PL242738B1 - Sulfur concrete mix - Google Patents

Abstract

The subject of the application is a sulphur-concrete mass containing a binder in the form of sulfur contaminated with bitumens or technically pure sulfur, which are used together or only one of them, but always constitute at least 70% of the final weight of the binder mixture, and preferably its 90% to 94% and they are supplemented with ingredients in a total amount not exceeding 30% of the final weight of the mixture in the form of: dicyclopentadiene or turpentine or furfural or styrene. The described binder constitutes from 15% to 26% by weight of the sulphur concrete mass. In addition, this mass contains mineral aggregates in the amount of 74% to 85% by weight of the sulfur concrete mass or, alternatively, waste products, preferably waste products from the power industry, which together or separately: - ashes in the amount of up to 10% by weight of the sulfur concrete mass, dust in the amount of up to 10 % by weight of the mass of sulphur concrete, which are obtained as a result of flue gas cleaning. In addition to the fillers listed above, other waste products may be used jointly or separately, or alternatively: - slags in the amount of up to 60% by weight of the sulphur concrete mass, phosphogypsum in the amount of up to 20% by weight of the sulphur concrete mass. Preferably, the mineral aggregates contained in the prepared sulphur-concrete mass are sand or gravel contaminated with salt.

Description

The subject of the invention is a sulfur concrete mass produced from a combination of sulfur-organic polymers and waste products from the energy, chemical, metallurgical, mining and petrochemical industries. It contains sulfur-organic polymers based on elemental sulfur or bitumen-contaminated sulfur and mineral aggregates, which can be replaced by waste products from the energy industry (combustion by-products such as dust, ashes and slag), as well as products from the chemical industry (such as phosphogypsum ), from petrochemical (such as sulfur contaminated with bitumen) and mining (such as non-standard sands and gravels or pebble aggregate).

Concrete is the most popular building material in the world. It is usually traditional concrete made by mixing:

• mineral binder (cement, binding agent) and • fillers (which are standardized mineral aggregates), • any admixtures that give the desired characteristics, and • water.

In these materials, after adding water, chemical reactions take place, as a result of which the binding and hardening process takes place.

The most common types of cements (i.e. mineral binders) are Portland or blast cements.

The main difference between traditional concrete and sulfur concrete mass, which is the subject of the present invention, is the chemical binder used in it, i.e. a binding agent and fillers, which (replacement for natural aggregates) can be by-products of combustion from the energy industry, waste products from the chemical industry, metallurgy and mining.

Traditional concrete can be defined as a composite material consisting of solid phases and a proportionately small amount of liquid and gaseous phases. Its functional properties are mainly determined by the physicochemical properties of the phases present in it and their mutual proportions (as a result of their composition, both chemical and physical factors can cause destruction of concrete).

The known sulphur concretes are a type of concrete that is particularly acid-resistant. They are obtained by melting sulfur polymers as a binder (usually from 12 to 22%) at a temperature of about 130-140°C and combining them with fillers, which are mainly mineral aggregates.

An exemplary binder is known from the invention, patent no. PL. 190343 (protected with priority from August 6, 2002) entitled "Method of obtaining stable polymeric sulfur for the production of sulfur concretes and waste protection", which also describes the technological process of obtaining stable polymeric sulfur.

The setting of sulfur concrete takes place relatively quickly after cooling down the sulfur concrete mass and is the result of solidification of the binder - i.e. a stable sulfur polymer (it lasts about 24 hours). This is a physical process, unlike the setting of traditional concrete, which is a practically irreversible chemical transformation.

Sulfur concrete is characterized by high resistance to acids and salts, good mechanical properties and impermeability to water. It can be used at a certain temperature. The upper temperature limit of its applicability is 120°C.

Traditional concrete requires a proportionally large amount of the liquid phase - water. On the other hand, in sulfur concretes, the liquid phase is a molten sulfur polymer. Neither water nor air are needed to bind the components of sulphur-concrete masses.

Another known binder is a sulfur polymer from the Polish invention PL. 213685 "Method for the production of a polymeric construction binder based on blast furnace slag and waste sulfur" (submitted for protection on January 14, 2009 - publication WUP 04/13). The method of producing a polymeric construction binder based on the ingredients indicated in the title is presented here. For its production, phosphogypsum is also used as a filler. During the process described here, sulfur is modified due to the presence of metals contained in the metallurgical slag, including selenium, arsenic, phosphorus, their sulfides and oxides.

Phosphogypsum (phosphorogypse) - a waste that is a by-product of obtaining phosphoric acid from phosphate rock by extraction with sulfuric acid, as well as a waste that is a by-product in the production of phosphate and nitrogen fertilizers.

The publication in the journal Chemik Rok XLI 1988:9, 243-245 presents the possibility of using slightly more complex sulfur-organic copolymers as a continuous phase of sulfur concretes and at the same time dipentene (DP), cyclopentadiene (CPD), dicyclopentadiene (DCPD), isobutene, diisobutene , polybutene and styrene as organic comonomers most commonly used in sulfur-organic copolymers, in the amount from a few to several % by weight.

US 4,391,969 describes methods for producing sulfur concretes with a continuous phase in the form of sulfur-organic copolymers containing dicyclopentadiene as an organic comonomer or a mixture of organic compounds in which dicyclopentadiene is at least 37% by weight, used in an amount of 2-20% by weight.

However, in the description of the Polish invention entitled "Method of obtaining stable polymeric sulfur for the production of sulfur concretes and waste protection" PL-190343 (protected with priority since August 6, 2002, pub. WUP 11/2005) - a method of obtaining stable polymeric sulfur was presented, consisting in the fact that unsaturated hydrocarbons , which is a mixture of cyclopentadiene and its oligomers with an optional admixture of styrene constituting 0-50% by weight of all hydrocarbons, is introduced in the amount of 1-20% by weight of reactants into molten and constantly stirred elemental sulfur at a temperature of 125-130°C, and then the temperature of the mixture is raised gradually, no faster than 5°C over 30 minutes until a temperature of 140-145°C is reached and maintained at this temperature for 3 hours. The temperature of the mixture is then lowered by no more than 5°C in 30 minutes to 130-135°C and maintained at this temperature for at least 3 hours. The process is carried out in an oxygen-free atmosphere, in the presence of nitrogen, carbon dioxide or other inert gas. The obtained stable polymeric sulfur is used for the production of sulfur concretes.

There is also known (basic for this solution) Polish invention P. 422069 entitled "Method of obtaining stable polymeric sulfur as a binder for the production of sulphur concrete and stable polymeric sulfur as a binder for the production of sulphur concrete" (submitted with priority on June 28, 2017) describing a binder for sulphur concrete in the form of stable polymeric sulfur. The supplementary components are: dicyclopentadiene or turpentine or furfural or styrene in different weight percentages, different from those known from the state of the art.

Turpentine - is a mixture of low molecular weight organic compounds obtained from the resin of coniferous trees. It is a by-product of the cellulose industry.

Furfural, in turn, is a low-molecular organic compound obtained by chemical reactions from food waste, including confectionery waste. It can be obtained from biomass (e.g. ground corn cobs). The name furfural comes from the term "furfur" (Latin bran), from which furfural, among others, is obtained.

In contrast, styrene is an organic chemical compound, an aromatic hydrocarbon with an alkene side chain. It is the starting compound for the production of polystyrene. Under normal conditions, it is a colorless or slightly yellowish liquid with a faint, characteristic, unpleasant odor, which polymerizes easily and quickly, even under the influence of sunlight or not too intense heating, forming polystyrene.

The aim of the invention is the development and use of waste materials, e.g. from the energy, petrochemical, metallurgical, chemical and mining industries and their economic use in accordance with the circular economy policy.

The sulfur concrete mix according to the invention includes:

a) sulfur polymer (binder, i.e. binder), where the sulfur polymer consists of sulfur contaminated with bitumen or pure sulfur and supplementary components (dicyclopentadiene or turpentine or furfural or styrene),

b) fillers, i.e. mineral aggregates or waste products.

The essence of the developed sulfur concrete mix, which contains a sulfur polymer, is that the sulfur polymer consists of: bitumen-contaminated sulfur or technically pure sulfur, which are used together or only one of them, which sulfur constitutes at least 70% of the final weight of the binder , i.e. a sulfur polymer, and preferably it is 90% to 94%, and additional binder components, i.e. a sulfur polymer in a total amount not exceeding 30% by weight of the binder, i.e. a sulfur polymer in the form of: dicyclopentadiene or turpentine, or furfural, or styrene .

Sulfur polymer (pure sulfur or sulfur with impurities and supplementary components) constitutes from 15% to 26% by weight of the sulfur concrete mass, which, apart from the sulfur polymer, contains mineral aggregates in the amount of 74% to 85% by weight of the sulfur concrete mass, including mineral aggregates used exclusively or together with waste products, preferably waste products that are jointly or separately substitutes for mineral aggregates:

- dusts that are obtained as a result of flue gas cleaning in the amount of up to 10% by weight of the sulphur-concrete mass or

- ashes in the amount of up to 10% by weight of the sulfur concrete mass,

In addition to the listed fillers (which are mineral aggregates or waste products), other waste products may be used, either jointly or separately:

- phosphogypsum in the amount of up to 20% by weight of sulfur concrete or

- slags in the amount each time determined as a result of a series of technical tests up to 60% by weight of the sulphur concrete mass - slags as an alternative to ashes.

Preferably, the mineral aggregates contained in the prepared sulphur-concrete mass are sand or gravel contaminated with salt.

The sulphur concrete mass, which is the subject of the present invention, can be melted down and reused after use.

In the developed sulphur concrete mass, sulfur polymers are a binder for natural aggregates, such as sand and gravel, used for traditional concretes and sulphur concretes, which in the invention are replaced in certain proportions by weight with waste products from the power industry, such as dusts and ashes, or waste products from chemical industry, such as, for example, phosphogypsum, or waste products from the mining industry, such as non-standard aggregates not used in traditional concretes and known sulphur concretes. The technology of the developed sulfur concrete mass makes it possible to solve the problem of waste stored in heaps (e.g. by-products of combustion, post-mining minerals).

Sand and gravel contaminated with salt can also be used for the production of prepared sulphur-concrete masses. This is of great importance, as it enables the use of aggregates from the coastal belt for their production. Mineral materials from post-mining and post-production heaps can also be used for the production of sulphur-concrete masses.

The developed sulfur concrete mass, which is the subject of the invention, shows high bacteriostatic properties, which enables the use of the developed sulfur concrete masses in the agricultural industry, e.g. for the construction of rooms for storing agricultural products, animal husbandry, in health centers, etc. places.

The sulfur concrete mix according to the invention includes:

a) sulfur polymer (binder, i.e. binder), sulfur polymer consists of sulfur contaminated with bitumen or pure sulfur and supplementary components (dicyclopentadiene or turpentine or furfural or styrene),

b) fillers, i.e. mineral aggregates or waste products, and also

c) optionally admixtures.

The binder used in the prepared sulphur-concrete mass is sulfur contaminated with bitumens (present in the amount of approx. 2.5% by weight of sulfur mass) or technically pure sulphur. They are used together or only one of them, but they always constitute at least 70% of the final weight of the binder, i.e. the sulfur polymer, and preferably 90% to 94% thereof, and they are supplemented with components in a total amount not exceeding 30% of the final weight of the sulfur polymer in the form of: dicyclopentadiene or turpentine or furfural or styrene.

The prepared sulfur concrete mass may also contain waste products from the chemical industry, preferably in the form of phosphogypsum in an amount of up to about 20% by weight of the sulfur concrete mass, and mineral aggregates that can be replaced with waste from the energy industry, for example in the form of dust (up to 10% by weight of the sulfur concrete mass), ashes (up to 10% by weight of the sulfur concrete mass), or slags (up to 60% by weight to the weight of the sulfur concrete mass produced, alternatively to natural aggregates in the amount each time determined as a result of a series of technical tests).

Mineral aggregates in the form of sand or gravel contaminated with salt can also be introduced into it, which makes it possible to use aggregates from the coastal belt. Similarly, dusts (in the amount of up to 10% of the sulfur concrete mass) or ashes (in the amount of up to 10% of the sulfur concrete mass) may be introduced into the prepared mass. The developed sulphur-concrete mass shows excellent properties after the introduction of minerals and waste from post-mining and post-production heaps, or dust from the treatment of flue gases emitted and treated in power plants, or ashes.

Fillers used as substitutes for natural fillers in the form of sand and gravel in the sulfur concrete mass, having the character of post-production waste - they are substitutes that do not reduce the usable values of the sulfur concrete mass, and often increase its strength parameters. This is of great importance for the management of the above-mentioned waste materials, which occur in large quantities on the earth's surface in the form of heaps, and is in line with the circular economy policy currently promoted in the European Union, giving the possibility of restoring the earth's surface to its original functions (e.g. agricultural).

The subject of the invention is illustrated by the following examples of the developed sulfur concrete mass, in which a sulfur polymer was used, obtained as a result of the process described in the Polish application of the invention P.422069 "Method of obtaining stable polymeric sulfur as a binder for the production of sulfur concrete and stable polymer sulfur as a binder for the production of sulfur concrete of June 28, 2017.

Example 1

Sulfur polymer constituting 22.2% of the sulfur concrete mass (obtained from elemental sulfur + DCPD, constituting 10% of the polymer mass) was combined with fillers, i.e. mineral aggregates / waste products in the following proportions:

sand - 15.6% gravel - 54.4% silicate fly ash - 7.8% and a sulfur concrete mass with the following parameters was obtained:

compressive strength - 50.6 MPa ^ 68.7 MPa flexural strength - 10.4 MPa ^ 13.3 MPa

Example 2

Sulfur polymer constituting 25.8% of the sulfur concrete mass (sulphur contaminated with bitumen approx. 2.5% + DCPD, constituting 10% of the polymer mass), was combined with fillers, i.e. mineral aggregates / waste products in the following proportions:

sand - 13.1%

Gravel - 52.0%, silicate fly ash - 9.1% and a sulfur concrete mass with the following parameters was obtained:

compressive strength - 58.2 MPa ^ 58.7 MPa flexural strength - 10.0 MPa ^ 10.1 MPa

Example 3

The obtained sulfur polymer constituting 25.8% of the sulfur concrete mass (elemental sulfur + DCPD, constituting 10% of the polymer mass) was combined with fillers, i.e. mineral aggregates / waste products in the following proportions:

sand - 13.1% gravel - 52.0% phosphogypsum - 9.1% and a sulfur concrete mass with the following parameters was obtained:

compressive strength - 61.8 MPa, bending strength - 8.0 MPa

Claims (2)

1. Sulfur concrete mass, containing a binder in the form of a sulfur polymer and fillers, i.e. aggregates or waste products, characterized in that the sulfur polymer is: sulfur contaminated with bitumen or technically pure sulfur, which are used jointly or only one of them, constituting at least at least 70% of the final weight of the sulfur polymer, and preferably 90% to 94% thereof, and supplementary components in a total amount not exceeding 30% of the weight of the sulfur polymer in the form of: dicyclopentadiene or turpentine, or furfural, or styrene, the sulfur polymer being from 15 % to 26% by weight of the sulfur concrete mass, which, apart from the sulfur polymer, contains mineral aggregates in the amount of 74% to 85% by weight of the sulfur concrete mass, including mineral aggregates used exclusively or together with waste products, or waste products that are jointly or separately substitutes for mineral aggregates: - dusts in the amount of up to 10% by weight of the sulfur concrete mass or - ashes in the amount of up to 10% by weight of the sulfur concrete mass or - phosphogypsum in the amount of up to 20% by weight of the sulfur concrete mass or - slags in the amount of up to 60% by weight of the sulphur concrete mass - slags as an alternative to ashes, 2. Sulfur concrete mass, according to claim 1, characterized in that the mineral aggregates are sand or gravel contaminated with salt.