RU2630529C1 - Method for production of modified bituminous binders for road surfaces (versions) - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: method for production of modified bituminous binders for road surfaces includes preheating the raw material up to 70-90°C and activation in a hydropercussion cavitator 2. Then, the raw material is placed in a heating furnace and the raw material temperature reaches 250-300°C. Thermochemical treatment includes preliminary oxidation of raw materials by air oxygen, heated up to 250-300°C, in a continuous bubble oxidation column 3, followed by distillation in an atmosphere-vacuum column 4 at a temperature of 250-300°C with the separation of fuel gas and atmosphere-vacuum distillate. The heavy vacuum residue, resulting from the distillation, is fed to the reactor mixer 6, heated up to 130-180°C, after that modifiers are introduced, i.e.: rubber crumb in an amount of 5-20% wt of the weight of the heavy vacuum residue; an organomineral bituminous additive in an amount of 1-12% of the weight of the heavy vacuum residue and a granulated synthetic cord in an amount of 1-10% wt of the weight of the heavy vacuum residue. The components are mixed and the mixture is heated up to a temperature of 300-350°C. The mixture is then cooled down to 250-300°C, it is reactivated by passing through the second hydropercussion cavitator 11, and is then oxidized in the second continuous bubble oxidation column 9 at a temperature of 250-300°C by heated air oxygen along with distillation to produce the end product. When bitumen is used as a raw material, the temperature of the raw material in the heating furnace is up to 130-180°C.

EFFECT: obtaining high-quality modifiers and new modified binders used in place of road bitumen or mixed with road bitumen in road construction to produce road surfaces with improved performance.

4 cl, 1 dwg, 3 tbl, 2 ex

Description

The group of inventions relates to the field of processing heavy residues of the primary distillation and secondary processing of oil, heavy oil waste (TNO), bitumen, and can be used to produce high-quality modifiers and new modified binders used instead of road bitumen or mixed with road bitumen in road construction for receiving pavings with the increased operational properties.

There is a known method of producing a binder for paving, according to which bitumen, a high molecular weight modifier and other necessary ingredients are fed into a bitumen melting boiler, heated to a temperature of 110-200 ° C and the resulting liquid medium with solid particles of a high molecular weight modifier is pumped into a hydrodynamic mixing chamber for cavitation-cumulative processing in the frequency range of 10-80 Hz. During processing, under the influence of shock pressure, solid particles are destroyed, respectively, the specific contact surface between the solid and liquid phases increases, which intensifies the process of mass transfer between them. Processing in the mixing chamber is carried out until the desired degree of homogeneity of the binder is obtained.

(see RF patent No. 2162867, class C08L 95/00, 2001).

As a result of the analysis of the known method, it should be noted that it is characterized by the complexity of the process due to the low temperature of dispersion and dissolution of the high molecular weight modifier in bitumen, which, even with very long processing in the mixing chamber, leads to heterogeneity of the mixture and, as a result, to a decrease quality of the obtained binder.

A known method of producing a binder for road surfaces, including heating of heavy oil residues (fuel oil, tar, pyrolysis resin, asphalt deasphalting, cracked residues) in the presence of a modifier - a given amount of crumb rubber obtained from the processing of worn tires, and heating is carried out by thermolysis in two stages, thermolysis in the first stage is carried out at 100-250 ° C in the presence of a distillate solvent, taken in proportion to rubber crumb 1: 0.1-1, for 15-60 minutes and in the presence of activating up to Dilution, in the second stage, thermolysis is carried out at 350-450 ° C for 10-60 minutes, in a medium of heavy oil residue with constant evaporation of the distillate solvent.

(see RF patent No. 2415172, class C10C 3/02, 2008) - the closest analogue for each invention of the group.

As a result of the analysis of the known method, it should be noted that during its implementation, the modes of technological operations and the amount of rubber crumbs and modifiers introduced into the heated heavy oil residues are weakly related to the physicochemical characteristics of the residues and do not take into account their group chemical composition, including the content of saturated hydrocarbons and aromatic compounds , resinous substances, asphaltenes, in addition, the size of the modifiers is not regulated, and the need to use them is not taken into account anohimicheskoy activation processes of mixing operations, exposure and oxidation of durable materials and energy intensive. All this leads not only to an increase in the duration of the technological process, but also to a decrease in the quality of the resulting target product.

Thus, the known technical solutions for obtaining the target product are characterized by the difficulty of regulating the process of dissolution and homogenization of rubber components in the bitumen hydrocarbon phase, the composition of which is also not taken into account when the two components are mutually converted in the process of obtaining the target product. This significantly affects the quality of the binder obtained for road construction.

The technical result of this group of inventions is the creation of technologies for the production of higher quality bitumen binder through the use of modifiers to increase the content of components in the raw material that increase its operational properties.

The specified technical result is ensured by the fact that in the method for producing a modified bituminous binder for paving, including heating the feedstock, which is used as heavy residues of the primary distillation or secondary oil refining, and oil waste, the introduction of modifiers into them, followed by thermochemical treatment of the resulting mixture to of obtaining the target product, it is new that the raw materials are preheated before thermochemical treatment to a temperature of 70-90 ° C, after which its act they vibrate by passing a hydropercussion through a cavitator and placed in a heating furnace, in which the temperature of the raw material is brought to 250-300 ° C, and thermochemical treatment includes the preliminary oxidation of the raw material with air oxygen heated to 250-300 ° C in a continuous bubbler oxidizing column with its subsequent distillation in an atmospheric vacuum column at a temperature of 250-300 ° C with the separation of fuel gas and atmospheric vacuum distillate, and the heavy vacuum residue resulting from distillation is fed to a mixing reactor, before they are heated to a temperature of 130-180 ° C, after which modifiers are introduced into it, which use: rubber crumb in an amount of 5-20 wt. % by weight of a heavy vacuum residue; organic mineral bitumen-containing additive, in an amount of 1-12 wt. % by weight of a heavy vacuum residue and granular synthetic cord, in an amount of 1-10 wt. % of the mass of the heavy vacuum residue, the components are mixed and the temperature of the mixture is brought up to 300-350 ° С for the implementation of the thermocracking process, after which the mixture is cooled to 250-300 ° С, it is reactivated by passing through the second cavitator, water hammer, and oxidized to the second bubbler continuous oxidation column at a temperature of 250-300 ° C, heated with atmospheric oxygen with distillate distillation, to obtain the target product, while preliminary oxidation of the feedstock, mixing heavy residues with mod uyuschimi additives and final oxidation mixture can be performed by electromagnetic action on the feedstock.

In the method - the option of obtaining a modified bitumen binder for road surfaces, including heating the feedstock, which is used asphalt, the introduction of modifiers into it, followed by thermochemical treatment of the resulting mixture to obtain the target product, it is new that the raw materials are preheated before thermochemical treatment to temperature 70-90 ° C, after which it is activated, passing through a cavitator hydropercussion and placed in a heating furnace, in which the temperature of the raw material is brought to 130-180 ° C, and thermochemical treatment is carried out in a reactor-mixer at a temperature of 130-180 ° C, in the presence of modifiers, which use: rubber crumb in an amount of 5-20 wt. % by weight of bitumen; organic mineral bitumen-containing additive, in an amount of 1-12 wt. % by weight of bitumen and granular synthetic cord, in an amount of 1-10 wt. % of the mass of bitumen, moreover, during processing, the resulting mixture is mixed and its temperature is brought up to 300-350 ° C for the implementation of the thermocracking process, after which the mixture is cooled to 250-300 ° C, reactivated by passing through the second cavitator hydropercussion, and further oxidized in a second continuous bubble column oxidizing column at a temperature of 250-300 ° C, heated with atmospheric oxygen with distillate distillation, to obtain the target product, while the preliminary oxidation of the feedstock, mixing heavy residues with modifying additives and additional oxidation of the mixture can be carried out with electromagnetic effects on the processed raw materials.

The essence of the claimed group of inventions is illustrated in graphic and tabular materials, where:

- in FIG. 1 is a schematic flow diagram of an installation on which the claimed method and method variant can be implemented;

- tab. 1 - group chemical composition of heavy oil residues;

- tab. 2 - the results of determining the values of hydrocarbons, characterizing the group chemical composition of heavy oil residues and road bitumen;

- tab. 3 - the main characteristics of the obtained modified heavy oil residues and modified road bitumen with various values of modifying additives.

To implement the claimed method according to the first and second variants, the apparatus shown in FIG. one.

The installation contains a receiving tank 1, equipped with heating elements and designed to receive raw materials and warm them up to liquefy. The output of the installation 1 through the first cavitator hydropercussion 2 is connected with a heating furnace (P). The output of the furnace (P) is connected with a continuous bubble column oxidizing column 3. The output of column 3 is connected to an atmospheric vacuum column 4, and its output through the first heat exchange apparatus 5 is connected to a reactor-mixer 6.

The installation is equipped with three devices of electromagnetic influence 7. The output of the reactor-mixer 6 through the second heat exchanger 8 and the second cavitator hydropercussion 11 is connected to a continuous bubble column oxidizing column 9, the output of which is connected to the storage tank 10 for the target product.

Electromagnetic devices 7 are equipped with a bubbling oxidizing column 3, a reactor-mixer 6, a bubbling oxidizing column 9.

The installation intended for the implementation of the variant method, using low-grade bitumen, including low-grade, as a raw material, differs from the installation described above in that the furnace output (P) is directly connected to the input of the reactor-mixer 6. In the installation for implementation method - options, continuous bubbling oxidation column 3 atmospheric vacuum column 4 and heat exchanger 5 are absent.

All units included in the installation and its modification for implementing the method-variant are standard and are used for their intended purpose. The connections in the installation are understood as pipe masters, screw conveyors, etc.

The claimed group of inventions relates to objects of the same type, of the same purpose and provides the same technical result, that is, the claimed invention are options and the requirement of the unity of the invention is met.

Before obtaining the target product according to the method and method-variant, the preparation of its raw materials and modifying additives is carried out.

As a raw material for obtaining the target product - a modified bitumen binder, use, as already mentioned above, heavy residues of the primary distillation or secondary oil refining, heavy oil waste (according to the first option), bitumen, including poor quality (according to the second option) .

Before the start of processing, the group chemical composition of the feedstock is evaluated, which is carried out according to the samples taken, according to the standard thin-layer chromatography method using the Yatroskan instrument and includes determining the amount of saturated hydrocarbons, aromatic compounds, tarry substances, asphaltenes (generalized and enlarged group chemical compositions of heavy oil residues used as raw materials to obtain the target product are presented in table 1). After that, the ratio A: C is calculated, where A is the number of asphaltenes, and C is the number of resins. According to GOST 22245-90, according to calculations, all road bitumen have an approximate group composition with the following values: asphaltene content - 20-22%; the resin content is 27-31%. Then A: C = 0.72-0.84. To obtain high quality bitumen binders, A: C = up to 2 [G] is recommended.

Based on the theoretical and experimental studies of the influence of the group chemical composition of heavy oil residues on the quality of the obtained modified bitumen binders, it was established that asphaltenes and resins are the main structure-forming components of high-quality bitumen [2]. Moreover, the higher the ratio A: C = up to 2, the higher performance properties bitumen binder has. In this regard, for the implementation of the method and its variant with the achievement of the specified technical result, modifying additives are selected that contribute to the resulting binder increase in the content of asphaltenes and resinous substances and reduce the content of paraffins.

It was established that in order to obtain a high-quality binder, the optimal composition and amount of modifying additives is determined taking into account the group chemical composition of the feedstock and should include the following widespread components: rubber crumb obtained from the processing of worn automobile tires; organomineral bitumen-containing additives (oil shale, sapropelites, rhabdopissites, labtobiolites, etc.); granular synthetic cord made of kapron, nylon, lavsan.

Before use, each of the additives (modifiers) must be processed, the essence of which is disclosed below.

To implement the method, rubber crumb is used, in particular, from worn-out automotive tires with a grain size of up to 3-5 mm with removed metal and synthetic cord. The technology for producing such crumb rubber is known to those skilled in the art. Before use, the crumb is passed through a standard dispersant, in which it is exposed to temperature (up to 150 ° C) and increasing pressure (from 0.6 to 120 MPa). Due to compression with simultaneous shear deformation and heating, the crumb rubber, at the exit of the disperser dies, breaks up into particles with a size of 3-25 microns, with a large specific surface - up to 0.3-0.6 m ² / g. Intermolecular bonds in them are broken or weakened, which contributes to high activation with rubber devulcanization. The presence of such mechanochemically activated chips during thermo-oxidative processes of obtaining a binder provides:

- its accelerated dissolution, homogeneous mixing and chemical bonding with other components, including heavy oil residue;

- delayed aging of the paved road surface, in view of the presence in the rubber crumb of chemicals - antioxidants and antioxidants, which additionally stabilize the structure of bituminous binders. Their presence increases resistance to oxidative degradation under operating conditions, slows down the aging process at high operating temperatures, as well as under conditions of heating to high technological temperatures;

- improving fatigue, reducing rutting, increasing adhesion and resistance to the formation of temperature cracks, increasing the water resistance of road surfaces;

- improving the elasticity of the obtained modified bitumen binder;

- the transition during thermo-oxidative processes of paraffins and oils to asphaltenes and resins, which increases the ratio A: C and, therefore, improves the performance properties of bitumen binders;

- the ingress of sulfur into the prepared bitumen binder, which is contained in the rubber crumb, becomes a structuring and modifying component, which improves the strength, deformation resistance, increases adhesion to mineral fillers.

To implement the method, oil shale, sapropelites, rhabdopissites, liptobiolites and other combustible minerals of sapropelite origin can be used as organomineral bitumen-containing additives. These additives are complex modifying additives, since they play the role of activators of thermocracking rubber in the production of bituminous binders and activating mineral powders in the production of asphalt coatings.

Before use, these modifiers are subjected to grinding on standard vibration-impulse parabolic machines to obtain organomineral powder of high activity. The grinding is carried out in such a way that the particles of the finely divided powder have a comminuted shape. This significantly increases the activity of the powder, since the surface area of the particles increases by about 30% compared with their round shape. For such grinding, standard equipment is used. Grinding technologies are known to those skilled in the art.

The use of organomineral additives prepared in the above manner in the preparation of bituminous binders from heavy oil residues of primary or secondary oil refining provides:

- accelerated dissolution of rubber crumb during thermo-oxidative processes and increased compatibility of rubber crumb with heavy oil residues;

- the splitting of paraffin-naphthenic hydrocarbons in heavy oil residues with the formation of secondary asphaltenes with their increased molecular weight and partial additional formation of resinous substances;

- the allocation of the organic component, which has liquefying functions;

- reinforcing the resulting bitumen binder with the resulting powder of the mineral component;

- increased adhesive ability of a bitumen binder due to a decrease in the content of paraffins, naphthenes and an increase in the molecular weight of asphaltenes and resinous substances.

To implement the method, synthetic cord is used as a modifying additive, extracted from worn-out automotive tires and made of nylon, nylon, lavsan and other polymeric materials. The extracted cord is fed into the heating chamber, where it is heated to a temperature above the melting temperature of the polymer material of the cord, after which the molten cord, through the dispenser, is dropped in sizes of 2-3 mm, into water, where it is cooled and transformed into granulate.

Using to obtain the target product granular cord allows you to:

- increase the strength of the asphalt composition;

- increase the adhesion between the organic and mineral parts of the asphalt mixture; increase resistance to asphalt fatigue;

- prevent the formation of cracks in the asphalt and at the same time give it elasticity;

- reduce susceptibility to temperature fluctuations;

- increase ductility, expand the interval of the elastic-plastic state.

Thus, each of the modifying additives introduced into the feedstock, improves the quality of the target product, including by increasing the content of bitumen binders, asphaltenes, resins and other useful substances to optimal values.

The technologies described below are most effective in the case when the feedstock used to obtain the target product contains little asphaltene-resinous substances and by purging it is possible to increase their content by changing both the qualitative and quantitative composition.

The claimed method (in the first embodiment) is as follows.

To obtain the target product - a modified bitumen binder, the raw materials to be processed (heavy residues of the primary distillation and secondary oil refining, heavy oil waste, are placed (poured, laid) in a receiving tank 1, where it is heated to a temperature of 70-90 ° C with removal The formation of such an interval is justified by the fact that if the heating temperature is below 70 ° C, the oil residues will be viscous, poorly pumped by the pump and with difficult allocation of dropsy about condensate If the heating temperature of heavy oil residues is above the set interval, there will be a danger of intense boiling of water and steam emissions.

The specified heating temperature of the feedstock is also selected taking into account the softening and liquefaction temperatures of the feedstock.

Heated and liquefied in the receiving tank 1, the feedstock is pumped (not shown in the diagram) through a water hammer 2 and supplied to the heating furnace (P), where it is heated to 250-280 ° C, if the feedstock is highly resinous, and to 270-290 ° C, if the raw material is paraffinic with a minimum content of asphaltenes (less than 20%) and resinous substances (less than 27%) [1, 2].

The cavitator hydropercussion 2 installed behind the tank and in front of the heating furnace due to hydrodynamic effects on the heated and liquefied raw materials ensures its activation by reducing its viscosity by breaking Van der Waals bonds, as well as by changing the physicochemical composition with breaking bonds between individual parts of molecules, and due to the destruction of the contained paraffins.

From the heating furnace, the heated raw materials are sent to a continuous bubbler oxidizing column 3, in which the raw materials are pre-oxidized with air heated to about 300 ° C with a flow rate of 40 to 300 m ³ / t.

In order for the process of preliminary oxidation of raw materials to take place completely, without the formation of phenol and ester groups, it is advisable to carry out electromagnetic effects on the raw materials through apparatus 7. When conducting preliminary oxidation, the lower limit of the temperature of heating of the raw materials is limited to 250 ° C, and the upper limit to 290 ° C , since a higher heating temperature leads to the formation of carbenes and carbides, which worsen the properties of bitumen binders, including causing an increase in brittleness and lowering foams etrations and extensibility of bitumen binders [3].

The selected temperature range allows you to effectively control the preliminary oxidation process.

The preliminary oxidation of the feedstock with air heated to about 300 ° C with a flow rate of 40 to 300 m ³ / t is a necessary technological operation, since its implementation ensures the onset of growth of asphaltenes and resins contained in the raw material, which are preserved after this operation and their the amount will increase in the subsequent stages of the processing technology of raw materials with modifying additives, which will ensure the high quality of the prepared bitumen binders for road surfaces. The given interval of the volume of supplied air during the oxidation process is designed for different volumes of oxidation of the feedstock, and also depends on the design features of the apparatus that performs the oxidation process. The indicated volumes of oxidizing air are recommended in literary sources [1, 2, 3].

The heavy residues obtained as a result of pre-oxidation in column 3, heated to a temperature of 250-290 ° C, are fed to an atmospheric vacuum column 4. In an atmospheric vacuum column, pre-oxidized heavy oil residues are separated into fuel gas, atmospheric vacuum distillate and prepared to obtain a bituminous binder, purified heavy vacuum residue. The technology of such separation is standard.

The resulting heavy vacuum residue is passed through a heat exchanger 5, in which it is cooled to 130-180 ° C and fed to the reactor-mixer 6, where, after filling it (by about 2/3 of the volume), the following modifiers prepared in advance are metered: rubber crumb in the amount of 5-20 wt. % by weight of the vacuum residue; organic mineral bitumen-containing additives (oil shale) in an amount of 1-12 wt. % by weight of the vacuum residue [2, 5]; granular synthetic cord in an amount of 1-10 wt. % by weight of the vacuum residue.

The range of values of each modifier component is selected taking into account its real impact, both on the processes of thermal cracking and oxidation, and on the quality of the final product obtained.

In the reactor-mixer 6, at a temperature of 130-180 ° C, the raw materials and modifiers are mixed with a simultaneous increase in the heating temperature to 300-350 ° C and short-term exposure (up to 5 min) at this temperature for the complete implementation of the process of thermocracking the mixture.

When thermocracking the mixture in the reactor-mixer 6, the destruction of carbon-hydrogen bonds occurs with the dissolution of modifying additives and a change in the chemical composition of the mixture, a decrease in its viscosity and an increase in the content of asphaltenes and resins. The indicated temperature range is optimal, since an increase in temperature above the specified interval causes a sharp coke formation, and a decrease below the indicated interval of values slows down the process of thermal cracking with the possible incomplete dissolution of the modifying additives and the cessation of the growth of asphaltene content. The use of the electromagnetic exposure apparatus 7 promotes high-quality mixing and acceleration of thermocracking of the mixture with modifying additives.

From the reactor-mixer 6, the mixture is supplied to a heat exchanger 8, where it is cooled to a temperature of 250-280 ° C, passed through a second hydroshock cavitator 11, with the help of which a completely homogeneous mixture with a high reactivity intensifying the oxidation process is obtained, and enters a continuous bubbling oxidizing column 9, where at a temperature of 250-300 ° C the final oxidation (oxidation) of the mixture is carried out with atmospheric oxygen at a temperature of about 300 ° C and a flow rate of 40 to 300 m ³ / t, pressure of 0.3-0.8 MPa and air flow rates up to 150 m / s [1, 2, 3].

The use of heated air and an electromagnetic radiation apparatus 7 increase the oxidation rate. The optimum oxidation temperature is 250-300 ° C, since with increasing temperature, in addition to harmful intensive formation of carbenes and carbides, the softening temperature and the temperature of brittleness of bitumen binders increase, viscosity increases, and penetration, extensibility, heat resistance and ductility decrease.

When the oxidation temperature drops below 250 ° C, in addition to a sharp increase in the content of harmful phenols, the oxygen transfer efficiency of the air deteriorates, the oxidation process becomes economically irrational, the oxidation time and air consumption increase.

At the exit of the oxidation column, the target product, the finished modified bitumen binder, enters the storage tank 10, where it is cooled by air and then selected for use in road construction.

When implementing the method according to the second embodiment, which provides a binder from a raw material, which is bitumen, including low-quality raw materials heated in a furnace (P), bypassing a continuous bubbler oxidizing column 3, an atmospheric vacuum column 4, and a first heat exchanger 5, enters the reactor - mixer 6. Next, the process is carried out similarly to that described above for the first embodiment.

According to the method and its variant disclosed above, heavy oil residues and road bitumen produced by Russian oil refineries were processed (listed in Table 2) in order to modify them to produce high quality bituminous binders with an increase in A: C = to 2 ratio.

The claimed method will be more clear from the examples below. Example 1. Oil tar, with a group chemical composition shown in table 2, in a volume of 2 tons is loaded into a receiving tank 1, it is heated to a temperature of 90 ° C and the pump, through the first cavitator water hammer 2, activated highly reactive tar is fed into the furnace ( P), where it is heated to a temperature of 270 ° C. For cavitation treatment of heated oil tar, with a temperature of up to 90 ° C, a hydropercussion cavitator with a capacity of up to 3 m ³ / h is used, with a rotor speed of up to 3000 rpm, a rotor diameter of 200 mm, the number of channels in the rotor and stator is 18 , electric motor power - 5 kW, consumed voltage 380V. In the process of cavitation treatment, the limits of fluctuation of residual moisture in the tar are reduced, and the uniformity of the feedstock is ensured. Due to the destruction of molecular compounds, paraffin structures are destroyed and the content of tar-asphaltene substances increases, the activated tar is activated, which accelerates the pre-oxidation process.

Tar heated in the furnace enters a continuous bubbling oxidizing column 3, where it is blown with heated air at a temperature of 300 ° C and subjected to electromagnetic effects, which accelerates the oxidation of raw materials. For electromagnetic effects on the pre-oxidation process, an electromagnetic radiation apparatus is used with a current frequency of 50 Hz, a mains voltage of 220-230 V with a neutral earthed neutral, a current consumption of 0.5 A and a power of 90 VA. At the same time, under the influence of an electromagnetic field, a tension of up to 20 kV / m is created. Due to the electromagnetic effect, as shown by the practical use of the apparatus, in the process of preliminary oxidation of the heated tar, the formation of phenol and ester groups is reduced, the fluidity of the pre-oxidized tar is improved due to increased ionization and neutralization of the resulting electrostatic charges.

In column 3, pre-oxidation of the feed occurs. In the process of preliminary oxidation, the volume of supplied heated air is 80 m ³ per 1 ton of tar at a speed of 100 m / s. Pre-oxidized raw materials (tar) with a temperature of 280 ° C are sent to an atmospheric vacuum column 4, at the outlet of which it was obtained: hydrocarbon (fuel) gas 2.2 wt. %; atmospheric vacuum distillate - 37.9 wt. %; heavy vacuum residue - 58.3 wt. %; losses and water - 1.6 wt. %

The separated heavy vacuum residue with a heating temperature of 300 ° C passes through a heat exchanger 5, where with air up to 18 ° C, with a volume and speed of 0.05 m ³ / s per 1 ton of heavy residue, it is cooled to a temperature of 165 ° C. The cooled heavy vacuum residue enters the reactor-mixer 6, where the modifiers are fed at the same time: mechanochemically activated highly reactive crumb rubber up to 30 microns in size, 12% by weight of the heavy vacuum residue; granular synthetic cord with a grain size of 2-3 mm, in a volume of 3% by weight of a heavy vacuum residue; activated, finely divided oil shale with a particle size of up to 100 microns, in a volume of 10% by weight of a heavy vacuum residue.

The loading into the reactor-mixer 6 of the cooled heavy vacuum residue with a temperature of 165 ° C and modifiers with an ambient temperature of up to 20 ° C is carried out with simultaneous stirring at a speed of 60 rpm at a temperature in the reactor-mixer of 170 ° C. During mixing, in a reactor-mixer, at atmospheric pressure, by supplying a heating agent, the temperature rises to 320 ° C. At this temperature, the mixture is thermocracked with complete dissolution of the modifiers and the formation of a homogeneous modified mixture with a high content of asphaltenes. For electromagnetic exposure during thermocracking of the mixture in the reactor-mixer, a second electromagnetic exposure apparatus is used with a frequency of 50 Hz, a supply voltage with a grounded neutral 220-230V, a current consumption of 0.5A and a power of 90VA. This creates tension from the acting electromagnetic tulle - up to 25 kV / m. Due to the electromagnetic effect, as shown by the practical use of the apparatus, during the supply of a heavy vacuum residue and then modifying additives to the mixer, followed by thermocracking of the mixture, coagulation of the supplied ground fine particles of modifiers is excluded, mixing is improved and the uniformity of the mixture is increased, and the process of thermal cracking is accelerated .

The resulting reaction product enters the heat exchanger 8, where the mixture is cooled by air to a temperature of 270 ° C, and is passed through a hydropercussion cavitator 11, which provides the mixture with high uniformity and increased reactivity necessary for high-quality oxidation in a continuous bubbler oxidizing column 9. For cavitation processing the cooled second reaction product is used hydropercussion cavitator capacity of 5 m ³ / h, with a rotor speed - 3000 rev / min, diameter of mouth ra - 200 mm, the number of channels in the rotor and stator 36, elektodvigatelya power - 10 kW consumed by the voltage - 380V. In the process of cavitation treatment of the cooled reaction product, finely dispersed particles of modifiers are regrind, their activation and homogenization of the mixture, which contributes to high uniformity with increased reactivity, which accelerates the process of oxidation and makes the resulting product high quality.

The volume of supplied air, heated to a temperature of 290 ° C, for additional oxidation was 250 nm ³ / t, the pressure in the column was 0.03 MPa. In this case, distillate was distilled off, 3.5% of the mass of the mixture entering the column. The resulting finished liquid hot modified bitumen binder, with a temperature of 300 ° C, was fed into a storage tank with cooling air. The content of asphaltenes (A) was 23.92%, and the resin content was 15.6%. The ratio A: C = 1.53, which is significantly higher than indicated in table 2. In the process of additional oxidation of the reaction products, a third apparatus of electromagnetic influence is used with a frequency of 50 Hz, a supply voltage with a grounded neutral 220-230V, a current consumption of 0.5A, and power 90VA. This creates tension from the acting electromagnetic field - up to 15 kV / m. Due to the electromagnetic effect, as shown by the practical use of the apparatus, the ionization is enhanced and the electrostatic charges are neutralized, and this accelerates the process of additional oxidation of the reaction product.

Similarly to the specified example, the modification of fuel oil, straight-run pyrolysis resin was performed. The properties of the obtained modified bitumen binders are shown in table 3.

Example 2. Bitumen BND 60/90 with a ratio of A: C = 0.84, to increase its quality and increase the ratio A: C, was laid in a receiving tank 1 weighing 2 tons, where it was heated to a temperature of 90 ° C and a pump, through Cavitation hydropercussion 2, activated and highly reactive bitumen was fed into the furnace (P), where it was heated to a temperature of 150 ° C. For cavitation processing of warmed road low-quality bitumen, with a temperature of up to 90 ° C, a hydraulic shock cavitator with a capacity of up to 3 m ³ / h, with a rotor speed of up to 3000 rpm, a rotor diameter of 200 mm, the number of channels in the rotor and stator is used 24, the electric motor power is 5 kW, the consumed voltage is 380V. In the process of cavitation treatment, the destruction of molecular compounds is ensured with the destruction of paraffin structures and an increase in the content of tar-asphaltene substances, the activation and homogenization of the feedstock occurs, which contributes to the uniformity of the heated bitumen and acceleration of the pre-oxidation process.

Heated bitumen from the furnace was sent to a reactor-mixer 6, where it was mixed with modifiers in the composition: mechanochemically activated highly reactive rubber crumb with a size of up to 25 microns, in a volume of 8% by weight of bitumen; granular synthetic cord with a grain size of 2-3 mm, in a volume of 4% by weight of bitumen; activated, finely divided oil shale with a particle size of up to 100 microns, in a volume of 5% by weight of bitumen.

Loading into the reactor-mixer 6 heated bitumen with a temperature of 150 ° C and modifiers with a temperature of up to 20 ° C was carried out with simultaneous stirring of the raw material mass at a speed of 60 rpm at a temperature in the reactor-mixer 6 of 165 ° C. During mixing, in a reactor-mixer, at atmospheric pressure, by raising the heating agent, the temperature was raised to 340 ° C. At this temperature, the mixture is thermocracked with complete dissolution of the modifiers and the formation of a homogeneous modified mixture with a high content of asphaltenes. For electromagnetic exposure during thermocracking of the mixture in the reactor-mixer, an electromagnetic exposure apparatus with a frequency of 50 Hz, a supply voltage with a grounded neutral 220-230V, a current consumption of 0.5A and a power of 90VA is used. This creates tension from the acting electromagnetic field - up to 25 kV / m. Due to the electromagnetic effect, as shown by the practical use of the apparatus, in the process of feeding heated pre-oxidized bitumen and then modifying additives to the mixer-mixer followed by thermocracking of the mixture, coagulation of the supplied ground fine particles of modifiers is excluded, mixing is improved and the uniformity of the mixture is improved, and the process is accelerated thermocracking.

The resulting reaction product was sent to a heat exchanger 8, where the mixture was cooled with air to a temperature of 265 ° C and passed through a second hydropercussion cavitator 11, which provided the mixture with high uniformity and increased reactivity necessary for high-quality oxidation in a continuous bubble column 9. For cavitation processing the cooled second reaction product is used waterhammer cavitator capacity of 5 m ³ / h, with a rotor speed - 3000 rev / min, diameter ro ora - 200 mm, the number of channels in the rotor and stator 36, elektodvigatelya power - 10 kW consumed by the voltage - 380V. In the process of cavitation processing of the cooled reaction product, finely dispersed particles of modifiers are regrind, their activation and homogenization of the mixture, which contributes to high uniformity and increased reactivity, which accelerates the process of oxidation and makes the resulting product high quality.

To accelerate the oxidation process, a second apparatus of electromagnetic influence 7 was used. At the same time, a third apparatus of electromagnetic influence with a frequency of 50 Hz, a supply voltage with a grounded neutral 220-230V, a current consumption of 0.5A and a power of 90VA is used in the process of additional oxidation of the reaction products. This will create tension from the acting electromagnetic field - up to 15 kV / m. Due to the electromagnetic effect, as shown by the practical use of the apparatus, the ionization is enhanced and the electrostatic charges arising are neutralized, and this accelerates the process of the oxidation of the reaction product.

The volume of air supplied to the additional oxidation, heated to a temperature of 300 ° C, was 280 n.m ³ / t, the feed rate was 95 m / s, the pressure in the column was 0.035 MPa. In this case, distillate was distilled off, 1.8% of the mass of the mixture entering the column. The resulting finished liquid hot modified bitumen binder, with a temperature of 300 ° C, was fed into a storage tank with cooling air. The content in the target product of asphaltenes (A) was 29.5%, and the resin content was 18.3%. The ratio A: C = 1.61, which is significantly higher than indicated in table 2.

Similarly to the specified example, the modification of road bitumen BND 40/90 and BND 90/130 was performed.

The characteristics of the obtained modified bitumen binders are shown in table 3.

USED BOOKS

1 Pokonova Yu.V. Oil bitumen. SPb., Ed. Synthesis company, 2005.

2 Rudenskaya I.M., Rudensky A.V. Organic binders for road construction. M, INFRA-M, 2010.

3 Gun R.B. Oil bitumen. M., Chemistry, 1973.

4 Pokonova Yu.V. Oil residues. SPb., Ed. Ricon, 2008.

5 Gorlov E.G. Nefedov B.K., Gorlova S.E., Andrienko V.G. Processing of heavy oil residues in the presence of oil shale. M, HTT, 2006, No. 6.

Claims (4)

1. A method of obtaining a modified bitumen binder for road surfaces, including heating the feedstock, which is used as heavy residues of the primary distillation or secondary oil refining and oil waste, the introduction of modifiers into them, followed by thermochemical processing of the resulting mixture to obtain the target product, characterized in that the raw materials are preheated before thermochemical processing to a temperature of 70-90 ° C, after which they are activated by passing a hydroshock through a cavitator, and placed in a heating furnace, in which the temperature of the raw material is brought to 250-300 ° C, and thermochemical treatment includes the preliminary oxidation of the raw material with atmospheric oxygen heated to 250-300 ° C in a continuous bubbler oxidizing column with its subsequent distillation in an atmospheric vacuum column at a temperature of 250 -300 ° C with the separation of fuel gas and atmospheric vacuum distillate, and the heavy vacuum residue obtained from the distillation is fed to the mixer reactor, brought to a temperature of 130-180 ° C, after which modi cators, which are used as: rubber crumb in an amount of 5-20 wt.% by weight of a heavy vacuum residue; organomineral bitumen-containing additive in an amount of 1-12 wt.% by weight of a heavy vacuum residue and granular synthetic cord in an amount of 1-10 wt.% of a mass of heavy vacuum residue, mix the components and bring the temperature of the mixture to 300-350 ° C for the implementation of thermal cracking after which the mixture is cooled to 250-300 ° C, reactivated by passing through the second cavitator, water hammer, and further oxidized in a second continuous bubbler oxidizing column at a temperature of 250-300 ° C with heated oxygen xa with distillate distillation to obtain the desired product. 2. The method according to p. 1, characterized in that the operation of preliminary oxidation of the feedstock, mixing heavy residues with modifying additives and additional oxidation of the mixture is carried out under electromagnetic influence on the processed feedstock. 3. A method of obtaining a modified bitumen binder for paving, including heating the feedstock, which is used asphalt, the introduction of modifiers into it, followed by thermochemical treatment of the resulting mixture to obtain the target product, characterized in that the raw material is preheated before thermochemical treatment to a temperature of 70 -90 ° C, after which it is activated by passing through a cavitator hydropercussion, and placed in a heating furnace, in which the temperature of the raw material is brought to 130-180 ° C, and thermochemistry eskuyu treatment is carried out in a reactor-mixer at a temperature of 130-180 ° C in the presence of modifiers, which are mainly used: rubber crumb in an amount of 5-20% by weight of bitumen;. organomineral bitumen-containing additive in an amount of 1-12 wt.% by weight of bitumen and granular synthetic cord in an amount of 1-10 wt.% by weight of bitumen, and during processing the resulting mixture is mixed and its temperature is brought up to 300-350 ° C for the implementation of the process thermocracking, after which the mixture is cooled to 250-300 ° C, reactivated by passing through the second cavitator hydropercussion, and further oxidized in a second continuous bubbler oxidizing column at a temperature of 250-300 ° C with heated oxygen with distillation distillate to give the desired product. 4. The method according to p. 3, characterized in that the operation of preliminary oxidation of the feedstock, mixing heavy residues with modifying additives and additional oxidation of the mixture is carried out with electromagnetic effects on the processed feedstock.

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