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However transport of sulphur trioxide has been taking place in the United States of America in road tankers without the addition of an inhibitor since 1968. The tonnages which have been transported in this way are in the order of 30,000 tonnes per annum over distances such as from Chicago to California, a journey of at least three days duration. No problems have been encountered so far during some 25 years of transporting the substance in this way. The USA Code of Federal Regulations Title 49 has provisions included for the transport of sulphur trioxide without the addition of an inhibitor. 2.There is a need to transport this substance in the uninhibited state in other parts of the world. This should be facilitated by amending the UN Recommendations. GE.94 ),,,  X ST/SG/AC.10/R.454 page 2  r5  Production of Single Distilled Sulphur Trioxide   s= 3.Sulphur Trioxide (SO3) can exist in three forms in the solid state, ,  and *. Standard production methods, where the substance is distilled once only, result in sulphur trioxide in the liquid state at temperatures around  s= +35$C. Manufacturers of single distilled SO3 will add the inhibitor at this stage and will maintain it at around +35$C. When ready for transportation, the substance is loaded into tanks which are insulated (packagings are not known to be used). For most short duration journeys the substance remains  s= molten. Should the substance solidify, it will do so into solid SO3. Any polymerisation which immediately appears will be in the  form, likely to be in the order of 510%. The solidification temperature is +17$C. 4.Sufficient inhibitor is added to prevent any transition from the form to the form should the substance solidify. By the time it is reheated once to +32.5$C all polymer will have been completely remelted. 5.The form is very unlikely to appear unless there has been a catastrophic temperature failure with a temperature drop to below 5$C, a highly unlikely event which, if it did occur, would take weeks to happen with insulated tankers.  s= 6.It should be noted that with single distilled SO3 there will always be a certain amount of moisture present (sulphuric acid), in the order of 0.1% which will act as a catalyst for polymerisation.  r5]  Conditions under which Dangerous polymerisation may occur  7.Dangerous polymerisation reactions can only occur in extremely remote  s=R circumstances. SO3 would have to be repeatedly solidified and reheated over many cycles so that it is completely transformed into the form. Then it would have to be heated up to temperatures in excess 95$C. Experience shows that it is very difficult to produce a pure  and the conditions conducive to explosive polymerisation and rapid rise in pressure. Recent laboratory experiments have failed to produce complete polymerisation after 8 complete cycles.  r5:   The Problem of Selecting an Inhibitor   s= 8.There are five recognised methods of inhibiting SO3, i.e. by the addition of either Carbon Tetrachloride# Dimethyl Sulphate# Trimethyl Borate# Tributoxy Boroxine# Trimethyl Boroxine# 9.Production of Carbon Tetrachloride is scheduled to cease in the European Union from 01.01.95 as a result of the Montreal Protocol, so that it is no longer available in any significant quantity. _______________________ * In the USA the form is known as the form and the form as the form. In this paper the IUPAC system of identifying the isomers which is also the system commonly used in Europe has been used. Thus in this paper the form is taken to mean the form with a melting point of +62.2$C; the form having a melting point of +32.5$C; and the form a melting point of +16.8$C. ,---XXԌ` `  $+hh29AppHO  VST/SG/AC,10/R.454(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l(#(#l ` `  $+hh29AppHO  Vpage 3  s4   10.Dimethyl Sulphate (DMS) is a highly toxic substance (also with corrosive subsidiary risk) of Packing Group I. Because of its dangers, its use as an  s= inhibitor is not desirable. Users of SO3 complain that it generates side reactions in their processes which may result in further toxic substances being produced and released to atmosphere through venting systems. In addition, the use of DMS leads to residues being deposited in evaporation equipment which then has to be disposed of in the requisite manner for toxic wastes. Therefore it is in the interests of all if the use of DMS as the inhibitor can be avoided. 11.The three organoboron compounds are dissolved in hydrocarbon solvents.  s= When introduced to the SO3 they cause a localised exothermic reaction and a rise in pressure in tank shells. Downstream sulphonation reactions have been  s=) known to result in exothermic reactions when operating with SO3 stabilized in this way. For these reasons the use of this family of inhibitors is discouraged. 12.Therefore it is considered for many practical reasons that under  s=u stipulated conditions of transport the carriage of SO3 in the uninhibited state means a real progress.   r5  Production of Distilled and Fractionated Sulphur Trioxide  s=h 13.When SO3 is produced, by a distillation process, the purity level achieved is a minimum of 99.99%. In practice the purity is even higher, to the extent that the moisture level is so small that it is technically difficult to measure it. 14.As such, it is considered that there is no catalyst in the form of moisture (sulphuric acid) present to initiate polymerisation. Thus there is no need to add an inhibitor to double distilled material as long as the temperature is maintained at above +32.5$C.  r5  PROPOSAL   s= 15.CEFIC proposes the following to facilitate the transport of SO3 in the uninhibited state. 16.Amend the UN entry 1829 as follows : 18295` ` SULPHUR TRIOXIDE, INHIBITED#` or5` ` SULPHUR TRIOXIDE 99.8% 9A8ppHxxxOI  VM#` 17.Add a special provision No. XXX to read 'Sulphur Trioxide 99.8% pure and above may be transported in tanks without an inhibitor providing that it is maintained at a temperature equal to or in excess of +32.5$C'. 5