Process and apparatus for the settling separation of solid-laden heavy oil

Abstract

The present application relates to the technical field of petroleum chemical industry, in particular to a method and device for the sedimentation separation of solid-containing heavy oil, which comprises the following steps: (1) contacting vacuum residue and a first solvent stream to obtain an extraction phase containing deasphalted oil and a raffinate phase containing deoiled pitch; (2) mixing the solid-containing heavy oil and the raffinate phase as an additive, heating, and then extracting with a second solvent stream and performing sedimentation separation to obtain an extraction phase containing purified oil and a raffinate phase containing residue; (3) independently performing first solvent separation on the extraction phase and the extraction phase to obtain deasphalted oil and purified oil; (4) performing second solvent separation on the raffinate phase to obtain residue; and separating the solvent into the first solvent stream and the second solvent stream in a weight ratio of 1-3:1-5. The method effectively solves the problem of pipeline erosion caused by the easy deposition of solid particles, prolongs the stable operation period of the device, and the purified oil obtained by the method can be used as a raw material for high-value-added chemicals.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, in particular to a method for settling and separating solid-containing heavy oil, application of purified oil prepared by the method, and a device for settling and separating solid-containing heavy oil. BACKGROUND

[0002] With the increasing global environmental problems, domestic and foreign environmental protection regulations have been introduced to limit the sulfur content of marine fuel oil (hereinafter referred to as ship fuel). From a global perspective, with the continuous development of the shipping industry, the share of the Asia-Pacific region in the global ship fuel demand market has been growing continuously in recent years, and the market demand potential for low-sulfur ship fuel in China is huge.

[0003] The increasing demand for electric furnace steelmaking has accelerated the demand for ultra-high power and high-power graphite electrodes, and the increasing demand for artificial graphite negative electrodes for lithium-ion power batteries in recent years has further boosted the demand for needle coke in the market.

[0004] Catalytic oil slurry is a high-quality raw material for high-value-added chemicals such as needle coke, carbon fiber, and low-sulfur marine fuel. There is an urgent need for comprehensive utilization of catalytic oil slurry, and great market prospects, and it is of great significance to carry out research on high-value comprehensive utilization technology of catalytic oil slurry. However, catalytic oil slurry usually contains 1200-12000 μg / g of catalyst particles, which can cause coking, wear, and blockage of the catalytic cracking oil slurry circulation system, and is a key factor restricting the high-value comprehensive utilization of catalytic oil slurry. Removing catalyst particles from catalytic oil slurry has become a pressing problem. In addition, some slurry bed and ebullated bed residual oil hydrogenation technologies, coke-like precipitates formed during residual oil hydrogenation conversion or hydrocracking, and solid catalyst recovery, coal tar solid particles, and high-value utilization of heavy oil containing solid particles all face the problem of removing solids.

[0005] The existing oil slurry desolidification technologies mainly include filtration separation, centrifugal separation, additive settling, and electrostatic separation, etc. Specifically, (1) the filtration technology has simple equipment, high separation efficiency, stable operation, and less influence of oil slurry properties on separation effect, but has high initial investment, and the filter core and filter cloth are easily blocked by gum, asphaltene and fine catalyst in the oil slurry, resulting in gradually reduced flux, and the filter medium needs to be replaced or backwashed regularly, which is not suitable for continuous operation; (2) the centrifugal settling method has good separation effect and high desolidification efficiency, but the machine speed is high during operation, the equipment maintenance is inconvenient, and the processing capacity is small; (3) the additive settling is a modification of the traditional natural settling. When the settling additive is added to the oil slurry, the additive and the particles wrapped in the oil slurry form strong interfacial affinity, which can reduce the dispersion stability between the particles. Under the action of the interfacial affinity, the particles are adsorbed and bridged to form large flocs, which greatly shortens the settling time and significantly improves the separation efficiency; (4) the electrostatic separation method has poor adaptability to oil slurry with high content of gum and asphaltene or high water content, and the separation efficiency is unstable. Moreover, the equipment investment and maintenance cost are high, and it is difficult to realize industrialization at present.

[0006] CN202011394588.5 discloses a treatment method for desolidification of catalytic cracking off-spec oil slurry. In the method, the oil slurry is pretreated by an oil phase diluent and a water phase weighting agent, and then subjected to destabilization and coalescence treatment under the action of a coalescence aid, and then subjected to centrifugal separation. The ash content of the clarified oil slurry obtained by separation is less than 0.01wt%, and the oil slurry ash removal rate is more than 97%. Although the additive settling can improve the desolidification efficiency, the settling speed is still slow, and a centrifugal device is needed to accelerate it, which is difficult to adapt to large-scale industrial production.

[0007] CN201510144811.3 discloses a pretreatment method for catalytic oil slurry. C3-C5 light hydrocarbon fraction is used as a solvent for subcritical extraction of the oil slurry, and purified oil slurry substantially free of asphaltene and solid particles is prepared, which can be used as an excellent raw material for oil-based needle coke. However, the solid content in the purification residue is high, which is easy to deposit in the pipeline, causing erosion of the pipe wall and leading to leakage, affecting the stable operation of the device. Since the mass fraction of asphaltene in hydrogenated tail oil and coking wax oil is low, it is easy to mix, and this method is difficult to treat hydrogenated tail oil or coking wax oil.

[0008] Therefore, there is an urgent need for a new method for settling and separating solid-containing heavy oil. SUMMARY

[0009] The present application aims to overcome the problems of low desolidation rate, long settling time, pipeline erosion, unstable operation, easy plugging, flux reduction, and complex process equipment in the existing solid-containing heavy oil separation method, and provides a solid-containing heavy oil settling separation method, application of purified oil prepared by the method, and a solid-containing heavy oil settling separation device. The method shortens the settling time, improves the desolidation rate, and increases the stable operation period of the device. At the same time, the purified oil prepared by the method can be used as a raw material for high-value-added chemical products, realizing high-value utilization.

[0010] To achieve the above-mentioned purpose, the present application provides a solid-containing heavy oil settling separation method in the first aspect, which comprises:

[0011] (1) contacting vacuum residue and a first solvent stream and performing extraction to obtain an extraction phase containing deasphalted oil and a raffinate phase containing deoiled pitch;

[0012] (2) mixing the solid-containing heavy oil and the raffinate phase as an additive and heating, then extracting with a second solvent stream and performing settling separation to obtain an extraction phase containing purified oil and a raffinate phase containing residue;

[0013] (3) independently performing first solvent separation on the extraction phase and the extraction phase to obtain deasphalted oil and purified oil;

[0014] (4) performing second solvent separation on the raffinate phase to obtain residue;

[0015] Wherein, the solvent is divided into a first solvent stream and a second solvent stream with a weight ratio of 1-3:1-5.

[0016] Preferably, the solvent is selected from C1-C 10 alkanes, preferably selected from C3-C6 alkanes, more preferably selected from at least one of n-butane, isopentane and n-pentane.

[0017] Preferably, in step (3), the process of the first solvent separation comprises:

[0018] (3-i) independently performing supercritical solvent recovery on the extraction phase and the extraction phase to obtain recovered solvent, deasphalted oil-rich material and purified oil-rich material;

[0019] (3-ii) performing first stripping on the deasphalted oil-rich material to obtain the deasphalted oil and first stripping gas;

[0020] (3-iii) performing second stripping on the purified oil-rich material to obtain the purified oil and second stripping gas.

[0021] The second aspect of the present application provides the application of the purified oil prepared by the method provided in the first aspect in low-sulfur ship fuel and needle coke raw material.

[0022] The third aspect of the present application provides a device for the settling separation of solid-containing heavy oil, comprising an extraction column, a settling separation column, a first solvent separation unit and a second solvent separation unit;

[0023] The extraction column is used to contact and extract the vacuum residue and the first solvent, and the extraction phase containing deasphalted oil is obtained at the top of the column, and the raffinate phase containing deoiled pitch is obtained at the bottom of the column.

[0024] The settling separation column is connected to the bottom of the extraction column, and is used to mix and heat the raffinate phase and the solid-containing heavy oil, and then extract and perform settling separation with the second solvent, and the extraction phase containing purified oil is obtained at the top of the column, and the raffinate phase containing residue is obtained at the bottom of the column.

[0025] The first solvent separation unit is connected to the top of the extraction column and the settling separation column respectively, and is used to independently perform first solvent separation on the extraction phase and the extraction phase respectively, and obtain deasphalted oil and purified oil.

[0026] The second solvent separation unit is connected to the bottom of the settling separation column, and is used to perform second solvent separation on the raffinate phase, and obtain residue.

[0027] The solvent is divided into the first solvent and the second solvent.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] (1) The method provided by the present application uses solid-containing heavy oil as raw material, combines conventional solvents and specific additives to perform extraction, settling separation and solvent separation in turn, and obtains purified oil. In particular, deoiled pitch is used as an additive to shorten the settling time and improve the solid removal rate, which is easy to separate and utilize, effectively solves the problem that solid particles are easy to deposit and cause pipeline erosion and wear, and prolongs the stable operation period of the device. At the same time, the purified oil prepared by the method provided by the present application can be used for low-sulfur ship fuel and needle coke raw material, realizing high-value utilization.

[0030] (2) Compared with the existing vacuum distillation using high processing temperature, the present application uses the technical means of extraction and settling separation with reduced temperature, which avoids the cracking and condensation of the processing raw material under high-temperature distillation conditions, and increases the yield of high-value purified oil products. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is a structural schematic diagram of a device for the settling separation of solid-containing heavy oil provided by the present application.

[0032] MARKING OF THE DRAWINGS

[0033] I, extraction column II, settling separation column III, supercritical solvent recovery column III-1, first solvent recovery zone III-2, second solvent recovery zone IV, first stripping column V, second stripping column VI, third stripping column VII, cooling unit 1, vacuum residue 2, solvent 2-i, first solvent stream

[0034] 2-ii, second solvent stream 3, raffinate phase containing deoiled pitch 4, extraction phase containing deasphalted oil 5, heavy oil containing solid 6, extract phase containing purified oil 7, raffinate phase containing residue

[0035] 8, recovered solvent 9, material rich in deasphalted oil 10, material rich in purified oil 11, stripping gas 12, deasphalted oil 13, first stripping gas 14, purified oil 15, second stripping gas 16, residue

[0036] 17, third stripping gas 18, vertical baffle DETAILED DESCRIPTION

[0037] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numerical value, however, can include values up to and including the value of the lower limit, unless the context clearly indicates otherwise. Any numerical value, however, can include values up to and including the value of the lower limit, unless the context clearly indicates otherwise. Numerical ranges include all values from and including the lower and the upper values, in increments of one unit. In this disclosure and in the claims, the phrase "at least X" means "X or more", the phrase "at most X" means "X or less", and the phrase "at least X, or at most Y" means "at least X or at most Y, in other words, values that are X or more, or that are Y or less, but not including Y." In the context of the present application, the term "about" means ± 10% of the value of the cited numerical value. All such combinations and subcombinations are intended to be specifically encompassed by the application.

[0038] In the present application, without special circumstances, "first", "second" and "third" neither represent the order of precedence, nor represent the limitation of each material or step, but only for distinguishing or indicating that it is not the same material or step. For example, "first stripping", "second stripping" and "third stripping" in "first", "second" and "third" are only used to indicate that it is not the same stripping; similarly, "first solvent stream" and "second solvent stream" are only used to indicate that it is not the same solvent stream.

[0039] In the present application, without special circumstances, the "top" of the container refers to the position of 0-10% from top to bottom of the container; the "upper" of the container refers to the position of 10-40% from top to bottom of the container; the "middle" of the container refers to the position of 40-60% from top to bottom of the container; the "lower" of the container refers to the position of 60-90% from top to bottom of the container; the "bottom" of the container refers to the position of 90-100% from top to bottom of the container.

[0040] The first aspect of the present application provides a method for settling separation of heavy oil containing solid, the method comprising:

[0041] (1) contacting the vacuum residue and the first solvent stream and performing extraction to obtain an extraction phase containing deasphalted oil and a raffinate phase containing deoiled pitch;

[0042] (2) mixing and heating the heavy oil containing solid and the raffinate phase as an auxiliary agent, and then extracting with a second solvent and performing a settling separation to obtain an extract phase containing purified oil and a raffinate phase containing residue;

[0043] (3) independently performing a first solvent separation on the extract phase and the extract phase to obtain deasphalted oil and purified oil;

[0044] (4) performing a second solvent separation on the raffinate phase to obtain residue;

[0045] wherein the solvent is divided into a first solvent and a second solvent in a weight ratio of 1-3:1-5.

[0046] In the present application, unless otherwise specified, the solvent is composed of a first solvent and a second solvent, and the weight ratio of the first solvent and the second solvent is 1-3:1-5, for example, 1:1, 1:3, 1:5, 2:1, 2:3, 2:5, 3:1, 3:2, 3:5, and any value in the range composed of any two numerical values.

[0047] In the present application, the type of the solvent has a wide selection range, as long as the solvent can separate the de-oil asphalt in the vacuum residue and the residue in the heavy oil containing solid. Preferably, the solvent is selected from C1-C 10 alkanes, preferably selected from C3-C6 alkanes, more preferably selected from at least one of n-butane, isopentane and n-pentane.

[0048] In some embodiments of the present application, preferably, the weight ratio of the vacuum residue and the first solvent is 1:2-4, for example, 1:2, 1:2.5, 1:3, 1:4, and any value in the range composed of any two numerical values, preferably 1:2-3. In the present application, the more the amount of the first solvent, the more helpful for the dispersion of the vacuum residue, and the more inferior the raffinate phase, but the energy consumption of solvent recovery is higher; therefore, it is preferred to reduce the amount of the first solvent, and the product properties are adjusted by the extraction temperature.

[0049] In the present application, the type of the vacuum residue has a wide selection range. Preferably, the distillation range of the vacuum residue is ≥520℃, preferably 520-850℃, for example, 520℃, 550℃, 600℃, 650℃, 700℃, 750℃, 800℃, 850℃, and any value in the range composed of any two numerical values.

[0050] In some embodiments of the present application, preferably, the extraction conditions include: pressure of 3.5-6 MPa, for example, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 6 MPa, and any value in the range between any two of the values, preferably 4-5 MPa; temperature of 30-240℃, for example, 30℃, 40℃, 50℃, 80℃, 100℃, 150℃, 200℃, 240℃, and any value in the range between any two of the values, preferably 40-200℃. In the present application, the pressure parameters refer to gauge pressure.

[0051] In some embodiments of the present application, preferably, in step (2), the weight ratio of the solid-containing heavy oil and the additive is 1-15:1, for example, 1:1, 3:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 13:1, 15:1, and any value in the range between any two of the values, preferably 5-10:1. In the present application, when the weight ratio of the solid-containing heavy oil and the additive is less than 1:1, the raffinate phase solvent recovery will consume more energy and affect the technical economy; when the weight ratio of the solid-containing heavy oil and the additive is greater than 15:1, the adsorption separation effect of the additive will be affected.

[0052] In some embodiments of the present application, preferably, the solid content in the solid-containing heavy oil is ≤10 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 8 wt%, 10 wt%, and any value in the range between any two of the values, preferably 0.1-5 wt%. In the present application, the solid content includes, but is not limited to, the sum of the contents of Si, Al solid powder, coal powder, coke powder, catalyst, metal oxide particles, catalyst, etc.

[0053] In the present application, the types of the solid-containing heavy oil have a wide selection range as long as the solid-containing heavy oil meets the above-mentioned limitations. Preferably, the solid-containing heavy oil is selected from at least one of the following: a hydroprocessing tail oil containing catalyst solid particles, a non-solid-removed catalytic oil slurry, coking wax oil, and coal tar.

[0054] In some embodiments of the present application, preferably, the heating temperature is equal to the temperature of the settling separation.

[0055] In some embodiments of the present application, preferably, the conditions of the extraction and settling separation each independently comprise: a pressure of 3.5-6 MPa, for example, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 6 MPa, and any value in the range between any two of the numerical values, preferably 4-5 MPa; a temperature of 1-80 ℃ higher than the temperature of the extraction, preferably 5-30 ℃ higher than the temperature of the extraction; a residence time of 5-20 min, for example, 5 min, 8 min, 10 min, 12 min, 15 min, 20 min, and any value in the range between any two of the numerical values, preferably 8-12 min.

[0056] In some embodiments of the present application, preferably, in step (3), the process of the first solvent separation comprises:

[0057] (3-i) each of the extraction phase and the extraction phase is independently subjected to supercritical solvent recovery to obtain recovered solvent, deasphalted oil-rich material and purified oil-rich material;

[0058] (3-ii) the deasphalted oil-rich material is subjected to first stripping to obtain the deasphalted oil and first stripping gas;

[0059] (3-iii) the purified oil-rich material is subjected to second stripping to obtain the purified oil and second stripping gas.

[0060] In the present application, the conditions of the supercritical solvent recovery have a wide range of choices as long as the solvent in the extraction phase and the extraction phase is recovered, and the specific condition parameters depend on the type of the solvent.

[0061] In some embodiments of the present application, preferably, the recovered solvent is returned and mixed into the solvent as a circulating solvent.

[0062] In some embodiments of the present application, preferably, each of the first stripping gas and the second stripping gas is independently returned and mixed into the solvent as a circulating solvent after first cooling.

[0063] In some embodiments of the present application, preferably, in step (4), the process of the second solvent separation comprises: subjecting the raffinate phase to third stripping to obtain third stripping gas and the residue.

[0064] In some embodiments of the present application, preferably, the third stripping gas is returned and mixed into the solvent as a circulating solvent after second cooling.

[0065] The second aspect of the present application provides an application of the purified oil prepared by the method provided in the first aspect in low-sulfur ship fuel and needle coke raw material.

[0066] The third aspect of the present application provides a structural schematic diagram of a device for the settling separation of solid-containing heavy oil, as shown in Figure 1 It can be seen that the device comprises an extraction column I, a settling separation column II, a first solvent separation unit and a second solvent separation unit. Figure 1

[0067] The extraction column I is used to contact and extract the vacuum residue 1 and the first solvent 2-i, and the extraction phase 4 containing deasphalted oil is obtained at the top, and the raffinate phase 3 containing deoiled pitch is obtained at the bottom.

[0068] The settling separation column II is connected to the bottom of the extraction column I, and is used to mix and heat the raffinate phase 3 and the solid-containing heavy oil 5, and then extract and settle separate with the second solvent 2-ii, and the extraction phase 6 containing purified oil is obtained at the top, and the raffinate phase 7 containing residue is obtained at the bottom.

[0069] The first solvent separation unit is connected to the top of the extraction column I and the settling separation column II, respectively, and is used to independently perform first solvent separation on the extraction phase 4 and the extraction phase 6, respectively, to obtain deasphalted oil 12 and purified oil 14.

[0070] The second solvent separation unit is connected to the bottom of the settling separation column II, and is used to perform second solvent separation on the raffinate phase 7 to obtain residue 16.

[0071] The solvent 2 is divided into the first solvent 2-i and the second solvent 2-ii.

[0072] According to the present application, preferably, as shown in Figure 1 The first solvent separation unit comprises a supercritical solvent recovery column III, a first stripping column IV and a second stripping column V.

[0073] The supercritical solvent recovery column III is a packed column with a vertical partition plate 18, the vertical partition plate 18 is connected to the bottom and the wall of the packed column, and is not connected to the top of the packed column, the vertical partition plate 18 divides the inside of the packed column into a first solvent recovery zone III-1 and a second solvent recovery zone III-2, which are respectively used to independently perform supercritical solvent recovery on the extraction phase 4 and the extraction phase 6, respectively, to obtain recovered solvent 8 at the top, and to obtain deasphalted oil-rich material 9 and purified oil-rich material 10 at the bottom, respectively.

[0074] The first stripping column IV is connected to the bottom of the first solvent recovery zone III-1, and is used to perform first stripping on the deasphalted oil-rich material 9, to obtain first stripping gas 13 at the top, and to obtain the deasphalted oil 12 at the bottom; the second stripping column V is connected to the bottom of the second solvent recovery zone III-2, and is used to perform second stripping on the purified oil-rich material 10, to obtain second stripping gas 15 at the top, and to obtain the purified oil 14 at the bottom.​

[0075] In the present application, when the supercritical solvent recovery column III is a packed column with vertical partition 18, the vertical partition 18 connects the bottom of the packed column and the column wall, and does not connect the top of the packed column, thereby dividing the interior of the packed column into a first solvent recovery zone III-1 and a second solvent recovery zone III-2, unless otherwise specified.

[0076] In the present application, the first solvent recovery zone III-1 is connected to the top of the extraction column I for supercritical recovery of the extraction phase 4, and the top part obtains part of the recovered solvent, and the bottom part obtains the asphalt oil-rich material 9; the second solvent recovery zone III-2 is connected to the top of the settling separation column II for supercritical recovery of the extraction phase 6, and the top part obtains the remaining part of the recovered solvent, and the bottom part obtains the purified oil-rich material 10, unless otherwise specified.

[0077] According to the present application, preferably, as shown in Figure 1 The second solvent separation unit is selected from a third stripping column VI for third stripping of the raffinate phase 7, and the top part obtains the third stripping gas 17, and the bottom part obtains the residue 16.

[0078] According to the present application, preferably, as shown in Figure 1 The top part of the supercritical solvent recovery column III is connected to the lower part of the extraction column I and the settling separation column II, respectively, for returning and mixing the recovered solvent 8 into the solvent 2 as a circulating solvent, unless otherwise specified.

[0079] According to the present application, preferably, as shown in Figure 1 The device further comprises a cooling unit VII connected to the first stripping column IV, the second stripping column V, the extraction column I and the settling separation column II, for returning and mixing the first stripping gas 13 and the second stripping gas 15 into the solvent 2 as a circulating solvent after being cooled respectively.

[0080] According to the present application, preferably, as shown in Figure 1 The cooling unit VII is further connected to the third stripping column VI for returning and mixing the third stripping gas 17 into the solvent 2 as a circulating solvent after being cooled.

[0081] According to a particularly preferred embodiment of the present application, a method for settling separation of solid-containing heavy oil, the method comprises:

[0082] (1) contacting the vacuum residue and the first solvent and performing extraction to obtain an extraction phase containing deasphalted oil and a raffinate phase containing deoiled asphalt;

[0083] (2) mixing and heating the solid-containing heavy oil and the auxiliary agent, and then extracting with the second solvent and performing settling separation to obtain an extraction phase containing purified oil and a raffinate phase containing residue;

[0084] (3) independently performing supercritical solvent recovery on the extraction phase and the extraction phase to obtain recovered solvent, a deasphalted oil-rich material and a purified oil-rich material; performing first stripping on the deasphalted oil-rich material to obtain deasphalted oil and first stripping gas; performing second stripping on the purified oil-rich material to obtain purified oil and second stripping gas;

[0085] (4) performing third stripping on the raffinate phase to obtain third stripping gas and residue;

[0086] wherein the solvent is divided into the first solvent and the second solvent in a weight ratio of 1-3:1-5, and the solvent is selected from at least one of n-butane, isopentane and n-pentane;

[0087] wherein in step (1), the weight ratio of the vacuum residue and the first solvent is 1:2-3; and the extraction conditions include: a pressure of 4-5 MPa; and a temperature of 40-200℃;

[0088] in step (2), the weight ratio of the solid-containing heavy oil and the auxiliary agent is 5-10:1; the solid content in the solid-containing heavy oil is 0.1-5 wt%; and the extraction and settling separation conditions each independently include: a pressure of 4-5 MPa, a temperature that is 5-30℃ higher than the extraction temperature, and a residence time of 8-12 min;

[0089] wherein the first stripping gas, the second stripping gas and the third stripping gas each independently, after being cooled, are returned and mixed into the solvent as a circulating solvent.

[0090] The application will be described in detail below through examples.

[0091] Example 1

[0092] The apparatus for settling separation of the solid-containing heavy oil is as shown in Figure 1 The apparatus includes: an extraction column I, a settling separation column II, a supercritical solvent recovery column III, a first stripping column IV, a second stripping column V, a third stripping column VI and a cooling unit VII;

[0093] The bottom of the settling separation tower II is connected with the bottom of the extraction tower I; the supercritical solvent recovery tower III is a packed tower with a vertical partition plate 18, the vertical partition plate 18 is connected with the bottom of the packed tower and the wall of the packed tower, and is not connected with the top of the packed tower, the vertical partition plate divides the interior of the packed tower into a first solvent recovery zone III-1 and a second solvent recovery zone III-2; the supercritical solvent recovery tower III is connected with the top of the extraction tower I and the top of the settling separation tower II respectively; the bottom of the first solvent recovery zone III-1 is connected with the first stripping tower IV, and the bottom of the second solvent recovery zone III-2 is connected with the second stripping tower V; the third stripping tower VI is connected with the bottom of the settling separation tower II.

[0094] The top of the supercritical solvent recovery tower III is connected with the extraction tower I and the settling separation tower II respectively; the cooling unit VII is connected with the first stripping tower IV, the second stripping tower V, the third stripping tower VI, the extraction tower I and the settling separation tower II.

[0095] A method for settling separation of solid-containing heavy oil, the method comprising:

[0096] (1) contacting vacuum residue-1 (all the property parameters are listed in Table 1) with a first solvent in a weight ratio of 1:2.5 and performing extraction (the pressure is 5 MPa, and the temperature is 185 ℃) to obtain an extraction phase containing deasphalted oil and a raffinate phase containing deoiled asphalt S1;

[0097] (2) mixing catalytic slurry-1 (all the property parameters are listed in Table 1) with the raffinate phase as an auxiliary agent in a weight ratio of 10:1 and heating to 190 ℃, then extracting with a second solvent and performing settling separation (the pressure is 5 MPa, the temperature is 190 ℃, and the residence time is 10 min) to obtain an extraction phase containing purified oil and a raffinate phase containing residue;

[0098] (3) independently performing supercritical solvent recovery on the extraction phase and the extraction phase to obtain recovered solvent, deasphalted oil-rich material and purified oil-rich material; performing first stripping on the deasphalted oil-rich material to obtain deasphalted oil P1 and first stripping gas; performing second stripping on the purified oil-rich material to obtain purified oil Q1 and second stripping gas;

[0099] (4) performing third stripping on the raffinate phase to obtain residue W1 and third stripping gas;

[0100] The first solvent and the second solvent are both selected from n-pentane, and the weight ratio of the first solvent to the second solvent is 1:5; the recovered solvent is returned and mixed into the solvent as a circulating solvent; the first stripping gas, the second stripping gas and the third stripping gas are returned and mixed into the solvent as a circulating solvent after being cooled respectively.

[0101] The physical property parameters of the deoiled pitch S1, deasphalted oil P1, purified oil Q1 and residue W1 are listed in Table 2.

[0102] Example 2

[0103] The device provided in Example 1 was used.

[0104] The method provided in Example 1 was used, except that

[0105] In step (1), the weight ratio of the vacuum residue-I to the first solvent was replaced by 4:1.

[0106] In step (2), the weight ratio of the catalytic slurry-I to the assistant was replaced by 15:1.

[0107] The physical property parameters of the deoiled pitch S2, deasphalted oil P2, purified oil Q2 and residue W2 obtained under the same conditions except for the above are listed in Table 2.

[0108] Example 3

[0109] The device provided in Example 1 was used.

[0110] The method provided in Example 1 was used, except that

[0111] In step (1), the extraction conditions were replaced by a pressure of 6.2 MPa and a temperature of 190°C.

[0112] In step (2), the extraction and settling separation conditions were replaced by a pressure of 6 MPa and a temperature of 230°C.

[0113] The physical property parameters of the deoiled pitch S3, deasphalted oil P3, purified oil Q3 and residue W3 obtained under the same conditions except for the above are listed in Table 2.

[0114] Comparative Example 1

[0115] The catalytic slurry-1 provided in Example 1 was directly subjected to settling separation, and the settling separation conditions included a pressure of 4.5 MPa, a temperature of 190°C and a time of 30 min, to obtain purified oil DQ1 and residue DW1.

[0116] The physical property parameters of the purified oil DQ1 and residue DW1 are listed in Table 2.

[0117] Comparative Example 2

[0118] The device provided in Example 1 was used.

[0119] The method provided in Example 1 was used, except that

[0120] The weight ratio of the first solvent and the second solvent is replaced by 5:1, and due to the small amount of the second solvent, the catalytic oil slurry cannot form a stable phase separation interface, that is, the step (2) cannot obtain the extraction phase containing the purified oil and the raffinate phase containing the residue;

[0121] The step (1) obtains the extraction phase containing the deasphalted oil DP2 and the raffinate phase containing the deoiled asphalt DS2;

[0122] In the step (3), the extraction phase is subjected to supercritical solvent recovery to obtain recovered solvent and deasphalted oil-rich material; and the deasphalted oil-rich material is subjected to first stripping to obtain the deasphalted oil DP2 and first stripping gas;

[0123] In the step (3), the extraction phase is subjected to supercritical solvent recovery to obtain recovered solvent and deasphalted oil-rich material; and the deasphalted oil-rich material is subjected to first stripping to obtain the deasphalted oil DP2 and first stripping gas;

[0124] Comparative Example 3

[0125] The device provided in Example 1 is used;

[0126] The method provided in Example 1 is used, except that

[0127] The first solvent and the second solvent are different, that is, the first solvent is selected from n-pentane, and the second solvent is selected from n-butane; and the extraction and sedimentation separation conditions are replaced by a pressure of 4.5 MPa and a temperature of 120°C.

[0128] The remaining conditions are the same, and the physical property parameters of the deoiled asphalt DS3, the deasphalted oil DP3, the purified oil DQ3 and the residue DW3 obtained are all listed in Table 2.

[0129] Comparative Example 4

[0130] The device provided in Example 1 is used;

[0131] The method provided in Example 1 is used, except that

[0132] There is no step (1), and the catalytic oil slurry-1 is directly extracted with the second solvent and subjected to sedimentation separation;

[0133] The remaining conditions are the same, and the physical property parameters of the deoiled asphalt DS4, the deasphalted oil DP4, the purified oil DQ4 and the residue DW4 obtained are all listed in Table 2.

[0134] Table 1

[0135] Item Vacuum Residue-1 FCC Slurry-1 Mass Yield / % / / 20 °C density / (kg / m 3 )]]> 1041.8 1145.5 Carbon Residue / % 24.42 12.15 Asphaltene / wt% 12.7 4.6 Sulfur / wt% 6.38 1.00 Nitrogen / wt% 0.31 0.11 Nickel / (pg / g) 49 6.6 Vanadium / (pg / g) 154 13 Solid Content / (pg / g) / 5400

[0136] Table 2

[0137]

[0138] Note: * Mass yield of deasphalted oil = weight of deasphalted oil / weight of vacuum residue x 100%;

[0139] Mass yield of deoiled pitch = weight of deoiled pitch / weight of vacuum residue x 100%;

[0140] Mass yield of purified oil = weight of purified oil / weight of solid-containing heavy oil x 100%;

[0141] Mass yield of residue = weight of residue / weight of solid-containing heavy oil x 100%, and the sum of the mass yields of the purified oil and the residue can be greater than 100% if the residue contains part of the deoiled pitch additive.

[0142] Table 2 (continued)

[0143]

[0144] Table 2 (continued)

[0145]

[0146] Table 2 (continued)

[0147]

[0148]

[0149] As can be seen from the data in Table 2, compared with Comparative Example 1, Example 1 uses the method provided by the present application and uses deoiled pitch as an additive to adsorb solid particles in the catalytic oil slurry, shortens the residence time to 10 min, and improves the solid removal rate. At the same time, the solid content in Example 1 is reduced to 18400 μg / g, reducing the concentration of solid particles and thus greatly reducing the probability of pipeline wear. Compared with Comparative Example 1, the stable operation period of the device can be increased by 45.7% [(26800 / 18400-1) x 100% = 45.7%].

[0150] Compared with Example 1, Example 2 uses the technical solutions of “the weight ratio of vacuum residue-I to the first solvent is 4:1” and “the weight ratio of catalytic oil slurry-I to the additive is 15:1”, and the yield of purified oil Q2 is 81.5%, but the solid content in the purified oil Q2 is relatively high, which can not meet the feed requirements of the downstream device. This is mainly due to the small amount of additive used, which makes the solid adsorption effect in the catalytic oil slurry worse.

[0151] Compared with Example 1, Example 3 uses the technical solution of “the conditions of extraction and sedimentation separation are not within the preferred protection range”, and the yield of purified oil Q3 is 50%. This is mainly due to the excessively high temperature of extraction and sedimentation separation, which makes the solvent solubility worse.

[0152] Compared to Example 1, Comparative Example 3 adopts a technical solution where "the first solvent and the second solvent are different types". That is, the second solvent is n-butane, which has a worse dissolving ability than the first solvent n-pentane. The yield of purified oil DQ3 is only 60%, and the deoiled asphalt DP3 needs to be recovered from n-pentane solvent before it can be used as an additive. The two solvent systems increase the investment in the equipment.

[0153] Compared to Example 1, Comparative Example 4 adopted a technical solution without adding additives, resulting in a poorer desolidification effect. That is, the solid content in the purified oil DQ4 was 360 μg / g, and the solid content in the residue was high, which could easily cause wear and tear on equipment and pipelines.

[0154] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for the settling separation of a solid-laden heavy oil, characterized by, The method comprises: (1) contacting the vacuum residue and a first solvent stream and performing extraction to obtain an extract phase containing deasphalted oil and a raffinate phase containing deoiled pitch; (2) mixing the solid-containing heavy oil and the raffinate phase as an auxiliary agent, heating, then extracting with a second solvent stream and performing settling separation to obtain an extract phase containing purified oil and a raffinate phase containing residue; (3) independently performing first solvent separation on the extract phase and the extract phase to obtain deasphalted oil and purified oil; (4) performing second solvent separation on the raffinate phase to obtain residue; wherein the solvent is divided into a first solvent stream and a second solvent stream in a weight ratio of 1-3:1-5; wherein the solvent is selected from at least one of n-butane, isopentane and n-pentane; wherein in step (1), the weight ratio of the vacuum residue and the first solvent stream is 1:2-4; the extraction conditions include a pressure of 3.5-6 MPa and a temperature of 30-240 ℃; wherein in step (2), the weight ratio of the solid-containing heavy oil and the auxiliary agent is 1-15:1; the solid content in the solid-containing heavy oil is ≤10 wt%; the heating temperature is equal to the settling separation temperature; the extraction and settling separation conditions each independently include a pressure of 3.5-6 MPa; the temperature is 1-80 ℃ higher than the extraction temperature; and the residence time is 5-20 min.

2. The method of claim 1, wherein, In step (1), the weight ratio of the vacuum residue and the first solvent stream is 1:2-3; the extraction conditions include a pressure of 4-5 MPa and a temperature of 40-200 ℃.

3. The method of claim 1, wherein, The distillation range of the vacuum residue is ≥520 ℃.

4. The method of claim 1, wherein, The distillation range of the vacuum residue is 520-850 ℃.

5. The method of claim 1, wherein, In step (2), the weight ratio of the solid-containing heavy oil and the auxiliary agent is 5-10:1; the solid content in the solid-containing heavy oil is 0.1-5 wt%; and the extraction and settling separation conditions each independently include a pressure of 4-5 MPa; the temperature is 5-30 ℃ higher than the extraction temperature; and the residence time is 8-12 min.

6. The method of claim 1, wherein, The solid-containing heavy oil is selected from at least one of a catalyst solid particle-containing hydroprocessing tail oil, a catalyst oil slurry without solid removal, coker gas oil and coal tar.

7. The method of claim 1, wherein, In step (3), the first solvent separation process comprises: (3-i) independently performing supercritical solvent recovery on the extract phase and the extract phase to obtain recovered solvent, deasphalted oil-rich material and purified oil-rich material; (3-ii) performing first stripping on the deasphalted oil-rich material to obtain the deasphalted oil and first stripping gas; (3-iii) performing second stripping on the purified oil-rich material to obtain the purified oil and second stripping gas.

8. The method of claim 7, wherein, The recovered solvent is returned and mixed into the solvent as a circulating solvent; and the first stripping gas and the second stripping gas are each independently cooled and returned and mixed into the solvent as a circulating solvent.

9. The method of claim 1, wherein, In step (4), the second solvent separation process comprises: performing third stripping on the raffinate phase to obtain third stripping gas and the residue.

10. The method of claim 9, wherein, The third stripping gas is cooled and returned and mixed into the solvent as a circulating solvent.

11. The use of the purified oil produced by the method of any one of claims 1-10 in low-sulfur marine fuel, needle coke raw material.

12. An apparatus for use in the method of settling separation of a solid-laden heavy oil as claimed in any one of claims 1 to 10, characterized in that, The device comprises an extraction column, a settling separation column, a first solvent separation unit and a second solvent separation unit; The extraction column is used to contact and extract the vacuum residue and the first solvent stream, and the extraction phase containing deasphalted oil is obtained at the top, and the raffinate phase containing deoiled pitch is obtained at the bottom; The settling separation column is connected to the bottom of the extraction column, and is used to mix and heat the raffinate phase and the solid heavy oil-containing mixture, and then extract and settle with the second solvent stream, and the extraction phase containing the purified oil is obtained at the top, and the raffinate phase containing the residue is obtained at the bottom; The first solvent separation unit is connected to the top of the extraction column and the settling separation column respectively, and is used to independently separate the extraction phase and the extraction phase with the first solvent respectively, to obtain deasphalted oil and purified oil; The second solvent separation unit is connected to the bottom of the settling separation column, and is used to separate the raffinate phase with the second solvent to obtain the residue; The solvent is divided into the first solvent stream and the second solvent stream.

13. The apparatus of claim 12, wherein, The first solvent separation unit comprises a supercritical solvent recovery column, a first stripping column and a second stripping column; The supercritical solvent recovery column is a packed column with a vertical partition, the vertical partition is connected to the bottom and the wall of the packed column, and is not connected to the top of the packed column, the vertical partition divides the inside of the packed column into a first solvent recovery zone and a second solvent recovery zone, which are used to independently recover the extraction phase and the extraction phase with the supercritical solvent respectively, and the recovered solvent is obtained at the top, and the deasphalted oil-rich material and the purified oil-rich material are obtained at the bottom respectively; The first stripping column is connected to the bottom of the first solvent recovery zone, and is used to first strip the deasphalted oil-rich material, and the first stripping gas is obtained at the top, and the deasphalted oil is obtained at the bottom; The second stripping column is connected to the bottom of the second solvent recovery zone, and is used to second strip the purified oil-rich material, and the second stripping gas is obtained at the top, and the purified oil is obtained at the bottom; And / or, the second solvent separation unit is selected from a third stripping column, which is used to third strip the raffinate phase, and the third stripping gas is obtained at the top, and the residue is obtained at the bottom.

14. The apparatus of claim 13, wherein, The top of the supercritical solvent recovery column is connected to the lower part of the extraction column and the settling separation column respectively, and is used to return and mix the recovered solvent into the solvent as a circulating solvent; And / or, the device further comprises a cooling unit connected to the first stripping column, the second stripping column, the extraction column and the settling separation column, which is used to independently cool the first stripping gas and the second stripping gas as a circulating solvent and mix them into the solvent; And / or, the cooling unit is also connected to the third stripping column, which is used to cool the third stripping gas as a circulating solvent and mix it into the solvent.

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