suppression composition comprising CF 3 I and CO 2 , wherein the CF 3 I is present in an amount of greater than 83 weight %, for example from 83 weight % to 96 weight %, e.g. 83 weight % to 93 weight %, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     The CF 3 I may be present in an amount of from 83 to 96 weight %, 84 weight % to 95 weight %, 84 weight % to 94 weight %, 85 weight % to 94 weight %, 86 to 93 weight %, 87 to 92 weight %, 87 to 91 weight %, 87 to 90 weight %, 88 to 90 weight %, 89 to 90 weight %, or 90 to 91 weight % based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     In one aspect of the disclosed compositions, CF 3 I is present in an amount of 90.1, 90.2, 93.2, 93.3, 94.7, 94.8, 95.7, 95.7 weight %, or any ranges between any of these values, based on the total weight of CF 3 I and CO 2  present in the fire suppression composition. 
     As the amount of CF 3 I is expressed as proportion of the total of CF 3 I and CO 2 , it will be understood that the percentage of CO 2  (also expressed as a proportion of the total) is the remainder of this total (i.e. 100 minus the percentage of CF 3 I). Where the composition consists of, or consists essentially of, CF 3 I and CO 2 , these proportions will also be applicable to the composition as a whole. Fire suppression compositions comprising such blends of CF 3 I and CO 2 , e.g. those with molar ratios of CF 3 I to CO 2  of from 3:7 to 7:13, or 2:1 to 5:1 form a further aspect of this disclosure. 
     In addition to CF 3 I and CO 2 , the fire suppression composition as disclosed herein can further comprise one or more additional components. The additional components may be selected from a gas (e.g. an inert gas), an additional fire suppressant compound, odorants, or combinations thereof. 
     The total amount of additional components, if present, may be present in an amount of up to 20 weight %, based on the total weight of the fire suppression composition. 
     The total amount of additional components present in the fire suppression composition may be up to 18 weight %, up to 15 weight %, up to 10 weight %, up to 8 weight %, up to 5 weight % or up to 3 weight %, (e.g. from 0.1 weight % up to these limits) based on the total weight of the fire suppression composition. In some aspects, the total amount of additional components present in the fire suppression composition may be up to 2 weight % or up to 1 weight %, e.g. 0.1 weight % to 2 weight % or 0.1 weight % to 1 weight %. 
     The additional components, if present, may be one or more gases, e.g. an inert gas, or a propellant. Examples of suitable gases include nitrogen, argon, helium and neon, and combinations thereof. 
     The optional gas may be present in an amount of up to 1 weight %, based on the total weight of the fire suppression composition. For example, the gas may be present in an amount of up to 0.9 weight %, up to 0.8 weight %, up to 0.7 weight %, up to 0.6 weight %, up to 0.5 weight %, up to 0.4 weight %, up to 0.3 weight %, up to 0.2 weight % or up to 0.1 weight %, based on the total weight of the fire suppression composition. If present, a lower limit for the gas may be 0.05 weight %. 
     The additional component, if present, may be an additional fire suppressant compound, i.e. one that is not CF 3 I or CO 2 . 
     The additional fire suppressant compound, if present, may be present in an amount of up to 20 weight %, based on the total weight of the fire suppression composition. For example, the total amount of additional fire suppressant compound present in the fire suppression composition may be up to 18 weight %, up to 15 weight %, up to 10 weight %, up to 8 weight %, up to 5 weight % or up to 3 weight % based on the total weight of the fire suppression composition. If present, a lower limit for the additional suppressant may be 0.1 weight %. 
     The additional component, if present, can be an odorant. Examples of odorants include compounds which include one or more carbon-carbon double bonds, and/or compounds which are aromatic. The odorant compounds may further include a hydroxyl group, an iodine group, or both. 
     The odorant compound, if present, may be present in an amount of up to 1 weight % based on the total weight of the fire suppression composition. For example, the odorant may be present in an amount of up to 0.9 weight %, up to 0.8 weight %, up to 0.7 weight %, up to 0.6 weight %, up to 0.5 weight %, up to 0.4 weight %, up to 0.3 weight %, up to 0.2 weight % or up to 0.1 weight %, based on the total weight of the fire suppression composition. If present, a lower limit for the odorant may be 0.05 weight %. 
     The present disclosure also provides a device, e.g. a fire extinguisher, fire suppression device, or storage device, comprising a fire suppression composition as herein described. 
     Also disclosed is a device, e.g. a fire extinguisher, fire suppression device, or storage device, comprising at least two separate containers, wherein the first container comprises CF 3 I and the second container comprises CO 2 . The proportions of the CF 3 I and the CO 2  are as described herein. The contents of the containers can be combined immediately prior to use to produce a fire suppression composition as herein described. As would be understood, the first and/or second container can comprise one or more additional components (e.g. one or more additional components as herein described) or any additional components can be stored in a further container or containers. 
     Disclosed is a fire suppression system or device comprising a fire suppression composition as herein described, or the components thereof. The fire suppression system can comprise a fire suppression composition herein described and a dispensing component (such as one or more nozzles that disperse the fire suppression composition). In an alternative aspect, the fire suppression system can contain: (i) two separate containers, wherein the first container comprises CF 3 I and the second container comprises CO 2 , and (ii) a combining and dispensing component which is configured to combine the contents of the separate containers to form a fire suppression composition as herein described, and then dispense said resulting fire suppression composition. 
     Also disclosed is a method for extinguishing a fire comprising using a fire suppression composition as herein described. 
     Disclosed is a method for preparing a fire suppression composition as herein described, said method comprising combining CF 3 I and CO 2  such that CF 3 I is present in an amount as herein described in relation to the total amount of CF 3 I and CO 2 . The method may comprise the steps of (i) providing CF 3 I, (ii) providing CO 2  and (iii) combining CF 3 I and CO 2  such that CF 3 I is present in an amount as herein described in relation to the total amount of CF 3 I and CO 2 . The method can further comprise the additional step of adding one or more additional components as herein described. 
     In some aspects, the fire suppression composition of the present disclosure consists of, or consists essentially of, CF 3 I and CO 2  in the proportions described herein. 
    
    
     DETAILED DESCRIPTION 
     CF 3 I is an environmentally friendly alternative to fire suppression agents like Halon 1301 because CF 3 I has a lower ozone depletion potential. The lower ozone depletion potential is due to the lower stability of the molecule. However, the lower stability (or the increased tendency to degrade) presents a challenge for storage and use of CF 3 I or blends containing CF 3 I as a fire suppression agent. The lower stability has discouraged the use of CF 3 I in fire suppression applications as it can decompose, thus reducing its efficacy. The present disclosure involves addition of CO 2  to the CF 3 I, which has been found to improve stability of CF 3 I. 
     When released, the CO 2  is able to remove a large amount of heat from its surroundings (i.e. has a high latent heat of vaporization). This temperature reduction can reduce the severity of the fire, as well as reducing the decomposition rate of CF 3 I, maximizing the available CF 3 I present when the fire suppression composition is used to extinguish a fire. 
     The presence of CO 2  in the fire suppression composition can reduce the temperature of the atmosphere in the space to be protected to below 370° C. (700° F.), e.g. to below 360° C., to below 350° C., to below 340° C., to below 330° C., to below 320° C., or to below 315° C. (600° F.). 
     CO 2  is a physically acting fire suppression agent and CF 3 I is a chemically acting agent. Combining these two different types of agent as described herein results in a synergistic combination. More specifically, the blends of CO 2  and CF 3 I as disclosed herein have been shown to be a synergistic combination. The combination of these two components has surprisingly resulted in a fractional inerting composition number of less than the sum of the two components when measured separately. The effect of this is that the combination of these two components has an enhanced ability to extinguish a fire than the two components would have had if used separately in the same amount. 
     It has also been found that fire suppression compositions according to the present disclosure can have a reduced vapor pressure, and in some instances, a vapor pressure in the same range as that of conventional fire suppression agents such as Halon 1301. The reduced vapor pressure allows the fire suppression composition to be used in conventional hardware such as preexisting fire extinguishing containers and devices. 
     The present disclosure will now be further described by way of the following non-limiting examples. 
     Examples 
     Testing Procedure 
     Testing was carried out against propane-air explosions in a 42 L sphere. The most explosive propane-air mixture is 4% propane in air. This concentration was therefore used to assess the relative performance of extinguishing agents and blends thereof 
     The sphere was evacuated. Whilst monitoring the pressure transducer, propane was added to a pressure of 0.04 atm (4% in the final mix). The agent or agents were added at the desired concentration. Air was then added to raise the pressure in the sphere to 1.00 atm. A fan can then be used to ensure that all the gases are mixed homogeneously throughout the sphere. A spark was ignited using a center point spark ignition and the pressure rise was monitored by a data logger. A pressure rise of 1 psi or lower is designated as a pass. 
     The standards used for inerting testing are:
 
ASTM E2079-07—the standard test method for limiting oxidant concentration in gases and vapors
 
BS EN 1839:2012—determination of explosion limits in gases and vapors
 
BS EN 15967:2012—determination of maximum explosion pressure and the maximum rate of pressure rise of gases and vapors.
 
     Fractional Inerting Contribution 
     When assessing blends of components, the concept of fractional inerting contribution is used. This is defined as: 
     
       
         
           
             FIC 
             = 
             
               
                 ∑ 
                 
                   i 
                   = 
                   1 
                 
                 n 
               
               ⁢ 
               
                 
                   C 
                   i 
                 
                 
                   IC 
                   i 
                 
               
             
           
         
       
     
     Where C i  is the concentration of component i
 
And IC i  is the inerting concentration of component i.
 
Thus, inerting should be attained when FIC=1 (i.e. the sum of individual concentrations has reached the overall required amount to achieve inerting). It therefore follows that if inerting is achieved at FIC less than 1, then the blend is more effective than the sum of its components. In other words, the blend is exhibiting synergy.
 
Blends of CF 3 I and CO 2  
 
     Blends of CF 3 I and CO 2  were evaluated and it was found that successful inerting results were found at FIC values of lower than 1: 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE I 
               
               
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                 Rel. wt  
                 Rel. vol 
                   
               
               
                   
                   
                   
                   
                   
                 Pres 
                   
                 to 6% 
                 to 6% 
                   
               
               
                   
                 Propane 
                 CF 3 I 
                 CO 2   
                 Mol 
                 rise 
                   
                 Halon 
                 Halon 
                 Mol. % 
               
               
                 Example 
                 (Vol %) 
                 (Vol %) 
                 (Vol %) 
                 Ratio 
                 (psig) 
                 FIC 
                 1301 
                 1301 
                 CF 3 I* 
               
               
                   
               
             
            
               
                 1 
                 3.98 
                 2.93 
                 8.64 
                 1:3 
                 0.99 
                 0.76 
                 1.04 
                 1.36 
                 25.3 
               
               
                 2 
                 4.01 
                 3.24 
                 7.42 
                 3:7 
                 0.91 
                 0.76 
                 1.04 
                 1.27 
                 30.4 
               
               
                 3 
                 4.02 
                 3.31 
                 6.92 
                  6:13 
                 0.78 
                 0.76 
                 1.03 
                 1.22 
                 32.4 
               
               
                 4 
                 4.05 
                 3.49 
                 6.46 
                  7:13 
                 0.9  
                 0.77 
                 1.04 
                 1.2  
                 35.1 
               
               
                   
               
               
                 *Mol. % CF 3 I expressed as a proportion of the moles of CF 3 I and CO 2   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE II 
               
               
                   
               
               
                   
                   
                   
                   
                   
                   
                   
                 Rel. wt  
                 Rel. vol 
                   
               
               
                   
                   
                   
                   
                   
                 Pres 
                   
                 to 6% 
                 to 6% 
                   
               
               
                   
                 Propane 
                 CF 3 I 
                 CO 2   
                 Mol 
                 rise 
                   
                 Halon 
                 Halon 
                 Mol. % 
               
               
                 Example 
                 (Vol %) 
                 (Vol %) 
                 (Vol %) 
                 Ratio 
                 (psig) 
                 FIC 
                 1301 
                 1301 
                 CF 3 I* 
               
               
                   
               
             
            
               
                 5 
                 4.04 
                 5.19 
                 2.53 
                 2:1 
                 0.94 
                 0.89 
                 1.22 
                 1.06 
                 67.2 
               
               
                 6 
                 3.98 
                 5.47 
                 1.76 
                 3:1 
                 0.97 
                 0.90 
                 1.25 
                 1.03 
                 75.7 
               
               
                 7 
                 4.08 
                 6.01 
                 1.49 
                 4:1 
                 0.97 
                 0.98 
                 1.36 
                 1.09 
                 80.1 
               
               
                 8 
                 4.01 
                 6.49 
                 1.3  
                 5:1 
                 0.96 
                 1.04 
                 1.46 
                 1.15 
                 83.3 
               
               
                   
               
               
                 *Mol. % CF 3 I expressed as a proportion of the moles of CF 3 I and CO 2   
               
            
           
         
       
     
     As can be seen from Tables I and II above, all examples show a synergistic effect between the CF 3 I and CO 2  in the blend. Examples 1-4 show a particularly good synergistic effect, coupled with an acceptable vapor pressure/temperature characteristics. Examples 5-8 show a synergistic effect, and these examples have improved vapor pressure/temperature characteristics. 
     References to “comprises” and/or “comprising,” should be understood to also encompass “consist(s) of”, “consisting of”, “consist(s) essentially of” and “consisting essentially of”. 
     The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, element components, and/or groups thereof. 
     While the present disclosure has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present disclosure without departing from the essential scope thereof. Therefore, it is intended that the present disclosure not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this present disclosure, but that the present disclosure will include all embodiments falling within the scope of the claims.