da re aod TATE 25/11/2018 16:16 _ 81937545482 DaLIVERY A Review of Solid and Liquid Sulphur Specifications with Emphasis on Handling and Transportation P. D. CLARK Alberta Sulphur Research 2500 University Drive NW, Calgary, Alberta, Canada, T2N 1N4 this paper is to give a review of specifications for of impurit iquid and solid sulphur and comment on the relevance of the Specifications to the handling and use of sulphur. A description of the chemistry of liquid and solid sulphur is given and linked to the important issue of fabilty and dust formation during the transportation and use of solid sulphur. Overall, it can be concluded that standards and specifica- tons for sulphur have reached a high level of maturity. ive n Ti INTRODUCTION Elemental sulphur is a basic industrial commodity handled extensively throughout the industrialized world. Chemically, sulphur is a very interest- ing element, as it occurs in a variety of allotropes'. These different molecular forms are regponsible for both solid and liquid sulphur display- ing a variety of prop: , which, in turn, present chall handling and transportation, So as to standardize procedures and facilities across the world, specifications for solid form and impurity levels have been applied over the years. In addition, quality co1 is very important, as sulphur is used in fertilizer production and for a myriad industrial applications. -87- Supplied by The British Library - "The world's knowledge" oe he = PAGE 02/1825/11/2018 16:16 —e1g37S4B4a2 DELIVERY w is to examine the current status of spe Iphur in both the solid and liquid forms. In ar, standards applied in Canada will be addressed, as the Canadian sulphur industry has been prominent in developing advanced protocols for the handling and transportation of sulphur. At present, Canada produces approximately 8 million tonnes/annum of sulphur, which is exported either as liquid to the United States of America by rail or as solid through the Port of Vancouver to customers worldwide. SPECIFICATIONS FOR SOLID SULPHUR Impurity levels The i urity levels accepted in export grade sulphur are listed in Table I. Generally, on a dry basis, premium Product must contain no less than eee EEE EES Peer CPE Table I lity of Product Sulphur Orally ot 99.90% dry al) CANADIAN EXPORT SOME SPEC. MAXIMUM ADVERSE EFFECTS: 800 ppmw Fitermnozzle plugging ‘carryover into acid plant 250 ppmw Carsu! formation, plugging Residual HS 0-30 ppmw Toxic, odours Arsenic 0.25 pomw ‘Toxic in tertiiser, etc Selenium” 1.00 parm Limited tolerance in feritiser products made from H,SO, Tellurium 1.00 ppm from sulfur Water 10,000 ppm (1%) ‘Wet elemental suffur corrosion; (as produced) microbiological acidification Comman Values Acidity (H,SO, <0.01% corrosion; requires ime eee by weight neutralisation; filler plugging Chloride » <$0 ppmw forms VOC, (volatile) in sulfuric acid contact process — 88. ‘Supplied by The British Library - "The world's knowledge” PAGE 03/1625/11/2018 16:16 1937545482 DELIVERY 99.9% sulphur. However, as will be discussed later, sulphur is usually sold with significant water content (up to 1 weight-%). Ash content Ash content is critical to end users and must not exceed 500 ppmw. Most of the elemental sulphur traded ends up being converted to sulphuric acid. In this process, sulphar is liquefied and combusted to SO, by injection with air in specialized burners. Too much ash may cause clogging of burner nozzles and material erosion from the burner tips. In addition, ash carrying over into the catalyst beds used to convert SO, to SO, decreases their efficiency. In general, ash is not a major impurity in Claus-produced sulphur. Usually, only small quantities (< 50 ppmw) of aluminium sulphate are found in Claus sulphur as a result of slow degradation of the catalytic converter beds. However, despite rigorous efforts to exclude it, ash is more commonly encountered in Frasch-produced elemental sulphur, Ash from Frasch sulphur may contain clays, other alumino-silicates and mineral salts originally present in the sulphur-bearing formation. Nevertheless, Frasch sulphur usually has an ash content well below the 500 ppmw specification after filtration and processing of the crude sulphur. Carbon content ‘The specification level for residual carbon in pon ient is less than 250 ppmw. Again, this contaminant is important to sulphuric acid manufac- turers, as carbon or hydrocarbon may react liquid sulphur at temperatures above 130°C to form “carsul”, a carbon-sulphur polymer. In some instances carsul may precipitate from liquid sulphur and, in sulphuric acid plants, has a tendency to do so on the burner nozzles. Carsul is frequently observed at the bottom of the sulphur run-down pits of Claus plants. It has been produced by reaction of hydrocarbons which have survived the front-end reaction furnace with sulphur produced by the Claus reactions. Carsul may also be found in Frasch-produced sulphur, as the sulphur-bearing formations often occur in association with oil and gas. In this case, carsul may be generated in the sulphur-bearing formation because of the high temperatures associated with the steam injection. Carsul is most often responsible for sulphur having an off-yellow colour as opposed to the bright yellow appearance of the pure element. ‘The chemistry of carsul production is interesting in that it results in hydrogen sulphide formation as well as in the polymer. hydrogen sulphide production is of importance, as limits on the residual hydrogen sulphide ~ 89 - ‘Supplied by The British Library - "The world's knawledge" oe Pace 04/1825/L1/2e18 16:16 _e1937545482 DELIVERY P.D. Clark Fig. 1: CHEMICAL MECHANISM OF CARSUL FORMATION Qs-g eit 0 ©) NES T > 130%. eg Ng Elemental Sulfur (Sg) ‘sulfur diradical io. | Hee lene) CHS Se Tr He ag. (s)-s t Hye" | . Hy or Je Hg oa co] a HS. \ +SH Het @Repeat | @ Maturation Hs + & ‘Sequences ~ 90 - Supplied by The British Library - "Th een eer PAGE 05/18 |25/11/2818 16:16 01937545482 DELIVERY PASE 06/18 have also been set to safeguard people handling liquid and solid sulphur and also to eliminate nuisance odours resulting during handling. This opie will be discussed in detail in a later section, Figure 1 displays chemical mechanisms for carsul formation with concomitant hydrogen sulphide production. It details reaction of sulphur with only one hydrocarbon — p- xylene ~ but, in principle, most hydrocarbon types will undergo similar reactions. An important facet of these reactions is that new C-S bonds are formed which, with most hydrocarbons, will result in the generation of insoluble carbon-sulphur compounds (carsul) through cross-linking. Residual hydrogen sulphide The Canadian sulphur industry has set a limit of 30 ppmw residual hydrogen sulphide in solid sulphur leaving the plant gate. However, because hydrogen sulphide continues to be released during subsequent handling, solid sulphur exported from Canada usually contains much less than 30 ppmw, and, in most cases, much less than 10 ppmw. The standards in Canada were imposed so as to eliminate odours at the terminals in Vancouver and to provide the customer with a premium product. Levels of residual hydrogen sulphide in sulphur are checked before product is designated for export. The imposition of residual hydrogen sulphide standards has had a considerable impact on production of be by the modified Claus process. Before 1990, few sulphur plants any means of degassing sulphur, and d sulphur containing as much as 200 ppmw residual hydrogen sulphide ent the export market. Since 1990, most sulphur plants in Western Canada have been retrofitted with degassing units utilizing a variety of technology. The chemistry and basic designs of these systems have been studied and reviewed in detail’. An important facet of this business has been the introduction of analytical methodology for measuring residual hydrogen sulphide in liquid sulphur down to 1 ppmw. This analysis, which is based on infra-red spectros (see Fig. 2) and is now available as 4 commercial package’, not only allows quality control but also enables operation of the degassing units in an energy efficient manner. Limits for residual hydrogen sulphide in liquid sulphur have not been addressed in many parts of the world. Since liquid is transported in closed containers and is handled within closed systems at the point of delivery, there has been less concern about hydrogen sulphide release, However, this lack of concern is misplaced, as gaseous hydrogen sulphide may build up to dangerous levels in the headspaces of rail cars and road-tankers, even when relatively low levels of hydrogen sulphide are originally present in the liquid sulphur. Several accidents have resulted from transport of liquid -91- Supplied by The British Library - "The world’s knowledge" See