RU2495087C1 - Procedure for processing heavy hydrocarbon stock - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention is referred to method for processing of heavy hydrocarbon stock with production of synthetic crude oil that includes a stage of thermal treatment and/or stage of raw segregation with obtainment of one or more fractions, compounding of fractions with raw stock individually or in a mixture; at that organometallic salt is introduced into raw stock and this salt has the formula M(OOC-R)_n or M(SOC-R)_n or M(SSC-R)_n where R means alkyl, aryl, isoalkyl, tret-alkyl, alkylalaryl that can include hydroxyl, ketoxyl, aminoxyl, carboxyl or thiocarbamic group, n=1-3, and M means a transition metal from the periodic chart or nanoparticles of these metals based on 0.001-0.1% of metal weight per weight of raw stock.

EFFECT: improved quality of oil.

8 cl, 5 tbl, 8 ex

Description

The invention relates to the refining industry and can be used to improve the properties of heavy hydrocarbons, including heavy crude oils and natural bitumen.

A known method of preparing liquid hydrocarbon raw materials for further processing (RU 2261263, publ. September 27, 2005), comprising the stage of desalination and dehydration and separation of the dehydrated oil into fractions, before the stage of its separation into fractions to obtain marketable products, a high-boiling fraction with a boiling point of 340 is isolated -360 ° C and above, the stage of separation of high-boiling fractions is combined with cracking of the feedstock.

A known method of processing heavy oil and / or natural bitumen (RU 2264616, publ. 08/20/2009), including its separation into distillate and residual fractions, using the latter as boiler fuel and bitumen products, while before separating the flow of heavy oil and / or natural bitumen is divided into the main one, going to the separation, and an additional stream directed to compounding with distillate fractions separated from the main stream, with the production of "synthetic" oil.

A known method of obtaining from heavy crude oil crude oil suitable for transportation through pipelines and further processing (US 2006144754, publ. 06.07.2006). The method includes: 1) the separation of bituminous raw materials into two fractions, the first containing 20-80% by weight of the raw material, and the second 80-20% by weight of the raw material; 2) distillation of the first fraction obtained in step 1, preferably under vacuum, to a light fraction boiling up to 380 ° and the residual fraction; 3) thermal cracking, preferably the entire residual fraction obtained in the distillation process described in step 2; 4) distillation of the product obtained in step 3 into one or more light fractions boiling up to 350 ° C (alternatively, one or more intermediate fractions boiling between 350 ° C and 510 ° C) and a heavy fraction boiling above 350 ° C ; 5) combining the second fraction obtained in step 1, the light fraction obtained in step 2, and the light fraction and / or middle fraction obtained in step 4, in order to obtain crude oil that can be pumped through pipelines; 6) using the heavy fraction obtained in step 4 to generate heat and / or electricity.

However, by known methods, oil products are obtained that require further refinement (catalytic reforming, hydrotreating, hydrocracking), and also a residual fraction is obtained as one of the final products.

The objective of the present invention is to obtain from heavy hydrocarbons a refined synthetic oil suitable for transport through pipelines and further processing, improving its quality and grade, obtaining a high-octane gasoline component, as well as simplifying the process of their production without residue.

The solution to this problem is also achieved by the fact that the method of processing heavy hydrocarbon feedstocks to produce synthetic oil includes a heat treatment step to produce one or more fractions, and / or a step of dividing the feedstock into fractions to produce one or more fractions, compounding the fractions with the feedstock individually or in mixtures, wherein either an organometallic salt having the formula M (OOC-R) _n or M (SOC-R) _n or M (SSC-R) _n is introduced into the feed, where R is alkyl, aryl, isoalkyl, tert-alkyl alkylaryl optionally including hydroxyl silt. keto, amino, carboxyl, thiocarbamine group, n = 1-3, and M denotes a transition metal from elements of the Periodic system of elements, or nanoparticles of these metals at the rate of 0.001-0.1% wt. metal to the mass of raw materials.

Metal nanoparticles are obtained under the conditions of the stage of separation of raw materials into orations and the stage of heat treatment upon decomposition of the indicated organometallic salt, or are introduced into the feedstock.

Low boiling fractions (one or more) boiling up to 360 ° C are obtained at the heat treatment stage, possibly carried out in the presence of a hydrogen-containing gas, and low boiling fractions (one or more) boiling up to 360 ° C, and possibly high boiling fractions boiling within 360 ° C and above, obtained at the stage of separation of raw materials into fractions. A hydrogen-containing gas is hydrogen or a mixture of gases containing hydrogen. When compounding fractions with raw materials to produce synthetic oil, the ratio of fraction: raw materials is preferably (40-60): (60-40), while both low boiling fractions boiling up to 360 ° C and high boiling fractions boiling within 360 ° C and above, individually or in a mixture.

Under the stage of separation into fractions (fractionation) should be understood atmospheric distillation and / or vacuum distillation, or a single evaporation, or distillation, or distillation with distillation.

Heat treatment is thermal cracking (deep thermal cracking) or visbreaking (light thermal cracking), and heat treatment carried out in the presence of a hydrogen-containing gas is either hydrocracking or hydrobreaking.

The low-boiling fraction (n.c. - 180 ° C) can be isolated as a high-octane component of gasoline with an octane rating of at least 80 points by the motor method. At the same time, the high-octane gasoline fraction is chemically stable.

High-throwing fractions boiling within 360 ° C and above are sent for additional processing to extract the transition metal, or at least part of them can be recycled to the heat treatment stage, possibly carried out in the presence of a hydrogen-containing gas, and / or the stage of separation of the raw material into fractions .

Raw materials with a density of more than 0.850 g / cm ³ are used as heavy hydrocarbon raw materials (heavy crude oils, natural bitumen individually or in a mixture, as well as their mixture with oil shale).

Example 1. As a feedstock, oil is used that has the following indicators: kinematic viscosity - 579.21 cSt, density at a temperature of 20 ° C - 0.94 g / cm ³ , pour point - minus 20 ° C, flash point in a closed crucible - 135 ° C, content, wt.%: Water - 0.2, total sulfur - 0.407, mechanical impurities - 0.009, asphaltenes - 1.0.

Nickel nanoparticles (weight average size 38 nm) are added to the feed at the rate of 0.001% and 0.1% wt. nickel per mass of feedstock. Raw materials with and without the addition of nickel nanoparticles are subjected to atmospheric distillation into fractions. The results are presented in table 1

Table 1 Fractions Yield,% wt. No additives With the addition of 0.001% wt. nickel With the addition of 0.1% wt. nickel Fraction (140-180 ° C) 22 39 41 Fraction 2 (180-360 ° C) 25 45 56 Fraction 3 (360-500 ° C) 22 8 one Fraction 4 (above 500 ° C) thirty - -

Mix fraction 2 and fraction 3 obtained by adding 0.001% wt. nickel, with the original oil in a ratio of 50:50, while this produces crude synthetic oil with a density of 0.84 g / cm ³ , a viscosity of 12.47 cSt, pour point minus 59 ° C, sulfur content of 0.02 wt.%.

Example 2. As a raw material, oil of the Shugurovskoye field is used, which has the following indicators: density - 0.914 g / cm ³ , kinematic viscosity at 20 ° C - 220.23 cSt, conditional viscosity at 20 ° C - 29.73 ° C, pour point minus 20 ° C, content,% wt .: mechanical impurities - traces, asphaltenes - 5, sulfur - 3.82, coking ability - 13.5% wt., fractional composition: n.a. 71 ° C, boils,% vol .: 10% 92 ° C, 20% 218 ° C, 30% 268 ° C, 40% 319 ° C, 50% 373 ° C, 60% 437 ° C.

The raw material is added molybdenum salt of diethylthiocarbamic acid at the rate of 0.01% wt. molybdenum on the mass of the feedstock and is subjected to visbreaking at t = 410 ° C and P = 1.5 MPa.

When the fractionation of 180-360 ° C with the feedstock in the ratio of 50:50 was found out, the resulting product is a synthetic synthetic oil with a density of 0.86 g / cm ³ , kinematic viscosity of 16.83 cSt, pour point minus 52 ° C, sulfur content 0, 04 wt.%. The fraction boiling up to 180 ° C is a gasoline component with an octane rating of 80 points by the motor method.

A sample of intermediate raw materials was studied on a Рnotosor-Complex spectrometer and on a Solver Pro-M scanning probe microscope of the NT-MDT form. The measurement results show that the average weight size of the molybdenum nanoparticles is 58 nm.

Example 3. The process is carried out under the conditions of example 1, while using heavy oil as a raw material having the following parameters: density - 0.940 g / cm ³ , kinematic viscosity at 20 ° C - 1091 cSt, conditional viscosity at 20 ° C - 147, 29 ° WU, content,% wt .: no mechanical impurities, 6 asphaltenes, sulfur 2.35, flash point in an open crucible 68 ° C, fractional composition: nc. 85 ° C, boils,% vol .: 10% 265 ° C, 20% 303 ° C, 30% 352 ° C, 40% 406 ° C, 50% 465 ° C, 60% 492 ° C, and instead of nickel nanoparticles add Nickel stearate at the rate of 0.001% wt. and 0.1% wt. nickel per mass of feedstock. The results are presented in table.2.

table 2 Fractions Yield,% wt. With the addition of 0.001% by weight. nickel With the addition of 0.1% wt. nickel Fractions up to 360 ° С 82 89 Fraction 360-500 ° С 13 6

Further, in order to refine and obtain synthetic oil, the fractions boiling up to 360 ° C are mixed with the feedstock. The characteristics of synthetic oil obtained by mixing fractions boiling up to 360 ° C with the feedstock in various ratios are presented in Table 3.

Table 3 Qualitative and quantitative indicators of synthetic oil Name of indicator The ratio of oil and fractions NK-360 ° C,% wt. 60/40 55/45 50/50 45/55 40/60 Sulfur content,% wt. 0.9 0.76 0.6 0.5 0.4 Density (20 ° С), g / cm ³ 0.88 0.87 0.86 0.86 0.85 The output of the fraction up to 360 ° C,% wt. 56 59 62 64 67 The output of the total oil volume,% wt. 95 94 94 93 93

A sample of the intermediate feed was studied using a Pnotocor-Complex spectrometer and a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the weight average size of nickel nanoparticles is 26 nm.

Example 4. Conditions and raw materials are similar to example 1.

Get the gasoline fraction NK-180 ° C with an octane number of 82 according to the motor method, with an iodine number of 0.03, and a sulfur content of less than 0.01%.

Example 5. The raw materials of example 3 are mixed with chromium 2-ethylhexanoate at the rate of 0.1% wt. chromium per mass of raw materials and is subjected to soft hydrocracking at a temperature of 300 ° C and a hydrogen feed rate of 200 m ³ (ns) per m ^{3 of} raw materials. Fractions boiling up to 360 ° C are mixed with the starting oil in a ratio of 40:60, respectively. The result is a crude synthetic oil with a density of 0.852 g / cm ³ , kinematic viscosity of 14.4 cSt, pour point minus 50 ° C with a sulfur content of 0.2 wt.%.

Example 6. Fractions 2 and 3, obtained by atmospheric fractionation with the addition of 0.1% wt. nickel (example 1), is subjected to thermal cracking at a temperature of 450 ° C and a pressure of P = 0.5 MPa. The product obtained by mixing the fractions NK-180 ° C and 180-360 ° C with the initial oil in the ratio of 40:60, is a crude synthetic oil with a density of 0.84 g / cm ³ , kinematic viscosity 12.48 cSt, temperature solidification minus 52 ° C, sulfur content of 0.01 wt.%.

Example 7. Fractions boiling within 360-500 ° C (Example 3) are recycled in full to the stage of atmospheric distillation. The results are presented in table 4.

Table 4 Fractions Yield,% wt. With the addition of 0.001% wt. nickel With the addition of 0.1% wt. nickel Fractions up to 360 ° C 89 94 Fraction 360-500 ° C 5 -

Example 8. The raw material of example 1 with the addition of 0.05% wt. diethylthiocarbamate, diethyl dithiocarbamate, 2-hydroxyhexanote, 4-oxopentanoate nickel, 6-amino cobalt, chromium naphthenate, nickel adipate is subjected to thermal cracking at a temperature of 410 ° C and a pressure of 1.5 MPa to obtain a fraction of NK-180 ° C, which mixed with the original oil in a ratio of 60:40. The resulting product is a crude synthetic oil with the following characteristics (table 5):

The proposed method can significantly reduce the density, viscosity, pour point of oil, sulfur content, which makes the final product suitable for transportation without the use of diluents and further processing, to improve the quality of oil.

Claims (8)

1. A method of processing a heavy hydrocarbon feedstock to produce synthetic oil, comprising a heat treatment step to produce one or more fractions and / or a step of separating the feedstock into fractions to produce one or more fractions, compounding the fractions with the feedstock individually or in a mixture, characterized in that either an organometallic salt having the formula M (OOC-R) _n or M (SOC-R) _n or M (SSC-R) _n , where R is alkyl, aryl, isoalkyl, tert-alkyl, alkylaryl, is introduced into the feed possibly including hydroxyl, keto, amino, carboxyl, t okarbaminovuyu group, n = 1-3, a M is a transition metal element of the Periodic Table, these metals or nanoparticles based 0.001-0.1 wt.% metal on the weight of the feed. 2. The method according to claim 1, characterized in that the stage of heat treatment is possibly carried out in the presence of a hydrogen-containing gas. 3. The method according to claim 1, characterized in that in the conditions of the heat treatment stage or the stage of separation of the raw materials into fractions, transition metal nanoparticles are obtained by decomposition of the indicated organometallic salt. 4. The method according to claim 1, characterized in that it is possible to allocate a low boiling fraction as a high octane component of gasoline. 5. The method according to claim 4, characterized in that the low-boiling fraction has an octane rating of at least 80 points by the motor method. 6. The method according to claim 1, characterized in that when compounding the fractions with the feedstock to produce synthetic oil, the ratio of the fraction: feedstock is preferably (40-60) :( 60-40). 7. The method according to claim 1 or 2, characterized in that at least a portion of the high boiling fractions are recycled to the heat treatment stage and / or the raw material fractionation stage. 8. The method according to any one of claims 1 to 6, characterized in that the hydrocarbon feed with a density of more than 0.850 g / cm ^{3 is} used as a heavy hydrocarbon feed.