Malhotra, Ramesh Chandra (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Batra, Balwant Singh (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Ganesan, Kumaran (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Sekhar, Krishnamarthy (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Malhotra, Ramesh Chandra (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Batra, Balwant Singh (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
Ganesan, Kumaran (Defence Research & Development, Establishment Jhansi Roa, Gwalior 2 Madhya Pradesh, 474 00, IN)
| 1. | A process for the complete destruction of gelled sulphur mustard (SM), comprising the steps of : a) dissolving gelled sulphur mustard (SM) in organic solvent such as 2chloroethanol, methanol, methyl cellosolve or mixtures of these to obtain a clear mixture, b) incinerating the clear gelled sulphur mustard solvent mixture obtained from step (a) ; c) dissolving residual gelled SM obtained from step (c) into nontoxic products; d) chemically converting dissolved SM obtained from step (c) into nontoxic products. |
| 2. | A process as claimed in claim 1 wherein ratio of gelled SM to organic solvent is 2 : 1 to 1: 5 w/w. |
| 3. | A process as claimed in claim 1 wherein the gelled SM with organic solvent is maintained at a temperature of 20°C to 50'C temperature, and for a period of 10 to 90 days. |
| 4. | A process as claimed in claim 1 wherein gelled SM is dissolved in organic solvent in the presence of nitrogen gas bubbled through the mixture for 5 to 30 hours and at a rate of 1 to 10 litre per minute (LPM). |
| 5. | A process as claimed in claim 1 wherein clear liquid obtained from step (a) is incinerated at 8001500'C for a period of 16 seconds. |
| 6. | A process as claimed in claim 1 wherein the remaining gelled SM is dissolved by adding methyl cellosolve in the ratio of 2 : 1 to 1 : 3 w/w. |
| 7. | A process as claimed in claim 1 wherein the gelled SM is dissolved in methyl cellosolve by bubbling nitrogen gas for a period of 110 hrs and at a rate of 1 to 10 litre per minute. |
| 8. | A process as claimed in claim 1 wherein step (d) comprises in adding powdered sodium hydroxide to methyl cellosolvegelled SM mixture obtained in step (c) in the ratio of 1:10 to 1 : 20 w/w. |
| 9. | A process as claimed in claim 8 wherein the gelled SM is dissolved by bubbling nitrogen for a period of 110 hours at a rate of 1 to 10 litre per minute. |
| 10. | A process as claimed in claim 9 wherein diethylenetriamine is added to methyl cellosolvegelled SM mixture, equivalent to 2 to 4 tim es of methyl cellosolve used. |
| 11. | A process as claimed in claim 10 wherein the mixture is kept for 510 days at a temperature 20°C to 50°C. |
PRIOR ART Sulphur mustard (SM), chemically known a thiobis-(2-chloroeehàne3 is highly toxic and persistent liquid vesicant. SM on storage in the bulk containers and munitions become partly"gelled"or crusty. The extent of gelling or solidification depends on the process used for manufacture of SMs storage conditions and duration for which SM resided in the containers.
Processes known in the art for destruction of pare SM consist of high temperature reaction technology, which involve destruction of SM by heating at high temperature. The technologies are incineration, pyrolysis, plasma torch and molten metal systems. Among all these high temperature reaction technologies, incineration is a well-proven technology for the destruction of pure SM and is widely used for the destruction of pure SM.
The main disadvantage of incineration is that it cannot be used for'gelled', SM (heel) due to the difficulty in draining off the gelled SM from storage containers.
IN/PA-210 Another known process in the art for destruction of pure SM is thé ! ou temperature destruction technology based on hydrolysis of SM.
The main disadvantage of the technology involving hydrolysis is that gelled SM is insoluble in water and alkaline solution and hence cannot be used for the destruction of gelled SM.
Another known process in the art for destruction of pure SM is the low temperature destruction technology based on electrochemical oxidation. In this process SM is oxidized in Ag(II)/AG(I) electrochemical cell in acidic medium.
The main drawback of this technology based on electrochemical oxidation is that sulphone of SM is one of the products of oxidation of pure SM, which is toxic in nature.
Another drawback of this technology based on electrochemical oxidation is that the nature of oxidation products of gelled SM is not known because the chemical composition of gelled SM is uncertain.
Yet another drawback of this technology based on electrochemical oxidation is that it cannot be used for bulk destruction of pure SM.
Still another drawback of this technology based on electrochemical oxidation is that the cost involved is very high.
IN/PA-210 Another known process in the art for destruction of pure SM is the low temperature destruction technology based on solvated electron system in which pure SM is reduced by solution of metallic sodium in anhydrous liquid ammonia.
The main disadvantage of the above low temperature destruction process based on solvate electron system is that gelled SM cannot be transferred from storage container to the reaction vessel. Thus this technology cannot be applied for the destruction of gelled SM.
Another disadvantage of the above destruction process based on solvate electron system is that it requires precise conditions for the use of highly reactive metallic sodium. Since hydrogen chloride is present in the gelled SM it may lead to uncontrollable exothermic (highly flammable) reaction.
Another known process in the art of destruction of pure SM is the low temperature destruction technology based on chemical conversion using thiophilic agents.
The major drawback of the destruction process based on thiophilic agents is that this method is suitable only for pure SM. Since the chemical composition of the gelled SM is uncertain, it cannot be used for the destruction of gelled SM.
IN/PA-210 NEED FOR THE PRESENT INVENTION There is a need to develop either separate technology for the destruction of gelled SM (Heel) or to find out suitable organic solvent in which gelled SM is highly soluble and the resultant solvent-gelled SM mixture can be incinerated easily using incineration technology.
OBJECTS OF THE PRESENT INVENTION The main object of the present invention is to provide a process for the destruction of gelled sulphur mustard (SM)/Heel.
Another object of the present invention is to provide a process for the destruction of gelled SM, which is eco-friendly.
Yet another object of the present invention is to provide a process for the destruction of gelled SM, which does not require specialized plant/equipment for the bulk destruction.
Still another object of the present invention is to provide a process for the destruction of gelled SM, which is cost effective.
Yet another object of the present invention is to provide a process for the destruction of gelled SM, which meets the verification requirement of the Organisation for the Prohibition of Chemical Weapons (OPCW).
Yet further object of the present invention is to provide a process which completely destroys gelled SM.
DESCRIPTION OF PROCESS According to this invention there is provided a process for the complete destruction of gelled sulphur mustard (su), comprising the steps of : (a) Dissolving gelled sulphur mustard (SM) in organic solvent such as 2- chloroethanol, methanol, methyl cellosolve or mixture of these, preferably 2-chloroethanol.
(b)Incinerating the clear gelled sulphur mustard-solvent mixture obtained from step (a) ; (c) Dissolving remaining gelled SM obtained irom step (b) ; (d) Chemically converting dissolved SM obtained from step (c) into non- toxic products.
The exact chemical composition of the gelled SM varies depending on production method used, preservative added, storage period/conditions.
However, it is generally assumed to be polymeric cyclic and polysulphonium salts in varying percentages. There are also indications that in addition to these polymeric compounds, dithiane, 1, 2-dichloroethane, sulphone and sulphoxides of SM and sesquimustard are also present. If moisture is present in the SM during production, it hydrolyses pure SM slowly and hydrogen chloride (HCI) is generated. By the addition of preservatives like picoline, most of the te
IN/PA-210 picoline to form picoline hydrochloride, while remaining free HCL on long standing, reacts with container to form gaseous hydrogen and iron salts.
The present process for the destruction of gelled Sulphur Mustard (SM) comprises of the following steps: (a Dissohttion of seffed SM in organic solvents: Solvents like 2-Chloroethanol or methanol or methyl cellosolve or mixture of these solvents is added to gelled SM in the ratio 2 : 1 to 1 : 5 w/w preferably in the ratio 1 : 1. After addition of the solvent, it is left for 10 to 90 days, preferably 30 days at t 20°C to 50°C temperature, preferably at 30°C. To dissolve the gelled SM completely, nitrogen gas is then bubbled through the mixture for 5 to 30 hours, preferably 10 hrs at the rate of 1 to 10 Litre per minute (LPM), preferably 5 LPM.
(b) Incineration of solvent-gelled SM mixture : The clear liquid from step (a) is incinerated at 800-1500"C preferably at 1200°C. A residence time of 1-6 seconds, preferably 3 seconds, in the high- temperature area is sufficient to achieve complete destruction of gelled SM- solvent mixture. Sulphur dioxide and HCI, generated by combustion ; is neutralized by passing through a 5-20% solution of sodium hydroxide, preferably 10% solution. This process produces sodium sulphate and sodium chloride, both of which are non-toxic.
RiVA-210 (c) of remaining gelled SM: Gelled SM to the extent of about 10%, which is aot soluble in the above solvents remains, after the removal of clear-gelled SM-solvent mixture for incineration. Methyl cellosolve is added to the remaining gelled SM in the ratio 2: 1 to 1: 3, preferably in the ratio 1 : 1 and left for 2-3 hrs at temperature 2540qu preferably at 3QC. Nitrogen gas is bubbled through it for 1-10 hrs, preferably 5 hrs at the rate of 1 to 10 Litre per minute (LPM), preferably 5 LPM to dissolve the residue completely in methyl cellosolve.
(d) Chemical conversion of dissolved SM : To the mixture of methyl cellosolve and SM obtained in step (c), powdered sodium hydroxide (in the ratio sodium hydroxide: methyl cellosolve, 1:10 to 1 : 20 w/w, preferably 1 : 14 w/w) is added and nitrogen gas is again bubbled at the rate of 1 to 10 Litre per minute (LPM), preferably 5 LPM, for 1-10 hrs preferably 5 hrs. Then diethylenetrimine (DETA, equivalent to 1-5 times w/w, preferably 2. 5 times, w/w of methyl cellosolve) is added and the content is left for 5-15 days, preferably seven days. After this period of 15 days the mixture is free from SM completely and there is no gelled SM left in the container.
The present invention will now be illustrated with working examples) which are intended to be illustrative examples and are not intended to be taken restrictively to imply any limitation on the scope of the present invention.
WORKING EXAMPLE 1 :
IN/PA-210 One ton of 2-chloroethanol (2-CE) was added to one ton of gelled SM and left for 15 days at 30°C. Then, nitrogen gas was bubbled through it for 8 hrs at the rate of 3 LPM to dissolve the gelled SM completely. The clear liquid was then incinerated at 800°C, for 6 seconds. The remaining about 10% of gelled SM (100 kg), which was not soluble in 2-CE remained as residue. To this, methyl cellosolve 150 kg was added and left for 2 hrs at 30oC.
Nitrogen gas was bubbled for 1 hr to dissolve the residue completely in the methyl cellosolve. To this, methyl cellosolve 1550 kg was added and left for 2 hrs at 30°C. Nitrogen gas was bubbled for I hr to dissolve the residue completely in the methyl cellosolve. To this, 10. 5 kg of powdered sodium hydroxide is added and nitrogen was bubbled again for 2 hrs, then ETA (375 kg) was added and the mixture was left for one week for the destruction of SM.
WORKING EXAMPLE 2 : One ton of 2-chloroethanol (2-CE) was added to one ton of gelled SM and left for 30 days at 30oC. Then, nitrogen gas was bubbled through it for 10 hrs at the rate of 5 LPM to dissolve the gelled SM completely. The clear liquid was then incinerated at 1200"C, for 3 seconds. The remaining about 10% of gelled SM (100 kg), which was not soluble in 2-CE remained as residue. To this, methyl cellosolve 150 kg was added and left for 2 hrs at 30°C. Nitrogen gas was bubbled for 1 hr to dissolve the residue completely in the methyl cellosolve. To this, 10. 5 kg of powdered sodium hydroxide was added and nitrogen was bubbled again for 2 hrs, then DETA (375 kg) was added and the mixture was left for one week for the destruction of SM.
WORKING EXAMPLE-3 1. 5 ton of 2-chloroethanol (2-CE) was added to one ton of gelled SM and left for 20 days at t 30°C. Then, nitrogengas was bubbled through it for 25 hrs at the rate of 2 LPM to dissolve the gelled SM completely. The clear liquid was then incinerated at 1000°C, for 4 seconds. The remaining about 10% of gelled SM (100 kg), which was not soluble in 2-CE remains as residue. To this, methyl cellosolve ISO kg was added aad left for 2 hrs at 30°C. Nitrogen gas was bubbled for 1 hr to dissolve the residue completely in the methyl cellosolve. To this, 10. 5 kg of powdered sodium hydroxide was added and nitrogen was bubbled again for 2 hrs, then DETA (375 kg) was added and the mixture was left for one week for the destruction of SM.
It is to be understood that the present invention is susceptible to modifications, changes and adaptations are intended to be within the scope of the present invention which is further set forth under the following claims.