This invention relates to the method of production of polymeric construction binder and polymeric construction binder based on granular blast-furnace slag and waste sulfur as well as waste slag from copper smelting and waste sulfur.

Polymeric construction binder based on blast-furnace slag and waste sulfur is material similar to traditional concrete based on Portland cement, which, unlike traditional concrete, possesses the following advantages: high compression and bending strength, higher than that of traditional concrete, short setting time during a few hours, low absorbability, good tightness, acid environment resistance, which most of building materials are not resistant to.

There are known methods of sulfur binders manufacture described in the United States Patents No. 4058500 and No. 4348313, in which sulfur binder where sulfur is modified with olefin hydrocarbons, that is, with an organic modifier, appears.

Sulfur binders manufactured the same in Poland are based on organic modifiers of the olefin hydrocarbon type. Such solutions are dangerous in use due to the risk of fire or explosion during the modification process and their toxic effect on personnel.

The aim of the invention is to develop a method of production of polymeric construction binder and polymeric construction binder based on blast-furnace slag or waste slag from copper smelting and to use waste sulfur and waste phosphogypsum as blast-furnace slag or waste slag from copper smelting pH reaction regulator in the production process, that results in reduction of the accumulated noxious waste amounts and allows to utilize them in an environmentally safe way.

The polymeric construction material according to the invention is produced when blast-furnace slag, broken up to 10 mm granulation and previously subjected to pH reaction regulation from pH of about 10 to pH of about 6.5 that is, to slightly acidic, using waste phosphogypsum, is added to liquid waste sulfur in the temperature of 130°C - 135°C. As a result, metals contained in blast-furnace slag, such as arsenic, selenium, phosphorus and their sulfides, inhibit the sulfur crystallization process and stabilize its polymeric form. In specific technical conditions, that is, in the presence of a suitable temperature and large phase development of liquid sulfur, the disintegration of closed chains made of sulfur atoms into open chains resulting from scission of these chains in temperatures higher in the temperature range of 130 ⁰ C - 135°C occurs.

Sulfur S _x chain structures replacing the cyclic structure dominate in the temperature of 130°C - 135°C. Metals and their sulfides, including arsenic, selenium and phosphorus, which are sulfur modifiers, contained in blast-furnace slag undergo copolymerisation reaction with chain-structured sulfur and create a copolymer of highly-molecular compound qualities, such as occur in polymeric materials. Polymeric construction material related to in the invention is composed from 40% - 60% by weight of waste sulfur, 20% - 45% by weight of blast-furnace slag of up to 10 mm granulation, which contains about 90% by weight of silicates, about 5% by weight of metals, including arsenic, selenium, phosphorus and their sulfides as well as metallic oxides, about 5% by weight of water, mixed with waste phosphogypsum, that is, blast-furnace pH reaction regulator, in the amount of 15% - 23% by weight. Waste phosphogypsum mixed with blast-furnace slag in 1 :1 weight ratio changes the blast-furnace slag pH from the pH of about 10 to the pH of about 6.5, that is, to slightly acidic. When loaded to a rotating heater (Fig.1), sulfur is heated to the temperature of 130 ⁰ C - 135°C and takes the liquid form by disintegration of cyclic sulfur to linear form. Previously weighted amounts of blast-furnace slag mixed with waste phosphogypsum, that is, with blast-furnace slag pH reaction regulator, are batched to liquid sulfur. In the rotating heater, in the process of mixing liquid sulfur with blast-furnace slag containing metals and their sulfides, including selenium, arsenic, phosphorus as sulfur modifiers, modification of chain sulfur occurs, and as a result a copolymer of highly-molecular compound qualities is formed.

Polymeric construction binder created in this way can have a particular application through pouring it into a mould, pouring out on a particular surface instead of concrete based on construction cements. Polymeric construction binder has not been reported to initiate reinforcement steel corrosion, however, reinforcement should be protected from penetration of the surrounding during steel reinforcement works in wet environment. Polymeric construction material can be, after cooling, crushed in a jaw crusher and packed into bags, and then poured into a road machine called a road recycler, where, after the material is heated to an appropriate temperature, melted mass can be poured out onto a particular surface and used in roads and yards repairs. Appropriate amount of polymeric construction binder added to road surfacing compositions decreases the amount of used road asphalt in these compositions by about 2% by weight and thus, decreases the costs of road construction. In addition to this, polymeric construction material increases the temperature of road surface softening and prevents its rutting, that lengthens the period of road using. Polymeric construction binder based on sulfur and blast-furnace slag possesses very good functional properties, that is, high compression strength of about 55 MPa, breaking strength of about 5 MPa, bending strength of about 7.5 MPa, water absorbability of about 1 %. Watertightness and frost resistance depend on proper vibrating of profiles made of the binder. Polymeric construction binder is resistant to acidic environment; it has excellent adhesion to substrate and mineral materials used in road construction. In addition to this, it fills fissures and hollows in damaged concrete and road surfaces tightly.

Unexpected properties of such big improvement of mechanical compression strength, resistance to aggressive media, such as acids, salts, oils, in which ordinary concretes based on Portland cement fail, are due to blast-furnace slag, which is the source of metals, including arsenic, selenium, phosphorus and their sulfides, which are sulfur modifiers. Sulfur chains formed as a result of cyclic sulfur heating create with the modifier a linear or cross-linking form copolymer possessing typical qualities of a macromolecular compound as found in polymer material. Used blast-furnace slag composed of about 90% by weight of silicates, about 5% by weight of metals, including arsenic, selenium, phosphorus and their sulfides and metal oxides, about 5% by weight of water, is grey and it is used in broken-up form; to change its pH reaction from about 10 to pH reaction of about 6.5 it is mixed with waste phosphogypsum of pH reaction of about 4. Phosphogypsum is a waste product of industrial phosphoric acid production. Waste sulfur is a waste product of natural gas desulfurization or crude oil desulfurization, which assumes brown colour after it is melted. Production method of polymeric construction binder based on blast-furnace slag and waste sulfur according to the invention has been defined more closely in the examples of embodiment.

Example I

Polymeric construction binder of the composition specified in % by weight:

Waste sulfur 46

Blast-furnace slag 31

Waste phosphogypsum as blast-furnace slag pH reaction regulator 23

Prepared in the following way: weighted amount of waste sulfur is delivered to the BO rotating heater (Fig. 1) through ZS charge. In the rotating heater, with inside zone confined by two metal rings, sulfur is heated to the temperature of 130 ⁰ C - 135°C with the help of two P burners and it changes its form from solid to liquid brown. Temperature measurement in the sulfur heating zone is carried out by T thermometers. The heater is placed at the inclination angle of 0°, and thus the molten sulfur rotates on the inside circumference of the heater and it is not shifted to the heater outlet. Weighted amounts of dry blast-furnace slag mixed beforehand with waste phosphogypsum as the pH reaction regulator are batched through ZS charge to the heated sulfur. In the temperature of 130 ⁰ C - 135°C in the molten sulfur zone, contact of blast-furnace slag mixed with waste phosphogypsum and of liquid sulfur occurs. Mixing of the aforementioned ingredients lasts for about 10 minutes. The process of waste sulfur modification with blast-furnace slag by metals contained in the slag, including arsenic, selenium and phosphorus and their sulfides occurs. Polymeric construction binder is formed. After this time with the help of cylinders fixed under the BO heater frame (as presented on the B-B view), the BO heater gains the slope of about 15°, as a result of which polymeric construction binder is removed from the heater and poured into a mould, onto a specified surface or it is cooled, broken up and packed into bags. Polymeric construction binder obtained in this way is of colour grey similar to traditional concretes. It possesses high mechanical compression strength of about 55 MPa, resistance to acids, salts, oils. The short time of polymeric construction binder setting allows for fast using of elements made of it; the bending strength is of about 7.5 MPa and breaking strength is of about 5 MPa. The BO rotating heater possesses individual M drive and 00 gas exhaust draught. The BO rotating heater works in cycles, that is, after the produced polymeric construction binder has been removed from the heater, another cycle of loading waste sulfur, melting it and adding blast-furnace slag is repeated. In one cycle about 4 tons of polymeric construction binder are obtained.

Example Il

Polymeric construction binder of the composition specified in % by weight:

Waste sulfur 60

Blast-furnace slag 20

Waste phosphogypsum 20

Mode of preparation is identical with that from Example I; the difference is the percentage composition and the colour of the obtained polymeric construction binder lighter than of that obtained in Example I. The invention involves also the development of polymeric construction material based on waste slag from copper smelting and waste sulfur. Polymeric construction material according to this invention is formed when waste slag from copper smelting of 0 - 5 mm granulation is added to liquid waste sulfur at the temperature of 125°C - 135°C. Waste slag from copper smelting has the pH reaction of about 8.5 and thus it is subjected to the pH reaction regulation process by waste phosphogypsum to the pH reaction of about 6.0, which is slightly acidic. Waste slag from copper smelting contains metals such as copper, phosphorus and their sulfides, which are extremely valuable in the sulfur modification process; the amounts of these metals are significantly higher than in other slag types. Sulfur as an element of extremely electronegative character reacts vigorously with metals. Copper reacts with sulfur at room temperature, and at higher temperatures sulfur combines with almost every element. Moreover, waste slag from copper smelting has the pH reaction of about 8.5 unlike blast-furnace slag from steel melting, which has the pH reaction of 10.5; this is very important in the process of sulfur modification, since it is easier to obtain the pH reaction of below 7 with the help of waste phosphogypsum, which affects positively both the modification and the qualities of polymeric construction material formed as a result of modification of sulfur with waste slag from copper smelting. As a result, metals contained in waste slag from copper smelting, such as phosphorus, copper and their sulfides, inhibit sulfur crystallization process and stabilize its polymeric form. In specific technological conditions, that is, at high temperature, the disintegration of the closed chains made of sulfur atoms into open chains resulting from scission of these chains in temperatures higher in the temperature range of 125 ⁰ C - 135 ⁰ C occurs. Sulfur S _x chain structure replacing the rhombus structure dominates in the temperature range of 125°C - 135 ⁰ C. Metals and their sulfides, including copper, phosphorus, which are sulfur modifiers, contained in waste slag from copper smelting undergo copolymerisation reaction with chain-structured sulfur and create a copolymer of highly-molecular compound qualities, such as occur in polymeric materials. During the process of mixing of molten sulfur and waste slag from copper smelting, reactions also occur, in which metallic sulfides react with their oxides and pure metal and sulfur dioxide are formed. As a result, gas foaming caused by sulfur dioxide appears on the surface of melted ingredients. While pure metal is an excellent medium for molten sulfur chains modification and forms with it a copolymer of multi-molecular compound qualities. Polymeric construction material based on waste slag from copper smelting and waste sulfur related to in the invention is composed of 30% - 50% by weight of waste sulfur, 10% - 45% by weight of 0 - 5 mm granulation waste slag from copper smelting, which contains about 45% of silicates, about 12% of aluminium trioxide, about 11 % of iron trioxide, about 6% of magnesium oxide, about 15% of calcium oxide, about 0.2% of phosphorus pentaoxide, about 0.4% of copper, mixed with pH reaction regulator for waste slag from copper smelting, that is, with waste phosphogypsum in the amount of 15% - 30% by weight. When mixed with waste slag from copper smelting in 1 :1 weight ratio, waste phosphogypsum changes the pH reaction of waste slag from copper smelting from about 8.5 to about 6.0, that is, to slightly acidic. Liquid sulfur previously liquefied in tank no. 3 by indirect heating with heating oil is loaded to the mixer no.1 (Fig. 2). Then amounts of waste slag from copper smelting with the slag pH reaction regulator, that is, waste phosphogypsum, weighted beforehand, are batched to mixer no 1. In the mixer at the temperature of 125°C - 135°C and at constant mixing with the speed of ca. 16 revolutions per minute chain sulfur modification by metals and their sulfides contained in waste slag from copper smelting occurs; phosphorus and copper compounds are especially valuable. Copolymer of highly-molecular compound qualities is formed. By adding to the mixer no. 1 specified amounts of mineral fillers in the amount of 10% - 40% we obtain polymeric construction material that, depending on needs, can be poured into a mould or poured out on a particular surface instead of so far used concrete based on traditional cements, or used in the production of road surfacing compositions. All the equipment is heated with heating oil, which facilitates the heated machines temperature regulation and allows to avoid open fire in the equipment heating process. From mixer no. 1 the prepared construction material is batched to mixer no. 2 so that visual and temperature evaluation could be carried out; the construction material is then directed either to the mould or to the granulation process. Construction material in the above version intended to be poured into a mould or to be poured onto a specified surface differs in its percentage composition from polymeric construction material for the production of road surfacing compositions based on road asphalts and polymeric construction material intended for repairs and making of new road surfacing. The amount of the mineral filler of up to 2 mm granulation is reduced to 10% by weight in it. Appropriate amount of polymeric construction material based on waste slag from copper smelting and waste sulfur added to road surfacing compositions decreases the amount of used road asphalt in these surfaces by about 3% by weight, and thus, decreases the costs of road construction. In addition to this, polymeric construction material increases the temperature of road surfaces softening and prevents their rutting, that lengthens the period of these roads using. Polymeric construction material based on waste slag from copper smelting and waste sulfur possesses very good functional properties, that is, compression strength of about 40MPa - 50MPa, breaking strength of about 5MPa, which is significantly higher than the breaking strength of traditional concretes, bending strength of about 7MPa, low absorbability of about 1%, good frost resistance and proper roughness, that is significant in the road surfacing forming process. It is a polymeric construction material which is resistant to acids and which possesses excellent adhesion to substrate and mineral materials used in road construction. In addition to this, it fills fissures and hollows in damaged concrete and road surfaces tightly. Compounds contained in polymeric construction material, such as copper oxides, aluminium oxides, iron(ll) and iron(lll) compounds are hydrogen sulfide emission inhibitor when mixed with asphalt if there was a mixed asphalt and polymeric construction material temperature rise to the temperature higher than 150 ⁰ C, that improves work safety during the production of those road compositions. Unexpected properties of such big improvement of mechanical compression strength, resistance to aggressive media, that is, acids, salts, oils when compared to concrete based on Portland cement, and ability to road compositions making are due to waste slag from copper smelting, which is the source of metals, including copper and phosphorus and their sulfides, which are sulfur modifiers. Sulfur chains formed as a result of cyclic sulfur heating create with the modifier a linear or cross-linking form copolymer possessing typical qualities of a highly-molecular compound as found in polymer materials. Used waste slag from copper smelting composed of about 45% by weight of silicates, about 12% by weight of aluminium trioxide, about 11% by weight of iron trioxide, about 6% by weight of magnesium oxide, about 15% by weight of calcium oxide, about 0.5% by weight of phosphorus pentaoxide, about 0.4% by weight of copper, is of colour grey and of up to 5 mm granulation. To change its pH reaction from 8.5 to the pH reaction of 6 it is mixed with waste phosphogypsum of the pH reaction of about 4. Waste phosphogypsum is a product of industrial phosphoric acid production. Waste sulfur is a waste product of natural gas desulfurization or crude oil desulfurization, which assumes brown colour after it is melted. Production method of polymeric construction material based on waste slag from copper smelting and waste sulfur according to the invention has been defined more closely in the example of embodiment.

Example III

Polymeric construction material of the composition in % by weight to be cast in a mould or poured onto surfaces.

Waste sulfur 30 %

Waste slag from copper smelting 25 % Waste phosphogypsum as slag pH reaction regulator 15 %

Mineral filler 0-2 mm 30 %

Prepared in the following way: Weighted amounts of waste sulfur are delivered to the mixer no. 1 (Fig. 2). Mixer no. 1 is heated indirectly with heating oil which is heated in electric furnace. Mixer no. 1 has a rotating agitator of 16 revolutions per minute. Weighted amounts of waste slag from copper smelting mixed beforehand with waste phosphogypsum as the pH reaction regulator are batched to the mixer no. 1 at the temperature of 125 ⁰ C - 135°C. At the temperature of 125°C - 135 ⁰ C in the molten sulfur zone the contact of waste slag from copper smelting mixed with waste phosphogypsum and of liquid sulfur occurs. Mixing of the ingredients lasts for about 20 minutes. The process of waste sulfur modification with waste slag from copper smelting by metals contained in the slag, including copper, phosphorus and their sulfides, occurs. After 20 minutes of modification process in mixer no. 1 mineral material as filler is added to the mixer and mixed for about 10 minutes; polymeric construction material formed in this way is discharged cyclically to the intermediate mixer no. 2, manufactured construction material is evaluated visually and in the aspect of temperature and is cast into a mould or poured onto specified surface. Material manufactured in this way is of colour grey and possesses high mechanical compression strength of 40MPa - 50MPa, resistance to acids, oils, salts.

Example IV

Polymeric construction material of the composition in % by weight for road composition making

Waste sulfur 50 %

Waste slag from copper smelting of up to 2 mmgranulation 10 %

Waste phosphogypsum as slag pH reaction regulator 30 %

Mineral filler of up to 2 mm 10 % Mode of preparation is identical with that from Example III; the difference lies in the fact that from the intermediate mixer no. 2 polymeric construction material is directed to granulation. Granulate is used to prepare road surfacing compositions with increased softening temperature of 100 ⁰ C - 115°C according to the "Sphere and Ring" method. Mode of preparation of road surfacing composition based on polymeric construction material granulate is as follows: Warmed mineral materials used for road surfacing forming, that is, diabase, basalt of the temperature not exceeding 150 ⁰ C are batched in a paving plant to the mixer no. 1 (Fig. 3). To the mixer no. 1 (Fig. 3) road asphalt with polymeric construction material manufactured according to Example III recipe, mixed in the mixer no. 2, is batched. The mixture of asphalt and granulate forms bonding agent of the composition in % by weight:

Road asphalt 15 %

Polymeric construction material 85 %

100 % road bonding agent

Road surfacing forming material of the composition in % by weight

Road bonding agent 25 %

Diabase 55 %

Basalt 20 %

100 % road surfacing forming material

Obtained road surfacing layer is of colour black and excellently improves its properties, on which an opinion has previously been given.