RU2543173C1 - Bitumen composition (versions) and production method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: bitumen composition includes petroleum road bitumen BND 90/130, SKS-30ARKM-15 or SKS-30ARK rubber and polyethylene polyamine production wastes as an adhesive additive, with the following ratio of components, wt %: BND 90/130 bitumen - 83-93, SKS-30ARKM-15 rubber - 5-10 and polyethylene polyamine production wastes - 2-7 or BND 90/130 bitumen - 86-95, SKS-30ARK rubber - 3-7 and polyethylene polyamine production wastes - 2-7. The method of producing the bitumen composition is carried out by mixing bitumen while heating with a rubber-containing component and an adhesive additive, wherein the rubber is added in the form of 8-12% solution in an organic solvent, wherein the solvent used is hydrocarbons with final boiling point of no higher than 130°C. Preparation of the rubber solution in the solvent is carried out at 40-50°C while mixing for 5-6 hours. The obtained rubber solution and adhesive additive are then added to the bitumen. The mixture is homogenised for 3-4 hours while gradually raising temperature to 160-170°C. Further mixing is carried out until achieving 97% removal of the solvent. The remaining amount of solvent is removed by blowing with nitrogen.

EFFECT: obtaining a homogenous bitumen binder, having improved physical and mechanical properties.

4 cl, 2 tbl

Description

The invention relates to a method for producing bitumen compositions and may find application in road construction, production of roofing materials and waterproofing.

Bitumen is traditionally the main cementitious material in the construction of pavement. To improve the physical and mechanical properties of the latter, namely to expand the temperature range of the road surface operability, reduce brittleness (reduce crack resistance and increase elasticity), bitumen is used in combination with modifying additives and fillers. As modifying additives, first of all, high molecular weight compounds are used that provide the ability of bitumen to highly elastic deformations.

Known bitumen binder for paving [RF patent No. 2140947; C08L 95/00; C08L 53/02; publ. November 10, 1999], which contains bitumen, block copolymers of butadiene or isoprene with styrene and a plasticizing solvent, contains a black bitumen production polymer or polyalkylbenzene resin as a plasticizing solvent in the following ratio, wt.%: Bitumen 55.0-95 , 0, block copolymers of butadiene or isoprene with styrene 0.3-18.0, solvent plasticizer 4.5-27.0.

The disadvantage of this method is the high toxicity of the polyalkylbenzene resin.

A known method of producing a bitumen binder for road, airfield, hydraulic and other types of construction [RF patent No. 2162476; C08L 95/00; publ. January 27, 2001]. In the known method, a bitumen binder is obtained by mixing bitumen when heated with a rubber-containing component in the form of a solution in an organic solvent in an amount of 0.1-10.0% by weight of bitumen, characterized in that an 11-17% rubber solution is used as the rubber-containing component or its waste, prepared in stages. In the first stage, an organic solvent with a flash point of at least 62 ° C in an amount of 1/3 of the total calculated amount of solvent is used, and the dissolution process is carried out at a temperature of no higher than 20-25 ° C with stirring for 1 hour. In the second stage, 2 / 3 of the calculated amount of an organic solvent with a flash point of not more than 28 ° C and the dissolution process is carried out at 90-100 ° C with stirring for 10-11 hours. And then the rubber-containing component thus prepared is introduced into bitumen.

The disadvantages of this method of obtaining a bitumen binder are as follows: the process is two-stage, and an additional stage involves the introduction of a rubber-containing component in bitumen; modified bitumen is characterized by insufficient adhesion to mineral fillers (withstands, corresponds to control sample No. 2 according to GOST 11508-74). The method is applicable only to bitumen oil road liquid with a flash point, determined in an open crucible, not lower than 45 ° C.

It is known [RF patent No. 2162476; C08L 95/00; publ. January 27, 2001] the use of rubber of the SKS-30ARKM-15 and SKS-30ARK brand for the production of road-building materials, but its combination with the waste of the production of polyethylene polyamine is not described in the literature.

Closest to the proposed technical essence and the achieved result is a bitumen composition and a method for its preparation [RF patent No. 2119513; C08L 95/00, C08L 53/02, C08L 93/00; publ. September 27, 1998]. The bitumen composition includes petroleum road bitumen, styrene-butadiene thermoelastoplast as a rubber-containing component, and tall oil or the product of the interaction of tall oil and triethanolamine as an adhesive additive in the following ratio, wt.%:

Bitumen 97.3-77; Styrene butadiene thermoplastic elastomer 2-16; Specified Adhesive Additive 0.7-7.0.

A method of obtaining a bitumen composition is carried out by mixing the bitumen when heated with a rubber-containing component and an adhesive additive in which oil road bitumen is used, the rubber-containing component is styrene-butadiene thermoplastic elastomer, the adhesive additive is tall oil or the product of the interaction of tall oil and triethanolamine with a mass ratio: triethanolamine (66-68): (32-34). At 25-50 ° C, styrene-butadiene thermoplastic elastomer is mixed with an adhesive additive, then at a temperature of 150-160 ° C thermoplastic elastomer with an adhesive additive is mixed with bitumen in the ratio, wt.%: Bitumen 97.3-77.0, styrene-butadiene thermoplastic elastomer 2-16, the specified adhesive additive of 0.7-7.0. The resulting product is characterized as follows: depth of penetration of the needle (70-120 × 0.1 mm), extensibility (at 25 ° C - 40-51 cm), softening temperature along the ring and ball (54-88 ° C), brittleness according to Fraasu (-25 - -65 ° C), adhesion to marble and sand (can withstand control sample No. 2), i.e. low adhesion.

The disadvantages of this method for producing a bitumen composition are low physical and mechanical properties, such as a relatively high brittleness temperature and low softening temperature, as well as insufficient adhesion to sand, i.e. adhesion.

The purpose of the invention is to obtain a homogeneous bituminous composition having high physical and mechanical properties and an extended serviceability interval of materials, as well as the development of a method for producing a bituminous composition, due to which the optimal combination of high molecular weight compound and bitumen grade BND 90/130 is achieved.

This goal is achieved in that the bitumen composition, including oil road bitumen, a rubber-containing component and an adhesive additive, contains BND 90/130 grade bitumen, the rubber component SKS-30ARKM-15 or SKS-30ARK, and the adhesive component, as oil road bitumen additives - waste production of polyethylene polyamine in the following ratio of components, wt.%:

according to the first option - Bitumen grade BND 90/130 83-93, Rubber SKS-30ARKM-15 5-10, Polyethylene polyamine production waste 2-7. according to the second option - Bitumen grade BND 90/130 86-95, Rubber SKS-30ARK 3-7, Polyethylene polyamine production waste 2-7.

This goal is also achieved by the fact that in the method of producing a bitumen composition by mixing petroleum road bitumen when heated with a rubber-containing component and an adhesive additive, BND 90/130 grade bitumen is used as a rubber road bitumen; SKS-30ARKM-15 rubber is used in the amount of rubber component 5-10% by weight of the bituminous composition or SKS-30ARK - 3-7% by weight of the bituminous composition, adhesive additives - waste from the production of polyethylene polyamine (with OJSC Kaustik, Sterlitamak) in an amount of 2-7% by weight of b fog composition, rubber grades SKS-30ARKM-15 or SKS-30ARK are added to the process in the form of an 8-12% solution in an organic solvent, and hydrocarbons are used as the organic solvent, with a boiling point not exceeding 130 ° C, rubber dissolution in an organic solvent is carried out at a temperature of 40-50 ° C by stirring for 5-6 hours, then an adhesive additive and a rubber solution are introduced into the bitumen, the mixture is homogenized for 3-4 hours, gradually raising the temperature to 160-170 ° C, further mixing lead to removal 97 % hydrocarbon solvent, and the remaining amount of solvent by blowing with nitrogen.

Using this method allows to obtain a homogeneous bitumen binder due to the effective dissolution of the rubber component in a hydrocarbon solvent and the subsequent homogenization of the components of the composition. All this allows us to successfully carry out optimization both in the composition of the composition and in the physicomechanical properties achieved by it.

Obtaining a bitumen composition according to the proposed method by using bitumen grade BND 90/130 as rubber components, rubber grade SKS-30ARKM-15 or SKS-30ARK, waste production of polyethylene polyamine provides high physical and mechanical and adhesive properties of the target product that meet all the requirements of TU 35.1669 -88 for cementitious grades PBV.

Bitumen grade BND 90/130 is characterized by such indicators as: depth of penetration of the needle (at 25 ° C - 82 × 0.1 mm), softening temperature along the ring and ball (45.1 ° C), fragility temperature according to Fraas (-14.0 ° C), extensibility (at 25 ° C -> 100), adhesion to mineral material (can withstand control sample No. 3).

Rubber grade SKS-30ARKM-15 is characterized by a Mooney viscosity of MB _{1 + 4} (100 ° C), equal to 39. The optimal content of rubber grade SKS-30ARKM-15 in the bitumen composition is from 5 to 10 wt.%. When the rubber content is more than 10 wt.%, The softening temperature slightly decreases and the viscosity of the bitumen composition sharply increases and it becomes rubber-like, which complicates the technological process of its preparation. When the rubber content is less than 5 wt.%, The physical and mechanical properties of the polymer-bitumen composition deteriorate and its main indicators do not meet the requirements of TU 35.1669-88 for cementitious grades PBV.

SKS-30ARK rubber is characterized by Mooney viscosity MB _{1 + 4} (100 ° C),

 equal to 38. The optimum rubber content of the SKS-30ARK brand in the bitumen composition is from 3 to 7 wt.%. When the rubber content is more than 7 wt.%, The viscosity of the bitumen composition sharply increases, which complicates the technological process of its preparation. When the rubber content is less than 3 wt.%, The physical and mechanical properties of the polymer-bitumen composition deteriorate and its main indicators do not meet the requirements of TU 35.1669-88 for cementitious grades PBV.

Rubbers of the SKS-30ARKM-15 or SKS-30ARK brands are used in the form of an 8-12% solution; in this concentration range, rubber is completely dissolved. With an increase in concentration of more than 12 wt.%, The viscosity of the rubber-containing solution significantly increases, which complicates the process of homogenization, and also does not ensure the completeness of its dissolution. When the rubber content in the solution is less than 8 wt.%, The solvent consumption unreasonably increases.

The waste from the production of polyethylene polyamine has the following composition, wt.%: Polyethylene polyamine - 20-35, a mixture of carboxylic acids - 10-20, amido amines - 20-25, imidazolines - 30-35. It is known [RF patent No. 2226203; C08L 95/00, C08L 53/02, C08L 15/00; publ. March 27, 2004] that nitrogen-containing substances, in particular polyethylene polyamine, are used as additives that increase the adhesive properties of PBB. In this regard, a waste product for the production of polyethylene polyamine was chosen as an adhesive additive. The introduction of additives in an amount of 2-7 wt.% Improves not only the adhesive properties, but also positively affects the physicomechanical parameters of the bitumen composition as a whole. With a content of more than 7 wt.% And less than 2 wt.%, The physical and mechanical properties are not high enough (needle penetration depth at 25 ° C 143 × 0.1 mm and 95 × 0.1 mm; softening temperature along the ring and ball 47.6 ° C and 49.4 ° C; the fragility temperature according to Fraas is -25 ° C and -29.3 ° C, respectively) of the polymer-bitumen composition and do not meet the requirements of TU 35.1669-88 for cementitious grades of PBB.

The process of preparing rubber in an organic solvent is carried out at a temperature of 40-50 ° C by stirring for 5-6 hours. At temperatures below 40 ° C - the dissolution rate of rubber is low, at temperatures above 50 ° C - solvent losses increase. To obtain a homogeneous homogeneous solution of the rubber-containing component, it is optimal to conduct the dissolution process for 5-6 hours. With a decrease in the dissolution time of less than 5 hours, the rubber does not completely dissolve. An increase in the duration of the preparation of the solution of the rubber-containing component leads to unnecessary energy consumption.

Hydrocarbons with a boiling point of not more than 130 ° C are used as an organic solvent, since rubbers SKS-30ARKM-15 and SKS-30ARK are well soluble in them; they are inert with respect to the components of the bitumen composition. Hydrocarbons with a boiling point no higher than 130 ° C are selected in order to ensure that, during the mixing of the bitumen composition at a temperature of 160-170 ° C, the degree of removal of solvent from the reaction mass is up to 97%.

Physico-mechanical properties of bitumen compositions are determined by the following methods:

Determination of the penetration depth of the needle - according to GOST 11501-78.

Determination of the softening temperature of the ring and ball according to GOST 11506-73.

Determination of the fragility temperature according to Fraas - according to GOST 11507-78.

Determination of extensibility - according to GOST 11505-75.

Determination of adhesive properties by adhesion to marble or sand according to GOST 11508-74.

Data on the composition of bitumen compositions are presented in table 1, by properties - in table 2.

The invention is illustrated by an example of a specific implementation. Example 1

6 g of rubber SKS-30ARKM-15 (TU 38.40355-99) in the form of crumbs of 2-3 mm size and a hydrocarbon solvent in the amount of 60 g taken from the gasoline secondary distillation unit with a boiling point are loaded into a mixer equipped with a paddle mixer 130 ° C. The rubber solution is prepared at a temperature of 45 ° C by stirring for 6 hours. Obtain 66 g of a 9.1% solution of rubber.

91 g of BND 90/130 grade bitumen are charged into a reactor equipped with a paddle mixer, then 66 g of the resulting rubber solution and 3 g of polyethylene polyamine waste are introduced into the reactor. The reaction mixture was stirred for 4 hours, gradually raising the temperature to 165 ° C. Further mixing of the mixture at this temperature is carried out for 1 hour until the removal of 97% hydrocarbon solvent, which is sent for recycling. Then the reaction mixture was purged with nitrogen for 15 minutes to remove the remaining amount of solvent. 100 g of the bitumen composition are obtained. The rubber consumption of the SKS-30ARKM-15 brand was 6% by weight of the bitumen composition, and the waste consumption rate of polyethylene polyamine production was 3% by weight of the bitumen composition. A sample of the obtained bitumen composition is subjected to standard tests.

The feasibility of the selected limits of the technological process for producing a bitumen composition is presented in table 1.

The data of table 2 indicate that the samples of bitumen compositions have high adhesive properties and correspond to control sample No. 1 according to GOST 11508-74. The indicators of extensibility and softening temperature along the ring and ball of bituminous compositions obtained by the claimed technical solution are higher than similar indicators for the compositions obtained by the prototype. The highest values of these indicators are polymer-bitumen compositions containing rubber grades SKS-30ARKM-15 and SKS-30ARK and waste production of polyethylene polyamine. The use of rubber grades SKS-30ARKM-15, SKS-30ARK is cost-effective when used in road surfaces compared to DST-30-01.

Table 1 RECIPE OF BITUMINOUS COMPOSITIONS Mixture Components The content of components,% by weight of the bitumen composition, according to examples one 2 3 four 5 6 7 8 9 10* eleven* 12* 13* fourteen* 15 prototype one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen fifteen 16 1. Bitumen 93 91 88 91 88 95 93 91 97 90 93 8 94 87 95 2. Rubber
SKS-30ARKM-15
SKS-30ARK
Thermoelastoplast DST-30-01 5 7 10 5 5 3 5 7 one 8 3 12 5 5 four Adhesive additive
- polyethylenepolyamine production waste
- TMT product 2 2 2 four 7 2 2 2 2 2 2 2 one 8 one Total bituminous composition one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred one hundred

table 2 PHYSICAL AND MECHANICAL INDICES OF BITUMINOUS COMPOSITIONS Indicators The value of the indicator for examples one 2 3 four 5 6 7 8 9* 10* eleven* 12* 13* fourteen* 15 prototype TU 35.1669-88 for binders PBV 90/130 one 2 3 four 5 6 7 8 9 10 eleven 12 13 fourteen fifteen 16 17 Depth
needle penetration at 25 ° C, 0.1 mm 106 122 129 111 130 97 115 130 90 137 92 138 95 143 80 90-130 The softening temperature of the ring and ball, ° C 65 59 54 54 51 64 60 56 53 48 54 49 49 48 54 not lower than 50 Fraas fragility temperature, ° C -38 -35 -32 -35 -31 -37 -35 -34 -28 -thirty -29 -28 -29 -25 -37 no higher than -30 Tensile at 25 ° C, cm > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 > 150 43 not less than 15 Mineral adhesion No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 Number 2 Number 2 Number 2 No. 1 Number 2 Number 2 maintain on a control sample No. 2 * outside the boundary conditions

Claims (4)

1. Bitumen composition, including oil road bitumen, rubber component and adhesive additive, characterized in that as oil road bitumen use bitumen grade BND 90/130, rubber component is rubber grade SKS-30ARKM-15, and the adhesive additive is a waste product polyethylene polyamine in the following ratio of components, wt.%:
bitumen grade BND 90/130 83-93 rubber SKS-30ARKM-15 5-10 polyethylenepolyamine production waste 2-7. 2. A bituminous composition comprising oil road bitumen, a rubber-containing component and an adhesive additive, characterized in that as an oil road bitumen, bitumen of the BND 90/130 brand is used, the rubber-containing component is rubber of the SKS-30ARK brand, and the adhesive additive is waste from the production of polyethylene polyamine with the following ratio of components, wt.%
bitumen grade BND 90/130 86-95 rubber SKS-30ARK 3-7 polyethylenepolyamine production waste 2-7. 3. A method of obtaining a bitumen composition by mixing petroleum road bitumen when heated with a rubber-containing component and an adhesive additive, characterized in that the rubber is introduced into the bitumen composition in the form of an 8-12% solution in an organic solvent, and hydrocarbons with the boiling point is not higher than 130 ° C, the preparation of a solution of rubber in an organic solvent is carried out at a temperature of 40-50 ° C by stirring for 5-6 hours, then the resulting astvor rubber and an adhesive additive, the mixture was homogenized for 4.3 hours while gradually raising the temperature to 160-170 ° C, further stirring the mixture lead to remove 97% of the hydrocarbon solvent and the residual solvent was removed by blowing nitrogen. 4. The method according to claim 3, characterized in that a light hydrocarbon fraction from a gasoline secondary distillation unit with a boiling point of 130 ° C or a hydrocarbon fraction from an ABT unit (atmospheric vacuum distillation) with a boiling point of 115 ° C is used as hydrocarbons.