RU2276115C2 - Binding agent - Google Patents

Abstract

FIELD: BINDING AGENT COMPOSITION.

SUBSTANCE: claimed binding agent includes sulfur, dicyclopentadiene, fine dispersed filler, such as waste from neutralization containing (mass %) SiO₂ 38.56; Al₂O₃ 2.3; Fe₂O₃ 37.0; CaO 10.0; MgO 2.0; S 10; Cu 0.12; Co 0.016 in the next component ratio (mass %): sulfur 45.0-50.0; dicyclopentadiene 2.3-2.5; and balance: said waste.

EFFECT: environmental friendly binding agent of low cost, low water absorption, high chemical resistance, without losses of strength of prepared articles.

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Description

The invention relates to binders and can be used in the manufacture of sulfur concrete products and building structures based on sulfur binders, for pouring expansion joints in hydraulic structures, chemically resistant coatings to protect equipment and building structures from acid and salt corrosion, in the manufacture of acid and salt resistant sexes. The invention expands the use of industrial non-ferrous metallurgy wastes and provides for the utilization of waste, improving the environmental situation in the region.

Known astringent (copyright certificate No. 2176222, IPC ⁷ C 04 B 28/36), including sulfur, filler - finely divided diatomite and additive - biphenyl.

The disadvantages of this binder: high energy costs for the preparation of a special fine filler. The chemical resistance of the binder on diatomite is not high enough.

A concrete mixture is known (copyright certificate No. 1477714, IPC ⁷ C 04 B 28/36), the composition of which is essentially a sulfur binder, including ground sand, waste from the production of sulfuric acid (sulfur sludge) and gach as a filler.

The disadvantage of this mixture is that the grinding of quartz sand cannot be brought to dispersion, leading to a maximum density of the material. This entails excessive porosity, increased water absorption, as well as high cost of the material. Corrosion resistance coefficient 1.21 rather speaks not about the chemical resistance of the material, but about the fact that the material enters into chemical reactions with the environment, forming products that temporarily strengthen the structure. However, the authors do not present the results of a study of long-term chemical resistance.

Known raw mix (US No. 4348313, publ. 07/07/1982), including sulfur, quartz, limestone, dicyclopentadiene and cyclopentadiene oligomer.

The disadvantage of this mixture is that the method of its preparation has a tendency for the components of the mixture to absorb water, which leads to heterogeneity of the compositions.

Closest to the proposed (US No. 5004799, publ. 02.04.1991) is a raw material mixture of a similar composition, additionally subjected to granulation to achieve uniformity.

The disadvantage of this mixture (US No. 43438313, US No. 5004799) is that limestone or quartz is used as a filler mineral, and grinding of limestone or quartz flour cannot be brought to dispersion, leading to a maximum density of the material, which entails excess porosity.

The technical effect achieved by using the inventive binder is:

a) increasing the density of sulfur compositions while improving the properties of sulfur binder due to the high dispersion of the filler - dump "tailings" of neutralization with a specific surface area of 6400 cm ² / g and grain sizes less than 64 microns;

b) a decrease in porosity and water absorption due to the formation of a more uniform and finely crystalline structure of sulfur binder;

c) an increase in the corrosion resistance of sulfur binder, not only due to the chemical resistance of sulfur, but also due to the acid and salt resistance of the “tails”;

d) reducing the cost of sulfur binder by replacing natural fillers with acid-resistant finely divided waste from the metallurgical industry without significant loss of strength and chemical resistance.

The inventive sulfur binder for the manufacture of building structures and products containing sulfur, an inorganic finely divided filler and a modifying additive, according to the invention, contains dumping tails of composition neutralization as a filler, wt.%: SiO ₂ -38.56; Al ₂ O ₃ -2.3; Fe ₂ O ₃ -37.0; CaO-10.0; MgO-2.0; S-10; Cu-0.12; Co-0.016, and as a modifying additive dicyclopentadiene in the following components, wt.%:

sulfur 45.0 ÷ 50.0; dicyclopentadiene 2.3 ÷ 2.5; tails rest.

The technical effect is achieved by the fact that crystalline modifications of sulfur are successfully combined with the fineness of the “tails”, strengthening the structure of the samples. Sulfur has several allotropic modifications, two of which are α- and β-crystalline sulfur. Both contain corrugated rings S ₈ with a distance of SS 2.05 Å and an angle SSS of 108 °, which are located one above the other, forming columns. These columns, in turn, located parallel to one another, form layers, and the columns of each next layer are located perpendicular to the direction of the columns of the previous layer. The dispersion of the "tails" is quite suitable for filling the cavities of the columns, extremely compacting the structure, which leads to minimal porosity, minimal water absorption and maximum strength.

In addition to the α- and β-crystalline forms of sulfur in the melt, at a temperature above 160 ° С, a modification of μ-sulfur, namely polymer sulfur, is formed.

A three-component system is formed in the solidified melt, in which, under the action of loads, the polymer sulfur stretches, deforms, and redistributes stresses to the most high-modulus component — crystalline modifications of α- and β-sulfur.

For the preparation of the claimed composition are used:

- as a binder - sulfur technical lump or gas, meeting the requirements of GOST 127-93.1, with a melting point of 119 ° C; viscosity at a temperature of 149 ° C-6.6 × 10 Pa · s;

- as a filler, dump neutralization “tails” obtained by cleaning the liquid phase of the pulp of the sulfur-sulfide flotation waste of copper-nickel sulfide concentrate from iron and non-ferrous metals, which are a finely dispersed material with a specific surface of 6400 cm ² / g and grain sizes less than 64 microns. The dump "tails" are an inert product that reacts at temperatures above 300 ° C only with concentrated hydrochloric acid. Infrared spectroscopy showed that the chemical resistance of the dump "tails" is 0.98-0.99. Chemical composition, wt.%: SiO ₂ - 38.56; Al ₂ O ₃ - 2.3; Fe ₂ O ₃ - 37.0; CaO - 10.0; MgO - 2.0; S is 10; Cu - 0.12; Co - 0.016;

- dicyclopentadiene (TU 2416-024-05766801-94), which is a liquid that is a by-product in the manufacture of artificial rubber at rubber tire factories, is used as a modifying additive. The empirical formula is C ₁₀ H ₁₂ .

A method of manufacturing a binder is as follows.

The sulfur melt is brought to a temperature of 140 ° C and, with stirring, dicyclopentadiene (5% by weight of sulfur) is introduced into it in small portions.

After obtaining a homogeneous melt, tails heated to the same temperature are added to it. Then, after thorough mixing, the resulting composition is placed in heated molds and cooled to normal temperature. Test samples are prepared in the form of cubes with a rib size of 7.07 cm and prisms of 2 × 7 × 7 cm and 1 × 1 × 3 cm. In the study of astringent testing, samples of the sulfur composition are given in Table 1.

The strength of the composites was evaluated.

To assess the long chemical resistance for one year, the samples were kept in saline and acid solutions, as well as in the environment of an electrolysis bath of a copper plant. No signs of failure or loss of strength were observed.

The composition and advantages of the inventive binder in comparison with the prototypes are presented in table 1.

The use of the inventive binder will increase the density and chemical resistance against acid aggression, significantly reduce water absorption, cost, solve environmental problems through waste disposal.

Table 1 No. of compositions The content of components, wt.% Concrete Quality Indicators Sulfur Dicyclo-pentadiene Oligomer Sulfuric acid production waste (sulfur sludge) Dump "tails" Ground sand Quartz sand Gach Limestone Initial strength, MPa Water absorption,% The coefficient of chemical resistance in 94% H ₂ SO ₄ Known composition (as.with. 1477714) one - - - 60.0 - 35.0 - 5,0 - 11,4 0.325 1.21 Known Formulations (US No. 4348313) 2 21 3.75 1.25 - - - - - 21 56.3 - one 3 23 3.75 1.25 - - - 77 - - 42.6 - one Suggested formulations four 40,0 2.0 - - 58.0 - - - - 36,2 0.09 0.94 5 42.5 2.1 - - 55,4 - - - - 37.1 0,07 0.97 6 45.0 2,3 - - 52.7 - - - - 37.6 0.05 0.99 7 47.5 2,4 - - 50.1 - - - - 38,2 0.04 0.99 8 50,0 2,5 - - 47.5 - - - - 37.7 0.05 0.99 9 52,5 2.6 - - 44.9 - - - - 37,2 0.06 0.98 10 55.0 2,8 - - 42,2 - - - - 36.8 0.06 0.96

Claims (1)

An astringent, including sulfur, dicyclopentadiene, a finely divided filler, characterized in that it contains dump “tailings” of composition neutralization as a specified filler, wt.%: SiO ₂ 38.56, Al ₂ O ₃ 2,3, Fe ₂ O ₃ 37 , 0, CaO 10.0, MgO 2.0, S 10, Cu 0.12, Co 0.016 in the following ratio of binder components, wt.%: Sulfur 45.0-50.0 Dicyclopentadiene 2.3-2.5 Specified Tails Rest