DECREASING H2S EMISSION IN BITUMEN/SULPHUR MIXTURES

Abstract: There is disclosed a process for preparing a mixture com­ prising bitumen and sulphur, wherein bitumen and elemental sulphur are mixed at an elevated temperature preferably 130°C to 150°C, in the presence of at least one metal carboxy­ late or naphthenate which is at least partially soluble in the bitumen at the mixing temperature. Preferred are metal salts of carboxylic acids of at least 12, preferably 16 to 18, carbon atoms per molecule. Suitably the quantity of metal organic salt employed is from 0.05 to 0.5 wt%, calculated as zinc metal, based on the weight of the bitumen. Zinc stearate is especially suitable.

Description: DECREASING R2S EMISSION IN BITUMEN/SULPEUR MIXTURES This invention relates to the preparation of mixtures containing bitumen and elemental sulphur, and is more especially concerned with decreasing the emission of hydrogen sulphide during the production and/or use of such mixtures. It is known that the addition of sulphur to bitumen leads to modified binding materials having improved handling properties, especially when hot, and improved mechanical properties in service. However, the bitumen/sulphur blending operation, whether conducted in advance or on site, for example when road-making, must take place above 1200C, the melting point of sulphur. Formation and/or use of the binder is, however, accompanied by the evolution of significant amounts of hydrogen sulphide. This is due to reaction of sulphur and hydrocarbons of the bitumen component at the temperatures involved. Indeed, the temperature at which the binder is employed is a significant factor and temperatures below 1400C are recommended in practice in an attempt to keep hydrogen sulphide evolution to a permissible level. However, it is often very difficult, sometimes impossible, not to exceed this temperature in practice at the central mixing plant, at least for short intervals of time; sudden temperature rises are frequently observed with accompanying' increases in hydrogen sulphide formation and emission. It is an object of the present invention to provide a process for mixing bitumen and sulphur in which evolution of hydrogen sulphide is decreased. According to the present invention there is provided a process for preparing a mixture of bitumen and sulphur, wherein bitumen and elemental sulphur are mixed at an elevated temperature in the presence of at least one metal carboxylate or naphthenate which is at least partially soluble in the bitumen at the mixing temperature. Generally the mixing will be conducted at a temperature of from 130 C to 160 C, preferably 130 C to 150 C, but an advantage of the process of the invention is that it can accommodate temperature surges up to 1700C and yet still maintain hydrogen sulphide evolution at an acceptably low level. The said organic salt employed will react in a manner which results in the formation of a substantially stable sulphide. The quantity of the metal organic salt employed is conveniently expressed by weight based on the weight of bitumen employed. The quantity is also conveniently expressed in terms of zinc; the quantity being readly convertible to take into account the particular salt and/or metal actually employed. Thus, on this basis, it is preferred to employ from 0.05 to 0.4y, especially 0.1 to 0.2, of the salt. The said metal organic salts employed will be at least partially, preferably, substantialy, soluble in the bitumen under the chosen mixing conditions. The preferred metals thereof are zinc (which is especially preferred), iron and cadmium. Less preferred are copper and lead. The preferred carboxylates are salts of alkyl or alkylaryl carboxylic acids. Especially suitable are such acids having 12 or more carbon atoms per molecule. Thus, laurates, palmitates and oleates may be employed. The preferred carboxylate is, however, a stearate; especially zinc stearate. Zinc stearate is a particularly suitable compound for employment in the process of the invention. The naphthenates and carboxylates are normally readily available compounds and have surprising and unexpected properties as H2S-emission suppressants. The organic salts employed in the process of the present invention are essentially chemically different from the hydrogen sulphide suppressants disclosed in UK-A-1494198, which'latter are free radical inhibitors and/or the reducing components of redox catalyst systems. The process of this invention is applicable to the manufacture of simple bitumen/sulphur blends, but finds especial importance in the manufacture of paving mixes. In such paving mixes any suitable aggregate material may be employed. In all cases it is highly preferred that the said metal organic salt be present before the addition of the sulphur. The most preferred procedure is to first mix the bitumen and the said organic metal salt and then add aggregate (if employed) and finally the sulphur. Normally the amount of sulphur employed will be up to 45 wt y based on the weight of bitumen, preferably up to 30 wt , suitably 20 to 30 wt . The bitumen employed in the process may be any suitable type. For example, the penetration grades 40/60 to 180/220, preferably 80/100, may be employed. It is also possible to employ the mildly oxidised bitumen product of the process described in our copending U.K. Patent Publication 2108998-A, and European Patent Publication 78701-A2. The two types may be used together. The invention will now be illustrated by reference to the following non-limitative examples: Example 1 A standard 80/100 pen bitumen was taken. A first mix was made by blending, at 1500C, 8009 of the bitumen with 2009 of elemental sulphur. A second mix was made by first blending 1.25 wt y of zinc stearate into the same quantity of bitumen and then blending with the same quantity of sulphur, again at 1500C. A third mix was made exactly as for the second but replacing the zinc stearate by 0.54 wt of powdered zinc oxide. All three samples were maintained at l500C, under vigorous stirring, and a measurement was taken for each sample of the time required for 1000 ml H2S emission to be released. The results are shown in the Table 1 below. Table 1 EMI5.1 <SEP> j <tb> Additive <SEP> Type <SEP> None <SEP> Zinc <SEP> Oxide <SEP> Zinc <SEP> Stearate <tb> in <SEP> bitumen <SEP> (%) <SEP> - <SEP> 0.54 <SEP> 1.25 <tb> Zinc <SEP> in <tb> bitumen <SEP> (%) <SEP> - <SEP> 0.43 <SEP> 0.13 <tb> Time <SEP> (minutes) <SEP> 37 <SEP> 38 <SEP> 75 <tb> r <SEP> 1000 <SEP> MI <SEP> tl,.S <tb> It will be seen that the addition of zinc oxide has virtually no effect on the rate of H S emission, whereas the zinc stearate addition doubles the time taken before the 1000 ml was collected. Example 2 Two samples of the said bitumen were taken. To one of them 1 wt % of zinc stearate was blended in. Both samples were then blended with elemental sulphur to give mixtures having 20 wt % of sulphur. The bitumen /sulphur blends at 135 C and aggregate at 1700C were rapidly blended and the resulting mixes transferred into a closed box whose cover was fitted with a thermometer and a device allowing a slow nitrogen flow over the surface of the mix. The box was immediately put into an oven regulated at 1450C : the temperature of the mixes then progressively (within two hours) decreased from 160 to 1470C. The results are shown in Table 2 below: Table 2 EMI6.1 <tb> Bitumen <SEP> type <SEP> H2S <SEP> evolution <SEP> (calculated <SEP> as <SEP> P/1000 <SEP> kg <SEP> mix) <tb> employed <tb> <SEP> After <SEP> 1 <SEP> hr <SEP> After <SEP> 2 <SEP> hrs <tb> <SEP> 80/100 <SEP> pen <SEP> 28 <SEP> 57 <tb> Ditto <SEP> plus <SEP> 1 <SEP> wtt <SEP> 15 <SEP> 33 <tb> of <SEP> zinc <SEP> stearate <tb> It will be seen that the addition of the zinc stearate reduced the H2S evolution by 47% after 1 hr and 43% after 2 hrs

Claims: CLAIMS: 1. A process for preparing a mixture comprising bitumen and sulphur, characterised in that bitumen and elemental sulphur are mixed at an elevated temperature in the presence of at least one metal carboxylate or naphthenate which is at least partially soluble in the bitumen at the mixing temperature. 2. A process as claimed in claim 1, wherein the mixing temperature is in the range 1300C to 1700C, preferably 1300C to 1500C. 3. A process as claimed in claim 1 or claim 2, wherein the salt is derived from an alkyl or alkylaryl carboxylic acid, preferably having at least 12 carbon atoms per molecule. 4. A process as claimed in claim 3, wherein the said carboxylic acid is a C16 to C18 such acid. 5. A process as claimed in any preceding claim, wherein the metal of the salt is zinc, iron or cadmium. 6. A process as claimed in any preceding claim, wherein the salt employed is zinc stearate. 7. A process as claimed in any preceding claim, wherein the amount of the metal organic salt employed is from 0.05 to 0.4 wt , when calculated as zinc, based on the weight of the bitumen. 8. A process as claimed in any preceding claim, wherein the sulphur is employed in an amount of up to 30 wt ç based on the bitumen. 9. A process as claimed in any preceding claim, wherein the bitumen is mixed with the metal carboxylate or naphthenate prior to mixing with the sulphur. 10. A process as claimed in claim 9, comprising the, further step of adding aggregate after the metal salt and prior to the mixing with the sulphur.

Inventors: MULLER, JEAN-MARIE ALFRED FRANCOIS, TOUZARD, BENOIT, Muller, Jean-Marie Alfred François
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1984
Main classification: C08L95
IPC codes: C08K5, C08K3