PROCESS BULLETIN

Sulfur Dispersions
SIC 28793.15 Aqueous dispersions of elemental sulfur are used in large quantities for a wide variety of applications. These include rubber making and paper manufacturing, in addition to agricultural applications as a fungicide or fertilizer. All of these applications require sulfur which is in the form of small particles and which can be supplied as a concentrated dispersion that is readily diluted with water. There are two distinct problems confronting any potential producer of sulfur dispersions. First, the most efficient means of reducing the sulfur to wettable particles of the desired size must be found. Second, a formulation that leads to a stable and flowable dispersion with the highest possible sulfur concentration must be established. The required particle-size reduction is achieved by mechanical methods, and three types of equipment are in common use. Two of these devices, ball mills and air attritors, function by actually grinding the solid sulfur until the desired particle size is achieved. This process consumes much time and energy. Ultimate particle sizes of 10-15 µm can be achieved with a wet-grinding ball mill system, and particle sizes of 5 -10 µm can be produced with a dry grinding air attritor method. The third alternative, a Gaulin homogenizer, not only consumes the least amount of energy (as little as 5% of that used in either of the grinding methods), but it also produces the smallest sulfur particles (less than 5 µm). The reason for this apparent contradiction is that the homogenization process does not require the actual grinding of solid sulfur. Instead, molten sulfur is directly emulsified into water. A Gaulin homogenizer is extremely efficient at producing very small sulfur particles under such conditions. This emulsification of two liquids requires far less energy than the mechanical grinding of a solid. A clarification of terminology is in order here. The homogenizer produces an "emulsion", because both the sulfur and the water are liquids within the homogenizer. However, the final product (after cooling) is still a dispersion, because it consists of solid sulfur particles dispersed in water. In addition to its advantages with regard to the ultimate particle size of the sulfur and the energy input required to achieve this particle size, a Gaulin homogenizer system has a substantial production-rate advantage over the grinding methods. Whereas a grinding method results in a batch-type processing system, homogenization permits continuous-type operation. That is, the Gaulin homogenizer produces finished product instantly and continuously, as long as the raw materials are being fed to it. This advantage alone would be sufficient to make a homogenization the preferred method. To illustrate the emulsification approach to preparing sulfur dispersions, a sketch of a typical sulfur dispersion plant is attached. As shown in the sketch, both the molten sulfur and the aqueous phase of the product must be heated to a temperature of about 260°F. (125°C.), before they are metered together at the inlet of the homogenizer. This means that the feed pumps to the homogenizer must generate sufficient pressure in the pipelines to prevent flashing of the superheated water, and the discharge path from the homogenizer outlet to the cooler outlet must also be kept under pressure for the same reason.
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Sulfur Dispersions Page2 Beyond the cooler, the product will be well below the boiling point of water, and pressurized lines are no longer necessary. If a good chemical formulation has been developed, a homogenizing pressure of about 2000 psi (138 bar) should produce a finished dispersion with sulfur particles of less than 5 micrometers. However, pressures as high as 3000 psi (207 bar) may be required in some instances to attain the necessary level of product stability. This will depend upon the type and percentage of stabilizer in the formulation. One must be certain that the proper construction parameters are specified for the Gaulin homogenizer to be used in this application. The cylinder should have a pressure capability of 3000 psi (207 bar), and a single-stage homogenizing valve assembly would normally be specified. However, wear-resistant valves and seats must be used, if any abrasive solids will be included in the formulation. Examples of such solids are oxides, carbonates, and basic sulfates. These are sometimes included in agricultural sulfur dispersions as micronutrients. In addition, the options of using 316 stainless-steel wettable parts for better corrosion resistance and coring the cylinder for steam heating should be considered. Coring the cylinder will reduce the possibility of cold spots in its interior. Such cold spots represent potential locations for the molten sulfur to solidify and accumulate, and this can result in erratic operation of the machine. It should be pointed out that the potential problem of cold spots has to be avoided in all areas of the entire processing system, and not just in the homogenizer. Two basic formulations have been developed for the preparation of homogenized sulfur dispersions, and each has its good points and its bad points. The older formulation uses a lignosulfonate as a dispersant and wetting agent and a stabilizer, such as carboxymethyl cellulose (CMC), is used to retard settling of the sulfur particles. The advantage of this formulation is its simplicity and low cost. However, stability at sulfur levels greater than about 55% is poor, and product quality can be erratic. The former problem is due to limitations in the wetting ability of the lignosulfonate, while the latter is due to unavoidable variations in the quality of the lignosulfonate. If one limits the sulfur level to 50-55% or does not require long-term stability, this formulation is acceptable. More recently, a new family of surfactants called "Morwet" (Akzo Nobel Industrial Specialties, Inc.) has proven to be very useful for this application. Using formulations based upon these surfactants, homogenized sulfur dispersions which are readily flowable and which exhibit excellent long -term stability have been prepared at sulfur levels in excess of 70%. A Xanthan gum (such as Kelzan S) is usually used as the stabilizer in these products. However, this family of surfactants is more costly than the lignosulfonate, and one must make a choice between the low cost of a lignosulfonate formulation and the excellent product stability and reproducibility of the Morwet formulations. In any case, homogenizing in the molten state yields the smallest final particle size and the lowest operating cost, as well as being the only continuous procedure. Two typical formulations are listed below:
Formulation I* 55% sulfur 5% Marasperse N22 1% CMC 39% water Formulation II** 70% sulfur 1.5% Morwet D425 0.5 Morwet EFW 0.13% Kelzan S 27.87% water

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Sulfur Dispersions Page 3 In addition to the basic ingredients above, some applications might require such additives as: propylene glycol for freeze/thaw stability, an antifoaming agent and a bactericide. After preparation, the finished product should be evaluated for viscosity, particle size, solids level, stability and ease of dispersibility in water. It should be noted that some sulfur dispersions show not only an increase in particle size with time but, also, a change in shape of the particles due to crystal structure transformations. Thus, spherical 1 µm particles can become needle-like 5 µm crystals within 24 hours. Such a change is not necessarily detrimental, and it is even desirable in some instances. This is especially true in the agricultural applications, where too small a sulfur particle can enter the pores on the plant and cause damage to it. The sulfur particles must be large enough to remain on the surface of the leaves. Therefore, an effort should be made to repeat any particle-size measurements after the first 24 hours, and no further changes should occur beyond that point in time.
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Sulfur Page 4

40 psi Relief Valve

Excess hot water

Water Final Heating

Regeneration Cooling

Cold Water for Heat Exchanger Venturi

Dispersing Agent

Hot Water (260ºF/125°C)

Plate Heat Exchanger

Pressure Reducing Valve Steam in Homogenizing Pressure Indicator Venturi Sulfur Melt Supply (260ºF/125°C) Venturi Homogenizing Pressure Control

Insulated Metering Pumps

APV Homogenizer (Gaulin)

Storage or Drying System

Continuous Sulfur Dispersion Unit
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