BG65947B1 - Method for treatment of heavy oil products with subsequent stabilization - Google Patents

Abstract

The invention relates to a method for treatment of heavy oil products with subsequent stabilization through distillation under a lower pressure, dephlegmation and condensation of the vapours produced, the residual oil product being mixed before the distillation with a distillate fraction and, at will, with an admixture in a ratio of 50-80:5-20:1-5. The admixture represents a mixture of biologicalproducts for oil spills removal or dissolvent.

Description

Technical field

The invention relates to a method for the treatment of heavy petroleum products with subsequent stabilization and the use of components of heavy distillate and residual mixtures to produce heavy oils intended for combustion in marine engines and steam boilers, in other combustion plants or for use in subsequent processing operations .

The expansion of the range of motor and industrial fuels for use in agriculture, forestry, construction and mining follows the trend towards fuller mechanization and automation of these sectors. The expansion of the machine fleet with universal and specialized machines is part of the choice of technical and economic indicators, including low cost, small dimensions, low fuel consumption, high reliability, convenient service and repairs. But the extension of that park is also part of the type of fuel included in the nomenclature and the designation of the machinery. The expansion of the assortment of fuels has been particularly evident in the creation of gas turbines. Compared to other heat engines, these turbines have significant advantages due to their small overall dimensions, compact design, operational safety and low maintenance cost. Gas turbine installations allow the burning of liquid fuels at a relatively high efficiency. This circumstance contributes to the use of gas turbines in stationary and portable power plants, in the metallurgy, oil and chemical industries, in the river, sea, rail and others. There is no fundamental difference in design and thermodynamics between the steam and gas turbines, except that the gas turbines for the working body use the exhaust gases with the subsequent conversion of energy into kinetic and mechanical ones.

Expanding the range of low-viscosity and high-viscosity marine fuels can complement processing options and operations to obtain fuel mixtures with expanded fractional composition and therefore to the full and efficient use of the raw material in the processing process.

US 3959119 discloses a method of producing a refined petroleum product from low quality petroleum products containing a relatively large amount of water and / or sludge, which includes the steps of introducing the low quality petroleum product directly into a fluidized bed cracking furnace and subjecting it to thermal cracking; introducing the resulting effluent from the cracking furnace into a distillation column operating at a pressure of one atmosphere and separating it into an upper, lightweight, water vapor component which is removed from the top of the column and a heavy component which is removed from the bottom of that column. column. The above light vapor component is then cooled to a temperature above the dew point of the water and fed into a gas-liquid separator where it is separated into a gas-phase stream and a liquid-phase, refined petroleum product, part of which is recycled to the top of the rectification column as reflux to restore the balance of the column while the rest is the final product and the gas phase is directed to the combustion furnace.

A disadvantage of the known method is the presence of a thermal cracking step for converting the heavy fractions into light ones, as well as carrying out a distillation process at atmospheric pressure above the dew point of the water, which requires a subsequent stage of its separation, and the related technological complications and scarring of refining low quality fuels.

SUMMARY OF THE INVENTION

The present invention is directed to optimizing the distillation process under reduced pressure by increasing the low-boiling fractions and components in heavy distillate fuels.

The problem which is the subject of the invention is solved by a method of processing heavy oil products with subsequent stabilization to produce high calorie products,

65947 B1 heavy distillate and mixed fuels, which undergo low-pressure distillation distillation, condensation of the resulting vapors and collection of the fractions obtained. Before the distillation process is carried out, the residual oil is mixed with the distillate fraction and an additive in the ratio of 45-80: 5-50: 0-5 is added if desired.

In a preferred embodiment of the process, the distillate fractions obtained are arranged at temperature ranges up to 420 ° C and up to 500 ° C.

In another preferred embodiment of the method, the additive is a mixture of biological products for the purification of petroleum contaminants and / or deparaffinization of petroleum fractions (desolvent).

The advantage of the process according to the invention is that as a result of this treatment, the dispersed state and homogeneity of the heavy residual oil products are transformed, which leads to an intensification of the processes of heat exchange and mass transfer, and in turn, to an increase in the yield of the commodity products.

Explanation of the annexed figures

The invention is explained in more detail with the aid of the accompanying figures, of which:

Figure 1 is a simple distillation process accomplished by: (a) gradual evaporation, (b) single evaporation and (c) multiple evaporation;

FIG. 2 is an exemplary diagram for carrying out the process of the invention by vacuum distillation with simultaneous processing and stabilization of heavy fuels and residual petroleum fractions. FIG.

The development of the method and its application in the design of the installation originates from the hypothesis of distorting the balance between the amount of distillate and the residue, including between the amount of heat and the amount of condensation and cooling water.

This form of imbalance is that the resulting distillate is enriched with low-boiling components, but not at the expense of the amount of distillate in the starting mixture. For the complete enrichment of the distillate, it is not enough just to use low boiling components and winter additives. Changes in the installation's mode are also required, including limiting its capacity to 60% with an optimum low boiling point component.

For the purpose of the method, distillation is limited by the pursuit of low cost and reduces to products with slightly different temperature limits: distillates with a limited boiling range and residual mixture with fuel oil characteristics.

Part of the distillate produced, collected in section vessel 4, is returned to the cube through the mixer 5 into which the enzyme and oxygen-containing additives are injected. The newly formed mixture is not less than 15% by weight. % irrigates the raw material. In the heat transfer in separator 2 from the bottom up, the interval of concentrations of heavy components is continuously reduced to form a lasting homogeneous mixture.

Permanently stabilized, the residual mixture is brought to the bottom of the separator 2 for transportation and use as a residual with increased distillation rate while the collected distillate is removed from the receiver 4 as a low boiling component for use in heavy distillate fuels or as a final product. A concentrated enzyme supplement may be added to the residual petroleum product prior to distillation. These enzymes are widely used to clean up oil spills. The enzyme can be used in concentrated form or pre-diluted with water at a concentration of 1:50 to 1:75. It is recommended that the enzyme be added to the water at dilution and not vice versa to avoid strong foaming. The aqueous solution may be heated to 50 ° C before mixing. The solution should be heated immediately before mixing, as prolonged heating may cause the enzyme to decompose. The enzyme can be added to the mixer 5 with an injector in addition to ordinary mixing, for more efficient mixing. The processing time does not depend very much on the amount of residual oil, since the enzyme is affected by neutralizing the electrostatic forces rather than by dissolving it. The enzyme has the greatest impact on decomposing paraffins. However, the processing time depends on the temperature and it should not

65947 B1 should be lower than 10 ° C as the process becomes ineffective at this temperature. The optimum temperature is above 25 ° C. The concentration of the enzyme relative to the treated mixture is in the range 1: 5000-10000. Suitable for use in the conditions of the invention are enzymes of the FYRE-ZYME type (International Enzymes Co.), OBT R Oil Degradation Treatment (United-Tech Inc.) or Petro-ffin (Hobe Associates). Common to these additives is that they are biological products for the purification of petroleum pollution and for the deparaffining of petroleum fractions, i.e., they are microbiological destructions of petroleum products based on industrially produced molds (RU 2228953, 1999; EP 1132462, 2001; US 5656169, 1997). The advantages of these additives are that they are environmentally friendly, easy to use, relatively inexpensive, non-toxic, can be used both surface and volume, and are effective for working with a wide range of petroleum fractions. The degradation products of these additives, including those obtained from the treatment of petroleum fractions, are safe for the environment and microflora.

The method of the invention is directed to the processing of residual petroleum products obtained from the primary or secondary processing of oil and petroleum fractions and which by their combustion characteristics are not best suited for direct combustion in industrial and process furnaces, in steam boilers and in other combustion installations .

The processing of these residual petroleum products results in high-calorie products, heavy distillate and mixed fuels for combustion in marine and stationary combustion plants, in industrial, technological and domestic installations. One group of commodity products is characterized in that by distillation by the ASTM D 86 to 250 ° C method, less than 10 vol. %. The other group of heavier fractions, the percentage of distillation at 250 ° C cannot be determined by this method, and are characterized by their kinematic viscosity at 50 ° C, determined by the ASTM D 445 method, which in any case exceeds 8 mm ² / s. This group of heavy commodities includes a subset of fractions for which the distillation rate at 250 ° C cannot be determined, but kinematic viscosity at 50 ° C can be determined. The third group includes products with reduced boiling range: from 10 to 65 ° C to 250 ° C and up to 85 ° C to 350 ° C. This product group is characterized and standardized best by the relationship between their color with dilution where it can be determined and viscosity. "Dilution color" means the color measured by the ASTM D 1500 method which acquires the product after dilution with tetrachloromethane per unit volume of the product up to 100 volume units. The color is determined immediately after dilution of the product. "Viscosity" means kinematic viscosity at 50 ° C, expressed in 10 ' ⁶ m ² s ^_1 by the ASTM D 445. Method "ASTM method" means the methods laid down in the 1976 edition of the Standard Definitions and Specifications for Petroleum and Lubricants. by the American Society for Testing and Materials (ASTM).

The density of the fractions studied can range from 870 to 950 kg / m ³ .

Examples of carrying out the invention

Example 1.0 (Comparative) A residual oil product with a density at 20 ° C of 955 kg / m ³ was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics were sequentially separated in section vessel 2: up to 350 ° C distilled 4 vol. %, to 400 ° C distilled 14 vol. %, to 450 ° C distilled 29 vol. to 500 ° C. 43% vol.

Example 1.1. Residual oil with a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with a first fraction of Example 1 in an 80:20 ratio, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 34 vol. %, up to 400 ° C distilled 52 vol. %, to 450 ° C. distilled ^: 56 vol. %, up to 500 ° C 64 vol. %.

Example 1.2. The residual oil product at a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 and a 45: 50: 5 ratio of diluent, after which the mixture was vacuum-distilled.

65947 Blation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics were separated into section vessel 2, up to 350 ° C, distilling 52% by volume. %, up to 400 ° C distilled 64 vol. %, to 450 ° C distilled 72 vol. %, up to 500 ° C 80 vol. %.

Example 1.3. The residual oil with a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 and a 75: 20: 5 ratio of the solvent, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. . Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 38 vol. %, up to 400 ° C distilled 47 vol. %, up to 450 ° C distilled 57 vol. %, up to 500 ° C 67 vol. %.

Example 1.4. The residual oil with a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 and a 60: 35: 5 ratio of the solvent, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. . Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 40 vol. %, up to 400 ° C distilled 68 vol. %, to 450 ° C, distilled 76 vol. %, up to 500 ° C 78 vol. %.

Example 2.0 (Comparative) A residual oil product at a density of 20 ° C 936 kg / m ³ was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 8 vol. %, up to 400 ° C distilled 19 vol. %, up to 450 ° C distilled 38 vol. %, up to 500 ° C 52 vol. %.

Example 2.1. Residual oil with a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with a first fraction of Example 1 in an 80:20 ratio, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 24 vol. %, up to 400 ° C distilled 38 vol. %, to 450 ° C, distilled 51 vol. %, up to 500 ° C 76 vol. %.

Example 2.2. The residual oil with a density at 20 ° C of 955 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 and a 75: 20: 5 ratio of the solvent, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. . Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 29 vol. %, up to 400 ° C distilled 58 vol. %, up to 450 ° C distilled 78 vol. %, up to 500 ° C 95 vol. %.

Example 3.0 (Comparative) Residual oil product at a density of 20 ° C 905 kg / m ³ was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are successively separated in section vessel 2: up to 350 ° C distillate 10 vol. %, to 400 ° C distilled 24 vol. %, up to 450 ° C distilled 52 vol. %, up to 500 ° C 63 vol. %.

Example 3.1. The residual oil product at a density at 20 ° C of 905 kg / m ^{3 was} pre-mixed in a heating vessel 1 with a first fraction of Example 1 in an 80:20 ratio, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 21 vol. %, up to 400 ° C distilled 38 vol. %, to 450 ° C. %, up to 500 ° C 72 vol. %.

Example 3.2. Heavy fuel at a density of 20 ° C 925 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 and a 75: 20: 5 ratio of the solvent, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. . Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 18 vol. %, up to 400 ° C distilled 35 vol. %, up to 500 ° C 54 vol. %.

Example 4.0 (Comparative) Heavy fuel at a density of 20 ° C 875 kg / m ^{3 was} pre-mixed in a heating vessel 1 with a first fraction of Example 1 in a ratio of 80:20, after which the mixture was subjected to vacuum distillation at a residual pressure of 0.016 kPa. Under these conditions, four fractions having the following distillation characteristics are separated into section vessel 2; to 350 ° C distilled 74 vol. %, up to 400 ° C distilled 89 vol. %, to 450 ° C distilled 94 vol. %.

65947 Bl

Example 4.1. The residual oil with a density at 20 ° C of 875 kg / m ^{3 was} pre-mixed in a heating vessel 1 with the first fraction of Example 1 in an 80:20 ratio, after which the mixture was vacuum distilled at a residual pressure of 0.016 kPa. Under these conditions, four fractions were separated into section vessel 2 having the following distillation characteristics; to 350 ° C. distillate 81 vol. %, up to 400 ° C distilled 92 vol. %, up to 450 ° C distilled 97 vol. %.

Example 4.2. Repeating Example 3.1, but with the addition of a dissolvent in the indicated size, the fractions obtained had the following characteristics: up to 350 ° C distilled 82 vol. %, to 400 ° C distilled 94 vol. %, up to 450 ° C distilled 97 vol. %.

Sample tables for derived fuels

Table No 1 (Marine fuels)

Indicators Values obtained 1 2 Conditional viscosity at 50 ° C, max 2.0 1.5 Lower caloric effect, kj / kg, max 40.750 41,500 Ash%, chess 0.025 0.QI5 Vanadium%, tah 0.00035 0.0003 Sulfur% max 0.95 0.75 Resinous Substances% max 20.0 10.0 Flash point in closed crucible ° C, min 65 60 Standing temperature not higher than 5 -3 Density at 20 ° C 0.925 0.895

Table No 2 (Low-viscosity marine fuels)

I. Components I n w 1. Diesel fraction 160-320 ° C 20 15 10 2. Broad distillate fraction 175-405 ° C Up to 100% Up to 100% Up to 100% P. Sulfur content 0.25 0.30 0.45 S.Flaming temperature 60 65 68 IV. Kinematic viscosity at 20 ° C, mm / c 6.0 6.3 6.8 W. Temperature at standing -10 -8 -6

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Table No 3 (Boiler fuels)

Indicators Values obtained Viscosity, conditional At 50 ° C At 80 ° C ' 5 8.5 Ash%, max 0.1 0.15 Water%, max 1 2 Flash point in a closed crucible 85 Lower calorie effect 41.300 40,500 Standing temperature -1 +10 Flash point in an open crucible 100

Table No 4 (Household fuel)

Indicators Values obtained Kinematic viscosity at 20 ° C, mm / c 10.5 Composition fractions: Fraction 180-240 ° C from atmospheric distillation. Fraction 200-420 ° C from vacuum distillation 30% 70% Cetane number 40 Sulfur content 0.5 Standing temperature -3 Density 889

Table No 5 (Fractional composition of other low-viscosity marine fuels)

Fraction 240-420 ° C 5-25% Fraction 240-500 ° C 10-40% Fraction 160-360 ° C Up to 100%

Table No 6 (Fractional Composition of Tractor Fuels)

Distillations from atmospheric distillation 80-140 ° C 240-320 ° C 140-360 ° C '5-15 * - ·' 5-20 24-40 Vacuum distillation fraction 240-500 ° C 5-25 Antioxidant additives, by weight. % 0.05

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Table No Ί (Sunflower oil for processing into petroleum jelly and transformer oil) ________________________________

Indicators Mounted values Distillation range n ° C kC ° C 300-310 400-415 Viscosity at 50 ° C Kinematic, cSt Conditional, E 5.0-9.0 1.39-1.67 Flash point, ° C min 120 Freezing point, ° C max -15 Sulfur content,% max 0.40 Ash content,% max 0.025 Additives for (storage and operation) The scoreboard is now 0-1

Table No 8 (Other examples of low-viscosity marine fuels)

Indicators Real values Density at 20 ° C 870 880 877 891 Cetane number 46 42 45.4 39.5 Standing temperature, ⁰ C -12 -10 -8 -7 Kinematic viscosity at 20 ° C, cSt 10.2 9.2 8.6 8.8 Combustion heat, kJ / kg 46.2 46.5 45.8 39.5 Low temperature, ⁰ C 78 80 82 76

Claims

Claims (3)

Claims 1. A method for the treatment of heavy petroleum products with subsequent stabilization to obtain high-calorie products, heavy distillate and mixed fuels, characterized in that the heavy petroleum products are subjected to distillation under reduced pressure by reflux, condensing the resulting vapors and collecting the resulting vapors. distillate fractions, wherein before the distillation process the heavy petroleum products are mixed with at least a portion of the distillate fraction and an additive in the ratio of 45-80: 5-50: 0-5 is added if desired. A method according to claim 1, characterized in that the distillate fractions obtained, separated at a distillation temperature up to 350 ° C, range from 18 to 82 vol. %. The method according to claims 1 and 2, characterized in that the additive is a mixture of biological products for the purification of petroleum contaminants and / or the deparaffinization of petroleum fractions (dissolvent).