FIELD OF THE INVENTION

The present invention relates to a process, which can be operated on an industrial scale for the production of fractions of a liquid-movable resinite tar from a resinite- containing product obtained in the development of coal deposits.

BACKGROUND OF THE INVENTION

Resinite or resinite tar (resin) is a natural organic formation that is fossilized resinite that, in the form of nodules of various shapes, is impregnated into coal and into the host rock of some coal deposits. Such deposits, in particular, include the Tkibuli-Shaorsky coal deposit, located in Georgia.

The reserves of this field are estimated at 50 million tons. It contains 60 - 65% of the humic coal with 5.2% of hydrogen and up to 15% of resinite with 9.9% of hydrogen. The rest is a host rock, represented mainly by silicon and aluminum oxides. The origin of the resinite component in this coal deposit is explained by the fossilization of tar leakages of ancient coniferous and sago trees during the same time as the formation of coals of the Tkibuli deposit. Interest in resinite is due to its hydroaromatic structure, which is largely similar to the structure of amber, copal and rosin. All mentioned above, in turn, were previously used in the manufacture of materials for the production of electrical devices. As noted above, the resinite makes up to 15% of the total volume of coai extracted from the mines of the Tkibuli deposit. The rest of the coal extracted from these mines consists of waste from enrichment of the humic coal itself and the rubber-containing shale and is transported to the mine dump, occupying a considerable area of tens of square kilometers, the accumulation of which is determined as 2 million tons. The humus component is the target for the manufacturing the product, which is used as raw material in a thermal power plant.

The methods for producing resinite tar and resinite tar concentrates from the coals of the Tkibuli deposit have been known for a long time. Therefore, for example, M.A. Suladze and al. in his invention of the USSR, registered under number SU 146487, describe the method for producing resinite concentrates from liptobiolite coals by crushing it in a mill with the screening of coal fines and subsequent separation of the concentrate on a centrifuge using heavy liquid.

Chen Shilin atal. in China Patent Application CN105238428(A) describe a medium temperature coal pitch modification method which includes the following steps: (1) mixing anhydrous AICI3 and medium temperature coal pitch which is crushed to the particle size of 0.1 mm or less according to the weight ratio of (2-12}:100 in a V- shaped mixer, and then sending into a reaction kettle; (2) introducing N ₂ to exclude air in the reaction kettle, heating up to 100° C, carrying out heat preservation for 25-35 min, then heating up to 200-320 °C, carrying out a reaction for 1-5 hours, cooling, and then taking out. Then there are crushing the material, obtained after reaction in the step (2), and washing with dilute hydrochloric acid, filtering, carrying out vacuum drying, removing the modifier AICI ₃ , and thus obtaining the modified medium temperature coal pitch.

Shi Weiwei at al. in their China Patent Application CN 106753545(A) describe the method for processing and modifying coal tar. The method is characterized by comprising the following steps: (1) mixing raw tar with a mixed solvent A according to the mass ratio of 1:(1 to 3), and carrying out extraction at the temperature of 40 °C to 75° C, so as to obtain a slag-containing tar phase and a pure tar phase; (2) carrying out flash-evaporation of solvent removing on the slag-containing tar phase, so as to obtain coal cinder asphalt; (3) mixing the pure tar phase with a mixed solvent B according to the mass ratio of 1:(0.5 to 2), and carrying out extraction at the raffinate phase. Then (4) subjecting the extraction raffinate phase to flash evaporation to remove the solvent A, then, carrying out water washing to remove a small volume of contained solvent B from the extraction raffinate phase, so as to obtain non-aromatic-hydrocarbon oil rich in aliphatic hydrocarbon components; (5) subjecting the extract phase to distilling solvent removing, thereby obtaining refined maltha which is rich in aromatic hydrocarbon distillate oil and low in quinoline insoluble.

Ren Xiangkun et al. in their China Patent Application CN 103881750(A) describe coal tar hydrogenation process for maximizing utilization of coal tar residues. The process comprises the following steps: (1), carrying out distillation onto the coal tar; (2), carrying out hydrogenation treatment onto distilled heavy distillate oil; (3), carrying out gas-liquid separation onto the hydrogenated product; (4), feeding a liquid-phase material obtained by gas-liquid separation into the first separator, and feeding a vapor-phase material into a low-temperature separator. Further is carried out: (5), mixing heavy residual oil obtained through separation of the first separator, a liquid-phase separated out by a low-temperature separator and light distillate oil, and then feeding into the second separator; (6), mixing light oil obtained by the first separator and the second separator and then filtering, and distilling the filtrate to obtain light oil, medium-weight oil and heavy oil; and (7), feeding the heavy oil into a delayed coking system to produce needle cokes and circulation oil, feeding the circulation oil into a slurry-bed reactor, and carrying out hydrorefining onto the light oil and the medium-weight oil to obtain petroleum and aviation kerosene.

Kenji Iguchi et al. in their China Patent Application CN 102786984(A) describe a method for preparing a needle coke raw material by using medium and low temperature coal tar. The method comprises the following steps: 1) distilling the medium and low temperature coal tar, separating it to obtain heavy distillate with the temperature more than 350°C; 2) sending the heavy distillate of the medium and low temperature coal tar to a reactor, under the existence of a catalyst, introducing hydrogen into the reactor, performing hydropyrolysis on the heavy distillate, wherein the catalyst is a Fe catalyst and the mass of the catalyst accounts for 0.01-3% of mass of the heavy distillate; the pressure during the hydropyrolysis is 7-12 MPa and the temperature is 350-550° C; 3) sending the products after hydropyrolysis in the step 2) to a separator, and separating to obtain lower oil and higher oil; and 4) performing physical separation on the higher oil, and removing the catalyst. According to the hydropyrolysis treatment of the medium and low temperature coal tar, the content of condensed polycyclic aromatic hydrocarbons can be greatly increased and the raw material suitable for preparing needle coke can be obtained.

The nearest to the proposed invention is the method of processing liptobiolite coals, described by Mikhail Kipnis and others in the Author's Certificate (patent) of the USSR under number SU507613. The method includes heating of the liptobiolite coals in a centrifugal field at the temperature of 390-440 ^e C and separating the heat- treated product into resinite tar and a solid residue followed by trapping the resin ite tar at the temperature of 40-100°C.

SUMMARY OF THE INVENTION

That problem may be solved, according to the proposed invention, by creating a new method for producing fractions of liquid-movable resinite tar, preferably from natural resinite found in coal deposits. The method is carried out under the influence of temperature and centrifugal forces affecting the initial resinite- containing product, placed into a centrifugal thermal separator.

According to the first embodiment of the present invention, this method includes some following successive steps. Firstly, it is adapted to at least one movable cylinder of the centrifugal thermal separator of the initial rotation speed with respect to the surrounding at least one grid and a stationary housing concentrically disposed to this grid. Secondly, the gap is filled between at least one movable cylinder and surrounding it at least one grid by resinite-containing product with particles size of not more than 3 mm. Further, there is sealing of this stationary housing, including at least one movable cylinder and said gap between said cylinder and the surrounding of it at least one grid. The next step is providing gas extraction from the gap between this cylinder and surrounding at least one grid, and supplying preheated gases into mentioned cylinder.

Further, it is increasing the rotation speed of the at least one movable cylinder in the centrifugal thermal separator to a value corresponding to a predetermined separation temperature range of separation from resinite certain fractions from the liquid-movable resinite tar.

Further, there is stopped the supply of preheated gases to the cylinder when the temperature of the Initial resinite-containing product loaded into this cylinder reaches the maximum within a predetermined temperature range.

The next step is maintaining the speed of rotation of at least one movable cylinder of the centrifugal thermal separator for a certain period of time necessary to final wringing out the corresponding fraction of the liquid-movable resinite tar, and also cooling it to a temperature that prevents the destruction of this fraction .

The last step is removal of the solid residue formed as a result of the process of centrifugal thermo-sepa ration of the resinite-containing product.

In order to ensure uniform loading of the at least one movable cylinder of the centrifugal thermal separator, the initial rotational speed of about 20 to 40 revolutions per minute relative to the surrounding at least one grid is reported to it.

According to this method, in mentioned at least one grid surrounding at least one cylinder, holes having a diameter of not more than 0.5 mm are pre-made. To this at least one movable cylinder, are supplied gases, which are preheated to the temperature of 250 to 280°C. These gases being inert relative to the resulting fractions of the liquid-mobile resinite tar. This at least one movable cylinder can be preheated by means of electric heaters.

According to this embodiment of proposed method,the liquid-movable resinite fraction for modifying the e poxy-based laminate can be produced in this centrifugal thermal separator during at the rotational speed of about 1500-1600 rpm from resinite heated to the temperature of 290 to 370°C by the heating rate of 10-16 degrees Celsius per minute.

According to this embodiment of proposed method,the liquid-movable resinite fraction for modifying the epoxy resin and epoxy phenol formaldehyde resins can be obtained in this centrifugal thermal separator during the rotational speed of about 1600-1800 rpm from the resinite heated to the temperature from 350 to 420 °C by the heating rate of 14-26 degrees Celsius per minute.

According to this embodiment of proposed method,the liquid-movable resinite fraction for modifying road paints and resin-plastic for road markings can be obtained in this centrifugal thermal separator during the rotational speed of about 1800-2200 rpm from the resinite heated to a temperature of 420 up to 480 °C by the heating rate of 25-35 degrees Celsius per minute.

Further, according to this embodiment of proposed method, at least two of these fractions of the liquid-movable resinite tar can be sequentially separated during one operating cycle of the centrifugal thermal separator. The removable solid residue resulting from the end of the centrifugal thermo-separation process of the resimte-containing product can be used as a household fuel. The second embodiment of this method also can be carried out under the influence of temperature and centrifugal forces affecting the initial resinite- containing product, placed into a centrifugal thermal separator.

According to the second embodiment of the present invention, some other following successive steps can carry out this method. Firstly, it is filled the initial resinite-containing product with a particle size of not more than 3 mm into the gap between at least one movable cylinder and surrounding it at least one grid. Then the gap is sealed between this at least one movable cylinder with at least one grid.

The next step is heating, preferably by means of electric heaters, of the initial resinite-containing product located in at least one cylinder with at least one grid.

The next step is adapting the rotation speed of the at least one movable cylinder in said centrifugal thermal separator to a value corresponding to a predetermined separation temperature range of separation from resinite certain fractions of the liquid-movable resinite tar.

The next step is maintaining the speed of rotation of at least one movable cylinder of the centrifugal thermal separator for a certain period of time, necessary to final wringing out the corresponding fraction of the liquid-movable resinite tar, and cooling it to the temperature that prevents the destruction of this fraction.

The last step is removal of the solid residue formed as a result of the process of centrifugal thermo-sepa ration of the resinite-containing product.

In at least one grid there are pre-made holes, having a diameter of not more than 0.5 mm. According to the second embodiment of the present invention, the liquid- movable resinite fractions for modifying the epoxy-based laminate can be produced in this centrifugal thermal separator with the rotational speed of about 1500-1600 rpm from resinite heated to the temperature of 290 to 370 ⁹ C by the heating rate of 10-16 degrees Celsius per minute.

Further, according to this second embodiment, the liquid-movable resinite fraction for modifying the epoxy resin and epoxy-phenol-formaldehyde resins can be obtained in this centrifugal thermal separator with the rotational speed of about 1600-1800 rpm from a resinite heated to the temperature from 350 to 420 °C by the heating rate of 14-26 degrees Celsius per minute.

Further, according to this second embodiment,the liquid-movable resinite fraction for modifying road paints and resin-plastic for road markings can be obtained in this centrifugal thermal separator at the rotational speed of about 1800-2200 rpm from a resinite heated to the temperature of 420 up to 480 °C by the heating rate of 25-35 degrees Celsius per minute.

According to this second embodiment,at least two of mentioned fractions of the liquid-movable resinite tar can be sequentially separated during one operating cycle of the centrifugal thermal separator. The removable solid residue resulting from the end of the centrifugal thermo-sepa ration process of the resin ite- containing product can be used as a household fuel. BRIEF DESCRIPTION OF THE DRAWINGS

FIG.l is a schematic diagram of an industrial installation for producing fractions of liquid-movable resinite tar from natural resinite;

FIG.2 illustrates the general view of the working part of the pilot installation for obtaining fractions of liquid-movable resinite tar from natural (solid) resinite;

FIG.3 illustrates a schematic diagram of a pilot installation for producing fractions of liquid-movable resinite tar, and

FIG.4 illustrate the sectional view of a movable cylinder of this pilot installation.

Table 1 showing the main parameters of the method for obtaining fractions of liquid resinite tars.

Table 2 directions for the use of fractions of liquid-movable resinite tar from coal and rocks resinite of the Tkibuli-Shaorsky coal deposit.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

A schematic diagram of an industrial installation 1 for obtaining fractions of liquid- movable resinite tar from natural resinite, according to the first embodiment of the invention, is shown in FIG. 1. Installation 1 is a centrifugal thermal separator comprising a fixed housing 10 made of stainless steel, inside which there is mounted pallet 12 with an annular groove 14 for installing grid 16. Grid 16 is made in the form of a stationary cylinder of stainless steel perforated with holes of diameter no more than 0.5 mm. Inside housing 10, and coaxial to it and grid 16, there is movable cylinder 18 rotatable by actuator 44 with electric motor 42. Cylinder 18 is connected to a source for supplying preheated gases - which is furnace 24, via conduit 26 provided with connecting flange 28.

Stationary housing 10, grid 16 and movable cylinder 18 are covered with sealed lid 30. The initial resinite-containing product is poured from hopper 32 into the gap between cylinder 18 and grid 16. Pump 34 creates a vacuum in the gap between cylinder 18 and grid 16, pumping the finished product into the resinite tar fraction receiver 36 and into sampler 38. The installation is also provided with exhaust device 40 for gases seeping from housing 10. Centrifuge motor 42 causes cylinder 18 to rotate by mechanical transmission 44.

The operating principle of the industrial installation according to the first embodiment of the invention

The operating principle of the industrial installation 1 according to the first embodiment of the invention and the main steps of the process for obtaining the fractions of liquid-movable resinite tar (LMRT) from resinite are set below. The used apparatus 1 is a centrifugal thermal separator, an apparatus that uses the principle of separation of LMRT under the influence of temperature and a centrifugal field.

Movable stainless steel cylinder 18 is placed into stationary housing 10 of centrifugal separator 1, and grid 16 - concentrically to it into circular groove 14 of pallet 12. Grid 16 is made in the form of a fixed cylinder of stainless steel, perforated with holes of 0.5 mm.

In the gap formed by the two cylinders, 18 and 16, an initial resinite-containing product is filled from the hopper 32, with a particle size of less than 3 mm. At the same time, to ensure a uniform loading of the initial product, cylinder 18 rotates at a speed of 20-40 rpm. Then, lid 30 of apparatus 1 closes, thereby providing a seal in cylinder 18 and in the inner gap space between cylinder 18 and grid 16. Then, by means of flange connection 28, pipeline 26 is fastened and the motor of pump 34 is turned on to create additional discharging in mentioned inner gap space, then there are fed from furnace 24 by flue gases, preheated to 250-280 ° C, but not affecting the course of the process.

The preheated gas is supplied directly to the resinite layer by means of a special device (not shown in the drawing). One minute before the flue gas is fed, the exhaust device 40 is turned on, and after 1 or 2 minutes after the feed, the rotational speed of cylinder 18 is adjusted to the required speed, depending on the temperature range at which the desired fraction of LMRT from the resinite is separated.

In order to control the process of centrifugal thermal separation (CTS), and also in the assumption of possible utilization of passing gases, the latter fall into the sampler 38 for composition analysis.

When the temperature of the processed resinite is reached to the maximum in a given interval, the supply of flue gases is automatically terminated, but the rotation of cylinder 18 continues for some time at a predetermined rate in order to more fully squeeze out the LMRT, and also to cool it, preventing the destruction of organic matter for the intended purpose.

At 120°C, centrifuge motor 42 is switched off. After motor 42 stops and cools the coke-similar mass containing high-temperature heavy resinite tars (remnants of cracking of resinite), 18 is taken out and the solid product formed is extracted from the inner surface of grid 16 which after appropriate grinding can be used as high-calorie fuel, because its calorific value is about 9000 kcal / kg.

A schematic diagram of an experimental installation for producing fractions of liquid-movable resinite tar from natural resinite according to a second embodiment of the present invention is shown in the drawings of FIGS. 2 - 4.

The installation (FIG 2) is a centrifugal thermal separator 100 comprising a plurality of movable cylinders 110 made of stainless steel and fixed by hinges 112 on holder 114. Holder 114 (Figures 2, 3) is rotatable mounted on a vertical shaft connected via coupling 116 to engine 118 (Figure 3). Holder 114, together with cylinders 110, are housed within the stationary body 120 of this separator 100, and its housing 120 is attached to frame 122 surrounding motor 118 and rigid fixed to base plate 124. Current collector 126 is designed to supply electric current to movable cylinders 110.

Each of movable cylinders 110 of separator 100 comprises housing 128 with cover 130, thermal insulation 132, and electric heating element 134. Charging cartridge 136 is disposed within housing 128 and has resinite loader 138, grid 140, and resinite tar fraction receptacle 142.

The operating principle of the experimental installation according to the second embodiment of the invention

The operating principle of the experimental installation according to the second embodiment of the invention and the main steps of the process for obtaining the fractions of the liquid-movable resinite tar (LMRT) from resinite largely coincide with the operating principle described above in the first embodiment.

The second embodiment of this method also can be carried out under the influence of temperature and centrifugal forces affecting the initial resinite containing product, placed into a centrifugal thermal separator 100.

According to the second embodiment of the present invention, the following successive steps can be carried out. Firstly, there is performed filling by the initial resinite-containing product with a particle size of not more than 3 mm into charging cartridges 136 of each of movable cylinders 110, more specifically their resinite loaders 138 with grid 140. Further, all of these movable cylinders 110 are sealed.

The next step is heating, preferably by means of electric heating elements 134, of the initial resinite-containing product located in each of these cylinders 110, supplied with grid 140.

The next step is adapting the rotation speed of these movable cylinders 110 of centrifugal thermal separator 100 to a value corresponding to a predetermined separation temperature range of separation from resinite a certain fraction of the liquid-movable resinite tar.

The next is maintaining the speed of rotation of these movable cylinders 110 of centrifugal thermal separator 100 for a certain time, necessary to final wringing out the corresponding fraction of the liquid-movable resinite tar, and cooling it to a temperature that prevents the destruction of this fraction. The last step is removal of the solid residue formed as a result of the process of centrifugal thermo-separation of the resinite-containing product. In all grids 140, there are pre-made holes with a diameter of not more than 0.5 mm.

According to the second embodiment of the present invention, the liquid- movable resinite fraction for modifying the epoxy-based laminate can be produced in this centrifugal thermal separator 100 with the rotational speed of about 1500- 1600 rpm from resinite heated to the temperature of 290 to 370 ^* C by the heating rate of 10-16 degrees Celsius per minute.

Further, according to this second embodiment, the liquid-movable resinite fraction for modifying the epoxy resin and epoxy- phenol- formaldehyde resins can be obtained in this centrifugal thermal separator 100 with the rotational speed of about 1600-1800 rpm from a resinite heated to the temperature from 350 to 420 °C by the heating rate of 14-26 degrees Celsius per minute.

Moreover, according to this second embodiment, the liquid-movable resinite fraction for modifying road paints and resin-plastic for road markings can be obtained in this centrifugal thermal separator 100 with the rotational speed of about 1800-2200 rpm from the resinite heated to the temperature of 420 up to 480 °C by the heating rate of 25-35 degrees Celsius per minute. .

According to this second embodiment, at least two of mentioned fractions of the liquid-movable resinite tar can be sequentially separated during one operating cycle of the centrifugal thermal separator 100. The removable solid residue resulting from the end of the centrifugal thermo-separation process of the resinite- containing product can be used as a household fuel. More detailed the parameters of the method for obtaining fractions of liquid- movable resinite tars are shown in Table 1., page 19.

The present invention is based on the distinguishing feature of fossilized (solid) natural resinite formations containing in their structure unsaturated hydroaromatic hydrocarbons of the terpene series, due to which they were used earlier in the production of plastics with increased electrical insulation, resistant to mold and water resistant.

Such resinite formations include rosins, copals, amber and other natural resinous formations. Such formations include also resinite, which is contained in some coal deposits, in particular in the Tkibuli-Shaorsky coal deposit, located in Georgia. Investigation of the liquid fractions from resinite showed similarity of its structure with the structure of the mentioned petrified natural formations. From this fact, a conclusion was made about the prospects of increasing liquid-movable resinite tar (LMRT) obtaining from the resinite of the Tkibuli-Shaorsky deposit also because:

- firstly, LMRT are able to dissolve in the same solvents as epoxy resins, as a prerequisite for obtaining mutually-reversible impregnation compounds, as well as in the manufacture of paintwork materials;

- secondly, LMRT from resinite can be applied without additional processing, providing their compatibility with the modifying product, and

- thirdly, it has been proved possible to combine mutually compatible fractions of LMRT from resinite to modify widely used compounds and mixtures based on epoxy and phenol-formaldehyde resins, in order to improve the index of tear resistance of products based on them. Table 2

Directions for the use effractions of liquid-movable resinite tar from coal and rocks resinite of the Tkibuli-Shaorsky coal deposit.

The present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, and it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be constructed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims. or equivalences of such meets and bounds are therefore intended to be embraced by the appended below claims.