CN111849549B

CN111849549B - Method for treating light oil in slurry bed

Info

Publication number: CN111849549B
Application number: CN201910363284.3A
Authority: CN
Inventors: 任亮; 梁家林; 张毓莹; 许双辰; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-04-30
Filing date: 2019-04-30
Publication date: 2022-02-08
Anticipated expiration: 2039-04-30
Also published as: CN111849549A

Abstract

The invention relates to the technical field of oil refining, and discloses a method for treating light oil in a slurry bed. The method comprises the steps of mixing light oil in a slurry bed with hydrogen, reacting in a first hydrofining reaction zone, carrying out reverse contact reaction on the obtained first liquid phase material flow and the hydrogen in a second hydrofining reaction zone, and fractionating the obtained second liquid phase material flow to obtain a light naphtha product, a heavy naphtha product and a diesel product. The method of the invention can obtain products with excellent quality, reduce the reaction severity and prolong the running period of the device.

Description

Method for treating light oil in slurry bed

Technical Field

The invention relates to the technical field of oil refining, in particular to a method for treating light oil in a slurry bed.

Background

With the continuous exploitation and use of petroleum resources, the trend of deterioration and heaviness of petroleum resources is increasing, and how to develop and utilize heavy oil resources is an important topic of petrochemical industry.

CN104560174B discloses a method for heavy oil hydroconversion. The method comprises a hydrocracking system, a hydrocracking system and a hydrotreating system: heavy oil is firstly subjected to a hydro-thermal cracking reaction in a first reactor; separating the reaction product into light distillate oil, heavy distillate oil and residual oil; wherein, the residual oil, the hydrocracking catalyst and the hydrogen enter a second reactor to further carry out hydrocracking reaction; the heavy distillate oil and hydrogen enter a hydrocracking reactor, contact with a hydrocracking catalyst, and undergo a hydrocracking reaction under a hydrocracking condition to obtain light oil; and the light distillate oil and hydrogen enter a hydrofining reactor, contact with a hydrofining catalyst and react to obtain the hydrofined light distillate oil. The method can improve the conversion rate of heavy oil and the yield of light oil, and can obtain gasoline and diesel oil products with excellent performance.

CN103059915B discloses a hydro-upgrading method of inferior heavy oil, which comprises contacting the inferior heavy oil, heavy distillate oil, hydro-upgrading catalyst with hydrogen, wherein the hydro-upgrading catalyst contains 2-15 wt% of metal elements and 85-98 wt% of non-metal elements, more than 95 wt% of the metal elements are V, Ni and lanthanide series metal elements and/or VIB group metal elements; more than 95 weight percent of the nonmetal elements are C and S, at least part of the S and the metal elements exist in the form of sulfides of the metal elements, the heavy fraction oil is the residual part after separating a light fraction from a product obtained by hydro-upgrading of the inferior heavy oil, and the distillation temperature of the light fraction is lower than 500 ℃; the hydro-upgrading method has better hydro-upgrading effect by using the hydro-upgrading catalyst, can improve the conversion rate of raw oil and the yield of light oil, and reduces the yield of coke.

CN107629816A discloses a heavy oil hydrogenation method, which adopts an on-line hydrogenation combined process of a boiling bed and a fixed bed, light oil obtained by hydrogenation of the boiling bed directly enters the fixed bed reactor for hydrogenation reaction without the processes of temperature reduction, pressure reduction and fractionation, thereby avoiding the defect of complex process caused by the conventional off-line hydrogenation combined process that product depressurization separation is carried out first and then pressure rise and temperature rise hydrogenation is carried out, and simultaneously reducing the number of devices in the process flow and reducing energy loss; meanwhile, the method also has the advantages of high light oil yield, low catalyst consumption, reasonable energy utilization and low device energy consumption.

CN103789036B discloses a poor-quality heavy oil combined processing method, which comprises the following steps: a. the heavy oil raw material enters a liquid phase fluidized bed reactor, and is subjected to hydrocracking reaction under the action of hydrogen and a dispersed hydrocracking catalyst; b. fractionating the obtained hydrogenation product to obtain light oil and heavy oil, wherein the cutting point is 320-380 ℃, and the light oil is led out of the device; c. performing solvent extraction on the heavy oil obtained by fractionation to obtain deasphalted oil and deoiled asphalt; d. wherein the deasphalted oil is contacted with a catalytic cracking catalyst, the cracking reaction is carried out under the catalytic cracking condition, and light oil, heavy cycle oil and oil slurry are obtained by fractionation; e. and (c) recycling the deoiled asphalt obtained in the step (c) to the liquid phase flow bed reactor in the step (a). The method integrates various processes to treat the inferior heavy oil, not only can realize the full conversion of the heavy oil, but also can obtain more gasoline and diesel oil with excellent performance.

The slurry bed process technology can convert inferior residual oil and heavy oil into naphtha, diesel oil and wax oil, and improves the utilization rate of resources. However, the properties of the distillate products produced by the slurry bed technology are inferior, and further processing is needed to obtain qualified products. In the prior art, diesel oil is produced by treating light oil in a slurry bed through a hydrofining technology, but the naphtha and the diesel oil in the slurry bed have high sulfur and nitrogen contents, most of sulfides and nitrides in the naphtha and the diesel oil are macromolecular low-activity compounds, so that the removal difficulty is high, the reaction conditions are severe, and the diesel oil product cannot meet the clean diesel oil standard of China VI and can only be used as a blending component of the diesel oil.

Disclosure of Invention

The present invention has been made to overcome the problems of the prior art and an object of the present invention is to provide a method for treating light oil in a slurry bed, which can make reasonable use of light oil in a slurry bed to obtain products of excellent quality, and at the same time, can reduce the severity of the reaction and prolong the operating period of the apparatus.

In order to achieve the above object, the present invention provides a method of treating slurry bed light oil, the method comprising:

(1) mixing light oil of the slurry bed with hydrogen, and reacting in a first hydrofining reaction zone to obtain a first reaction effluent;

(2) carrying out gas-liquid separation on the first reaction effluent to obtain a first gas phase material flow and a first liquid phase material flow;

(3) carrying out reverse contact reaction on the first liquid phase material flow and hydrogen in a second hydrofining reaction area to obtain a second reaction effluent;

(4) carrying out gas-liquid separation on the second reaction effluent to obtain a second gas-phase material flow and a second liquid-phase material flow;

(5) desulfurizing the first gas-phase material flow and the second gas-phase material flow, and recycling hydrogen obtained after desulfurization to the step (1) and/or the step (3);

(6) fractionating the second liquid phase stream to obtain a light naphtha product, a heavy naphtha product, and a diesel product.

Compared with the prior art, the method provided by the invention has the following advantages:

(1) the product quality is excellent. The process of the present invention enables the production of light naphtha products, heavy naphtha products and clean diesel products from slurry bed light oils. The heavy naphtha product can be used as a reforming raw material with high aromatic hydrocarbon potential, the light naphtha product can be used as a high-quality steam cracking raw material, and the diesel oil product can be used as clean diesel oil in China VI.

(2) The reaction activity of the compound difficult to desulfurize and denitrify is obviously improved, thereby reducing the reaction severity.

(3) The method also enables a significant extension of the run length.

Drawings

FIG. 1 is a schematic process flow diagram according to a preferred embodiment of the present invention;

FIG. 2 is a schematic representation of the process flow used in comparative example 1 of the present invention.

Description of the reference numerals

1-slurry bed light oil 2-fresh hydrogen

3-first hydrofining reaction zone 4-second hydrofining reaction zone

5-gas-liquid separation tank 6-recycle hydrogen desulfurization system

7-high pressure separator 8-Low pressure separator

9-fractionating column 10-low partial gas

11-overhead gas 12-light naphtha product

13-heavy naphtha product 14-diesel product

15-recycle hydrogen 16-first gas phase stream

17-second gas phase stream 18-second liquid phase stream

19-first liquid phase stream

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a method for treating light oil in a slurry bed, which comprises the following steps:

In the present invention, the slurry bed light oil refers to light oil fractions having an end point of 400 ℃ or lower obtained by subjecting a liquid product obtained in a slurry bed unit to atmospheric and vacuum fractionation, and includes naphtha fractions and diesel fractions. The raw material of the slurry state unit can be atmospheric residue, vacuum residue and coalHeavy materials such as tar, direct coal liquefaction oil, ethylene tar, shale oil, heavy oil and biomass heavy oil. The processing of the slurry bed unit may be carried out according to the method in CN103059915B or CN104560170B, but the present invention is not limited to this method. Preferably, the distillation range of the light oil in the slurry bed is 50-400 ℃, and the density is 0.75-0.88g/cm³The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%. In the present invention, the distillation range is measured by ASTM D-86.

The research finds that the slurry bed light oil has the following characteristics: (1) the nitrogen content is ultrahigh and is as high as more than 1000 mug/g, and part of light oil exceeds 2500 mug/g, which is obviously different from the knowledge and processing experience of common diesel oil fractions and has little referential experience; (2) the heteroatom content such as sulfur and nitrogen is high, and the molecular reactivity such as sulfur, nitride and the like with steric hindrance is low; (3) the nitrogen content of naphtha fraction in light oil is ultrahigh, and the conventional low-pressure reforming pre-hydrogenation device is difficult to treat; (4) the diesel oil fraction in the light oil has high density, high aromatic hydrocarbon content and low cetane number.

According to the conventional diesel hydrodenitrogenation reaction law: firstly, high-content organic nitrogen molecules in diesel oil compete and are adsorbed on an active center of a catalyst, so that ultra-deep desulfurization (HDS) reaction and hydrogenation saturation reaction of aromatic hydrocarbon are inhibited; secondly, under the condition of lower hydrogen partial pressure, nitrides can be adsorbed on the acid center on the surface of the catalyst, thereby accelerating the carbon deposition inactivation of the catalyst, reducing the reaction activity of hydrodesulfurization and hydrodenitrogenation and shortening the running period.

The inventors of the present invention have found, through studies, that it is difficult to remove the sulfur content to a very low level, particularly to remove both the sulfur content and the nitrogen content of the naphtha fraction to below 0.5 μ g/g, and to maintain a stable operation for a long period of time, using conventional hydrofinishing processes and catalysts. While sulfur content in diesel fractions can be removed to below 10 μ g/g using conventional hydrofinishing processes and catalysts, long cycle operation is a significant challenge.

In the present invention, the hydrogen gas in step (1) may be recycled hydrogen gas obtained in step (5) and/or supplemented fresh hydrogen gas.

In the present invention, the hydrogen gas in step (3) comprises the recycle hydrogen gas obtained in step (5) and the fresh hydrogen gas for replenishment, and the inventors have found in the research that, in step (3), the second hydrofining reaction zone is set to be in reverse contact, and the fresh hydrogen gas is replenished into the hydrogen gas, so that the reaction in the second hydrofining reaction zone can be significantly promoted, thereby improving the quality of the final product. In the present invention, the countercurrent contact reaction of the first liquid-phase stream with hydrogen can be achieved by feeding hydrogen from the bottom of the second hydrofining reaction zone and feeding the first liquid-phase stream from the top of the second hydrofining reaction zone.

According to the present invention, in the step (3), the temperature of the introduced hydrogen is the same as the reaction temperature of the first hydrofining reaction zone, and preferably the temperature of the introduced hydrogen is 50 to 200 ℃ lower than the reaction temperature of the first hydrofining reaction zone, preferably 100 to 200 ℃ lower. Due to the existence of temperature rise, the temperature of each bed layer is generally gradually raised along the direction of liquid phase material flow, and after low-temperature hydrogen is introduced in a countercurrent manner, the temperature rise along the direction of the liquid phase material flow is reduced, even the temperature is distributed isothermally, so that the reduction of the aromatic hydrocarbon saturation rate caused by the limitation of thermodynamic equilibrium at the end stage of operation can be avoided or reduced; in the second aspect, the temperature raising space can be increased, and the operation period can be prolonged.

In the present invention, the gas-liquid separation in the step (2) and the step (4) may be performed in a gas-liquid separation tank, which may be a flash tank, or a fractionation column, which is conventional in the art. The skilled person can select suitable gas-liquid separation device and separation operation conditions according to the needs, and the invention is not limited herein.

In the present invention, preferably, the conditions of the reaction in the first hydrofinishing zone comprise: the hydrogen partial pressure is 8.0-14.0MPa, preferably 8.5-14.0 MPa; the reaction temperature is 300-450 ℃, preferably 350-430 ℃; the volume ratio of the hydrogen to the oil is 500-1500, preferably 500-1200; the liquid hourly space velocity is 0.5-4.0h^-1Preferably 0.5 to 2.0h^-1。

Preferably, the reaction conditions of the second hydrofinishing reaction zone include: the hydrogen partial pressure is 8.0-14.0MPa, preferably 8.3-14.0 MPa; the reaction temperature is 300 ℃ and 450 DEG CPreferably 350-430 ℃; the volume ratio of the hydrogen to the oil is 300-1500, preferably 300-800; the liquid hourly space velocity is 0.5-4.0h^-1Preferably 2.0-4.0h^-1。

In the present invention, the first hydrofining reaction zone or the second hydrofining reaction zone can be reacted at a lower temperature, thereby reducing the severity of the reaction. Preferably, the difference between the reaction temperature of the first hydrofining reaction zone and the reaction temperature of the second hydrofining reaction zone is 0.1 to 30 ℃, preferably 10 to 30 ℃.

According to a preferred embodiment of the present invention, the reaction temperature of the first hydrofining reaction zone is 380 ℃ or less, and the reaction temperature of the second hydrofining reaction zone is 0.1 to 30 ℃, preferably 10 to 30 ℃ higher than the temperature of the first hydrofining reaction zone.

According to another preferred embodiment of the present invention, the reaction temperature of the first hydrofinishing reaction zone is >380 ℃ and the reaction temperature of the second hydrofinishing reaction zone is 0.1 to 30 ℃, preferably 10 to 30 ℃ lower than the temperature of the first hydrofinishing reaction zone.

In the present invention, the first and second hydrofining reaction zones contain a hydrofining catalyst, respectively, and the catalysts in the two hydrofining reaction zones may be the same or different. The hydrofinishing catalyst is commercially available and can also be synthesized according to the methods provided by the present invention. Preferably, the first hydrofinishing reaction zone and/or the second hydrofinishing reaction zone contain a high activity hydrofinishing catalyst; the high-activity hydrofining catalyst contains an inorganic refractory component, a hydrodesulfurization catalytic active component, alcohol and carboxylic acid; wherein the inorganic refractory component contains at least one of silica, magnesia, calcia, zirconia and titania and a part of the hydrodesulfurization catalytic active component; the high-activity hydrofining catalyst has a pore diameter of 2-40nm and a pore diameter of 100-300nm, wherein the pore volume of the pore diameter of 2-40nm accounts for 60-95% of the total pore volume, and the pore volume of 100-300nm accounts for 0.5-30% of the total pore volume.

The inventors of the present invention have found that introduction of an alcohol, preferably an organic alcohol compound, into a hydrorefining catalyst can effectively protect active components in the catalyst, and introduction of a carboxylic acid compound into the hydrorefining catalyst can improve the activity of the catalyst, and can also exert a synergistic effect when both are present. Therefore, it is possible to protect the catalyst active component and to improve the catalyst activity by introducing an alcohol and a carboxylic acid in a weight ratio of the number of moles of the alcohol to the dry basis weight of the inorganic refractory component of 0.005 to 0.03: 1, preferably 0.01 to 0.02: 1; the weight ratio of the carboxylic acid to the inorganic refractory component on a dry basis is from 0.002 to 0.1, preferably from 0.02 to 0.06.

Preferably, the alcohol is selected from at least one of C1-18 monohydric alcohols, preferably C1-10 monohydric alcohols (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 monohydric alcohols) (such as but not limited to methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol), ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, and trimethylolethane.

Preferably, the carboxylic acid is selected from at least one of C1-18 monobasic saturated carboxylic acids (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 monobasic saturated carboxylic acids) (e.g., but not limited to, formic acid, acetic acid, propionic acid, octanoic acid, valeric acid, hexanoic acid, decanoic acid, pentanoic acid), C7-10 phenyl acids (e.g., C7, C8, C9, C10 phenyl acids) (e.g., but not limited to, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid), citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and the like.

According to a preferred embodiment of the present invention, in order to further improve the performance of the high-activity hydrorefining catalyst, the high-activity hydrorefining catalyst further contains a phosphorus element, preferably P₂O₅Exist in the form of (1). Preferably, based on the dry weight of the high activity hydrofinishing catalyst and on P₂O₅The content of the phosphorus element is 0.8 to 10% by weight, more preferably 1 to 8% by weight.

According to the present invention, preferably, the high-activity hydrofining catalyst is a shaped catalyst, and the shape of the high-activity hydrofining catalyst is preferably a cylinder, a cloverleaf, a clover or a honeycomb.

The pore channel structures of the high-activity hydrofining catalyst are respectively concentrated between 2-40nm and 100-300 nm. The pore canal with the size of 100-300nm in the high-activity hydrofining catalyst can provide a sufficient place for the diffusion of reactants, and promotes the accessibility of the reactants and an active center, thereby improving the performance of the catalyst.

In the course of research, the inventors of the present invention found that the carrier of the hydrorefining catalyst is usually obtained by extruding a carrier precursor (such as pseudo-boehmite powder) with a peptizing agent and an extrusion aid to form a strip, and then drying and calcining the strip. Since the hydrorefining reaction requires a catalyst with a larger pore structure, and before calcination, the pores are generally concentrated at 2-12nm, so that the pore size of the catalyst is generally increased by calcining the molded carrier to increase the pore size of the carrier, the pores of the calcined carrier are generally concentrated at 2-100nm, the average pore size of the carrier is increased, and it is generally considered that the pore size is larger as the calcination temperature is higher. However, the inventors of the present invention found in their studies that collapse condensation occurs in the pore walls of the carrier with an increase in the calcination temperature. Although pore wall condensation may increase the average pore size of the support, the condensed pore walls may reduce the utilization of alumina, thereby reducing the catalytic activity of the catalyst. According to the preparation method of the hydrofining catalyst, the precursor of the carrier is preferably roasted before extrusion molding, so that on one hand, the number of hydroxyl groups in the precursor particles of the carrier can be reduced through heat treatment, the probability of channel condensation is reduced, and the aperture of the hydrofining catalyst is increased. In the second aspect, the formed hydrofining catalyst does not need to be processed at a higher temperature, and the pore wall of the carrier does not need to be subjected to excessive condensation, so that the utilization rate of the carrier is improved. In the third aspect, the carrier precursor is subjected to heat treatment before molding, and partial secondary particles are also condensed, so that the size of the formed alumina particles tends to be single, and the pore channels in the molded hydrofining catalyst are more uniform, which is beneficial to the diffusion of reactants. Especially for heavier and inferior oil products, the catalyst is more effective than the conventional hydrofining catalyst.

The inventor of the present invention has found that the hydrofining catalyst prepared by the conventional impregnation method has a low metal loading, the content of the group VIII metal is usually less than 10%, and the content of the group VIB metal is usually less than 35%. This limits the number of active metal sites of the hydrofinishing catalyst, which do not reach higher levels of activity. The hydrofining catalyst prepared by the kneading method can improve the loading capacity of active metal in the hydrofining catalyst, but the hydrofining activity of the catalyst is not high, and the utilization rate of the active metal is low. Currently, hydrofinishing catalysts are generally not prepared by this method. In the present invention, a portion of the hydrodesulfurization catalytically active component, and more preferably a portion of the group VIII metal, is mixed into a support precursor and calcined to form the inorganic refractory powder. And then mixing the impregnation liquid containing the residual active metal with the inorganic refractory powder, thereby improving the content of the active components in the hydrofining catalyst and further improving the hydrofining performance of the catalyst.

In a preferred aspect, the high-activity hydrorefining catalyst of the present invention comprises an inorganic refractory component containing at least one of silica, magnesia, calcia, zirconia and titania and a part of the group VIII metal element, a group VIB metal element, an organic acid and an alcohol, wherein the content of the inorganic refractory component is not more than 40%.

In addition, the highly active hydrorefining catalyst of the present invention may contain no pore-expanding agent such as carbon black, graphite, stearic acid, sodium stearate, aluminum stearate, or may contain no component such as a surfactant, and thus the demand for reactivity is directly satisfied.

The silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide contained in the inorganic refractory component are basically inert substances and are difficult to combine with the VIII family element to form a compound with a stable structure, so that the utilization rate of the VIII family element is improved. In addition, the inorganic refractory components have weak acting force with other active components of the hydrofining catalyst, so that the growth of an active phase of the hydrofining catalyst can be promoted, and the performance of the hydrofining catalyst is further promoted.

Preferably, in the high-activity hydrofining catalyst, the pore volume with the pore diameter of 2-40nm accounts for 75-90% of the total pore volume, and the pore volume with the pore diameter of 100-300nm accounts for 5-15% of the total pore volume. Wherein the pore volume of pores with a diameter of 2-4nm is not more than 10% of the total pore volume.

According to the invention, the specific surface area, the pore distribution, the pore diameter and the pore volume of the high-activity hydrofining catalyst are measured by a low-temperature nitrogen adsorption method (meeting the GB/T5816-1995 standard), and the pore distribution, the pore diameter and the pore volume of the high-activity hydrofining catalyst are measured by a mercury intrusion method at 100-300 nm. The pore volume of the high-activity hydrofining catalyst with the pore diameter smaller than 100nm is determined by adopting a low-temperature nitrogen adsorption method, the pore volume of the high-activity hydrofining catalyst with the pore diameter larger than 100nm is determined by adopting a mercury intrusion method, and the pore volume of the high-activity hydrofining catalyst is the sum of the pore volume and the pore volume; the average pore diameter was calculated according to the cylindrical pore model (average pore diameter ═ total pore volume × 4000/specific surface area).

Preferably, the high-activity hydrofining catalyst has a specific surface area of 70-200m²A/g, preferably from 90 to 180m²Pore volume of 0.15 to 0.6mL/g, preferably 0.2 to 0.4mL/g, and average pore diameter of 5 to 25nm, preferably 8 to 15 nm. The specific surface area, pore volume and average pore diameter are measured after the high-activity hydrogen purification catalyst is calcined at 400 ℃ for 3 hours.

According to the invention, the pore diameter of 2-40nm means a pore diameter of 2nm or more and less than 40nm, and the pore diameter of 100-300nm means a pore diameter of 100nm or more and less than 300nm, unless otherwise stated. The average pore diameter of 5 to 25nm means that the average of the pore diameters of all pores of the high-activity hydrorefining catalyst is not less than 5nm and not more than 25 nm. The pore diameter of 2-4nm is larger than or equal to 2nm and smaller than 4 nm.

According to the invention, the hydrodesulphurization catalytically active component may be a component of an active component that is currently available for hydrofinishing catalysts, for example, the active component may comprise elements of group VIII metals and elements of group VIB metals. Wherein the content of the active component can also vary within wide limits, preferably, in the highly active hydrorefining catalyst, the content of the group VIII metal element is 15 to 35 wt.%, preferably 20 to 30 wt.%, calculated as oxide and based on the dry weight of the catalyst; the content of group VIB metal elements is from 35 to 75% by weight, preferably from 40 to 65% by weight.

According to a preferred embodiment of the present invention, the group VIII metal element is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, and the group VIB metal element is selected from at least one of chromium, molybdenum and tungsten.

The inventors of the present invention have found in their studies that, by preferably including a part of the group VIII metal element in the inorganic refractory component, the content of the active component in the highly active hydrorefining catalyst can be further increased, thereby further improving the hydrorefining performance of the catalyst. The amount ratio of the group VIII metal element contained in the inorganic refractory component is not particularly limited and may be selected from a wide range, and preferably, the content of the partial group VIII metal element is 60 to 90% of the total content of the group VIII metal elements.

According to the present invention, the inorganic refractory component is preferably present in an amount of 5 to 40 wt.%, more preferably 10 to 30 wt.%, based on the dry weight of the high activity hydrofinishing catalyst.

Here, the dry weight of the inorganic refractory powder is a weight measured by calcining a sample at 600 ℃ for 4 hours, and the dry weight of the high-activity hydrorefining catalyst is a weight measured by calcining a sample at 400 ℃ for 3 hours. The dry basis weights appearing hereinafter are equally applicable to this definition. That is, in the absence of a contrary indication, the dry weight of the inorganic refractory powder as described herein is the weight determined by calcining the sample at 600 ℃ for 4 hours and the dry weight of the high activity hydrofinishing catalyst is determined by calcining the sample at 400 ℃ for 3 hours. It will be appreciated by those skilled in the art that the alcohol and organic acid contained in the high activity hydrofinishing catalyst will decompose and volatilize at high temperatures when calculated on a dry weight basis, and therefore the alcohol and organic acid content is not calculated on a dry weight basis.

In the present invention, the high-activity hydrorefining catalyst can be prepared by the following method:

(1) mixing and roasting a precursor containing at least one of silicon oxide, magnesium oxide, calcium oxide, zirconium oxide and titanium oxide and a precursor of a part of hydrodesulfurization catalytic active component to obtain an inorganic refractory component;

(2) mixing alcohol, carboxylic acid and the precursor of the residual hydrodesulfurization catalytic active component to obtain impregnation liquid;

(3) and mixing the inorganic refractory component with the impregnation liquid, and molding and drying the obtained mixture to obtain the high-activity hydrofining catalyst.

According to the invention, the precursors of the hydrodesulfurization catalytic active components are preferably precursors of group VIII metal elements and of group VIB metal elements; the precursors of the VIII group metal elements and the VIB group metal elements are used in amounts which are based on the dry weight of the catalyst and calculated by oxides, the contents of the VIII group metal elements and the VIB group metal elements are respectively the contents described in the above, and the selection of the specific elements is also performed as described in the above.

According to the present invention, in the precursor of the hydrodesulfurization catalytic active component, the precursor of the iron element may include, but is not limited to, one or more of iron nitrate, iron oxide, basic iron carbonate and iron acetate, the precursor of the cobalt element may include, but is not limited to, one or more of cobalt nitrate, basic cobalt carbonate, cobalt acetate and cobalt oxide, the precursor of the nickel element may include, but is not limited to, one or more of nickel nitrate, basic nickel carbonate, nickel acetate and nickel oxide, the precursor of the ruthenium element may include, but is not limited to, one or more of ruthenium nitrate, ruthenium acetate, ruthenium oxide and ruthenium hydroxide, the precursor of the rhodium element may include, but is not limited to, one or more of rhodium nitrate, rhodium hydroxide and rhodium oxide, and the precursor of the palladium element may include, but is not limited to, one or more of palladium nitrate, palladium oxide and palladium hydroxide, the precursors of the chromium element can include but are not limited to one or more of chromium nitrate, chromium oxide, chromium hydroxide and chromium acetate, the precursors of the molybdenum element can include but is not limited to one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate and molybdenum oxide, and the precursors of the tungsten element can include but is not limited to one or more of ammonium metatungstate, ammonium ethylmetatungstate and tungsten oxide.

The inventor of the present invention found in research that, preferably, by preparing a part of the precursor of the group VIII metal element into the inorganic refractory component and preparing an impregnation solution by using the rest of the precursor of the group VIII metal element and the precursor of the group VIB metal element together to impregnate the inorganic refractory component, the content of the active component in the hydrorefining catalyst can be further increased, thereby further improving the hydrorefining performance of the catalyst. While the amount ratio of the precursor of the group VIII metal element used for preparing the inorganic refractory component is not particularly limited and may be selected from a wide range, it is preferable that the amount of the partial precursor of the group VIII metal element is 60 to 90% of the total amount of the precursor of the group VIII metal element in step (1).

According to the invention, in the step (1), the precursor of silica, magnesia, calcia, zirconia, titania can be various substances which can provide silica, magnesia, calcia, zirconia, titania under the roasting condition, for example, the silica precursor can be silica sol, silica white, silica dioxide, etc.; the magnesium oxide precursor is magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium oxide and the like; the precursor of the calcium oxide is calcium hydroxide, calcium carbonate, calcium oxalate, calcium nitrate, calcium acetate, calcium oxide and the like; the zirconia precursor is zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium acetate, zirconia and the like; the precursor of the titanium oxide is titanium hydroxide, titanium nitrate, titanium acetate, zirconium oxide and the like.

In step (3), the inorganic refractory component is used in an amount such that the content of the inorganic refractory component in the hydrofinishing catalyst is 5 to 40% by weight, preferably 10 to 30% by weight, based on the dry weight of the hydrofinishing catalyst.

In step (2), the amounts and selection of the alcohol and the carboxylic acid have been described in detail above, and will not be repeated here.

According to the invention, the alcohol and the carboxylic acid substances are introduced into the impregnation liquid, so that the hydrodesulfurization catalytic active component can be effectively protected, and the catalyst forming can be promoted, thereby effectively improving the performance of the high-activity hydrofining catalyst.

In order to further improve the performance of the finally prepared high-activity hydrofining catalyst, the average pore diameters of the precursors of the silicon oxide, the magnesium oxide, the calcium oxide, the zirconium oxide and the titanium oxide are not less than 10nm, the pore volume of the pore diameters of 2-6nm accounts for no more than 15% of the total pore volume, and the pore volume of the pore diameters of 6-40nm accounts for no less than 75% of the total pore volume.

According to the invention, in order to further improve the solubility of the precursor of the hydrodesulfurization catalytic active component in the prepared impregnation liquid and improve the performance of the finally prepared high-activity hydrofining catalyst, a phosphorus-containing substance is preferably added in the preparation process of the impregnation liquid, and the phosphorus-containing substance is preferably a phosphorus-containing inorganic acid and is further preferably at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate. Further preferably, the phosphorus-containing material is used in an amount such that the final high activity hydrofinishing catalyst is prepared on a dry weight basis and is P₂O₅The content of the phosphorus element is 0.8 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 8% by weight.

According to a preferred embodiment of the invention, in the process of preparing the impregnating solution, the alcohol compound and the precursor respectively containing the VIB group metal element and the VIII group metal element are firstly added into the aqueous solution of the phosphorus-containing substance, and then stirred for 1-8 hours at 40-100 ℃ until the alcohol compound and the precursor are completely dissolved. Finally, the organic acid is added until the organic acid is completely dissolved. The order of addition of the organic alcohol compound, the organic carboxylic acid compound, the phosphorus-containing substance, and the metal element precursor may be changed.

According to the invention, in the step (1), the roasting conditions can be selected within a wide range, and preferably, the roasting temperature is 300-900 ℃, preferably 400-700 ℃; the roasting time is 1-15h, preferably 3-8 h.

According to the present invention, in the step (3), the drying conditions can be selected within a wide range, and preferably, the drying temperature is 50-250 ℃, preferably 100-200 ℃; the drying time is 2-10h, preferably 3-8 h.

According to the invention, the forming mode can be various existing forming methods, such as extrusion molding and rolling ball molding. The extrusion molding can be performed according to the prior art, and the inorganic refractory component to be extruded and molded and the impregnation solution containing the metal component are uniformly mixed and then extruded into a required shape, such as a cylinder, a clover shape, a honeycomb shape and the like.

In the present invention, the hydrofining catalyst is sulfided before use, and the sulfiding conditions of the hydrofining catalyst may be the conditions used for sulfiding the hydrofining catalyst, and the sulfiding method is not particularly limited, and may be dry sulfiding or wet sulfiding.

According to a preferred embodiment of the present invention, in order to prevent coking of the hydrofining catalyst by the coking precursors such as olefins and gums in the slurry bed light oil and to protect the hydrofining catalyst, a hydrogenation protecting agent is loaded upstream of the hydrofining catalyst in the first hydrofining reaction zone. Preferably, the loading of the hydrogenation protective agent is 5-30 vol% of the loading of the hydrofining catalyst. The hydrogenation protective agent can be obtained commercially, and can be a hydrogenation protective agent with a commercial product number RG-30A, RG-30B from Changjingtai, China petrochemical engineering, Inc. Preferably, the hydrogenation protective agent contains 1.0-5.0 wt% of nickel oxide, 5.5-10.0 wt% of molybdenum oxide and 85-93.5 wt% of alumina carrier with double pore distribution.

In the present invention, the desulfurization in the step (5) may be carried out by a method commonly used in the art, as long as the sulfur in the first gas phase stream and the second gas phase stream can be removed to obtain the recycle hydrogen, and the present invention is not particularly limited thereto.

In the present invention, the fractionation in the step (6) may be carried out by a method commonly used in the art, as long as the desired product can be obtained, and the present invention is not particularly limited thereto.

The following provides a preferred embodiment of the invention:

as shown in fig. 1, after mixing the slurry bed light oil 1 with the recycle hydrogen 15, firstly entering the first hydrofining reaction zone 3 to react with the hydrofining catalyst; the first reaction effluent enters a gas-liquid separation tank 5 and is separated into a first gas-phase material flow 16 and a first liquid-phase material flow; the first liquid phase material flow and the recycle hydrogen 15 and the supplemented fresh hydrogen 2 are in reverse contact reaction in the second hydrofining reaction zone 4 (namely, the first liquid phase material flow enters the second hydrofining reaction zone 4 from top to bottom, and the mixture of the recycle hydrogen 15 and the fresh hydrogen 2 enters the second hydrofining reaction zone 4 from bottom to top); the second reaction effluent enters the high pressure separator 7 and is separated into a second gas phase stream 17 and a second liquid phase stream 18. The first gas phase material flow 16 and the second gas phase material flow 17 are mixed and then enter the recycle hydrogen desulfurization system 6, and the desulfurized gas is compressed by a recycle gas compressor to obtain recycle hydrogen 15. The second liquid phase material flow 18 passes through a low-pressure separator 8, acid water, low-fraction gas 10 and low-fraction oil are separated, and the low-fraction oil enters a fractionating tower 9 and is separated into tower top gas 11, a light naphtha product 12, a heavy naphtha product 13 and a diesel oil product 14.

The present invention will be described in detail below by way of examples.

In the following preparation examples, the composition of the catalyst was calculated from the amounts charged. The mass fractions of sulfur and nitrogen in the product were analyzed using a sulfur-nitrogen analyzer (model number TN/TS3000, available from seimer feishei), and the content of aromatic hydrocarbons was analyzed by near infrared spectroscopy. The specific surface area of the catalyst and the pore distribution, the pore diameter and the pore volume of the catalyst between 2 and 40nm are measured by a low-temperature nitrogen adsorption method (meeting the GB/T5816-1995 standard), and the pore distribution, the pore diameter and the pore volume of the catalyst between 100 and 300nm are measured by a mercury intrusion method. The average pore diameter of the catalyst was calculated according to the cylindrical pore model (average pore diameter ═ total pore volume × 4000/specific surface area).

In the following examples and comparative examples, the hydrofining catalyst RN-32V, the hydrofining catalyst RS-2100, the hydrogenation protecting agent RG-30A and the hydrogenation protecting agent RG-30B were obtained from Changjingtie, Inc., petrochemical Co. The catalyst needs to be presulfided before use, and the presulfiding process is a conventional industrial sulfurization method well known in the field.

The properties of the raw slurry bed light oil A are shown in Table 1, the properties of the raw slurry bed light oil B are shown in Table 2, and the properties of the raw slurry bed light oil C are shown in Table 3.

The yield of each product fraction is defined as the weight percentage of each product to the feedstock obtained by fractional distillation.

TABLE 1

TABLE 2

TABLE 3

Preparation example 1

(1) Commercially available white carbon black (specific surface area: 220 m)²The average pore diameter is 12.7nm), and basic nickel carbonate powder are evenly mixed and then roasted for 4h at 700 ℃ to obtain the nickel-containing inorganic refractory powder.

Wherein the amount of basic nickel carbonate used corresponds to a nickel content (calculated as nickel oxide) of 15.0 wt.% in the catalyst.

(2) Adding a certain amount of MoO₃Basic nickel carbonate and glycol are added into the water solution containing phosphoric acid respectivelyHeating and stirring the mixture until the mixture is completely dissolved, and then adding a certain amount of acetic acid until the mixture is completely dissolved to obtain the impregnation solution containing the active metal.

Wherein the mass ratio of the mole number of the ethylene glycol to the inorganic refractory component is 0.015, and the mass of the acetic acid is 3 wt% of the mass of the inorganic refractory component.

(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst is dried for 5h at 200 ℃ to prepare an oxidation state catalyst with the particle size of 1.6mm, which is marked as a high-activity hydrofining catalyst Z-1.

Wherein the impregnating solution and the nickel-containing inorganic refractory powder are mixed in such a proportion that the content of molybdenum oxide, the content of nickel oxide and the content of P in the catalyst are 46.0 wt%, 20.0 wt% and 20.0 wt%, respectively, based on the dry weight of the catalyst and calculated as an oxide₂O₅The content was 4% by weight, and the content of the inorganic refractory component was 30.0% by weight.

After the high-activity hydrofining catalyst Z-1 is roasted for 3h at 400 ℃, the pore size distribution of the catalyst is analyzed by utilizing a low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-1 is 145m²(ii)/g, the pore diameter distribution was 2 to 40nm and 100-300nm, wherein the proportion of the pore volume of 2 to 40nm to the total pore volume was 85.5% (wherein the proportion of the pore volume of 2 to 4nm to the total pore volume was 7.6%), the proportion of the pore volume of 100-300nm to the total pore volume was 13.2%, the pore volume was 0.36mL/g, and the average pore diameter was 9.9 nm.

Preparation example 2

(1) Commercially available white carbon black (specific surface area: 220 m)²The average pore diameter is 12.7nm), and basic nickel carbonate powder are evenly mixed and then roasted for 8 hours at the temperature of 600 ℃ to obtain the nickel-containing inorganic refractory powder.

The amount of basic nickel carbonate used corresponds to a nickel content (calculated as nickel oxide) of 27.0% by weight of the catalyst.

(2) Adding a certain amount of MoO₃Ammonium metatungstate, basic nickel carbonate and ethylene glycol are respectively added into an aqueous solution containing phosphoric acid, heated and stirred until the ammonium metatungstate, the basic nickel carbonate and the ethylene glycol are completely dissolved, then a certain amount of acetic acid is added until the acetic acid is completely dissolved, and an impregnation solution containing active metals is obtained。

Wherein the mass ratio of the mole number of the ethylene glycol to the inorganic refractory component is 0.012, and the mass of the acetic acid is 6 wt% of the mass of the inorganic refractory component.

(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst was dried at 300 ℃ for 3h to obtain an oxidized catalyst with a particle size of 1.6mm, which was designated as hydrofinishing catalyst Z-2.

Wherein the mixing ratio of the impregnating solution and the nickel-containing inorganic refractory powder is such that the content of molybdenum oxide in the catalyst is 22.5 wt%, the content of tungsten oxide is 22.5 wt%, the content of nickel oxide is 27.0 wt%, and P is calculated by oxide based on the dry weight of the catalyst₂O₅The content was 4.0% by weight, and the content of the inorganic refractory component was 15.0% by weight.

And roasting the hydrofining catalyst Z-2 at 400 ℃ for 3 hours, and analyzing the pore size distribution of the hydrofining catalyst by using a low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-2 is 120m²(ii)/g, the pore diameter distribution was 2 to 40nm and 100-300nm, wherein the ratio of the pore volume of 2 to 40nm to the total pore volume was 76.9% (wherein the ratio of the pore volume of 2 to 4nm to the total pore volume was 9.5%), the ratio of the pore volume of 100-300nm to the total pore volume was 20.3%, the pore volume was 0.26mL/g, and the average pore diameter was 8.7 nm.

Preparation example 3

(1) Commercially available white carbon black (specific surface area: 220 m)²The average pore diameter is 12.7nm), magnesium nitrate and basic nickel carbonate powder are evenly mixed and then roasted for 3h at 400 ℃ to obtain the inorganic refractory powder containing nickel, silicon dioxide and magnesium oxide.

Wherein the amount of basic nickel carbonate used corresponds to 21.0 wt.% of the nickel content (calculated as nickel oxide) in the catalyst.

(2) Respectively adding a certain amount of ammonium metatungstate, nickel nitrate and glycerol into the aqueous solution, heating and stirring until the ammonium metatungstate, the nickel nitrate and the glycerol are completely dissolved, and then adding a certain amount of citric acid until the citric acid is completely dissolved to obtain an impregnation solution containing active metals.

Wherein the mass ratio of the mole number of the glycerol to the inorganic fire-resistant component is 0.008, and the mass of the citric acid is 8 wt% of the mass of the inorganic fire-resistant component.

(3) The impregnating solution and the inorganic refractory component are uniformly mixed, and then extruded into strips for forming. The catalyst is dried for 5h at 180 ℃ to obtain an oxidation state catalyst with the particle size of 1.6mm, and the catalyst is marked as a high-activity hydrofining catalyst Z-3.

Wherein the impregnation solution and the nickel-containing inorganic refractory powder are mixed in such proportions that the content of tungsten oxide, the content of nickel oxide, the content of silica and the content of magnesium oxide in the catalyst are 53.0 wt%, 25.0 wt%, 15 wt% and 7.0 wt%, respectively, based on the dry weight of the catalyst and in terms of oxides.

And roasting the hydrofining catalyst Z-3 at 400 ℃ for 3 hours, and analyzing the pore size distribution of the hydrofining catalyst by using a low-temperature nitrogen adsorption and mercury intrusion method. The specific surface area of the hydrofining catalyst Z-3 is 165m²(ii)/g, the pore diameter distribution was 2 to 40nm and 100-300nm, wherein the ratio of the pore volume of 2 to 40nm to the total pore volume was 87.5% (wherein the ratio of the pore volume of 2 to 4nm to the total pore volume was 8.7%), the ratio of the pore volume of 100-300nm to the total pore volume was 7.8%, the pore volume was 0.32mL/g, and the average pore diameter was 7.8 nm.

Preparation example 4

Commercially available white carbon black (specific surface area: 220 m)²The average pore diameter is 12.7nm), and basic cobalt carbonate powder are uniformly mixed without a roasting step to obtain the inorganic refractory powder containing cobalt. Wherein the amount of basic cobalt carbonate used corresponds to a cobalt (calculated as cobalt oxide) content of the catalyst of 22.0 wt.%. Then, an impregnation solution was prepared in accordance with the procedure (2) in preparation example 1, and a catalyst was prepared in accordance with the procedure (3) in preparation example 1, and the composition of the inorganic refractory component and the metal in the dry basis of the catalyst was the same as that of the catalyst in preparation example 1, to obtain a hydrorefining catalyst Z-4.

Preparation example 5

A catalyst was prepared by extruding the inorganic refractory precursor, the active component precursor, and the organic alcohol and the organic acid used in preparation example 1, and the content of the inorganic refractory component, the content of the active metal component, and the amounts of the organic alcohol and the organic acid in the dry basis of the catalyst were maintained the same as in preparation example 1, to obtain a hydrorefining catalyst Z-5.

Preparation example 6

A hydrorefining catalyst Z-6 was obtained in the same manner as in preparation example 3 except that the organic alcohol and the organic acid were not added in the preparation of the active component solution.

Preparation example 7

The procedure of preparation 3 was followed. In the step (1), the group VIII metal element is not introduced, the group VIII metal element is completely introduced in the step (2), and the rest is the same, so that the hydrofining catalyst Z-7 is obtained.

Example 1

The slurry gas oil B was used as the feed oil, and the process flow shown in FIG. 1 was followed. Mixing slurry bed light oil B and hydrogen, reacting in a first hydrofining reaction zone, performing gas-liquid separation on the obtained first reaction effluent, and performing reverse contact reaction on the first liquid phase material flow and the hydrogen in a second hydrofining reaction zone, wherein the temperature of the hydrogen introduced from the bottom of the second hydrofining reaction zone is 100 ℃ lower than that of the first reaction zone. And the obtained second reaction effluent enters a separation system and a fractionation system to be cut to obtain a light naphtha product, a heavy naphtha product and a diesel product.

Wherein, the first hydrofining reaction zone is filled with a high-activity hydrofining catalyst Z-1, and the top of the reaction zone is filled with a hydrogenation protective agent RG-30A, and the filling amount of the hydrogenation protective agent RG-30A is 10 volume percent of the filling amount of the high-activity hydrofining catalyst Z-1; the second hydrofining reaction zone is filled with a hydrofining catalyst RS-2100.

The process conditions and the product properties of the fractions are shown in tables 4 and 5, respectively.

Example 2

The slurry gas oil C was used as the feed oil, and the process flow shown in FIG. 1 was followed. The method comprises the steps of mixing slurry bed light oil C and hydrogen, reacting in a first hydrofining reaction zone, carrying out gas-liquid separation on the obtained first reaction effluent, and carrying out reverse contact reaction on a first liquid phase material flow and the hydrogen in a second hydrofining reaction zone, wherein the temperature of the hydrogen introduced from the bottom of the second hydrofining reaction zone is 120 ℃ lower than that of the first reaction zone. And the obtained second reaction effluent enters a separation system and a fractionation system to be cut to obtain a light naphtha product, a heavy naphtha product and a diesel product.

Wherein, the first hydrofining reaction zone is filled with a high-activity hydrofining catalyst Z-2, and the top of the reaction zone is filled with a hydrogenation protective agent RG-30B, and the filling amount of the hydrogenation protective agent RG-30B is 10 volume percent of the filling amount of the high-activity hydrofining catalyst Z-2; the second hydrofining reaction zone is filled with a hydrofining catalyst RS-2100.

Example 3

The slurry gas oil A was used as the feed oil, and the process flow shown in FIG. 1 was followed. The method comprises the steps of mixing slurry bed light oil A and hydrogen, reacting in a first hydrofining reaction zone, carrying out gas-liquid separation on the obtained first reaction effluent, and carrying out reverse contact reaction on a first liquid phase material flow and the hydrogen in a second hydrofining reaction zone, wherein the temperature of the hydrogen introduced from the bottom of the second hydrofining reaction zone is 200 ℃ lower than that of the first reaction zone. And the obtained second reaction effluent enters a separation system and a fractionation system to be cut to obtain a light naphtha product, a heavy naphtha product and a diesel product.

Wherein, the first hydrofining reaction zone is filled with a high-activity hydrofining catalyst Z-2, and the second hydrofining reaction zone is filled with a hydrofining catalyst RN-32V.

Example 4

The procedure of example 1 was followed except that the high-activity hydrofinishing catalyst Z-1 charged in the first hydrofinishing reaction zone was replaced with the high-activity hydrofinishing catalyst Z-3.

The process conditions were the same as in example 1, and the product properties of each fraction are shown in tables 4 and 5, respectively.

Example 5

The procedure is as in example 3 except that the first hydrofinishing reaction zone is charged with the highly active hydrofinishing catalyst Z-2 and replaced with the hydrofinishing catalyst RN-32V.

Examples 6 to 9

The procedure was carried out as in example 1, except that the highly active hydrofinishing catalyst Z-1 charged in the first hydrofinishing reaction zone was replaced with the hydrofinishing catalysts Z-4, Z-5, Z-6 and Z-7 obtained in production examples 4-7, respectively, the process conditions were the same as in example 1, and the properties of the respective fractions are shown in Table 6.

Comparative example 1

The process was carried out as in example 5, except that it was carried out as in FIG. 2, which is the following process as shown in FIG. 2:

as shown in fig. 2, after mixing the slurry bed light oil 1 with the recycle hydrogen 15, firstly entering the first hydrofining reaction zone 3 to react with the hydrofining catalyst; the first reaction effluent enters a gas-liquid separation tank 5 and is separated into a first gas-phase material flow 16 and a first liquid-phase material flow 19; the first liquid phase material flow 19 is mixed with the circulating hydrogen 15 and the supplemented fresh hydrogen 2 and then is subjected to a cocurrent contact reaction in the second hydrofining reaction zone 4 (namely, the first liquid phase material flow 19 is mixed with the circulating hydrogen 15 and the supplemented fresh hydrogen 2 and then enters the second hydrofining reaction zone 4 from top to bottom); the second reaction effluent enters the high pressure separator 7 and is separated into a second gas phase stream 17 and a second liquid phase stream 18. The first gas phase material flow 16 and the second gas phase material flow 17 are mixed and then enter the recycle hydrogen desulfurization system 6, and the desulfurized gas is compressed by a recycle gas compressor to obtain recycle hydrogen 15. The second liquid phase material flow 18 passes through a low-pressure separator 8, acid water, low-fraction gas 10 and low-fraction oil are separated, and the low-fraction oil enters a fractionating tower 9 and is separated into tower top gas 11, a light naphtha product 12, a heavy naphtha product 13 and a diesel oil product 14.

The process conditions were the same as in example 5, and the product properties of each fraction are shown in Table 6.

Comparative example 2

And (3) carrying out contact reaction on the slurry bed light oil A and a hydrofining catalyst RN-32V in a hydrofining reaction zone, and cutting a light naphtha product, a heavy naphtha product and a diesel product from a hydrofining reaction effluent in a fractionation system.

The process conditions and the product properties of the fractions are shown in tables 4 and 6.

As can be seen from the results in tables 5 and 6, the method provided by the present invention enables the production of light naphtha products, heavy naphtha products and clean diesel products from slurry bed light oils. The heavy naphtha product can be used as a reforming raw material with high aromatic hydrocarbon potential, the light naphtha product can be used as a high-quality steam cracking raw material, and the diesel oil product can be used as clean diesel oil in China VI. Particularly, when the specific high-activity hydrofining catalyst provided by the invention is used for participating in hydrofining reaction, better product quality is obtained, and the light naphtha paraffin mass fraction exceeds 90%, so that the light naphtha paraffin mass fraction is a high-quality ethylene cracking raw material. The sulfur content of the heavy naphtha product is less than 0.5 mu g/g, the nitrogen content is less than 0.5 mu g/g, the aromatic hydrocarbon exceeds 50 percent, and the heavy naphtha product is a high-quality reforming device raw material; the sulfur content of the diesel oil product is less than 10 mu g/g, the polycyclic aromatic hydrocarbon content is less than 7 percent, and the diesel oil product is a high-quality blending component of the national VI clean diesel oil.

TABLE 4

	Example 1	Example 2	Example 3	Example 5	Comparative example 2
						Raw oil	Raw material B	Raw material C	Starting materials A	Starting materials A	Starting materials A
A first hydrofining reaction zone
						Partial pressure of hydrogen/MPa	8.5	12.5	14.0	10.5	10.5
Reaction temperature/. degree.C	390	365	350	355	365
						Volume space velocity/h^-1	2.0	1.2	0.5	1.0	0.8
Volume ratio of hydrogen to oil in standard state	1000	1200	500	600	600
						Second hydrofining reaction zone
Partial pressure of hydrogen/MPa	8.3	12.1	13.0	10.0
						Reaction temperature/. degree.C	361	385	360	368
Volume space velocity/h^-1	4.0	2.5	3.5	4.0
						Volume ratio of hydrogen to oil in standard state	800	400	300	600

TABLE 5

TABLE 6

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method of treating slurry bed light oil, the method comprising:

(6) fractionating the second liquid phase stream to obtain a light naphtha product, a heavy naphtha product, and a diesel product;

the first hydrofining reaction zone and/or the second hydrofining reaction zone contain a high-activity hydrofining catalyst; the high-activity hydrofining catalyst contains an inorganic refractory component, a hydrodesulfurization catalytic active component, alcohol and carboxylic acid;

wherein the inorganic refractory component contains at least one of silica, magnesia, calcia, zirconia and titania and a part of the hydrodesulfurization catalytic active component;

the high-activity hydrofining catalyst has a pore diameter of 2-40nm and a pore diameter of 100-300nm, wherein the pore volume of the pore diameter of 2-40nm accounts for 60-95% of the total pore volume, and the pore volume of 100-300nm accounts for 0.5-30% of the total pore volume.

2. The process of claim 1, wherein the conditions of the reaction of the first hydrofinishing reaction zone comprise: the hydrogen partial pressure is 8.0-14.0 MPa; the reaction temperature is 300-450 ℃; the volume ratio of hydrogen to oil is 500-1500; the liquid hourly space velocity is 0.5-4.0h^-1。

3. The process of claim 2, wherein the conditions of the reaction in the first hydrofinishing zone compriseComprises the following steps: the hydrogen partial pressure is 8.5-14.0 MPa; the reaction temperature is 350-430 ℃; the volume ratio of hydrogen to oil is 500-1200; the liquid hourly space velocity is 0.5-2.0h^-1。

4. The process of claim 1, wherein the reaction conditions of the second hydrofinishing reaction zone comprise: the hydrogen partial pressure is 8.0-14.0 MPa; the reaction temperature is 300-450 ℃; the volume ratio of the hydrogen to the oil is 300-1500; the liquid hourly space velocity is 0.5-4.0h^-1。

5. The process of claim 4, wherein the reaction conditions of the second hydrofinishing reaction zone comprise: the hydrogen partial pressure is 8.3-14.0 MPa; the reaction temperature is 350-430 ℃; the volume ratio of the hydrogen to the oil is 300-800; the liquid hourly space velocity is 2.0-4.0h^-1。

6. The process of any of claims 1-5, wherein the difference between the reaction temperature of the first hydrofinishing reaction zone and the reaction temperature of the second hydrofinishing reaction zone is from 0.1 to 30 ℃.

7. The process of claim 6, wherein the difference between the reaction temperature of the first hydrofinishing reaction zone and the reaction temperature of the second hydrofinishing reaction zone is 10-30 ℃.

8. The process of any of claims 1-5, wherein the first hydrofinishing reaction zone has a reaction temperature of 380 ℃ or less and the second hydrofinishing reaction zone has a reaction temperature of 0.1-30 ℃ higher than the first hydrofinishing reaction zone.

9. The process of claim 8, wherein the reaction temperature of the first hydrofinishing reaction zone is 380 ℃ or less and the reaction temperature of the second hydrofinishing reaction zone is 10-30 ℃ higher than the temperature of the first hydrofinishing reaction zone.

10. The process of any of claims 1-5, wherein the first hydrofinishing reaction zone has a reaction temperature of >380 ℃ and the second hydrofinishing reaction zone has a reaction temperature of 0.1-30 ℃ lower than the first hydrofinishing reaction zone.

11. The process of claim 10, wherein the reaction temperature of the first hydrofinishing reaction zone is >380 ℃ and the reaction temperature of the second hydrofinishing reaction zone is 10-30 ℃ lower than the temperature of the first hydrofinishing reaction zone.

12. The process as claimed in any one of claims 1 to 5, wherein the pore volume at a pore diameter of 2 to 40nm is 75 to 90% of the total pore volume and the pore volume at a pore diameter of 100 and 300nm is 5 to 15% of the total pore volume.

13. The process according to any one of claims 1 to 5, wherein the hydrodesulphurization catalytically active component comprises a group VIII metal element and a group VIB metal element;

wherein, in the high-activity hydrofining catalyst, the content of the VIII group metal element is 15-35 wt% based on the dry weight of the catalyst and calculated by oxide; the content of the group VIB metal elements is 35-75 wt%.

14. The process of claim 13 wherein the group VIII metal element is present in the high activity hydrofinishing catalyst in an amount of from 20 to 30 wt.% based on dry weight of the catalyst and calculated as the oxide; the content of the VIB group metal element is 40-65 wt%.

15. The method according to claim 14, wherein the group VIII metal element is selected from at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, and the group VIB metal element is selected from at least one of chromium, molybdenum and tungsten.

16. The process of claim 13 wherein the portion of the hydrodesulfurization catalytically active component is a portion of the group VIII metal elements in an amount of from 60 to 90 wt.% of the total group VIII metal elements.

17. The process of claim 1, wherein the high activity hydrofinishing catalyst is a shaped catalyst having a shape selected from at least one of cylindrical, cloverleaf, honeycomb.

18. The process of claim 1, wherein the high activity hydrofinishing catalyst has a specific surface area of from 70 to 200m²Per g, pore volume of 0.15-0.6mL/g, average pore diameter of 5-25 nm.

19. The process of claim 1, wherein in the high activity hydrofinishing catalyst, the pore volume of 2-4nm is no more than 10% of the total pore volume.

20. The process of claim 1 wherein the inorganic refractory component is present in the high activity hydrofinishing catalyst in an amount of from 5 to 40% by weight based on the dry weight of the catalyst.

21. The process of claim 20 wherein the inorganic refractory component is present in the high activity hydrofinishing catalyst in an amount of from 10 to 30 wt.%, based on the dry weight of the catalyst.

22. The method of claim 1, wherein the carboxylic acid to inorganic refractory component weight ratio on a dry basis is from 0.002 to 0.1: 1.

23. the method of claim 22, wherein the weight ratio of carboxylic acid to inorganic refractory component on a dry basis is from 0.02 to 0.06: 1.

24. the method of claim 1, wherein the carboxylic acid is selected from at least one of C1-18 monobasic saturated carboxylic acids, C7-10 phenyl acids, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, and tartaric acid.

25. The method of claim 1, wherein the ratio of moles of alcohol to dry weight of the inorganic refractory component is from 0.005 to 0.03: 1.

26. the method of claim 25, wherein the ratio of moles of alcohol to dry weight of the inorganic refractory component is from 0.01 to 0.02: 1.

27. the method according to claim 1, wherein the alcohol is at least one selected from the group consisting of C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, and trimethylolethane.

28. The process of claim 1 wherein the high activity hydrofinishing catalyst further comprises phosphorus, based on the dry weight of the catalyst and P₂O₅The content of the phosphorus element is 0.8-10 wt%.

29. The process of claim 28 wherein the high activity hydrofinishing catalyst further comprises phosphorus, based on the dry weight of the catalyst and P₂O₅The content of the phosphorus element is 1-8 wt%.

30. The process of any of claims 1-5, wherein the high activity hydrofinishing catalyst is prepared by:

31. The method of claim 30, wherein the impregnating solution obtained in step (2) further contains a phosphorus-containing substance.

32. The method of claim 31, wherein the phosphorus-containing substance is selected from at least one of phosphoric acid, hypophosphorous acid, ammonium phosphate, and ammonium dihydrogen phosphate.

33. The method of claim 30, wherein in step (1), the roasting conditions comprise: the roasting temperature is 300-900 ℃; the roasting time is 1-15 h.

34. The method of claim 33, wherein in step (1), the roasting conditions comprise: the roasting temperature is 400-800 ℃; the roasting time is 3-8 h.

35. The method of claim 30, wherein in step (3), the drying conditions comprise: the drying temperature is 50-250 ℃; the drying time is 2-10 h.

36. The method of claim 35, wherein in step (3), the drying conditions comprise: the drying temperature is 100-200 ℃; the drying time is 3-8 h.

37. The method of claim 30, wherein the silica precursor is at least one of silica sol, silica and silica; the magnesium oxide precursor is at least one of magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium acetate and magnesium oxide; the precursor of the calcium oxide is at least one of calcium hydroxide, calcium carbonate, calcium oxalate, calcium nitrate, calcium acetate and calcium oxide; the zirconia precursor is at least one of zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium acetate and zirconia; the precursor of the titanium oxide is at least one of titanium hydroxide, titanium nitrate and titanium acetate.

38. The method of claim 37, wherein the silica, magnesia, calcia, zirconia, and titania precursors have an average pore diameter of no less than 10nm, a pore volume fraction of 2-6nm pore diameter of no more than 15% of the total pore volume, and a pore volume fraction of 6-40nm pore diameter of no less than 75% of the total pore volume.

39. The method as claimed in claim 1, wherein the light oil in the slurry bed has a boiling range of 50 to 400 ℃ and a density of 0.80 to 0.90g/cm³The sulfur content is 5000-20000 mu g/g, the nitrogen content is 1000-4000 mu g/g, and the mass fraction of aromatic hydrocarbon is 30-80%.