Residual oil pretreatment method, residual oil pretreatment device, residual oil processing method and residual oil processing system

Abstract

The invention relates to the technical field of residual oil processing, in particular to a residual oil pretreatment method, a residual oil pretreatment device, a residual oil processing method and a residual oil processing system. Cooling the obtained hydrothermal conversion reaction product or heavy components in the hydrothermal conversion reaction product, carrying out ultrasonic dispersion with a solvent, carrying out centrifugal separation on the obtained mixed slurry, and carrying out solvent recovery on the obtained filtrate to obtain pretreated residual oil and a recovered solvent; wherein the content of Ni in the residual oil is 10-200 [mu] g / g, and the content of V in the residual oil is 10-450 [mu] g / g. The method has the advantages that the residual oil raw material adaptability is high, and the metal removal rate is high; meanwhile, the pretreated residual oil is subjected to hydrofining, and a better hydrofining product can be obtained and can be used for producing alpha-olefin.

Description

Technical Field

[0001] The invention relates to the technical field of residual oil processing, and in particular to a residual oil pretreatment method and device thereof, a residual oil processing method and processing system thereof, and an application of a hydrorefined product obtained by the processing method. Background Art

[0002] In recent years, crude oil has become heavier and inferior, and the metal content in it has also shown an increasing trend year by year. Therefore, efficient demetallization of crude oil or heavy oil to meet the requirements of subsequent processing technology has become an inevitable trend and research hotspot.

[0003] CN114426866A discloses a method for removing metals from residual oil, which treats the residual oil by preheating and applying positive and negative electric fields, so that polar components such as colloids and asphaltene rich in metal impurities in the residual oil are aggregated, grown, and settled, and most of the metal impurities in the residual oil are removed, and finally a purified residual oil with a low metal content is obtained, thereby achieving the demetallization treatment of the residual oil. However, this method requires controlling the preheating temperature and preheating time within a certain range. However, due to the high aromatic content in the residual oil, when the pretreatment temperature is too high or the pretreatment time is too long, the residual oil is prone to coking, which seriously affects the quality of the residual oil; however, when the pretreatment temperature is too low or the pretreatment time is too short, the heavy components such as colloids and asphaltene in the residual oil have a large viscosity and are difficult to move, which affects the effect of the electrostatic agglomeration reaction.

[0004] CN113046116A discloses a method for hydrodemetallization of residual oil, which comprises: under hydrotreatment reaction conditions, the residual oil raw material is contacted with a hydrodemetallization catalyst I and a hydrodemetallization catalyst II in sequence for hydrogenation reaction to obtain a hydrogenated product; wherein the hydrodemetallization catalyst I adopts a zinc-modified alumina-based carrier I, and the hydrodemetallization catalyst II adopts a copper or copper and zinc-modified alumina-based carrier II. However, this method is only applicable to residual oil raw materials with a metal Ni content of less than 30 μg / g and a V content of less than 100 μg / g, and is not applicable to residual oil raw materials with high Ni and high V contents, that is, the method is not highly adaptable to residual oil raw materials. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of the existing residual oil pretreatment methods, such as the limitation of the metal content in the residual oil raw material, the low metal removal rate, the deactivation of the catalyst due to metal deposition during the pretreatment process, the short operation cycle of the device, etc., and to provide a residual oil pretreatment method and a device thereof, a residual oil processing method and a processing system thereof, and an application of a hydrorefining product obtained by the processing method. The method not only has strong adaptability to the residual oil raw material and a high metal removal rate, but also realizes the continuous operation of the residual oil pretreatment.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a method for pretreating residual oil, the method comprising: subjecting the residual oil to a hydrothermal conversion reaction in the presence of a first catalyst, cooling the obtained hydrothermal conversion reaction product or the heavy component in the hydrothermal conversion reaction product, ultrasonically dispersing the obtained mixed slurry with a solvent, centrifuging the obtained mixed slurry, recovering the solvent from the obtained filtrate, and obtaining the pretreated residual oil and the recovered solvent;

[0007] The Ni content in the residual oil is 10-200 μg / g, and the V content is 10-450 μg / g.

[0008] Preferably, the first catalyst is selected from an oil-soluble catalyst and / or a liquid homogeneous catalyst.

[0009] The second aspect of the present invention provides a residual oil pretreatment device, the device comprising: a hydrothermal conversion reaction unit, a cooling unit, an ultrasonic dispersion unit, a centrifugal separation unit and a solvent recovery unit connected in sequence;

[0010] The hydrothermal conversion reaction unit is used to carry out a hydrothermal conversion reaction on residual oil and hydrogen in the presence of a first catalyst to obtain a hydrothermal conversion reaction product; the cooling unit is used to cool the hydrothermal conversion reaction product or the heavy components in the thermal conversion reaction product to obtain a cooled material; the ultrasonic dispersion unit is used to mix the cooled material and a solvent to obtain a mixed slurry; the centrifugal separation unit is used to centrifugally separate the mixed slurry to obtain a filtrate and a metal residue; the solvent recovery unit is used to recover the solvent from the filtrate to obtain a pretreated residual oil and a recovered solvent.

[0011] The third aspect of the present invention provides a method for processing residual oil, which comprises: subjecting the pretreated residual oil obtained by the method provided by the first aspect to hydro-refining in the presence of a second catalyst to obtain a hydro-refining product.

[0012] The fourth aspect of the present invention provides a residual oil processing system, which comprises: the device provided in the second aspect, and a fixed bed reactor connected to the solvent recovery unit in the device, which is used to hydrotreat the pretreated residual oil in the presence of a second catalyst to obtain a hydrotreating product.

[0013] The fifth aspect of the present invention provides an application of the hydrogenated refined product obtained by the processing method provided in the third aspect in the preparation of α-olefins, preferably in the preparation of ethylene, propylene and butene.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] (1) The method provided by the present invention uses residual oil with a Ni content of 10-200 μg / g and a V content of 10-450 μg / g as a raw material, and sequentially adopts the technical means of hydrogen thermal conversion reaction, cooling, ultrasonic dispersion, centrifugal separation and solvent recovery, which not only effectively removes metals and asphaltene from the residual oil, but also has the characteristics of strong raw material adaptability; at the same time, the method also avoids the deactivation of the first catalyst due to metal deposition during the pretreatment process, shortens the operation cycle of the device, and realizes continuous operation;

[0016] (2) The method provided by the present invention also has the advantages of simple operation, simplified process, etc., and is convenient for industrial production;

[0017] (3) The pretreated residual oil obtained by the method provided by the present invention is further subjected to hydrorefining, which not only obtains a higher quality hydrorefining product, but also prolongs the operation cycle of the fixed bed hydrogenation unit; at the same time, the hydrorefining product is used to prepare α-olefins, especially ethylene, propylene, and butene. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The present invention provides a schematic diagram of the structure of a residual oil pretreatment device;

[0019] Figure 2 The present invention is a schematic structural diagram of a residual oil processing system.

[0020] Description of Reference Numerals

[0021] I, hydrogen thermal conversion reaction unit; II, cooling unit; III, ultrasonic dispersion unit; IV, centrifugal separation unit; V, solvent recovery unit; VI, fixed bed reactor;

[0022] 1. Residual oil; 2. Hydrogen; 3. First catalyst; 4. Hydrothermal conversion reaction product; 5. Cooled material; 6. Solvent; 7. Mixed slurry; 8. Filtrate; 9. Residual oil after pretreatment; 10. Recovered solvent; 11. Metal residue; 12. Hydrorefining product. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] In the present invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit the materials or steps, but are only used to distinguish or indicate that they are not the same material or step. For example, "first" and "second" in "first catalyst" and "second catalyst" are only used to indicate that they are not the same catalyst.

[0025] The first aspect of the present invention provides a method for pretreating residual oil, the method comprising: subjecting the residual oil to a hydrothermal conversion reaction in the presence of a first catalyst, cooling the obtained hydrothermal conversion reaction product or the heavy component in the hydrothermal conversion reaction product, ultrasonically dispersing the obtained mixed slurry with a solvent, centrifuging the obtained mixed slurry, recovering the solvent from the obtained filtrate, and obtaining the pretreated residual oil and the recovered solvent;

[0026] The Ni content in the residual oil is 10-200 μg / g, and the V content is 10-450 μg / g.

[0027] In the present invention, unless otherwise specified, Ni and V in the residual oil exist in the form of porphyrin compounds, mainly in asphaltene, and are prone to coking under high temperature conditions. Therefore, the residual oil is subjected to hydrogenation and in the presence of a liquid homogeneous first catalyst having high dispersibility, oil solubility and high affinity with asphaltene, while removing metals, and strengthening the lightness of asphaltene, which has the advantages of high metal removal rate and high yield of residual oil after pretreatment.

[0028] In some embodiments of the present invention, preferably, the Ni content in the residual oil is 20-150 μg / g, and the V content is 50-400 μg / g. In the present invention, the metal content (Ni and V) parameters are measured by the residual metal content (ICP method) method.

[0029] In some embodiments of the present invention, preferably, the physical property parameters of the residual oil also meet the following requirements: density ≥ 1 g / cm 3 , preferably 1-1.15 g / cm 3 ; Asphaltene content ≥ 10wt%, preferably 10-20wt%.

[0030] In the present invention, unless otherwise specified, density parameters are measured using the GB 13377 method; asphaltene content and colloid content parameters are measured using the "Determination of Four Components of Heavy Oil by Alumina Adsorption Method"; and distillation range parameters are measured using the "Determination of Boiling Range Distribution of Residue Oil Samples by High Temperature Gas Chromatography".

[0031] In the present invention, the type of the residual oil has a wide selection range, as long as the physical property parameters of the residual oil meet the above-mentioned limitations. Preferably, the residual oil is selected from at least one of atmospheric residual oil, vacuum residual oil, catalytic cracking slurry, coal tar, heavy oil and oil sands asphalt.

[0032] In the present invention, the hydrothermal conversion reaction is intended to remove the metals (Ni and V) in the residual oil from the porphyrin compounds. Preferably, the conditions of the hydrothermal conversion reaction include: a temperature of 350-460°C, preferably 380-440°C; a hydrogen partial pressure of 4-25MPa, preferably 5-20MPa; a volume space velocity of 0.1-2h -1 , preferably 0.2-0.5h -1 ; The first catalyst concentration is 50-2000μg / g, preferably 200-1000μg / g; the hydrogen-oil ratio is 100-2000Nm 3 / m 3 , preferably 200-1000Nm 3 / m 3 The hydrogen-to-oil ratio is equivalent to 1m 3 For residual oil, the amount of hydrogen is 100-2000Nm 3 , preferably 200-1000Nm 3 The use of optimal conditions is more conducive to the removal of metals from residual oil.

[0033] In some embodiments of the present invention, preferably, the first catalyst is selected from an oil-soluble catalyst and / or a liquid homogeneous catalyst.

[0034] In some embodiments of the present invention, preferably, the first catalyst is selected from compounds containing at least one element selected from Group VB metal elements, Group VIB metal elements and Group VIII metal elements, preferably selected from organic compounds containing at least one element selected from Group VB metal elements, Group VIB metal elements and Group VIII metal elements, more preferably selected from at least one of molybdenum-containing organic compounds, tungsten-containing organic compounds, nickel-containing organic compounds, cobalt-containing organic compounds, iron-containing organic compounds, vanadium-containing organic compounds and chromium-containing organic compounds.

[0035] In some embodiments of the present invention, more preferably, the first catalyst is selected from at least one of carbonyl molybdenum, carbonyl iron, molybdenum naphthenate, iron naphthenate, ethyl-molybdenum hexanoate, ethyl-nickel hexanoate and dialkyldithiocarbamate molybdenum.

[0036] In some embodiments of the present invention, preferably, the boiling point of the heavy components in the hydrogen thermal conversion reaction product is ≥350°C, for example, 350°C, 380°C, 400°C, 430°C, 450°C, 480°C, and any value in the range consisting of any two values, preferably 350-480°C.

[0037] In some embodiments of the present invention, preferably, the cooling temperature is ≤200°C, for example, 25°C, 40°C, 50°C, 60°C, 80°C, 100°C, 120°C, 150°C, 180°C, 200°C, and any value in the range consisting of any two values, preferably 25-150°C, more preferably 25-100°C, and most preferably 25-60°C.

[0038] In the present invention, the ultrasonic dispersion is intended to fully mix the hydrogen thermal conversion reaction product or the heavy components in the hydrogen thermal conversion reaction product with the solvent under the action of ultrasound after cooling, effectively reduce the viscosity of the mixed slurry, and make the metal residue (the component enriched with metal, the first catalyst and asphaltene) and the other components well dispersed, which is convenient for subsequent centrifugal separation. Preferably, the conditions of the ultrasonic dispersion include: ultrasonic frequency of 20-100kHz, for example, 20kHz, 40kHz, 50kHz, 60kHz, 80kHz, 100kHz, and any value in the range of any two values, preferably 40-80kHz; temperature of 25-100℃, preferably 25-60℃; time of 0.1-10h, preferably 0.1-5h.

[0039] In some embodiments of the present invention, preferably, the mass ratio of the hydrogen thermal conversion reaction product or the heavy component in the hydrogen thermal conversion reaction product to the solvent is 1:0.01-8, for example, 1:0.01, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:8, 1:10, and any value in the range of any two values, preferably 1:0.5-5. The mass ratio meeting the above range is more conducive to improving the metal removal rate.

[0040] In the present invention, the solvent is intended to dilute the demetallized residue in the hydrothermal conversion product and reduce the residue viscosity. Preferably, the solvent is selected from polar solvents and / or non-polar solvents, preferably polar solvents.

[0041] In some embodiments of the present invention, preferably, the solvent is selected from by-products of refinery processing equipment, such as aromatic compounds and / or petroleum fractions rich in aromatic compounds, preferably selected from at least one of naphtha, toluene, C9 aromatics, catalytic diesel and aromatic extracted oil.

[0042] In the present invention, the centrifugal separation method has a wide range of options, as long as the metal residue (components enriched in metal, first catalyst and asphaltene) removed from the residual oil in the mixed slurry can be effectively separated from the remaining components to obtain metal residue and filtrate.

[0043] In some embodiments of the present invention, preferably, the conditions for centrifugal separation include: a rotation speed of 1000-10000 rpm, preferably 3000-7000 rpm; a temperature of 25-100°C, preferably 25-60°C; and a time of 0.1-10 h, preferably 0.1-5 h.

[0044] In some embodiments of the present invention, it is further preferred that the centrifugal separation further obtains metal residues, wherein the metal residues refer to solid residues enriched with metal, the first catalyst and asphaltene components.

[0045] In the present invention, the conditions for the recovery of the solvent have a wide range of selection, as long as the recovered solvent in the filtrate and the pre-treated residual oil are separated. Preferably, the conditions for the recovery of the solvent include: a temperature of 50-350°C, preferably 80-200°C; a time of 0.2-2h, preferably 0.4-1h.

[0046] In the present invention, there is a wide range of options for the solvent recovery method. Preferably, the solvent recovery method includes but is not limited to flash evaporation, atmospheric distillation, reduced pressure distillation, etc.

[0047] In some embodiments of the present invention, preferably, the method further comprises: returning the recovered solvent as a circulating solvent and mixing it into the solvent.

[0048] The second aspect of the present invention provides a schematic diagram of the structure of a residual oil pretreatment device. Figure 1 As shown by Figure 1 It can be seen that the device comprises: a hydrogen thermal conversion reaction unit I, a cooling unit II, an ultrasonic dispersion unit III, a centrifugal separation unit IV and a solvent recovery unit V which are connected in sequence;

[0049] The hydrogen thermal conversion reaction unit I is used to carry out a hydrogen thermal conversion reaction on the residual oil 1 and hydrogen 2 in the presence of a first catalyst 3 to obtain a hydrogen thermal conversion reaction product 4; the cooling unit II is used to cool the hydrogen thermal conversion reaction product 4 or the heavy components in the thermal conversion reaction product 4 to obtain a cooled material 5; the ultrasonic dispersion unit III is used to mix the cooled material 5 and the solvent 6 to obtain a mixed slurry 7; the centrifugal separation unit IV is used to centrifugally separate the mixed slurry 7 to obtain a filtrate 8 and a metal residue 11; the solvent recovery unit V is used to recover the solvent from the filtrate 8 to obtain a pretreated residual oil 9 and a recovered solvent 10.

[0050] According to the present invention, preferably, Figure 1 As shown, the recovery solvent outlet of the solvent recovery unit V is connected to the solvent inlet of the ultrasonic dispersion unit III, so as to return the recovery solvent 10 as a circulating solvent and mix it into the solvent 6.

[0051] In the present invention, the hydrothermal conversion reaction unit I is selected from a slurry bed reactor.

[0052] The third aspect of the present invention provides a method for processing residual oil, which comprises: subjecting the pretreated residual oil obtained by the method provided by the first aspect to hydro-refining in the presence of a second catalyst to obtain a hydro-refining product.

[0053] In the present invention, the second catalyst is selected from a single catalyst or a combination of catalysts having functions such as hydrodemetallization, hydrodesulfurization, and hydrodenitrogenation, and the second catalyst is selected from a supported catalyst, and the active components include but are not limited to nickel, cobalt, manganese, etc.; the carrier includes but is not limited to metal oxides, molecular sieves, etc.

[0054] In the present invention, the hydrofining is intended to further remove metals from the pretreated residual oil to obtain high-quality hydrofining products. Preferably, the conditions of the hydrofining include: a temperature of 330-450°C, preferably 350-420°C; a hydrogen partial pressure of 6-25MPa, preferably 8-20MPa; a volume space velocity of 0.1-0.5h -1 , preferably 0.1-0.3h -1 ; Hydrogen to oil ratio is 200-2000Nm 3 / m 3 , preferably 500-1200Nm 3 / m 3 .

[0055] In some embodiments of the present invention, preferably, the hydrofining is carried out in a fixed bed reactor.

[0056] A fourth aspect of the present invention provides a schematic diagram of a residual oil processing system. Figure 2 As shown by Figure 2 It can be seen that the processing system includes: the device provided in the second aspect, and a fixed bed reactor VI connected to the solvent recovery unit V in the device, which is used to hydrotreat the pretreated residual oil 9 in the presence of a second catalyst to obtain a hydrotreating product 12.

[0057] The fifth aspect of the present invention provides an application of the hydrogenated refined product obtained by the processing method provided in the third aspect in the preparation of α-olefins, preferably in the preparation of ethylene, propylene and butene.

[0058] According to a particularly preferred embodiment of the present invention, a method for pretreating residual oil comprises: subjecting the residual oil to a hydrothermal conversion reaction in the presence of a first catalyst, cooling the obtained hydrothermal conversion reaction product or the heavy component in the hydrothermal conversion reaction product, ultrasonically dispersing the obtained mixed slurry with a solvent, centrifuging the obtained mixed slurry, recovering the solvent from the obtained filtrate, and obtaining the pretreated residual oil and the recovered solvent;

[0059] Wherein, the Ni content in the residual oil is 20-150 μg / g, and the V content is 50-400 μg / g;

[0060] Wherein, the first catalyst is selected from at least one of carbonyl molybdenum, carbonyl iron, molybdenum naphthenate, iron naphthenate, ethyl-molybdenum hexanoate, ethyl-nickel hexanoate and dialkyl dithiocarbamate molybdenum;

[0061] The conditions of ultrasonic dispersion include: ultrasonic frequency of 40-80kHz; temperature of 50-150°C; time of 0.1-5h;

[0062] The conditions of the hydrogen thermal conversion reaction include: temperature of 380-440°C; hydrogen partial pressure of 5-20 MPa; volume space velocity of 0.2-0.5 h -1 ; The first catalyst concentration is 200-1000μg / g; The hydrogen-oil ratio is 200-1000Nm 3 / m 3 ; The mass ratio of the hydrogen thermal conversion reaction product or the heavy component in the hydrogen thermal conversion reaction product to the solvent is 1:0.5-5; the solvent is selected from at least one of naphtha, toluene, C9 aromatics, catalytic diesel and aromatics extracted oil.

[0063] The present invention will be described in detail below through examples.

[0064] Calculation formula:

[0065]

[0066]

[0067]

[0068] Example 1

[0069] (1) Residue oil P1 (specific components are listed in Table 1) is subjected to a hydrothermal conversion reaction in the presence of a first catalyst (ethyl molybdenum hexanoate) to obtain a hydrothermal conversion reaction product; the conditions of the hydrothermal conversion reaction include: a temperature of 420° C.; a hydrogen partial pressure of 10 MPa; a volume space velocity of 0.33 h / min -1 ; The first catalyst concentration is 600μg / g; The hydrogen-oil ratio is 450Nm3 / m 3 ;

[0070] (2) cooling the above-mentioned hydrogen thermal conversion product to 50° C., and ultrasonically dispersing it with a solvent (toluene) at a mass ratio of 1:3, and centrifuging the obtained mixed slurry to obtain a metal residue and a filtrate;

[0071] The ultrasonic dispersion was carried out at an ultrasonic frequency of 40 kHz, a temperature of 50° C. and a time of 0.2 h; the centrifugal separation was carried out at a speed of 5000 rpm, a temperature of 50° C. and a time of 0.2 h;

[0072] (3) The filtrate was distilled to recover the solvent (temperature: 150° C., time: 0.5 h) to obtain a recovered solvent and pretreated residual oil S1, wherein the recovered solvent was returned as a circulating solvent and mixed into the solvent; the physical properties of the pretreated residual oil S1 are listed in Table 2.

[0073] Example 2

[0074] (1) Residue oil P1 (specific components are listed in Table 1) is subjected to a hydrothermal conversion reaction in the presence of a first catalyst (ethyl molybdenum hexanoate) to obtain a hydrothermal conversion reaction product; the conditions of the hydrothermal conversion reaction include: a temperature of 435° C.; a hydrogen partial pressure of 10 MPa; a volume space velocity of 1 h -1 ; The first catalyst concentration is 600μg / g; The hydrogen-oil ratio is 450Nm 3 / m 3 ;

[0075] (2) cooling the above-mentioned hydrothermal conversion product to 50° C., ultrasonically dispersing it with a solvent (C9 aromatic hydrocarbon) at a mass ratio of 1:3, and centrifuging the obtained mixed slurry to obtain a metal residue and a filtrate;

[0076] The ultrasonic dispersion was carried out at an ultrasonic frequency of 40 kHz, a temperature of 50° C. and a time of 0.2 h; the centrifugal separation was carried out at a speed of 5000 rpm, a temperature of 50° C. and a time of 0.2 h;

[0077] (3) The filtrate was distilled to recover the solvent (temperature: 150° C., time: 0.5 h) to obtain a recovered solvent and pretreated residual oil S2, wherein the recovered solvent was returned as a circulating solvent and mixed into the solvent; the physical properties of the pretreated residual oil S2 are listed in Table 2.

[0078] Example 3

[0079] The method of Example 1 is followed, except that in step (2),

[0080] The mass ratio of the hydrogen thermal conversion product and the solvent was replaced to 1:1, and the other conditions were the same to obtain the pretreated residue S3; the physical properties of the pretreated residue S3 are listed in Table 2.

[0081] Example 4

[0082] The method of Example 3 is followed, except that in step (2),

[0083] The type of solvent was replaced with catalytic diesel (specific composition see Table 1), and other conditions were the same to obtain pretreated residue S4; the physical properties of the pretreated residue S4 are listed in Table 2.

[0084] Example 5

[0085] The method of Example 3 is followed, except that in step (2),

[0086] The type of solvent was replaced with n-heptane, and the other conditions were the same to obtain the pretreated residue S5; the physical properties of the pretreated residue S5 are listed in Table 2.

[0087] Example 6

[0088] The method of Example 1 is followed, except that in step (2),

[0089] The ultrasonic frequency of ultrasonic dispersion was replaced with 20 Hz, and the other conditions were kept the same to obtain the pretreated residue S6. The physical properties of the pretreated residue S6 are listed in Table 2.

[0090] Example 7

[0091] The method of Example 1 is followed, except that in step (2),

[0092] The rotation speed of the centrifugal separation was replaced with 1000 rpm, and the other conditions were kept the same to obtain the pretreated residue oil S7; the physical properties of the pretreated residue oil S7 are listed in Table 2.

[0093] Example 8

[0094] According to the method of Example 1, except that in step (1), the type of residual oil is replaced by residual oil P2, the specific components of which are listed in Table 1; the heavy component (boiling point of 350-718° C.) in the hydrogen thermal conversion reaction product is ultrasonically dispersed with the solvent (toluene) at a mass ratio of 1:3;

[0095] The other conditions were the same, and the pretreated residue S8 was obtained; the physical properties of the pretreated residue S8 are listed in Table 2.

[0096] Comparative Example 1

[0097] The method of Example 1 is followed, except that in step (2),

[0098] The above-mentioned hydrogen thermal conversion product was cooled to 50°C, and solid-liquid separation was performed by filtering to obtain pretreated residual oil DS1; the physical properties of the pretreated residual oil DS1 are listed in Table 2.

[0099] Comparative Example 2

[0100] The method of Example 1 is followed, except that in step (2),

[0101] The above-mentioned hydrogen thermal conversion product was cooled to 50°C, and ultrasonic dispersion and centrifugal separation were performed in sequence to obtain the pretreated residual oil DS2; the physical properties of the pretreated residual oil DS2 are listed in Table 2.

[0102] Comparative Example 3

[0103] The method of Example 1 is followed, except that in step (2),

[0104] The mixed slurry was precipitated (temperature was 50°C, time was 5 h), and other conditions were the same to obtain the pretreated residual oil DS3; the physical properties of the pretreated residual oil DS3 are listed in Table 2.

[0105] Table 1

[0106]

[0107] Table 2

[0108]

[0109]

[0110] Table 2

[0111]

[0112] Table 2

[0113]

[0114] It can be seen from the data in Table 1-2 that the method provided by the present invention can effectively remove metals from residual oil, especially under preferred conditions, the metal removal rate is as high as 98.5%, so that the residual oil after pretreatment meets the feed demand for residual oil deep processing.

[0115] Compared with Example 1, Example 2 adopts different hydrothermal conversion process conditions (high temperature and short residence time) to carry out hydrothermal conversion reaction. Although the metal residue yield is low, the corresponding metal removal rate is also low. Compared with Example 1, Example 3 reduces the amount of solvent used, the metal residue yield is improved, and the corresponding metal removal rate is reduced.

[0116] Compared with Example 3, Example 4 uses catalytic diesel as the solvent, and the metal residue yield is slightly higher, and the corresponding metal removal rate is reduced; compared with Example 3, Example 5 uses a polar solvent n-heptane within the non-preferred range. Although the metal removal rate is slightly higher, the metal residue yield is also higher.

[0117] Compared with Comparative Examples 1 and 3, Example 1 uses ultrasonic dispersion and centrifugal separation, and the metal residue yield is lower and the demetallized oil yield is higher; compared with Comparative Example 2, Example 1 adds a solvent during the ultrasonic dispersion process, and the metal residue yield is lower, and the corresponding demetallization rate is higher.

[0118] Test Case

[0119] The pretreated residue S1 obtained in Example 1 is subjected to hydrorefining in the presence of a second catalyst (a supported catalyst, the active component is nickel, the carrier is alumina, and the nickel content is 10 wt%) to obtain a hydrorefining product P1; the residue P1 is directly subjected to hydrorefining in the presence of the second catalyst to obtain a hydrorefining product DP1;

[0120] The conditions for hydrofining include: temperature of 383°C; hydrogen partial pressure of 15.5 MPa; volumetric space velocity of 0.2 h -1 ; Hydrogen to oil ratio is 600Nm 3 / m 3 ;

[0121] Among them, the physical property parameters of the hydroprocessing product P1 and the hydroprocessing product DP1 are listed in Table 3.

[0122] Table 3

[0123] Product properties Hydrogenation product P1 Hydrorefined product DP1 <![CDATA[Density at 20°C, kg / m 3 > 882.8 916.9 <![CDATA[Viscosity at 100 °C, mm 2 / s]]> 3.54 17.65 Residual carbon, %(w) 1.14 4.47 Ni, mg / kg <0.1 5.9 V, mg / kg <0.1 8.6

[0124] It can be seen from the data in Table 3 that the hydrorefined product obtained by treating the residual oil with the processing method provided by the present invention has a low viscosity, low carbon residue and low metal content, which meets the requirements of the raw material for producing α-olefins.

[0125] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for pretreating residual oil, characterized in that: The method comprises: subjecting the residual oil to a hydrothermal conversion reaction in the presence of a first catalyst, cooling the obtained hydrothermal conversion reaction product or the heavy component in the hydrothermal conversion reaction product, ultrasonically dispersing the obtained mixed slurry with a solvent, centrifuging the obtained mixed slurry, recovering the solvent from the obtained filtrate, and obtaining the pretreated residual oil and the recovered solvent; The Ni content in the residual oil is 10-200 μg / g, and the V content is 10-450 μg / g.

2. The method according to claim 1, wherein: The Ni content in the residual oil is 20-150 μg / g, and the V content is 50-400 μg / g; And / or, the physical property parameters of the residual oil also meet the following requirements: density ≥ 1 g / cm 3 , preferably 1-1.15 g / cm 3 ; Asphaltene content ≥ 10wt%, preferably 10-20wt%; And / or, the residual oil is selected from at least one of atmospheric residual oil, vacuum residual oil, catalytic cracking slurry, coal tar, heavy oil and oil sand bitumen.

3. The method according to claim 1 or 2, wherein: The conditions of the hydrogen thermal conversion reaction include: temperature of 350-460°C, preferably 380-440°C; hydrogen partial pressure of 4-25MPa, preferably 5-20MPa; volume space velocity of 0.1-2h -1 , preferably 0.2-0.5h -1 ; The first catalyst concentration is 50-2000μg / g, preferably 200-1000μg / g; the hydrogen-oil ratio is 100-2000Nm 3 / m 3 , preferably 200-1000Nm 3 / m 3 ; and / or, the first catalyst is selected from an oil-soluble catalyst and / or a liquid homogeneous catalyst; and / or, the first catalyst is selected from compounds containing at least one element selected from Group VB metal elements, Group VIB metal elements and Group VIII metal elements, preferably selected from organic compounds containing at least one element selected from Group VB metal elements, Group VIB metal elements and Group VIII metal elements, more preferably selected from at least one of molybdenum-containing organic compounds, tungsten-containing organic compounds, nickel-containing organic compounds, cobalt-containing organic compounds, iron-containing organic compounds, vanadium-containing organic compounds and chromium-containing organic compounds; Further preferably, the first catalyst is selected from at least one of carbonyl molybdenum, carbonyl iron, molybdenum naphthenate, iron naphthenate, ethyl-molybdenum hexanoate, ethyl-nickel hexanoate and dialkyl dithiocarbamate molybdenum; And / or, the boiling point of the heavy components in the hydrothermal conversion reaction product is ≥350°C, preferably 350-480°C.

4. The method according to any one of claims 1 to 3, wherein: The cooling temperature is ≤200°C, preferably 25-150°C, more preferably 25-100°C; And / or, the conditions of ultrasonic dispersion include: ultrasonic frequency of 20-100 kHz, preferably 40-80 kHz; temperature of 25-200° C., preferably 50-150° C.; time of 0.1-10 h, preferably 0.1-5 h; and / or, the mass ratio of the hydrothermal conversion reaction product or the heavy component in the hydrothermal conversion reaction product to the solvent is 1:0.01-8, preferably 1:0.5-5; and / or, the solvent is selected from polar solvents and / or non-polar solvents, preferably selected from polar solvents; And / or, the solvent is selected from at least one of naphtha, toluene, C9 aromatics, catalytic diesel and aromatics extracted oil.

5. The method according to any one of claims 1 to 4, wherein: The centrifugal separation conditions include: a rotation speed of 1000-10000 rpm, preferably 3000-7000 rpm; a temperature of 25-150° C., preferably 25-100° C.; a time of 0.1-10 h, preferably 0.1-5 h; And / or, the centrifugal separation also obtains metal residue.

6. The method according to any one of claims 1 to 5, wherein: The conditions for solvent recovery include: temperature of 50-350°C, preferably 80-200°C; time of 0.2-2h, preferably 0.4-1h; And / or, the method further comprises: returning the recovered solvent as a circulating solvent and mixing it into the solvent.

7. A device for pre-treating residual oil, characterized in that: The device comprises: a hydrogen thermal conversion reaction unit, a cooling unit, an ultrasonic dispersion unit, a centrifugal separation unit and a solvent recovery unit which are connected in sequence; The hydrothermal conversion reaction unit is used to carry out a hydrothermal conversion reaction on residual oil and hydrogen in the presence of a first catalyst to obtain a hydrothermal conversion reaction product; the cooling unit is used to cool the hydrothermal conversion reaction product or the heavy components in the thermal conversion reaction product to obtain a cooled material; the ultrasonic dispersion unit is used to mix the cooled material and a solvent to obtain a mixed slurry; the centrifugal separation unit is used to centrifugally separate the mixed slurry to obtain a filtrate and a metal residue; the solvent recovery unit is used to recover the solvent from the filtrate to obtain a pretreated residual oil and a recovered solvent.

8. The device according to claim 7, wherein: The recovered solvent outlet of the solvent recovery unit is connected to the solvent inlet of the ultrasonic dispersion unit for returning the recovered solvent as a circulating solvent and mixing it into the solvent.

9. A method for processing residual oil, characterized in that: The processing method comprises: subjecting the pretreated residual oil obtained by the method according to any one of claims 1 to 6 to hydrofining in the presence of a second catalyst to obtain a hydrofining product.

10. The processing method according to claim 9, wherein: The conditions of the hydrofining include: temperature of 330-450°C, preferably 350-420°C; hydrogen partial pressure of 6-25MPa, preferably 8-20MPa; volume space velocity of 0.1-0.5h -1 , preferably 0.1-0.3h -1 ; Hydrogen to oil ratio is 200-2000Nm 3 / m 3 , preferably 500-1200Nm 3 / m 3 ; And / or, the hydrofining is carried out in a fixed bed reactor.

11. A residual oil processing system, characterized in that: The processing system comprises the device according to claim 7 or 8, and a fixed bed reactor connected to a solvent recovery unit in the device, for hydrotreating the pretreated residual oil in the presence of a second catalyst to obtain a hydrotreating product.

12. Use of the hydrorefined product obtained by the processing method according to claim 9 or 10 in the preparation of α-olefins, preferably in the preparation of ethylene, propylene and butene.

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