There are known methods of sulphur binder production consisting in adding modifying agents in form of olefins such as dicyclopentadiene, cyclopentadiene, cyclodecadiene, dipentene, styrene, vinyl cyclohexane as well as their various mixtures to sulphur that has been melted and heated to the temperature between 135°C and 140°C.

Based on an Austrian patent specification No. 355976 and American patent specifications Nos. 4058500,4293463,4311826,4391926 and 4348313 the sulphur binders composed mainly of sulphur with modifying agents being such olefins as dicyclopentadiene, cyclopentadiene, cyclodecadiene, dipentene, styrene, vinyl cyclohexane or their mixtures, are known.

Also olefinic pyrolyzates are used which are obtained as postpyrolysis oils at the petrochemical crude oil refining and are known by their trade names as RP-120, RP-020, CTLA,. ESCOPOL, although they are mixtures of the above mentioned olefins as in the referred patent specifications.

The inconvenience of the use of the known methods of sulphur binder production is a necessity to carry out sulphur modification processes with extra care due to hole for outlet of cooled fluid and the second part of divided direct cover has a hole for inlet of cooled fluid and both holes are connected to pipe coi ! throughout sealing bush connectors. Outer cover partition for two parts may be made either alongside surface perpendicular to axis of symmetry of block of cooler and face seal or alongside horizontal surface situated through longitudinal axis of symmetry of block of cooler with face seal.

The cooler in question is characterised by very simplifie construction having a few components and contemporaneously considerably reduced temperature on rotating shaft and on its seal throughout direct continuous cooling and thereby acceptable assembly and internal cleaning of the whole system.

Subject of the invention in samples is presented on drawings where Fig. 1 shows a longitudinal semi-sight/semi-section of a the cooler with outer casing of face seal of rotating shaft and divided alongside surface perpendicular to longitudinal axis of symmetry of block of cooler with face seal and Fig. 2 shows a semi-sight/ semi-section of the cooler with outer housing divided alongside horizontal surface through longitudinal axis of symmetry of block of cooler with face seal of rotating shaft.

As presented on Fig. 1 and Fig. 2, cooler according to the invention creates one construction block with face seal of rotating shaft and pipe coil 11 containing of cooled fluid is built in a divided outer casing. 9/1,9/2 of face seal of rotating shaft 1 connected with divided direct cover 7/1,7/2 of the seal. Moreover, divided outer casing 9/1,9/2 has internal chamber K for cooling whereas one part of divided direct cover 7/1 has a hole x4for outlet of cooled fluid and a second part of divided direct cover 7/2 has a hole x3for inlet of cooled fluid and both holes are connected decomposition during melting and crystallized until anisotropic crystals in a- rhombic system are obtained that do not undergo polymorphous transformation, where the content of p-monoclinic sulphur due to polluants does not exceed 0.1 % by weight.

The suphur binders that contain sulphur and the mixture of olefins are characterized by the fact that they are the eutectic mixture formed of the substitutional solid solution of sulphur in the quantity of 93% to 98% by weight and olefins dissolved in it where total content of the olefins does not exceed 7% by weight.

The main advantage of sulphur binders according to the invention is their homogeneity and anisotropy of all their properties which has been achieved through the method of their production in order to obtain only homogeneous solid solutions excluding any possibility of chemical compounds forming, especially polymers between sulphur and the modifying agents.

An additional advantage is the fact that sulphur binders produced according to the invention, at the temperature of sulphur concrete mixtures preparation, i. e. from +130°C to +140°C, are characterized by a very low viscosity within the range between 15 cP and 40 cP, that ensures full vettability of the mineral aggregate grains used in the production of sulphur concrete materials.

The mixtures of modifying agents used do not enter into any chemical reactions, but they partly dissolve in cyclo-octasulphur, and partly form the dispersed phase. As a result, a homogeneous substitutional solid solution, in which modifying agent molecules in the form of a solved component replace adequate elements in the structure of cyclo-octasulphur as a solvent, is formed at the first stage of homogenization process.

At the second stage, on the other hand, the components of the modifying agents that have been dispersed in the output from the first stage become dissolved.

A homogeneous two-component system, the eutectic mixture that melts congruently, i. e. without decomposition during melting process, is formed as the result of these actions.

The eutectic formed as the sulphur binder crystallize forming crystals in a-rhombic system with the parameters of a crystallographic cell similar to those of sulphur.

A thermogravimetric analysis shows that unlike in elementary sulphur, no cells in P-monoclinic system and no polymorphous changes take place in any case of melting and crystallization processes, and as a result the homogeneous eutectic mixture is obtained, i. e. the sulphur binder with anisotrophous properties at set, permanent and stable physicochemical properties.

The sulphur binders obtained are new cements of different chemical constitution and phase composition in comparison with other known cements and they are characterized with high resistance to aggressive chemical reacting substances in a broad temperature range, high resistance to external mechanical and thermal impacts and, therefore, they can be used as binders for production of construction materials, floors and foundations, production facilities and components of technological plants working in especially severe environmental conditions.

There are also possibilities to use the obtained sulphur binders for production of cheap sulphur concretes working together with for example concretes based on Portland cement, which set during their cooling and do not require seasoning to obtain full mechanical properties.

The sulphur binders mentioned above were obtained through modification of sulphur with olefin mixtures, i. e. postpyrolysis oils, and furfural extracts obtained in processes of selective furfural refining of fractions resulting from conservative crude oil distillation.

In the examples mentioned below olefins known under the trade names of: "Pirolizat BF" (BF Pyrolisate),"Olej sklarowany ZPKK II" (ZPKK II Clarified Oil), diene fractions from PETROCHEMIA Ptock olefinic installation (containing up to 70% by weight of dicyclopentadiene) were used in various proportions to one another in the mixture with styrene, and the total quantity of modifying agents used was between 3% and 7% by weight in proportion to sulphur undergoing modification process.

The process of sulphur modification in order to obtain sulphur binders was carried on in the following way: the recipe amount of sulphur was melted in the carbon dioxide atmosphere and heated up to the temperature of 130°C-135°C, where the temperature rose gradually in the heating process by 5°C-7°C per minute, and upon obtaining this temperature, the recipe amount of styrene was slowly fed, then about 15 minutes after the styrene feeding a diene modifier was added in small batches, and after that the whole mixture was maintained without air access in the carbon dioxide atmosphere at the temperature of 135°C for 2.5-3 hours until the eutectic mixture was formed. After the process of conditioning, the whole was cooled to room temperature at the cooling rate of 10°C-15°C per minute.

Example I. 95.0 parts by weight of sulphur were melted in the carbon dioxide atmosphere and heated to the temperature of 135°C, then 2.0 parts by weight of styrene-monomer were added to the melted sulphur, and 15 minutes after the styrene feeding, 3.0 parts by weight of modifying agents consisting by halves of ZPKK Clarifie Oil and BF Pyrolysate were added. The mixture was maintained at the temperature of 130°C in the carbon dioxide atmosphere for 2.5 hours mixed intensively, and then was cooled to room temperature at cooling rate of 12°C per minute. The obtained sulphur binder was of dark brown colour, density of 2.05 g/cm3, melting temperature of 104°C; crystallographic cell parameters: a-rhombic system: a = 10.07; b = 12.10; c = 24.43. Sulphur binder viscosity at the temperature of 135°C: 35 cP. Contraction in volume after crystallization and cooling to room temperature: 2.5% by volume.

The curve of the differential thermal analysis of the sulphur binder obtained is shown in Figure 1, Example II. 93.0 parts by weight of sulphur were melted in the carbon dioxide atmosphere and heated to the temperature of 135°C, then 2.0 parts by weight of styrene-monomer were added to the melted sulphur, and 15 minutes after the styrene feeding, 5.0 parts by weight of modifying agents mixture, consisting of one-third of BF Pyrolysate and of two-thirds of diene fraction containing 70% by weight of dicyclopentadiene, were added. The melted mixture was continuously mixed and maintained at this temperature in the carbon dioxide atmosphere for about 3 hours, and then it was cooled at the cooling rate of 10°C per minute until the sulphur binder of pale brown colour was obtained with density of 1.95 g/cm3, melting temperature of 100°C, crystallographic cell parameters: a-rhombic system: a = 10.24; b = 12.44; c = 24.25. Sulphur binder viscosity at the temperature of 135°C: 22 cP. Contraction in volume after crystallization and cooling to room temperature: 1.8% by volume.

The diagram of the differential thermal analysis of the sulphur binder obtained is shown in Figure 2.

Example 111.97.0 parts by weight of sulphur were melted in the carbon dioxide atmosphere and heated to the temperature of 135°C, then 1.0 part by weight of styrene-monomer was added to the melted sulphur, and 15 minutes after the styrene feeding, 2.0 parts by weight of modifying agent, consisting of diene fraction of cycloolefins installation containing 70% by weight of dicyclopentadiene, were added. The melted mixture was conditioned by maintaining it at the temperature of 135°C for 2.5 hours in the carbon dioxide atmosphere Then the mixture was cooled to room temperature at the cooling rate of about 12°C per minute, by which the sulphur binder of pale yellow colour was obtained with density of 2.02 g/cm3, melting temperature of 108°C and crystallographic cell parameters: a-rhombic system: a = 10.65; b = 12.15, c= 23.15. Sulphur binder viscosity at the temperature of 135°C: 18 cP. Contraction in volume after crystallization and cooling to room temperature: 0.7% by volume.

The diagram of the differential thermal analysis of the sulphur binder obtained is shown in Figure 3.

Example IV. 96.0 parts by weight of sulphur were melted in the carbon dioxide atmosphere and heated to the temperature of 135°C, then 1.5 parts by weight of styrene-monomer was added to the melted sulphur, and 15 minutes after the styrene feeding, 2.5 parts by weight of modifying agent, consisting by halves of diene fraction of cycloolefins installation containing 70% by weight of dicyclopentadiene and ZPKK Light Clarified Oil, were added. The melted mixture was maintained in the carbon dioxide atmosphere at the temperature of 135°C for about 2.5 hours. Then the mixture was cooled to room temperature at the cooling rate of about 15°C per minute, by which the sulphur binder of yellow-greenish colour was obtained. with density of 2.05 g/cm3, melting temperature of 106°C and crystallographic cell parameters: a-rhombic system: a = 11.05; b = 12.25; c= 24.25. Sulphur binder viscosity at the temperature of 135°C: 24 cP. Contraction in volume after crystallization process and cooling to room temperature: 1.4% by volume.

The diagram of the differential thermal analysis curve of the sulphur binder obtained is shown in Figure 4.

The sulphur binders obtained in this way were additionally tested in respect to their properties as sulphur cements in model sulphur concretes. Two types of aggregate were used for testing: -K1 aggregate composed of-barite flour in the quantity of 85 parts by weight with fraction graining of 0.1-0.5 mm in minimum 95%, glass fibre cut to the length of 0.5 cm and section d = 0.1 mm2, in the quantity of 15 parts by weight; -K2 aggregate composed of: quartz sand in the quantity of 42 parts by weight with fraction graining of 0.2-2.0 mm in minimum 95% of weight, quartz sand in the quantity of 43 parts by weight with fraction graining of 1.0-4.0 mm in minimum 90% of wieght, fly-ashes (microphase) in the quantity of 15 by weight.

In every case all the sulphur binders obtained with the methods as described in the above examples were mixed with the aggregate in recipe proportions, respectively: 1. With the K1 aggregate-14.0 parts by weight of the sulphur binder, 86.0 parts by weight of the K1 aggregate.

2. With the K2 aggregate-7.0 parts by weight of the sulphur binder, 93.0 parts by weight of the K2 aggregate.

The mixtures of sulphur-concrete mass were continuously mixed in the air atmosphere at the heating rate of about 7.0°C per minute until the temperature of 140°C was reached, at which temperature they were additionally mixed for 1.5 hours. Cast stones for strength tests were cast from the hot sulphur-concrete mixtures and cooled at the rate of 15°C per minute.

Test results obtained are shown in Figure 5 in a table illustrating the properties of the sulphur concretes obtained with the use of sulphur binders.