EA026096B1 - Method of partially upgrading heavy oil at well-site - Google Patents

Abstract

The invention provides a method of partial upgrading of heavy oil at well-site, the heavy oil having an API gravity of 20 or less, by thermal cracking at well-site, using the thermal cracked residue as the fuel to produce the steam for recovering heavy oil from reservoir. The thermal cracking may be conducted at a pressure of 0 to 0.1 MPaG at a temperature of 370 to 440°C for 15 to 150 minutes in a soaking drum, simultaneously injecting stripping steam to separate a thermal cracked oil, generated in a liquid phase of the soaking drum, as a gaseous thermal cracked oil, from a thermal cracked residue, to obtain a thermal cracked oil product, provided that the liquid phase of the soaking drum is maintained to have an S-value of 2.0 or larger at a thermal cracking extent of fractions having boiling points of 500°C or higher in the starting heavy oil is 30% or larger.

Description

The present invention relates to an installation for partial improvement of oil at a drilling site, which provides a lighter fraction by thermal cracking of heavy oil having a density of 20 degrees ΑΡΙ (American Petroleum Institute) or less, and mainly provides a fuel source for producing steam to produce heavy oil by injection of steam into the reservoir ^and r.

State of the art

For ίη-δίΐιι heavy oil production, technologies 8ΑΟΌ (gravity drainage during steam injection) and C88 (cyclic steam injection) are used, in which steam is used. Steam is generated in steam boilers by burning natural gas, the cost of which will account for more than half of the total operating costs for the recovery of heavy oil. Therefore, it is necessary to find alternatives other than natural gas for reasons of availability of natural gas and lower costs associated with fuel for the production of steam.

The extracted heavy oil does not meet the technical conditions for pipeline transportation due to the low density in degrees ΑΡΙ and poor fluidity due to high viscosity at ambient temperature. Therefore, in Canada, heavy oil diluted with naphtha or condensate is transported through pipelines in the form of so-called ΌίΙΒίΐ (diluted fuel oil) directly to the market or for processing, where the diluent is recovered and then returned to the drilling site through the diluent pipeline. In the first of these cases, the amount of diluent is about 30 vol.% Relative to the total volume ΌίΙΒίΐ, the cost of which is largely determined by the cost of the diluent, and the availability of the diluent will be an additional problem. In the latter case, the pipeline must be designed to accept the volume of the heavy oil mass increased as a result of dilution, and two pipelines are required between the drilling site and the refinery, one for transportation and one for the return of diluent.

Heavy oil deals in the market are concluded at lower prices than traditional crude oils, due to the higher content of contaminants such as sulfur, nitrogen and heavy metals (nickel and vanadium), and their price decreases even more when they have a high value of ΤΑΝ (total acid number).

In the above situation, it is necessary to optimize the processing of heavy oils at the drilling site to improve performance and increase suitability for transportation.

Processes such as thermal cracking, solvent deasphalting (8ΌΑ), and hydrocracking, which are usually used to treat atmospheric or vacuum residues in traditional oil refining technologies, are not suitable for improving the quality of heavy oils at a drilling site for the following reasons.

Among the methods of thermal cracking, a coking unit is not suitable for use on a drilling site due to the large amount of coke as a by-product, which requires rather complex labor-intensive work and related equipment. A visbreaker (cracker for soft cracking) has a narrower range of quality improvements due to its limited conversion ability due to the stability of cracked oil.

Solvent deasphalting (8ΌΑ) is an extraction method for the separation of asphaltene-containing fractions and ΌΑΘ (deasphalted oil) in heavy oil as a raw material by certain solvents and under certain technological conditions, without any reaction to destroy or modify the starting molecules in the raw material.

As described in patent document I8-B 635752 6, §CO (synthetic crude oil), consisting of a gas oil fraction previously separated from bitumen, and ΌΑΟ of the residue obtained by the 8ΌΑ method, provides a density increase in degrees ΑΡΙ of only 4-5 degrees . Ultimately, this means that the density of СОCO in degrees ΑΡΙ obtained from bitumen having, for example, a value of 8 degrees ΑΡΙ, is only 12-13, which is a lesser effect of improving quality than is provided by the present invention.

The catalyst used in the hydrocracking process exhibits a decrease in activity due to contamination with nitrogen and heavy metals (nickel and vanadium), which are present in high concentrations in heavy oils. The hydrocracking process requires high pressure equipment and a plant for producing hydrogen and a source of hydrogen. Thus, the hydrocracking process may be less applicable to improve the quality at the drilling site due to its operational and economic disadvantages.

Steam production by gasification of the residue, asphaltene from the 8ΌΑ process and coke has been reported. However, the gasification method is not applicable to improve the quality at the drilling site due to its scale and complexity.

Patent Document 1Ρ-Α 688079 discloses the thermal cracking of heavy oil and the treatment of a cracked product with process steam, that is, the H8C process (Cracking in a high conversion socking chamber).

The traditional visbreaker and the commonly used H8C process are featured in the Nubgoogoyi magazine.

- 1 026096

Rgosekksd, September 1989, p. 69.

Among the approaches cited above, the H8C process is technically and cost-effective to improve the quality of heavy oil at the drilling site due to the replacement of natural gas with thermal cracking residue, a by-product of the H8C process, for use in δΆΟΌ and C88 technologies, for reasons of natural gas availability and cost reduction, associated with fuel for the production of steam.

SUMMARY OF THE INVENTION

The invention provides a method for partial improvement of a heavy oil having a density of 20 in degrees AP1 or less, fractions having a boiling point of 500 ° C. or less, in an amount of 45 wt.% Or less, with residual carbon (MSC) in an amount of 10 wt.% Or more, with a total acid number (ΤΑΝ) of 1.0 or more, and kinematic viscosity at a temperature of 50 ° C at a level of 1000 mm ² / s or more, the method comprising thermal cracking of heavy oil at a drilling site using thermal cracking residue as fuel for steam production used to produce heavy oil from a reservoir.

The invention provides a method of piping a thermal oil cracking product. In addition, the invention provides a method of piping a mixture of a thermal cracked oil product with heavy oil recovered at a drilling site for piping without being subjected to thermal cracking.

DETAILED DESCRIPTION OF THE INVENTION

The method for partial improvement of heavy oil according to the invention may further include a stage in which thermal cracking of heavy oil is carried out at a pressure of from 0 to 0.1 MPa (gauge), at a temperature of from 370 to 440 ° C. for a time of from 15 to 150 minutes in the reaction chamber (K1), and at the same time injecting process steam into the reaction chamber to separate the thermally cracked oil formed in the liquid phase of the reaction chamber as gaseous products of thermal oil cracking from the residue thermal cracking, to obtain a thermal oil cracking product, provided that the liquid phase of the reaction chamber is maintained at a δ-value (stability) of 2.0 or more, even when the degree of thermal cracking of fractions having a boiling point of 500 ° C. or higher in The original heavy oil is 30% or more.

The method for partial improvement of heavy oil according to the invention may further include the stages in which heat-cracked oil flows together with gaseous products of thermal cracking and water vapor through an outlet line (b1) located above the reaction chamber, and the lighter fraction is cooled directly with the heavier fraction subjected to thermal cracking of oil in the exhaust pipe (b1), the non-condensed lighter fraction, gaseous thermal cracked products, steam and the condensed heavier fraction of the thermally cracked oil in the separator (Ό1) to separate the heavy fraction of the improved oil, the heavier fraction of the thermally cracked oil is removed from the bottom of the separator (Ό1), the original heavy oil is heated using a heat exchanger ( C2) to extract heat, steam is generated in the heat exchanger (C3), a part of the heavier fraction of the thermally cracked oil is recirculated into recirculation as a cooling medium into the outlet pipeline (b1), the rest of the heavier fraction is withdrawn as a product, the non-condensed lighter fraction is cooled, gaseous products of thermal cracking and steam are cooled by means of a heat exchanger (air cooler) (C1), the condensed lighter fraction is separated from the water in the separator (Ό2) to separate oil and water, a condensed lighter fraction is mixed with a heavier product fraction to produce a thermal oil cracking product for pipeline transportation.

The invention provides the method or step shown above for partially improving heavy oil.

In the invention by thermal cracking of heavy oil using the H8C technology (Cracking in a conversion chamber with a high conversion), an improved oil is obtained with a reduced viscosity, increased density in degrees AP1 and a lower content of contaminants. This increases the suitability of heavy oil for transportation and separates the remainder of thermal cracking, which is used as fuel for the production of steam injected into the reservoir of heavy oil. This is directly related to the reduction in investment in improving the quality of heavy oil at the drilling site and operating costs for the production of heavy oil by injection of steam into the reservoir. Below the invention is explained in comparison with traditionally existing problems.

1. Heavy oils have a higher viscosity and lower density in degrees AP1 than traditional crude oils, and are difficult to pump through pipelines. Moreover, heavy oils have a high content of contaminants such as sulfur, nitrogen and heavy metals (nickel and vanadium), and a high total acid number (ΤΑΝ). Thermal cracking of heavy oil using the H8C technology (Cracking in a high conversion socking chamber) provides improved oil with a reduced viscosity, increased density in degrees AP1 and a lower content of contaminants, and separates

- 026096 residue of thermal cracking.

2. In a visbreaker, a common thermal cracking technology, a high degree of conversion is avoided because the combined presence of a lighter fraction and a cracked residue in the same liquid phase in the reactor exhibits a very high tendency to asphaltene precipitation, which leads to coking of the reactor and clogging of pipelines.

By thermal cracking using the H8C technology, a higher degree of conversion can be achieved by avoiding the joint presence of a lighter fraction and a cracking residue in the same liquid phase.

3. Heavy oils are highly viscous and have low fluidity, so that they can be transported by pipeline after dilution with diluent or condensate. The cost of the diluent and the costs associated with pumping through the pipeline are reduced by the fact that the volume of the diluent is reduced using the H8C technology. In the extreme case, neither diluent nor piping is required to return the diluent.

4. The cost of natural gas for steam production is more than half of the total operating costs for the production of heavy oil. Replacing natural gas for steam production with thermal cracking residue, a by-product of H8C technology, reduces energy costs.

5. Traditional methods such as thermal cracking, solvent deasphalting (δΌΑ) and hydrocracking, which are usually used to treat atmospheric or vacuum residues in traditional oil refining technologies, are unsuitable for partial improvement of heavy oil at the drilling site for reasons of economically acceptable scale of production, reached the limits improving the quality and technical characteristics of the oil product for pipeline transportation. The H $ C technology with a simplified scheme is more economically acceptable than traditional methods, and is therefore suitable for partial improvement of heavy oil and for obtaining heavy oil suitable for transportation at a drilling site.

The invention solves the above problems as follows.

(1) Thermal cracking using H5C 'technology can work stably, achieving a higher degree of conversion, and asphaltenes are kept in a finely dispersed state in the reaction liquid phase while simultaneously separating the thermally cracked oil from the reaction liquid phase, in order to avoid the joint presence of the cracked residue in that same liquid phase.

(2) The H $ C technology produces improved oil with a reduced viscosity, increased density in degrees ΑΡΙ and a lower content of contaminants such as sulfur, nitrogen and heavy metals (nickel and vanadium), and with less ΤΑΝ.

(3) In a process flow diagram in which heavy oil is thermally cracked using the H $ C technology, improved oil with reduced viscosity, increased density in degrees граду and a lower content of contaminants is obtained, and the cracked residue is separated. The product of thermal cracking of oil as improved oil, after heat removal, is transported by pipeline.

(4) In the method and in the scheme, the separated cracking residue is used as fuel for the production of steam injected into the heavy oil reservoir.

(5) The amount of cracking residue corresponding to the amount of steam required according to δΘΚ (the ratio of steam to oil = water volume to oil volume, converted to the amount of steam injected for one unit volume of heavy oil) when injected into a reservoir to recover heavy oil, regulate the feed rate of heavy oil in the FS process.

The invention preferably relates to a partial increase in quality by thermal cracking of heavy oils to improve their performance and suitability for pipeline transportation at a drilling site, and heavy oils, whose density in degrees ΑΡΙ is less than 20, such as superheavy crude oil such as oil sands and Orinoco tar sands bitumen, or heavy crude oil, is produced by injecting steam into a heavy oil reservoir.

In the invention, thermal cracking and injection of process steam is carried out in a drum or reactor. Heavy oil is easily separated into thermal oil cracking product and thermal cracking residue. The invention can preferably be performed at the drilling site of a heavy oil field, that is, it preferably creates a method of improving quality at the drilling site by thermal cracking.

In the invention, the thermal oil cracking product contains sulfur, nitrogen, and heavy metals (nickel / vanadium) in reduced amounts. Thermal cracking is preferably carried out at a temperature of from 400 to 440 ° C., and the thermal oil cracking product has a reduced total acid number (ΤΑΝ). The thermal oil cracking product has a viscosity so reduced as to be suitable for pipeline transportation. The thermal oil cracking product has a higher density in degrees ΑΡΙ than the original heavy oil. Thermal oil cracking product

- 3 026096 has stable properties while excluding contact with air during storage or transportation.

The method of the invention may further include stages in which the separated thermal cracking residue is burned in a steam boiler to produce steam, and steam is used to produce heavy oil according to 8ΛΟΌ, C88 or steam injection technologies to enhance oil recovery. The separated thermal cracking residue can be used in the amount needed to generate the amount of steam that is required according to 8OK (steam to oil ratio) at the drilling site. The separated thermal cracking residue can be obtained by thermal cracking of the heavy oil produced at the drilling site.

The method of the invention may further include a step in which the thermal cracking product is mixed with the heavy oil produced at the drilling site for pipeline transportation.

Preferably, the starting heavy oil has a density in degrees ΑΡΙ of 20 or less. More preferably, the starting heavy oil has a density in degrees ΑΡΙ at a level of 10 or less, and a total acid number (ΤΑΝ) of 2.0 or more, such as that of oil sands bitumen and Orinoco tar sands bitumen.

Brief Description of the Drawings

FIG. 1 includes (b) a conventional visbreaker and (a) an H8C unit, and shows a conventional visbreaker and an H8C unit in comparison. FIG. 2 shows a flowchart of an H8C process at a drilling site. FIG. 3 shows mixing schemes, including section 3.1, showing a commonly used scheme, section 3.2-1, showing a variant where all of the extracted heavy oil is processed using the H8C technology, and section 3.2-2, showing the option where part of the extracted heavy oil is subjected to processing using the H8C technology oil. FIG. 4 shows a simple block diagram of an autoclave experimental setup. FIG. 5 is a graph showing thermal cracking yield and ΤΑΝ value of high quality oil. FIG. 6 is a graph showing the reaction temperature and ΤΑΝ of the improved oil.

The invention will be explained in more detail with reference to examples and drawings.

FIG. 1 shows a traditional Visbreaker (cracking oven for soft cracking) and an H8C unit in comparison. The visbreaker, both the coil type and the type of socking chamber, operates at elevated pressure, and the thermally cracked oil and the thermal cracking residue are present together in the same reaction liquid phase, which leads to a situation in which the precipitation of asphaltenes in the liquid accelerates phase. In order to avoid such a situation, the process using the visbreaker essentially has a degree of conversion limitation. In the H8C process, the thermal cracking reaction is carried out at atmospheric pressure, and the resulting oil, subjected to thermal cracking, is simultaneously evaporated from the reaction liquid phase using such an effect that, when water vapor is injected into the reaction liquid phase, a reduced vapor pressure of the distillate is sufficient for distillation. This allows the H8C thermal cracking process to be carried out beyond the conversion level that is limiting for the traditional visbreaking process.

One method for assessing the stabilization of thermally cracked oil is known as the 8 value. The 8-value is determined by diluting the oil sample with toluene until the asphaltenes are completely dispersed, and then adding n-heptane to the diluted liquid before the precipitation of the asphaltenes. In the Α8ΤΜ Ό-7157-05 standard, the start point of the asphaltene precipitation is determined visually by automatically titrating with n-heptane a sample diluted with toluene. Based on this principle, in the present invention, in order to detect the start point of the asphaltene precipitation, they resort to observing the appearance of a dark spot mark in the center of the spot on chromatographic paper when applying small amounts of the test sample in the form of drops with uniform addition of a known amount of n-heptane to the sample, diluted with toluene. The higher the 8 value, the more stable the dispersed asphaltenes. When precipitation of asphaltenes is observed without adding any amount of n-heptane, this is denoted as an 8-value equal to 1.0. As noted, for a stable technological mode of operation of a visbreaker, an 8-value of at least 2.0 is required.

FIG. 2 shows a block diagram of an installation for improving heavy oil in an H8C process at a drilling site. In FIG. 2, NUO: supply of heavy oil, ISO: improved oil, P1: feed pump, P2: circulation pump for heavy fraction of improved oil, P3: pump for removing light fraction of improved oil, P4: pump for removing condensate, P5: circulation pump for thermal cracking residue, H1: furnace heater, C1: heat exchanger 1, C2: heat exchanger 2, C3: heat exchanger 3, C4: heat exchanger 4, C5: heat exchanger 5, K1: reaction chamber, Ό1: separator for separating the heavy fraction of improved oil, Ό2: separator for the separation of oil and water, 81: steam, b1: labor plumbing 1. First, in the NLF stage, with the help of pump P1, a feed is supplied through a heat exchanger C2 to heat and pump charge into the heater H1 to the design temperature. Heated NLO is fed into the reaction chamber K1, in which the thermal cracking reaction takes place in the liquid zone, where steam superheated in H1 is pumped. Thermally cracked oil (refined oil), which is vaporized from the liquid zone in the form of vapor as a result of the action of water vapor, which reduces the pressure of the vapor injected into the reaction liquid phase, flows through the top of K1 together with gaseous cracked products and steam into the separator Ό1 to separate the heavy fraction of improved oil through the exhaust pipe b1. The improved oil is subjected to direct sharp cooling with the help of a circulating cold heavier fraction subjected to thermal cracking of oil in L1 from K1 to N1. The condensed heavier fraction of the thermally cracked oil is separated from the vapors of the lighter fraction of the thermally cracked oil, gaseous products of thermal cracking and steam in the separator No. 1. The vapors of the lighter fraction of the thermally cracked oil, the gaseous products of thermal cracking and the steam are cooled with a heat exchanger C1, and the non-condensed gaseous products of thermal cracking flow from the separator No. 2 to separate oil and water. The condensed water vapor and the lighter fraction of the thermally cracked oil are separated from each other in a separator Ό2, and the water condensate is removed using a pump P4. The separated lighter fraction of the thermally cracked oil is removed by pump P3 and mixed with the heavier fraction of the thermally cracked oil. The separated heavier fraction of thermally cracked oil at Ό1 with the help of pump P2 is drawn into the circulation, during which it is cooled with the help of heat exchangers C2 and C3, and is used for direct cooling of gaseous products of thermal cracking, improved oil and steam that leave K1 to L1 . A portion of the heavier fraction of the thermally cracked oil cooled in C3 is mixed with the lighter fraction of the thermally cracked oil and transported through the pipeline as product improved OSI oil after cooling in the heat exchanger C4.

It is also possible to preliminarily separate the lighter fraction originally contained in the NLO before the implementation of the above-described technological scheme and mix it with OSI.

The mixing scheme will be explained below with reference to FIG. 3.

Section 3.1 shows a commonly used scheme using natural gas to produce steam and diluting the extracted heavy oil with a diluent for pipeline transportation. Water separated from the mixture of heavy oil and hot water from the underground zone is drawn into recirculation and, after necessary treatment, is reused as water to power the steam boiler.

Section 3.2-1 schematically shows a diagram for a situation in which all produced heavy oil is processed using H8C technology, and improved oil, which meets the technical conditions of suitability for pipeline transportation, is pumped through the pipeline without dilution. The remainder of thermal cracking is used as fuel to produce steam instead of natural gas.

Section 3.2-2 schematically shows a diagram for a case in which the amount of thermal cracking residue corresponding to the amount of steam required according to 8OK for injection into the reservoir for heavy oil production is controlled by the feed rate of the heavy oil to the H8C process. The remaining untreated heavy oil is mixed with the improved oil obtained by the above method, and the mixture is diluted with a diluent to adjust the characteristics for pipeline transportation.

In this case, the water is also sent for recycling and reused after the necessary treatment of water, separated from the mixture of heavy oil and hot water from the underground zone.

FIG. 4 is a simple block diagram of an experimental autoclave (ASK) plant. About 500 g of heavy oil is placed in an LSC autoclave with a capacity of 1 (one) liter and weighed with high accuracy. After closing the lid on the flange of the ASK autoclave and purging the system with nitrogen, the system was evacuated to a predetermined vacuum using a URIMR vacuum pump. ASA is immersed in a molten tin bath and the mixer is turned on in ASA at a temperature above the melting point of heavy oil. The reaction duration starts when the heavy oil sample in the ASA reaches a predetermined reaction temperature. During the reaction, the products leaving the ASA are first cooled in an HC condenser with hot water, and the condensed heavier fraction of the thermally cracked oil is collected in the NOC receiver of heavy oil. The lighter fraction of the thermally cracked oil is collected in a LOC receiver of light oil after cooling with cold water and using a cooled CC trap with cold water. All gaseous products of thermal cracking are collected in a TeD1ag bag after volume measurement using an OM gas flow meter.

After the reaction, the bath is quickly lowered to cool the ASA and terminate the reaction. After cooling to room temperature, the lid is removed from the flange and the ASA is weighed. The weight of the contents is determined by subtracting the weight of the ASA itself as the weight of the thermal cracking residue.

The oils in the NOC and LOC are weighed as a whole as the amount of thermal cracked oil product.

Having selected part of the gaseous products of thermal cracking in HLW, the concentration of hydrogen sulfide was measured using an indicator tube, and the remaining gas components were analyzed using gas chromatography. The weight of gaseous products of thermal cracking was obtained from the values of gas volumes and gas composition.

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The properties of heavy oils, bitumen oil sands, and Orinoco tar sands used for experiments are listed in Table. 1. Both raw materials are superheavy oil with a density in degrees of 10 less than 10.

The comparison with traditional visbreaking is explained below.

Examples are listed in table. 2 (1). examples 1, 2 and 3 were carried out with a variation in the reaction time to obtain different cracking yields under constant vacuum and temperature conditions, 118 mm Hg. (15.73 kPa) and 410 ° C, respectively. The δ-values of only the thermal cracking residue itself and the improved oil mixture with the thermal cracking residue were measured and compared, the former simulating the reaction liquid phase of the Н8С process, in which the improved oil was simultaneously separated in the form of vapors using process steam from the liquid phase, and the latter simulated the reaction Visbreaker liquid phase.

As in example 1, the δ-value of the mixture of improved oil with the residue of thermal cracking at the exit of thermal cracking (gas + improved oil) of 58.3 wt.% Is 1.9, which is lower than the 2.0 limit value for stable operation of the process using a visbreaker. This means that additional cracking leads to a very risky situation, which can lead to contamination, clogging and eventually coking of the reactor as a result of asphaltene precipitation. On the other hand, the δ value of only the thermal cracking residue is 2.8 at the same thermal cracking yield, which implies well dispersed asphaltenes.

The δ value of the mixture of improved oil and the thermal cracking residue in Example 2 is 1.6, with a thermal cracking yield (gas + improved oil) of 62.4 wt.%, which means worse dispersion of asphaltenes. However, the δ value of only the thermal cracking residue itself is 2.5 at the same thermal cracking yield, which implies that the dispersion of asphaltenes is maintained at a satisfactory level.

The δ value of the mixture of improved oil and the thermal cracking residue in Example 3 is 1.4, with a thermal cracking yield (gas + improved oil) of 67.4 wt.%, which means worse dispersion of asphaltenes. However, the δ value of only the thermal cracking residue itself is 2.0 at the same thermal cracking yield, which means that the dispersion of asphaltenes is still kept within the range acceptable for the visbreaker. Of the above examples, ΗδΟ undoubtedly has an advantage over the traditional cracking furnace for soft cracking, while maintaining the stability of asphaltenes in the reaction liquid phase even above the limit for the visbreaker.

Tab. 2 (2) shows the δ-values of thermal cracking residues from the vacuum residue of Middle Eastern oils. Although the softening point of the thermal cracking residue in comparative example 1 is the same as for example 1, the δ-value of comparative example 1 is 2.2, which is lower than the value of example 1, namely 2.8.

In the same way, although the softening point of the thermal cracking residue of comparative example 2 is the same as for example 2, the δ-value of comparative example 2 is 1.7, which is lower than the value in example 2, this time exactly 2, 5. Thus, ΗδΟ is an excellent technology for improving heavy oil, especially oil bitumen.

Below, a reduction in contaminants will be explained.

As shown in the table. 3 (1), nitrogen content of 0.4 wt.%, Sulfur of 5.02 wt.% And heavy metals (nickel / vanadium) 85/220 parts per million (etr) in the tar sands of oil sands as a raw material improved to 0 , 1-0.2 wt.%, 3.4-3.66 wt.% And <1 / <1 tert, respectively, in improved oils.

As also shown in the table. 3 (2), the levels of nitrogen are 0.58 wt.%, Sulfur 3.61 wt.%, And heavy metals (nickel / vanadium) 92/439 \\ ppm in bitumen oil sands as a raw material improved to 0.2- 0.3 wt.%, 3.29-3.52 wt.% And <1 / <1 tert, respectively, in improved oils.

Below, the reduction ΤΑΝ will be explained.

The results of reducing ΤΑΝ in examples 1, 2, 3, 4, 5 and 6 are shown in table. 4 (1), FIG. 5 and 6. When bitumen oil sands with a value of ΤΑΝ 2.80 mg KOH / g are treated in the ΗδΟ process, ΤΑΝ of the improved oils is reduced to 2.12-1.66 mg KOH / g.

It was found that the degree of decrease in thermal cracking at a temperature of 390 ° C is the smallest and tends to increase with increasing temperature. To reduce ΤΑΝ, temperatures above 400 ° C are effective.

Tab. 4 (2) shows the results of Examples 11 and 12 for Orinoco oil sands bitumen. When the Orinoco oil sands bitumen with ΤΑΝ 3.3 mg KOH / g is treated in the ΗδΟ process, the ΤΑΝ value of the improved oils is reduced to 2.0 mg KOH / g.

The storage stability of the improved oil will be explained below.

Tab. 5 shows the results of storage stability tests of improved oil. The density in degrees ΑΡΙ and the kinematic viscosity of the improved oil increase with increasing storage time in the air, as in comparative example 4. However, the properties of the improved oil stored in a nitrogen atmosphere do not change after 60 days of storage, as in example 9.

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The stability of the improved oil is maintained while avoiding contact with air for a long storage time.

Reduced diluent and improved properties of blended oil by improving the quality of heavy oil

In Canada, one of the technical conditions of suitability for transportation of heavy oil through a pipeline is a viscosity of not higher than 350 mm ² / s and a density in degrees of ΑΡΙ more than 19. The corresponding viscosities in Examples 1, 2 and 3 are 158, 142 and 130 mm ² / s even at a temperature of 7.5 ° C (annual lowest reference temperature of climatic conditions), which are significantly lower than 350 mm ² / s, as shown in table. 3 (1).

The corresponding density in degrees ΑΡΙ of improved oils in examples 1, 2 and 3 of the table. 3 (1) are 19.0, 19.1 and 19.3, which meets the technical requirements for transportation through the pipeline without dilution.

Tab. 6 shows the degree of dilution, when the technical conditions for transportation by pipeline require a density in degrees ΑΡΙ of level 21. Relative to comparative example 3, for which 29.8% by volume of diluent is required for the case without quality improvement, oil improved in the Н8С process requires 18% by volume of diluent at §ОК 3.0 (example 7), and 11.5% by volume of diluent at §ОК 4.0 (example 8). Thus, when bitumen is processed using H8C, a smaller amount of diluent is required for the technical conditions of pipeline transportation at a density in degrees ΑΡΙ at level 21.

At the same time, the levels of sulfur, nitrogen, heavy metals (nickel and vanadium) and ΤΑΝ of the mixed oils of examples 7 and 8 are lower than the values for comparative example 3, thus, the characteristics of the mixed oils are improved.

Below are described table. 1, tab. 2 (1), tab. 2 (2), tab. 3 (1), tab. 3 (2), tab. 4 (1), tab. 4 (2), tab. 5 and tab. 6.

Table 1

Raw Material Properties

Bitumen oil Athabasca sands Bitumen Cerro black pool Orinoco Analytical method Density at temperature 15 ° C g / cm ³ 1,0164 1,0133 Varden's pycnometer according to japanese industrial standard L5 K2249 Density b degrees ΑΡΙ 7.6 8.1 FROM % weight. 83.60 78.26 ΊΡΙ-53-65 TO % weight. 10.50 10, 68 N % weight. 0.40 0.58 3 % weight. 5, 02 3, 61 L5 K2541-3 Ηΐ weight. ppm 85 92 TRT-55-59 V weight. ppm 220 439 Insoluble in n-heptane % weight. 10,4 10.0 A5TM Ώ6560 Residual carbon % weight. 14.08 12.34 LZ K2270 Total acid number 2,8 3.3 L8 K2501 Potentiometric titration

Kinematic viscosity at 7.5 ° C mm ² / s LZ K2283 Kinematic viscosity at 50 ° C mm ² / s 6970 Kinematic viscosity at 75 ° C mm ² / s 874 Kinematic viscosity at 100 ° C mm ² / s 182 Absolute viscosity at 100 ° C MPa'sec 203 140 Brookfield Rheometer Absolute viscosity at 160 ° C MPa'sec 23 6 Absolute viscosity at 220 ° C MPa'sec 8 -

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Bitumen oil Athabasca sands Bitumen Cerro black pool Orinoco Analytical method Calorific value gross J / g 42530 40800 L5 K2279 Calorific value net J / g 40140 38650

Stability {3-value} 3,7 According to the standard AZTM 07157 Water % 0.3 LZ K2275 Colorimetric Karl Fischer titration Dry sludge residue % weight. 0.23 0.26 130 10307-1 Distillation% LZ K2254 Gas chromatographic method Boiling point ° C 194 145 5 ° s 276 238 10 ° s 318 285 twenty ° s 385 360 thirty ° s 4 4 2 441 40 ° s 500 490 45 FROM - 520 fifty ° s 548 - 60 ° s 598 - 70 ° s 652 - 80 ° s 714 - 90 ° s - -

95 ° C - - Boiling point ° s -

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Table 2 (1)

Thermal Cracking Test Results

Oil sands bitumen Athabasca Example 1 Example 2 Example 3 Improved oil Improved oil Improved oil Vacuum mmHg. 118 (15.73 kPa) 118 (15.73 kPa) 118 (15.73 kPa) Discharge level process steam equivalent to vacuum % by weight regarding raw material thirteen fifteen 15, 5 Reaction temperature 410 410 410 Reaction time minutes twenty 31 47 Thermal cracking yield % by weight Gas 1,0 1/1 sixteen Improved oil 57.3 61.3 65.8 Thermal Cracking Residue 41.7 37.6 32.6 Softening point thermal cracking residue ° C 85 99 125

Degree of thermal conversion fractions 500 ° C * % 30.6 37.4 | 45.8 Thermal fraction conversion 500 ° С *,% = (yield (gas + improved oil),% by weight - fraction 500 ° C in the raw material,% by weight)) / (fraction 100-500 ° C “in the raw material,% by weight) * 100 3-value - Thermal Cracking Residue 2,8 2,5 2 A mixture of improved oil and thermal cracking residue 1.9 1,6 1.4

Table 2 (2)

8-value residue thermal cracking of the vacuum residue of Middle East oil

Comparative Example 1 Reference Example 2 The softening temperature of the thermal residue 85 99 cracking, ^J C 3-value 2.2 1.7

Table 3 (1)

Thermal Cracking Test Results

Raw material Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Bitumen Improved Improved Improved The remainder The remainder The remainder oil oil oil oil thermally thermally thermally sand whom whom whom Athabasca cracking cracking cracking Vacuum mmHg. - 118 113 118 118 118 118 (15.73 kPa) (15.73 kPa) (15.73 kPa) (15.73 (15.73 (15, chz kPa) kPa) kPa) Discharge level % by weight - thirteen fifteen 15, 5 thirteen fifteen 15, 5 technological relate a pair is equivalent completely vacuum raw material Reaction temperature ° C - 410 410 410 410 410 410 Duration minutes - twenty 31 47 twenty 31 47 reactions Appearance Neproerach- Slightly Slightly Slightly Black Black Black naya transparent transparent transparent solid solid solid blackish naya, dark dark- dark- substance substance substance brown brown brown brown high viscosity liquid liquid liquid kaya

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Oil classification In excess of- heavy Heavy Heavy Heavy In excess of- heavy In excess of- heavy In excess of- heavy Density at temperature 15 ^ 0 g7sb? 1,0164 0.9403 0.9388 0.938 1,091 1,1104 1,1276 Density in degrees ΑΡΙ 7.6 nineteen 19, 1 19.3 N % weight. 0.40 0.1 0.2 0.1 0, 9 0, 9 1,1 5 % weight. 5.02 3.4 3,51 3.66 6.11 6.08 6.12 Νί weight. ppm 85 <1 <1 <1 200 230 260 V weight. ppm 220 <1 <1 <1 530 590 680 Insoluble in n- heptane % weight. 10,4 0.03 <0,01 0.05 27.5 30, 8 31.3 Residual carbon % weight. 14.08 0, 36 0.39 0.41 36, 02 40.33 46, 94 Total acid number mg KOH / g 2,8 1.8 1.73 1.66

Raw material Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Bitumen oil sand Athabasca Improved oil Improved oil Improved oil The remainder thermally whom cracking The remainder thermally whom cracking The remainder thermally whom cracking Kinematic viscosity at 7.5 ^a C mm ^g / s 157, 7 141.7 129, 7 Kinematic viscosity at 50 ° C mm ² / s 6970 15.75 14.9 14.21 I am viscosity at 75 ° C mm ² / s 874 7,042 6,723 6, 51 Kinematic mm ² / s 182 3,916 3, 794 3,695 Absolute viscosity MPa’s 203 Absolute viscosity at 160 * C MPa sec 23 Absolute viscosity at 220 ° C MPa'sec 8 77 141 534 Absolute viscosity at 260 ^& C MPa'sec 29th 46 108

Absolute viscosity at 280 ° C MPa'sec nineteen 29th 60 Temperature softening residue thermal cracking ° s 85 99 125 Stability 13- value) 3,7 No stain No stain No stain Dry slurry balance % weight. 0.01 0.01 <0.01

Table 3 (2)

Thermal Cracking Test Results

| Raw Example 11 Example 12 Example 11 Example 12 Bitumen Cerro 1 black 1 pool 1 Orinoco Improved oil Improved oil The remainder thermal cracking The remainder thermal Vacuum mmHg. 118 (15.73 kPa) 140 (18.66 kPa) 118 (15.73 kPa) 140 (18.66 kPa)

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Discharge level process steam equivalent to vacuum 1 by weight relate completely raw material thirteen fifteen thirteen fifteen Reaction temperature ^e C - 410 420 410 420 Reaction time minutes - twenty 10 twenty 10 Thermal cracking yield % weight. Gas - 0.3 0.4 - - Improved oil - 54.1 60,4 - Thermal Cracking Residue - 45, 6 39, 2 - - The softening temperature of the residue thermal cracking ° C 83 116 Degree of thermal conversion fractions 500 ° C * 29.6 39.5 Thermal conversion of the fraction 500 ^b C ',% = (yield (gae + improved oil),% by weight - fraction 5ΰ0 ° € “in the raw material, 1 by weight)> / {fraction 100-500 * 0' in the raw material, % by weight) ^x 10C Appearance Opaque blackish brown high Slightly transparent dark- brown liquid Slightly transparent dark- brown liquid Black solid substance Black solid substance Oil classification Super heavy Heavy Heavy Super heavy Super heavy Density at 15 ”s g / cm ³ 1,0133 0.9279 0.9304 1,0960 1,1250 Density in degrees ΑΡΙ 3,1 20.9 20.5 -

Table 3 (2)

Thermal Cracking Test Results (continued)

Raw material Example 11 Example 12 Example 11 Example 12 Bitumen Enhanced- Enhanced- The remainder The remainder serro oil oil thermally thermally black whom whom basin cracking cracking Orinoco N % weight. 0.58 0.2 0.3 1,2 0.9 3 % weight. 3, 61 3.52 3.29 4.22 6, 03 Νί weight. ppm 92 <1 <1 202 230 V weight. ppm 439 <1 <1 871 590 Insoluble in n-heptane % weight. 10.0 <0.01 <0.01 - 30.3 Residual carbon % weight. 12.34 0.23 0.26 33.6 40.33 Total acid number mg KOH / g 3, 3 2.0 twenty - - Kinematic viscosity at 7.5 ° C mm ² / s - - - - - Kinematic viscosity at 50 ° C mm ² / s to - 16,2 13.5 - - Kinematic viscosity at 75 ° C mm ² / s - 7.2 6, 2 - - Kinematic viscosity at 100 ^s ' C mm ² / s 4.2 3,5 - -

Absolute viscosity at 100 ° C MPa sec 150 - - - - Absolute viscosity at 160 ° C MPa sec eleven - - - - Absolute viscosity at 220 ° C MPa'sec 3 - - 90 320 Absolute viscosity at 2 ° C MPa'sec - - - 31 80 Absolute viscosity at 280 ° C MPa sec - - - twenty 45 The softening temperature of the residue thermal cracking ° C 88 116 Stability (3-value) - - - - - Dry sludge residue % weight. 0.28 - - - -

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Table 4 (1)

Total Acid Number of Improved Oil

Raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Bitumen oil sand Athabasca Enhanced- naya oil Enhanced- naya oil Enhanced- naya oil Enhanced- naya oil Enhanced- naya oil Enhanced- naya oil Vacuum mm RT, Art. 118 (15.73 kPa) 118 (15.73 kPa) 118 (15.73 kPa) 70 (9.33 kPa) 87 (11, 6 kPa) 140 (18.66 kPa) Reaction temperature ° C - 410 410 410 390 400 420

Duration reactions minutes twenty 31 47 91 56 17 Total acid number mg SPF / g 2,8 M 1.73 1, 66 2.12 1.77 1.73

Table 4 (2)

Total Acid Number of Improved Oil

Raw material Example 11 Example 12 Bitumen Cerro Negro Orinoco Basin Improved oil Improved oil Vacuum mm Hg 118 (15.73 kPa) 140 (18.66 kPa) Reaction temperature ° C - 410 420 Reaction time minutes - twenty 10 Total acid number MG KOH / g 3, 3 2.0 2.0

Table 5

Storage Stability Test

Reference Example 4 Example 9 Atmosphere Air Temperature ° C 37 37

Duration Days 0 10 thirty 60 0 eleven thirty 60 storage Hours 0 240 720 1440 0 164 720 1440 Appearance Dark- Dark- Dark- Dark- Dark- Dark- Dark- Dark- brown brown brown brown brown brown brown brown Neva Neva Neva Neva Neva. Neva Neva Neva slightly slightly slightly slightly pros pros pros pros pros pros pros pros crustacean crustacean crustacean crustacean crustacean crustacean crustacean crustacean Density at g / cm ^ 0.9380 0, 943 0.9449 0.9464 0, 9383 0.9386 0.9384 0.9384 temperature 15 ° С Density in degrees 19.1 18.5 18.2 17.9 19, 2 19,2 19, 2 19,2 ΑΡΙ Kinematic viscosity mm ² / s 14.9 17.81 19, 68 21.31 14.87 14.53 14.47 14, 49 at a temperature of 50 ⁼ C Dry sludge residue % weight. 0.01 0.02 <0.01 <0.01 <0,01 <0.01 0.05 <0,01

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Table 6

Mixed ratio for a density of 21 in degrees ΑΡΙ and mixed oil properties

Comparative example 3 Example 7 Example 8 Steam to oil ratio - 3.0 4.0 No increase qualities Quality improvement on technology of NZS Quality improvement on technology of NZS Diluent % vol. 29, 8 18.0 11.5 Oil sands bitumen % vol. 70,2 37,4 19,2 Improved oil % vol. - 44.6 69, 3 Mixed Oil Properties Density in degrees ΑΡΙ 21 21 21 5 % weight. 3.91 3, 64 3.73 N % weight. 0.31 0.15 0.21 Νί / ν weight. ppm 73/170 22/47 40/91 Total acid number mg KOH / g 2.15 1.75 1, 90

Density in degrees ΑΡΤ diluent 65, oil sands bitumen 7.6, improved oil 19.3.

Claims (15)

CLAIM 1. The method of partial improvement of heavy oil having a density of 20 in degrees ΑΡΙ or less, fractions having a boiling point of 500 ° C or lower, in an amount of 45 wt.% Or less, with residual carbon (MSC) in an amount of 10 wt.% Or more, the total acid number (ΤΑΝ) of 1.0 or more and kinematic viscosity at a temperature of 50 ° C at a level of 1000 mm ² / s or more, and the method includes thermal cracking of heavy oil at a drilling site that uses the remainder of thermal cracking as fuel for the production of steam used for up to yields of heavy oil from the reservoir reservoir and to separate the oil subjected to thermal cracking from the remainder of thermal cracking, while thermal cracking of heavy oil is carried out at a pressure of 0 to 0.1 MPa (gauge), at a temperature of 370 to 440 ° C over a period of 15 to 150 min in the reaction chamber (CT), at the same time, the produced stripping steam is injected into the reaction chamber to separate the thermally cracked oil formed in the liquid phase of the reaction chamber as gaseous products of thermal oil refining, from the thermal cracking residue, to obtain a thermal oil cracking product, provided that the liquid phase of the reaction chamber is maintained at a δ-value of stability of 2.0 or more, even when the degree of thermal cracking of fractions having a boiling point of 500 ° C or higher in the original heavy oil, is 30% or more. 2. The method according to claim 1, further comprising the steps of allowing the oil subjected to thermal cracking to flow together with the gaseous products of thermal cracking and steam through the exhaust pipe (b1) located in the upper part of the reaction chamber (K1), cool the lighter fraction directly with the heavier fraction thermally cracked oil in the exhaust pipe (b1), the non-condensed lighter fraction is separated - gaseous products of thermal cracking, steam and condensation the heavier fraction of the thermally cracked oil in the separator (Ό1) to separate the heavy fraction of the improved oil, the heavier fraction of the thermally cracked oil is removed from the bottom of the separator (Ό1), the original heavy oil is heated using a heat exchanger (C2) to extract heat, steam is generated in the heat exchanger (C3), a part of the heavier fraction of the thermally cracked oil is drawn into recirculation as a cooling medium into the exhaust pipe (b1), the rest of b the heavier fraction as a product, cool the non-condensed lighter fraction - gaseous products of thermal cracking and steam using a heat exchanger (C1), separate the condensed lighter fraction from water in a separator (Ό2) for oil and water separation, mix the condensed lighter fraction with product heavier fraction to obtain a product of thermal cracking of oil for transportation through the pipeline. 3. The method according to claim 1 or 2, in which the product of thermal cracking of oil contains reduced amounts of sulfur, nitrogen and heavy metals nickel and vanadium. 4. The method according to claim 1 or 2, in which thermal cracking is carried out at a temperature of from 400 to 440 ° C and the product of thermal cracking of oil has a reduced total acid number (ΤΑΝ). 5. The method according to any one of claims 1 to 4, in which the product of thermal cracking of oil has a reduced viscosity for transportation through the pipeline. - 13 026096 6. The method according to any one of claims 1 to 5, in which the product of thermal cracking of oil has a higher density in degrees LI than the original heavy oil. 7. The method according to any one of claims 1 to 6, in which the product of thermal cracking of oil has stable properties while excluding contact with air during storage or transportation. 8. The method according to any one of claims 1 to 7, which further comprises the steps of burning the separated thermal cracking residue in a steam boiler to produce steam and using steam to produce heavy oil using 3ΑΟΌ, SPZ or steam injection technologies to increase oil oil recovery. 9. The method of claim 8, in which the separated thermal cracking residue is used in such an amount as is necessary to generate the amount of steam required for the required steam to oil ratio at the drilling site. 10. The method according to claim 9, in which the separated residue of thermal cracking is obtained by thermal cracking of heavy oil produced at the drilling site. 11. The method according to any one of claims 1 to 10, further comprising the stage of mixing the product of thermal cracking of oil with heavy oil produced at the drilling site for transportation through the pipeline, without subjecting it to thermal cracking. 12. The method according to any one of claims 1 to 11, in which the original heavy oil has a density in degrees ΑΡΙ less than 10. 13. A method for transporting heavy oil produced at a drilling site, in which a portion of the heavy oil produced at a drilling site is treated with a partial improvement method for the heavy oil according to claim 1, and a product of thermal cracking of oil obtained from said processing is mixed with heavy oil produced at drilling site, and transport the resulting mixture through a pipeline. 14. The method according to any one of claims 1 to 13, in which the original heavy oil has a density in degrees ΑΡΙ less than 10 and a total acid number (ΤΑΝ) of 2.0 or more. 15. The method according to 14, in which the source of heavy oil is a bitumen oil sands or bitumen tar sands Orinoco.