EA018572B1 - The method of polymeric construction binder production and polymeric construction binder - Google Patents

Abstract

This invention relates to the method of production of polymeric construction binder and polymeric construction binder. The method of production of polymeric construction binder consists in delivering from 30 to 60% by weight of waste sulfur which is heated to the temperature of 125-135°C to the rotating drum of the mixer and after it is melted adding to it from 10 to 40% by weight of waste slag that contains selenium, arsenic, phosphorus and their sulfides and metallic oxides and that is broken up to the granulation of up to 10 mm and subjected beforehand to pH reaction regulation to about 6.5 with the help of waste phosphogypsum in the amount of 15-30% by weight, and then adding mineral filler in the amount of up to 30% by weight; the mixture is then mixed for about 10 minutes with the speed of about 16 to 20 revolutions per minute; the formed construction binder is then poured into moulds or poured onto a specified surface. Polymeric construction binder is composed of waste sulfur in the amount of 30-60% by weight, waste slag in the amount of 10-45% by weight, waste phosphogypsum in the amount of 15-30% by weight and mineral filler in the amount of 10-40% by weight.

Description

This invention relates to a method for the production of building polymer binder and to a building polymer binder, which is based on granulated blast furnace slag and sulfur waste, as well as dump slag from smelting copper and sulfur waste.

Polymer building binder, which is based on blast furnace slag and sulfur waste, is a material similar to ordinary concrete, based on Portland cement, which, unlike ordinary concrete, has the following advantages: high compressive and bending strength higher than ordinary concrete, short time setting for several hours, low absorption capacity, good density, resistance to the acidic environment, which most building materials lack.

Known methods for the production of sulfur binders are described in US patent No. 4058500 and 4348313, which discloses a sulfur binder in which sulfur is modified with olefinic hydrocarbons, that is, organic modifiers.

Sulfur binders produced in the same way in Poland are based on organic modifiers of the olefinic hydrocarbon type. Such solutions are dangerous to use because of the risk of ignition or explosion during the modification process and their toxic effects on personnel.

The aim of the invention is to develop a method for the production of building polymer binder and building polymer binder, which is based on blast furnace slag or waste slag from copper smelting and the use of sulfur waste and phosphogypsum waste in the form of blast furnace slag or dump slag from copper smelting as a regulator of the pH reaction in the production process , which leads to a decrease in the accumulated toxic waste and allows you to dispose of it in a safe for the environment way.

The polymer building material according to this invention is produced when blast furnace slag, crushed into granules up to 10 mm in size and previously adjusted to a pH of about 10 to about 6.5, i.e. to a slightly acidic state, using phosphogypsum wastes is added to liquid wastes sulfur at a temperature of 130-135 ° C. As a result, metals contained in blast furnace slag, such as arsenic, selenium, phosphorus and their sulfides, delay the process of sulfur crystallization and stabilize its polymer form. Under certain technical conditions, that is, at a suitable temperature and the development of a large phase of liquid sulfur, closed chains formed by sulfur atoms decompose into open chains, caused by the splitting of these chains at temperatures above the temperature range 130-135 ° C.

Chain structures of sulfur 8 _X , replacing the cyclic structure, prevail at a temperature of 130-135 ° C. Metals and their sulfides, including arsenic, selenium and phosphorus, which are sulfur modifiers contained in blast furnace slag, undergo a copolymerization reaction with sulfur having a chain structure and form a copolymer with the properties of high molecular weight compounds that are found in polymeric materials. The polymer building material associated with this invention consists of 40-60 wt.% Sulfur waste, 20-45 wt.% Blast furnace slag, crushed into granules up to 10 mm in size, which contains about 90 wt.% Silicates, about 5 wt. % of metals, including arsenic, selenium, phosphorus and their sulfides, as well as metal oxides, about 5 wt.% water mixed with phosphogypsum waste, that is, a domain regulator of the pH reaction, in the amount of 15-23 wt.%. Phosphogypsum wastes mixed with blast furnace slag in a weight ratio of 1: 1 change the pH of blast furnace slag from about 10 to about 6.5, that is, to a slightly acidic state.

When loaded into a rotating heater (Fig. 1), sulfur is heated to a temperature of 130-135 ° C and acquires a liquid form by the decomposition of cyclic sulfur into a linear form. A pre-weighed amount of blast furnace slag mixed with phosphogypsum waste, that is, with a reaction regulator of the pH of blast furnace slag, is loaded into liquid sulfur. In a 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, the sulfur chain is modified, and as a result a copolymer with the properties of a high molecular weight compound is formed.

A building polymer binder, created in this way, can have a specific application by pouring it into a mold, pouring it on a certain surface instead of concrete, which is based on building cement. There is no information that the construction polymer binder causes corrosion of reinforcing steel, however, the reinforcement must be protected from external influences when working with reinforcing steel in wet conditions. After cooling, the polymer building material can be crushed in a jaw crusher, packaged in bags and then poured into a road machine, called a road processing machine, where after heating the material to a suitable temperature, the molten mass can be poured on a certain surface and used to repair roads and yards. A suitable amount of building polymer binder added to the pavement reduces the amount of road bitumen used in these formulations by about 2 wt.% And, thus, reduces the cost of road construction. In addition, the polymer building material increases the softening temperature of the pavement and prevents the formation of a track on it, which increases the life of the road. Building polymer binder, based on sulfur and blast furnace slag, has very good functions

- 1 018572 national properties, that is, high compressive strength, about 55 MPa, tensile strength of about 5 MPa, bending strength of about 7.5 MPa, water absorption capacity of about 1%. Water resistance and frost resistance depend on proper vibration compaction of profiles made of binder. Building polymer binder is resistant to acidic environment; It has excellent adhesion to the substrate and the mineral materials used in road construction. In addition, it tightly fills cracks and voids in damaged concrete and pavement.

Unforeseen properties that provide such a significant improvement in mechanical compressive strength, resistance to aggressive environments such as acids, salts, oils, in which ordinary concrete, based on Portland cement, become unusable, are caused by blast furnace slag, which is a source of metals, including arsenic, selenium, phosphorus and their sulfides, which are sulfur modifiers. Sulfur chains formed by heating cyclic sulfur, together with a modifier, create a copolymer with a linear or mesh structure that has the typical qualities of a macromolecular compound that are present in the polymer material. Used blast furnace slag, consisting of about 90 wt.% Silicates, about 5 wt.% Metals, including arsenic, selenium, phosphorus and their sulfides and metal oxides, about 5 wt.% Water, has a gray color and is used in crushed form; to change its pH reaction from 10 to a pH reaction of approximately 6.5, it is mixed with phosphogypsum wastes with a pH reaction of approximately 4. Phosphogypsum is a waste product from the industrial production of phosphoric acid. Sulfur waste is a waste of natural gas desulfurization or crude oil desulphurization, which become brown after melting. A method of manufacturing a building polymer binder based on blast furnace slag and sulfur waste according to this invention is described in more detail in examples of embodiments.

Example I.

Building polymer binder with composition, in wt.%:

Sulfur Waste 46

Blast furnace slag 31

Phosphogypsum waste as a regulator of the reaction of blast furnace slag pH 23

Produced in the following way: a weighted amount of sulfur waste is placed in a rotary heater VO (Fig. 1) through the charging device Ζ8. In a rotating heater, where the inner zone is bounded by two metal rings, sulfur is heated to a temperature of 130-135 ° C using two burners P, and it changes its shape from solid to liquid and turns brown. The temperature in the sulfur heating zone is measured by thermometers T. The heater is positioned at an angle of 0 °, and thus molten sulfur rotates in the inner circumference of the heater and does not move to the outlet of the heater. Weighed quantities of dry blast furnace slag, pre-mixed with phosphogypsum waste as a pH reaction regulator, are charged via heated apparatus 8 to heated sulfur. At a temperature of 130-135 ° C in the zone of molten sulfur, blast furnace slag mixed with phosphogypsum wastes comes into contact with liquid sulfur. Mixing the above ingredients lasts approximately 10 minutes. The process of modification of sulfur wastes with blast furnace slag occurs, caused by metals contained in the slag, including arsenic, selenium, phosphorus and their sulfides. A building polymer binder is formed. After that, using the cylinders installed under the body of the BO heater (as shown in BB), the BO heater acquires an inclination angle of about 15 °, as a result of which the polymer binder is removed from the heater and poured into a mold on a given surface or cooled, ground and packaged in bags. The building polymer binder obtained in this way has a gray color, like ordinary concrete. It has high mechanical compressive strength, approximately 55 MPa, resistance to acids, salts, oils. The low setting time of the building polymer binder makes it possible to quickly use elements made from it; bending strength is approximately 7.5 MPa and tensile strength is approximately 5 MPa. The rotary heater BO has a separate drive M and a gas exhaust hood OO. The rotary heater BO operates cyclically, that is, after removing the manufactured polymer binder from the heater, the next cycle of loading sulfur waste, melting it and adding blast furnace slag is repeated. About 4 tons of a building polymer binder are obtained in one cycle.

Example II

Building polymer binder with composition, in wt.%:

Sulfur Waste 60

Blast furnace slag 20

Phosphogypsum waste 20

The preparation method is identical to the method of example I; the difference lies in the percentage composition and color of the resulting building polymer binder, lighter than in example I.

The invention also includes the creation of a polymer building material, which is based on waste slag from copper smelting and sulfur waste. Polymer building material

- 2 018572 according to this invention is produced when the waste slag from copper smelting, crushed into granules with a size of 0-5 mm, is added to the liquid sulfur waste at a temperature of 125-135 ° C. The waste slag from copper smelting has a pH reaction of about 8.5 and, thus, undergoes the process of regulating the pH reaction using phosphogypsum waste to a pH value of about 6.0, i.e. to a weakly acid state. The waste slag from copper smelting contains metals such as copper, phosphorus and their sulfides, which are extremely valuable for the sulfur modification process; the amounts of these metals are significantly higher than in other types of slag. Sulfur, as an element with an extremely electronegative character, enters into a strong reaction with metals. Copper reacts with sulfur at room temperature, and at higher temperatures, sulfur combines with almost all elements. In addition, the waste slag from copper smelting has a pH of about 8.5, in contrast to blast furnace slag from steel smelting, which has a pH of 10.5; this is very important for the sulfur modification process, since it is easier to obtain a pH reaction below 7 using phosphogypsum waste, which positively affects both the modification and the quality of the polymer building material formed as a result of sulfur modification using dump slag from copper smelting. As a result, metals contained in the waste slag from copper smelting, such as phosphorus, copper and their sulfides, delay the crystallization of sulfur and stabilize its polymer form. Under certain technological conditions, that is, at high temperature, closed chains formed by sulfur atoms decompose into open chains, caused by the splitting of these chains at temperatures above the temperature range 125-135 ° C. The chain structure of sulfur 8x, replacing the rhomboid structure, prevails at a temperature range of 125-135 ° C. Metals and their sulfides, including copper, phosphorus, which are sulfur modifiers contained in the waste slag from copper smelting, undergo a copolymerization reaction with sulfur having a chain structure and form a copolymer with the properties of high molecular weight compounds that are found in polymeric materials. In the process of mixing molten sulfur and waste slag from copper smelting, reactions also occur in which metal sulfides react with their oxides and pure metal and sulfur dioxide are formed. As a result, gas foam caused by sulfur dioxide appears on the surface of the molten ingredients. At the same time, pure metal is an excellent medium for modifying molten sulfur chains and forms a copolymer with sulfur with the properties of a multi-molecular compound. The polymer building material, which is based on the waste slag from copper smelting and sulfur waste associated with this invention, consists of 30-50 wt.% Sulfur waste, 10-45 wt.% Waste slag from copper smelting, crushed into granules of size 0 -5 mm, which contains approximately 45% silicates, approximately 12% aluminum trioxide, approximately 11% iron trioxide, approximately 6% magnesium oxide, approximately 15% calcium oxide, approximately 0.2% phosphorus pentoxide, approximately 0.4% copper, mixed with a reaction regulator, the pH of the waste slag from copper smelting, i.e., with waste E phosphogypsum in an amount of 15-30 wt.%. When mixed with waste slag from copper smelting in a weight ratio of 1: 1, phosphogypsum waste changes the pH of the waste slag from copper smelting from about 8.5 to about 6.0, that is, to a slightly acidic state. Liquid sulfur, previously melted in the tank No. 3 by indirect heating using heating oil, is loaded into the mixer No. 1 (Fig. 2). Then, pre-weighed amounts of waste slag from copper smelting with a slag pH regulator, that is, with phosphogypsum waste, are loaded into mixer No. 1. In a mixer at a temperature of 125-135 ° C and with constant stirring at a speed of approximately 16 rpm modification of the sulfur chain using metals and their sulfides contained in dump slag from copper smelting; phosphorus and copper compounds are especially valuable. A copolymer with the properties of a high molecular weight compound is formed. By adding to the mixer No. 1 certain quantities of mineral fillers in the amount of 10-40%, we obtain a polymer building material, which, depending on the need, can be poured into a mold or poured on a certain surface instead of the previously used concrete, which was based on ordinary cement, or used in the manufacture of paving compositions. All equipment is heated with heating oil, which facilitates the regulation of the temperature of heated mechanisms and eliminates the need for open fire during the heating of equipment. From mixer No. 1, the finished building material is loaded into mixer No. 2 so that a visual assessment and temperature assessment can be performed; the building material is then sent either to the mold or to the grinding step. The building material in the above embodiment, which is designed to be poured into molds or on a given surface, differs in its percentage composition from polymer building material for the manufacture of paving compositions based on road bitumen, and polymer building material intended for repair and creating a new road coverings. The amount of mineral filler, crushed into granules up to 2 mm in size, is reduced in it to 10 wt.%. A suitable amount of polymer building material, based on copper slag and sulfur waste added to the pavement, reduces the amount of road bitumen used in these surfaces by about 3% by weight and thus reduces the cost of road construction. In addition, the polymer building material increases the softening temperature of the pavement and prevents the formation of ruts on them, which increases the life of

- 3 018572 of these roads. Polymeric building material, which is based on waste slag from copper smelting and sulfur waste, has very good functional properties, that is, compressive strength of about 40-50 MPa, tensile strength of about 5 MPa, which is much higher than the tensile strength of ordinary concrete , bending strength of about 7 MPa, low absorption capacity, about 1%, good frost resistance and proper roughness, which is essential for the paving process. It is a polymeric building material that is resistant to acids and which has excellent adhesion to the substrate and mineral materials used in road construction. In addition, it tightly fills cracks and voids in damaged concrete and pavement. Compounds contained in polymer building materials such as copper oxides, aluminum oxides, iron (II) and iron (III) compounds are hydrogen sulfide release inhibitors when mixed with bitumen and raising the temperature of mixed bitumen and polymer building material above 150 ° C, which improves labor safety in the manufacture of these compositions for road marking coatings. Unforeseen properties that provide such a significant improvement in mechanical compressive strength, resistance to aggressive media, that is, to acids, salts, oils compared to concrete based on Portland cement, and the ability to create compositions for road marking coatings are caused by dump slag from smelting of copper, which is a source of metals, including copper, phosphorus and their sulfides, which are sulfur modifiers. Sulfur chains formed by heating cyclic sulfur, together with a modifier, create a copolymer with a linear or mesh structure, which has the typical properties of a high molecular weight compound that are found in polymeric materials. Copper smelting slag used, consisting of about 45 wt.% Silicates, about 12 wt.% Aluminum trioxide, about 11 wt.% Iron trioxide, about 6 wt.% Magnesium oxide, about 15 wt.% Calcium oxide, about 0 5 wt.% Of phosphorus pentoxide, about 0.4 wt.% By weight of copper, is gray in color and crushed into granules up to 5 mm in size. To change its pH reaction from 8.5 to a pH reaction of 6, it is mixed with phosphogypsum waste with a pH reaction of approximately 4. Waste phosphogypsum is a product of the industrial production of phosphoric acid. Sulfur waste is a waste of natural gas desulfurization or crude oil desulphurization, which become brown after melting. A method of manufacturing a polymeric building material based on copper slag and sulfur waste according to the invention is described in more detail in examples of embodiments.

Example III

Polymeric building material with a composition in wt.% For pouring into the mold or spill on the surface.

Sulfur Waste 30%

Copper smelting slag 25%

Phosphogypsum waste as a regulator of the reaction of slag pH 15%

Mineral filler 0-2 mm 30%

Made in the following way:

Weighted amounts of sulfur waste are placed in a No. 1 mixer (FIG. 2). Stirrer No. 1 is heated by indirect heating using heating oil, which is heated in an electric furnace. Mixer No. 1 has a blade that rotates at a speed of 16 rpm. Weighted amounts of waste slag from copper smelting, pre-mixed with phosphogypsum waste as a pH reaction regulator, are loaded into a No. 1 mixer at a temperature of 125-135 ° С. At a temperature of 125-135 ° C in the zone of molten sulfur, the dump slag comes in contact with the smelting of copper mixed with waste phosphogypsum and liquid sulfur. Mixing the ingredients lasts approximately 20 minutes. There is a process of modification of sulfur waste with dump slag from copper smelting, caused by metals contained in the slag, including copper, phosphorus and their sulfides. After 20 minutes of the modification process in mixer No. 1, the mineral material is added as a filler to the mixer and mixed for about 10 minutes; the polymer building material thus formed is cyclically discharged into intermediate mixer No. 2, the fabricated building material is visually evaluated, the temperature is also evaluated, and the material is poured into a mold or poured onto a predetermined surface. The material manufactured by this method has a gray color and has high mechanical compressive strength of 40MPa-50MPa, resistance to acids, oils, salts.

Example IV

Polymeric building material with a composition in wt.% For the manufacture of compositions for road marking coatings

Sulfur Waste 50%

Slag from copper smelting in granules up to 2 mm in size 10% Phosphogypsum waste as a regulator of the reaction of slag pH 30% Mineral filler up to 2 mm in size 10%

The preparation method is identical to the method of example III; the difference lies in the fact that from the intermediate mixer No. 2 the polymer building material is sent for grinding into granules.

- 4 018572

Granulate is used for the manufacture of pavement compositions with an increased softening temperature of 100-115 ° C in accordance with the Ring and Ball method. The method of preparing the composition of the pavement, based on the granulate of a polymer building material, is as follows. The heated mineral materials used to create the pavement, that is, diabase, basalt, with a temperature not exceeding 150 ° C, are loaded into mixer No. 1 of the installation for the manufacture of pavement (Fig. 3). In the mixer No. 1 (Fig. 3) load road bitumen mixed in the mixer No. 2 with polymer building material made according to the recipe from example III. A mixture of bitumen and granulate forms a binding agent with a composition in wt.%:

Road bitumen 15%

Polymeric building material 85%

100% binding agent for roads

Material for creating a pavement with a composition in wt.%

Coupling agent for roads 25%

Diabase 55%

Basalt 20%

100% paving material

The resulting pavement layer has a black color and excellent quality.

Claims (3)

CLAIM 1. The production method of a construction polymer binder, based on sulfur waste, comprising the following steps, from 30 to 60 wt.% Of sulfur waste is heated to a temperature of 125-135 ° C, is placed in a rotating drum of the agitator and after sulfur will melt, add from 10 to 45 wt.% crushed granules up to 10 mm dump slag containing selenium, arsenic, phosphorus and their sulfides, metal oxides, while the dump slag pre-regulates the pH to a value of about 6.5 with phosphogypsum waste . An amount of 15-30% by weight, mineral filler is further added in an amount up to 30 wt%, then the mixture was stirred for about 10 minutes at about 16 to 20 rev / min.; the resulting building binder is then poured into a mold or poured onto a given surface. 2. Construction polymer binder, characterized in that it is a product of modification of waste sulfur and metals contained in the blast furnace slag, including selenium, arsenic, phosphorus and their sulfides, and metal oxides and consists of 40-60 wt.% Sulfur waste, 20 -45 wt.% Blast furnace slag and 1523 wt.% Phosphogypsum waste. 3. Construction polymer binder, characterized in that it is a product of modification of waste sulfur and metals contained in waste slag from copper smelting, including copper, phosphorus and their sulfides and metal oxides, and consists of 30-50 wt.% Sulfur waste, 10-45 wt.% Waste slag from copper smelting, crushed into granules up to 5 mm in size, 15-30 wt.% Phosphogypsum waste as a regulator of the pH of the dump slag from copper smelting and 10-40 wt.% Mineral filler.