WO2021078186A1 - 液相反应器及其应用 - Google Patents
液相反应器及其应用 Download PDFInfo
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- WO2021078186A1 WO2021078186A1 PCT/CN2020/122683 CN2020122683W WO2021078186A1 WO 2021078186 A1 WO2021078186 A1 WO 2021078186A1 CN 2020122683 W CN2020122683 W CN 2020122683W WO 2021078186 A1 WO2021078186 A1 WO 2021078186A1
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- Prior art keywords
- cylinder
- reaction
- hydrogenation
- catalyst
- tube
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Definitions
- This application relates to the field of liquid phase catalytic reactions, and in particular to a liquid phase reactor and its application.
- Heavy oil hydrogenation reactors are divided into many types, such as fixed bed hydrogenation reactors, suspended bed hydrogenation reactors, fluidized bed hydrogenation reactors, etc.
- the fixed bed hydrogenation reactor is the most widely used, of which the upflow fixed
- the bed reactor can process many types of heavy oil products, and shows unique advantages in the oil hydrogenation process. For example, low-quality oil residues and coal liquefied oil have high impurity content, which can easily cause hydrogenation catalyst poisoning.
- the catalyst pores are blocked and quickly deactivated, and impurities may block the bed, causing the pressure drop to rise rapidly, causing the reactor to deteriorate and even fail to operate normally. If the upflow hydrogenation process is used to cause the gas and liquid to flow upwards.
- the expansion of the catalyst bed can increase the porosity of the bed and avoid the blockage of the catalyst bed.
- the liquid phase hydrogenation process In the heavy oil hydrogenation process, compared with the traditional fixed-bed gas/liquid/solid three-phase hydrogenation process, the liquid phase hydrogenation process has the advantages of fast hydrogenation reaction rate, high reaction efficiency, low energy consumption and low investment. Many advantages have been widely recognized and applied. Therefore, the upflow liquid phase hydrogenation reaction process combines the advantages of the upflow hydrogenation reactor and the liquid phase hydrogenation reaction process. The application of the hydrogenation process has shown Certain advantages.
- the heavy oil hydroprocessing system includes a main reactor and at least one sub-reactor.
- the main reactor includes a first cylinder.
- the first cylinder is used for holding materials and sub-reactors.
- the device includes: a mixing unit for mixing materials and hydrogen, the mixing unit includes a second cylinder, the second cylinder is provided with a material inlet, a hydrogen inlet and a first outlet, and the material inlet is in communication with the outlet of the first cylinder;
- the strengthening device the inlet of the strengthening device is connected with the first outlet of the second cylinder, and the outlet of the strengthening device is connected with the accommodating cavity of the first cylinder.
- the strengthening device is used to provide energy to the material to cause the material to undergo a cracking reaction.
- CN 108659882 A proposes a heavy oil hydrogenation method and a hydrogenation system thereof, wherein the heavy oil hydrogenation method includes: mixing heavy oil, circulating oil, sulfurizing agent, and catalyst, and hydrogenating with hydrogen in a first reactor Cracking to obtain the first reaction product; returning part of the first reaction product to the first reactor, and hydrocracking the remaining materials in the second reactor to obtain the second reaction product; separating the second reaction product into For light components and heavy components, part of the heavy components are returned to the second reactor, and the remaining heavy components are separated to obtain distillate oil as circulating oil; the light components are hydrorefined in the third reactor to obtain light oil products.
- the method of the invention is mainly to improve the heat transfer and mass transfer efficiency, ensure sufficient residence time of the materials in the reactor, and increase the conversion rate of heavy oil and the yield of light oil.
- it is only through the structure of the conventional hydrogenation reactor, and it is not effective.
- the control of the contact time between the catalyst and the raw material can not guarantee the conversion rate of heavy oil and the yield of light oil.
- CN202063881U discloses a liquid-phase hydrogenation reactor.
- a mixer is arranged in the top of the reactor.
- the mixer has a mixed oil inlet and a hydrogen inlet, a hydrogen-dissolved mixture outlet and a gas outlet, and the mixed hydrogen-dissolved mixture outlet is inserted into the reaction In the liquid phase of the vessel.
- the purpose of this patent is to increase the gas-liquid contact area through the structure of the hydrogen mixer in the reactor so that hydrogen can be dissolved in the mixed oil to improve the efficiency of the hydrogenation reaction.
- the upflow reactor includes an initial distributor at the bottom of the reactor and an intermediate distributor above the initial distributor.
- the initial distributor consists of a conical baffle and a
- the upper sieve plate is composed of; the middle distributor is composed of a perforated sieve plate and a sieve plate string structure.
- the purpose of the upflow reactor provided by this invention is to achieve uniform gas distribution, thereby improving the utilization rate of the catalyst.
- the purpose of this application is to provide a new type of liquid phase reactor and its application.
- the reactor adopts a specially designed inner and outer double cylinder structure, which is beneficial to reduce liquid phase reaction materials.
- the viscosity improves the mass transfer driving force and reaction rate of liquid phase reaction, so it is suitable for the liquid phase reaction of high viscosity liquid materials, especially the liquid phase catalytic hydrogenation reaction of heavy oil.
- a liquid phase reactor comprising an outer cylinder and an inner cylinder arranged along the axial direction of the reactor.
- the outer cylinder includes an upper head, a straight cylinder section, and a lower seal. Head, an annular space is formed between the inner cylinder and the outer cylinder, the top of the inner cylinder is open and communicates with the annular space, characterized in that: the inner cylinder includes upper Barrel and lower barrel, where,
- the upper tube is located in the straight tube section, the cross-sectional area gradually decreases from top to bottom, the top is open, and the bottom is connected with the top of the lower tube;
- the lower cylinder is located in the lower head, the cross-sectional area gradually increases from top to bottom, the bottom end is hermetically connected with the inner wall of the lower head, and an inorganic membrane tube extending along the axial direction of the reactor is provided in the lower cylinder, thereby A shell-and-tube structure is formed, and the tube wall of the inorganic membrane tube is provided with pores for gas to pass through;
- the lower head is provided with a liquid inlet, a gas inlet, and a product outlet.
- the liquid inlet and the gas inlet communicate with the bottom of the lower cylinder, and the product outlet communicates with the bottom of the annular space, wherein the liquid inlet is connected to the shell of the lower cylinder.
- One of the shell side or the tube side of the shell-and-tube structure is connected, and the gas inlet is connected with the other one of the shell side or the tube side of the shell-and-tube structure.
- the liquid inlet communicates with the shell side of the shell-and-tube structure of the lower cylinder, and the gas inlet communicates with the tube side of the shell-and-tube structure.
- the upper cylinder is filled with a first catalyst
- the annular space is filled with a second catalyst that is the same as or different from the first catalyst.
- Another aspect of the application provides a method for hydrogenation of heavy oil using the liquid phase reactor according to the application, which includes the following steps:
- reaction material enters the bottom of the upper cylinder, and the first hydrogenation reaction is carried out in the presence of the first hydrogenation catalyst packed in the upper cylinder during the process of passing through the upper cylinder from bottom to top, to obtain Partially hydrogenated reaction material;
- the partially hydrogenated reaction material enters the annular space, and the second hydrogenation is carried out in the presence of the second hydrogenation catalyst packed therein during the process of passing through the annular space from top to bottom Reaction to obtain a hydrogenation reaction product, wherein the second hydrogenation catalyst is the same as or different from the first hydrogenation catalyst.
- the lower tube with a shell-and-tube structure can play a role in reducing the viscosity of the material.
- the gaseous material diffuses into the liquid material through the pores provided on the tube wall of the inorganic membrane tube.
- the material is sheared and dispersed/dissolved evenly in the liquid material at the same time, thereby reducing its viscosity.
- gaseous materials enter the tube side of the shell-and-tube structure (that is, inside the inorganic membrane tube)
- liquid materials enter the shell side of the tube-and-shell structure (that is, between the tube wall of the inorganic membrane tube and the wall of the lower tube).
- the gas material can diffuse from the inside of the tube to the space outside the tube through the holes set on the tube wall of the inorganic membrane tube, generating a driving force from the inside to the outside, and the liquid material enters the shell side space, due to the cross-sectional area of the lower tube Gradually shrinking from bottom to top produces a driving force pointing to the center of the top of the lower cylinder. Therefore, the diffused gas material can produce a larger shear force on the liquid material, which greatly improves the dissolution of the gas material in the liquid material. The amount of dispersion and uniformity of dispersion reduce the viscosity of the reaction material obtained.
- the mixing between the macromolecules and small molecules in the reaction material is more uniform, which improves the fluidity of the material and also reduces The viscosity of the material.
- the reaction material in which a large amount of gas is dissolved and dispersed enters the upper cylinder.
- the gas gradually moves from the inner surface of the liquid phase body to the outside.
- Surface diffusion also has the effect of improving the fluidity of the reaction material.
- the reactor of the present application can maintain the effect of reducing the viscosity of the reaction material and improving the fluidity of the material during the feeding process and the entire liquid phase reaction process, thereby helping to improve the driving force and the driving force of the mass transfer process of the liquid phase reaction. reaction speed.
- the heavy oil hydrogenation method of the present application can improve the mass transfer of the heavy oil liquid phase hydrogenation reaction by reducing the viscosity of the reaction material in the lower cylinder of the reactor according to the present application and then sequentially passing through the upper cylinder and the annular space to undergo catalytic hydrogenation reaction.
- Process driving force and reaction rate control the contact time of reaction materials and catalysts (especially different active catalysts), slow down the coking of the catalyst surface, reduce the deep cracking reaction of light oil, and improve the liquid yield and heavy oil in the liquid phase hydrogenation reaction of heavy oil. Conversion rate of impurity removal.
- Figure 1 is a schematic diagram of a preferred embodiment of the liquid phase reactor and heavy oil hydrogenation method of the present application
- Fig. 2 is a partially enlarged schematic diagram of the lower cylinder part of the reactor shown in Fig. 1;
- Fig. 3 is a schematic bottom view of the lower cylinder part of the reactor shown in Fig. 1.
- 1 is hydrogen
- 2 is heavy oil feedstock
- 3 is hydrogen oil mixer
- 4 is liquid feed
- 5 is lower cylinder
- 6 is inorganic membrane tube
- 7 is gas feed
- 8 is straight section
- 9 is upper cylinder
- 11 is the annular space
- 12 is the reaction product
- 13 is the discharge valve
- 14 is the exhaust gas
- 15 is the exhaust valve
- 16 is the grid
- 17 is the first hydrogenation catalyst
- 18 is the second hydrogenation catalyst.
- 19 is the upper cylinder wall
- 20 is the gas space
- 21 is the liquid phase space.
- any specific numerical value (including the end point of the numerical range) disclosed in this article is not limited to the precise value of the numerical value, but should be understood to also cover values close to the precise value, for example, within the range of ⁇ 5% of the precise value All possible values.
- between the endpoints of the range, between the endpoints and the specific point values in the range, and between the specific point values can be arbitrarily combined to obtain one or more new Numerical ranges, these new numerical ranges should also be regarded as specifically disclosed herein.
- inorganic membrane tube has a well-known meaning in the art, and generally refers to a tubular semipermeable membrane made of inorganic materials, for example, an inorganic ceramic membrane tube.
- This application does not have any special restrictions on the diameter and wall thickness of the inorganic membrane tube. Generally, the diameter can be about 2-50 mm, and the wall thickness can be about 0.1-5 mm. Multiple inorganic membrane tubes can be integrated into a tube bundle.
- any matters or matters not mentioned are directly applicable to those known in the art without any changes.
- any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby shall be regarded as part of the original disclosure or original record of the present invention, and shall not be It is regarded as new content that has not been disclosed or anticipated in this article, unless those skilled in the art think that the combination is obviously unreasonable.
- the present application provides a liquid phase reactor, which includes an outer cylinder and an inner cylinder arranged along the axial direction of the reactor.
- the outer cylinder includes an upper head, a straight cylinder section, and a lower cylinder.
- the head, an annular space is formed between the inner cylinder and the outer cylinder, and the top of the inner cylinder is open and communicates with the annular space, and is characterized in that: the inner cylinder sequentially includes from top to bottom Upper tube and lower tube, among which,
- the upper tube is located in the straight tube section, the cross-sectional area gradually decreases from top to bottom, the top is open, and the bottom is connected with the top of the lower tube;
- the lower cylinder is located in the lower head, the cross-sectional area gradually increases from top to bottom, the bottom end is hermetically connected with the inner wall of the lower head, and an inorganic membrane tube extending along the axial direction of the reactor is provided in the lower cylinder, thereby A shell-and-tube structure is formed, and the tube wall of the inorganic membrane tube is provided with pores for gas to pass through;
- the lower head is provided with a liquid inlet, a gas inlet, and a product outlet.
- the liquid inlet and the gas inlet communicate with the bottom of the lower cylinder, and the product outlet communicates with the bottom of the annular space, wherein the liquid inlet is connected to the shell of the lower cylinder.
- One of the shell side or the tube side of the shell-and-tube structure is connected, and the gas inlet is connected with the other one of the shell side or the tube side of the shell-and-tube structure.
- the lower tube of the reactor has a shell-and-tube structure, and its tube side corresponds to the inner space of the inorganic membrane tube, and its shell side corresponds to the tube wall of the inorganic membrane tube and the lower tube The space between the walls of the cylinder.
- the liquid inlet of the liquid phase reactor is in communication with the shell side of the shell and tube structure of the lower cylinder, and the gas inlet of the liquid phase reactor is in communication with the tube side of the shell and tube structure.
- reaction material moves from bottom to top in the upper cylinder, diffuses into the annular space through the upper head, and then moves from top to bottom in the annular space.
- the upper middle and upper part of the upper cylinder wall is preferably provided at a position where the distance from the bottom end of the upper cylinder is at least about 1/3, preferably about 1/2, of the total vertical height of the upper cylinder.
- the shape of the opening is not strictly limited. For example, it may be one or more shapes selected from rectangular, square, diamond, circular, hexagonal, etc., preferably circular.
- the aperture size of the opening (for non-circular openings is the diameter of the inscribed circle) is generally about 0.1 mm-50 mm, preferably about 5-15 mm.
- part of the reaction material in the upper cylinder can diffuse to the annular space through the openings of the upper cylinder wall, thereby shortening the residence time of the reaction material in the upper cylinder to a certain extent and avoiding undesired side reactions .
- the residence time of the heavy oil raw material on the surface of the highly active catalyst filled in the upper cylinder can be avoided too long, so that the required conversion depth is reached and side reactions are reduced. And cracking reaction, and then can improve the liquid yield.
- the ratio of the vertical height of the cylinder wall of the perforated portion of the upper cylinder to the total vertical height of the upper cylinder is about 1:1.5 to about 1:20, preferably about 1:2 to about 1. : 8.
- the upper cylinder has a frusto-conical shape with a cross-sectional area gradually decreasing from top to bottom, and the ratio of the maximum cross-sectional diameter to the reactor diameter is about 1:1.05 to about 1:50, It is preferably about 1:1.5 to about 1:5, and the ratio of the largest cross-sectional diameter to the smallest cross-sectional diameter is about 1:1.1 to about 1:30, preferably about 1:2 to about 1:10.
- the lower cylinder has a frusto-conical shape with a cross-sectional area gradually decreasing from bottom to top, and the ratio of the maximum cross-sectional diameter to the reactor diameter is about 1:1.05 to about 1:50, It is preferably about 1:1.15 to about 1:5, and the ratio of the largest cross-sectional diameter to the smallest cross-sectional diameter is about 1:1.1 to about 1:30, preferably about 1:2 to about 1:10.
- the lower cylinder can serve as a viscosity-reducing component
- the shell side of the shell-and-tube structure is connected to one of the liquid inlet and the gas inlet of the reactor, and the tube of the shell-and-tube structure The side is connected to the other of the liquid inlet and the gas inlet of the reactor, wherein the tube wall of the inorganic membrane tube is provided with pores, so that the gas on the shell side or the tube side can diffuse to the space on the other side through the pores , Thereby reducing the viscosity of the liquid material on the other side.
- the pores on the tube wall of the inorganic membrane tube have an average pore diameter of about 0.5 nm-200 nm, so that the bubbles diffused through the pores have an average size of about 10-1000 nm, preferably about 50-500 nm.
- a catalyst is filled in the upper cylinder and/or the annular space.
- the upper cylinder is filled with a first catalyst, such as a first hydrogenation catalyst
- the annular space is filled with a second catalyst, such as a second hydrogenation catalyst, wherein the first catalyst and the second hydrogenation catalyst are
- the two catalysts can be the same or different.
- the catalytic activity of the first catalyst is higher than that of the second catalyst, for example, the hydrogenation activity of the first hydrogenation catalyst is higher than that of the second hydrogenation catalyst.
- the top of the outer cylinder of the reactor (that is, inside the upper head) is provided with a gas space, and the upper head of the reactor is provided with a gas outlet (for example, at the highest point of the upper head), It is used to continuously or intermittently discharge the gas in the reaction system during the reaction process.
- a grid is provided between the top of the upper cylinder and the upper head of the reactor to fix the catalyst bed in the upper cylinder and prevent the catalyst from entering the space in the upper head.
- the reaction mass is allowed to pass.
- the grille may be a sealing plate composed of grille bars or Johnson mesh.
- the present application provides a method for hydrogenating heavy oil using the liquid phase reactor of the present application, which includes the following steps:
- reaction material enters the bottom of the upper cylinder, and the first hydrogenation reaction is carried out in the presence of the first hydrogenation catalyst packed in the upper cylinder during the process of passing through the upper cylinder from bottom to top, to obtain Partially hydrogenated reaction material;
- the partially hydrogenated reaction material enters the annular space, and the second hydrogenation is carried out in the presence of the second hydrogenation catalyst packed therein during the process of passing through the annular space from top to bottom Reaction to obtain a hydrogenation reaction product, wherein the second hydrogenation catalyst is the same as or different from the first hydrogenation catalyst.
- the ratio of the feed amount of hydrogen (Nm 3 /h) in step (1) to the feed amount of heavy oil (m 3 /h) is also referred to in this application as
- the hydrogen-to-oil volume ratio or hydrogen-to-oil ratio is about 1500:1 to about 1:1, preferably about 500:1 to about 1:1.
- the reactor discharge is controlled by the liquid level in the upper part of the reactor to ensure that the hydrogenation reaction process is full liquid phase hydrogenation.
- the conditions of the first hydrogenation reaction include: a reaction temperature of about 60-500°C, preferably about 320-460°C; a reaction pressure of about 0.5-20.0 MPa, preferably about 6.0-15.0 MPa; when fresh feed liquid hourly space velocity of about 0.01-10.0h -1, preferably about 0.1-2.0h -1.
- the conditions of the second hydrogenation reaction include: the reaction temperature is about 120-550°C, preferably about 350-500°C; the reaction pressure is about 0.5-20.0 MPa, preferably about 6.0-15.0 MPa ; when fresh feed liquid hourly space velocity of about 0.1-10.0h -1, preferably from about 0.5-5.0h -1.
- the heavy oil can be various types of heavy oil, for example, it can be a heavy oil with a specific gravity ⁇ 0.91, a high viscosity and poor fluidity, such as vacuum residue, wax oil, coal tar, lubricating oil, Oil products such as anthracene oil, deasphalted oil, biodiesel, animal oil or vegetable oil.
- the heavy oil raw materials pre-mixed with hydrogen are generally obtained by mixing with a hydrogen oil mixer, such as using static mixers, dissolved air pumps, colloid mills, microporous plate nano/micro hydrogen dispersion components, ceramic membrane nano/micro hydrogen Obtained by equipment with gas-liquid mixing function such as dispersing components.
- a hydrogen oil mixer such as using static mixers, dissolved air pumps, colloid mills, microporous plate nano/micro hydrogen dispersion components, ceramic membrane nano/micro hydrogen Obtained by equipment with gas-liquid mixing function such as dispersing components.
- the mass content of hydrogen is generally about 0.01 wt% to 20%, preferably about 2.0 wt% to 8.0 wt% of the weight of the heavy oil feedstock.
- the activity of the first hydrogenation catalyst is higher than that of the second hydrogenation catalyst.
- the ratio of the activity of the first hydrogenation catalyst to the activity of the second hydrogenation catalyst is about 1.05:1 to about 10. :1.
- the level of activity mentioned is for the chemical reactions occurring in the upper cylinder and the annular space. It is expressed in terms of the number of reactants converted to raw materials per unit volume (or mass) of the catalyst per unit time.
- the level of catalytic activity can be determined by The specific surface area of the catalyst carrier, the nature of the active center on the surface, and the number of active centers per unit surface area are selected or adjusted during the preparation process.
- the catalyst activity evaluation method is as follows: Under the same raw material composition and reaction conditions, the same volume of catalyst is used for hydrogenation reaction on the same set of equipment, after the same residence time, the product composition data is measured, and the conversion ratio is calculated as the judgement activity. The basis of high and low.
- the first and second hydrogenation catalysts can select suitable hydrogenation catalysts according to the needs of the reaction to achieve different hydrogenation purposes.
- the first and second hydrogenation catalysts may each independently be selected from hydrorefining catalysts, pre-hydrorefining catalysts, hydro-upgrading catalysts, selective hydrogenation catalysts, hydrotreating catalysts, and hydrocracking catalysts. , Supplementary hydrogenation catalysts, etc.
- These catalysts can be commercial catalysts, or they can be prepared by conventionally used catalysts in the field, or prepared according to prior art methods.
- the first hydrogenation catalyst and the second hydrogenation catalyst may independently be catalysts used in existing heavy oil hydrogenation devices, such as 3936, 3996, FF-16, FF-24 developed by Fushun Petrochemical Research Institute , FF-26, FF-36, FF-46, FF-56 hydrotreating, UOP's HC-K, HC-P catalyst, Topsoe's TK-555, TK-565 catalyst, Akzo's KF-847 , KF-848 catalyst.
- existing heavy oil hydrogenation devices such as 3936, 3996, FF-16, FF-24 developed by Fushun Petrochemical Research Institute , FF-26, FF-36, FF-46, FF-56 hydrotreating, UOP's HC-K, HC-P catalyst, Topsoe's TK-555, TK-565 catalyst, Akzo's KF-847 , KF-848 catalyst.
- the first and second hydrogenation catalysts may each independently comprise a carrier and an active component.
- the carrier content may account for about 45-95% by weight, and the active component may account for About 5-55wt%, wherein the active component is preferably selected from one or more of the metal elements of Group VIB and Group VIII, and the carrier is preferably alumina and/or silicon-containing alumina.
- the group VIB metal element is generally Mo and/or W, and the group VIII metal element is generally Co and/or Ni.
- the first and second hydrogenation catalysts each independently contain about 5-40 wt% of a group VIB metal element and about 3- 15wt% Group VIII metal element.
- the activity of the first hydrogenation catalyst filled in the upper cylinder is higher than that of the second hydrogenation catalyst filled in the annular space, and the annular space can be filled with all or part of its activity lower than that of the upper Cartridge active hydrogenation catalyst.
- the catalytic reaction of this application can remove some or all of the impurities such as sulfur, nitrogen, oxygen, arsenic, metals, residual carbon, etc., or saturated/partially saturated olefins, aromatic hydrocarbons, diolefins, or hydrocarbon molecular isomerization. Reactions such as chemical reaction, alkylation, cyclization, aromatization, cracking, and pyrolysis.
- the general hydrogenation process of heavy oil has the following characteristics: 1) Heavy oil has the characteristics of high density and high viscosity. During the hydrogenation process, due to the large mass transfer interface resistance of the hydrogen oil, there is a low reaction rate and depth of impurity removal.
- the heavy oil hydrogenation method of the present application uses a specially designed liquid phase reactor. After the reaction material passes through the lower cylinder to reduce the viscosity, it then passes through the upper cylinder and the annular space to undergo hydrogenation reaction, thereby improving the heavy oil liquid phase hydrogenation reaction. The driving force and reaction rate of the mass transfer process. Further, by using a relatively high activity hydrogenation catalyst in the upper cylinder and a relatively low activity hydrogenation catalyst in the annular space, the contact time between the reaction material and the catalysts of different activities can be controlled, thereby reducing the coking of the catalyst surface , Reduce the deep cracking reaction of light oil, promote the hydrogenation conversion rate of heavy oil, and improve the liquid yield and heavy de-impurity conversion rate of the heavy oil liquid phase hydrogenation reaction process.
- the cross-sectional area of the lower cylinder gradually decreases from bottom to top, and its shell-and-tube structure reduces the viscosity of the material while increasing the dissolution and dispersion of hydrogen in the raw oil and the uniform dispersion. It can reduce the hydrogen oil mass transfer interface resistance and increase the hydrogenation reaction rate; the cross-sectional area of the upper cylinder gradually increases from bottom to top, which can realize that as the reaction progresses, the contact between the raw material and the catalyst is gradually in contact, and the reaction process is controlled.
- the temperature rise is more uniform to prevent the problems of concentrated heat release and coking on the surface of the catalyst; the upper part of the upper cylinder wall has holes, so that the reaction products in the upper cylinder can diffuse to a certain conversion rate after a certain residence time and a certain conversion rate.
- the annular space on the one hand, can reduce the excessive reaction of materials on the surface of the catalyst, on the other hand, it can take away the reaction heat in time to prevent local hot spots; the upper cylinder is filled with high-activity catalysts, which can increase the concentration of impurities and materials in the feed.
- the hydrogenation reaction rate in the early stage of the reaction is further improved; and the annular space is filled with a low-activity catalyst, which can reduce the coking of the material on the catalyst surface under the condition of higher temperature in the late stage of the reaction, thereby reducing the cracking reaction.
- the liquid phase reactor of the present application includes an outer cylinder and an inner cylinder arranged along the axial direction of the reactor.
- the outer cylinder includes an upper head, a straight cylinder section 8 and
- an annular space 11 is formed between the inner cylinder and the outer cylinder, the top of the inner cylinder is open and communicates with the annular space 11, and the inner cylinder sequentially includes Upper tube 9 and lower tube 5.
- the upper cylinder 9 is located in the straight cylinder section 8, the cross-sectional area gradually decreases from top to bottom, the top is open, and the bottom is connected with the top of the lower cylinder 5.
- the lower cylinder 5 is located in the lower head 10, the cross-sectional area gradually increases from top to bottom, and the bottom end is hermetically connected with the inner wall of the lower head 10.
- the lower cylinder 5 is provided with an inorganic membrane tube 6 extending along the axial direction of the reactor to form a shell-and-tube structure.
- the inorganic membrane tube has a channel for gas to pass through on the tube wall.
- the lower head 10 is provided with a liquid inlet, a gas inlet, and a product outlet.
- the liquid inlet and the gas inlet communicate with the bottom of the lower cylinder 5, and the product outlet communicates with the bottom of the annular space 11, wherein the liquid inlet and the lower cylinder 5 is in communication with one of the shell side or the tube side (preferably the shell side) of the shell and tube structure, and the gas inlet is connected to the other of the shell side or the tube side of the shell and tube structure (preferably the tube side). ) Connected.
- a grid 16 is provided, which can block the catalyst from entering the space inside the upper head And fix the catalyst bed in the upper cylinder, but allow the reaction material to pass through.
- the lower part of the grid 16 is a catalyst.
- a liquid level control can be set on the upper part of the catalyst bed of the reactor cylinder so that the catalyst is completely immersed in the liquid phase space 21.
- a plurality of inorganic membrane tubes 6 extending along the axial direction of the reactor are provided in the lower tube 5 of the reactor of the present application.
- the arrangement of the inorganic membrane tubes 6 is not particularly limited. For example, it may be arranged in a ring shape as shown in FIG. 3.
- the heavy oil feedstock 2 and hydrogen 1 are mixed by the hydrogen oil mixer 3 and used as the liquid feed 4 from the liquid phase reactor.
- the bottom part enters the shell side of the shell-and-tube structure of the lower cylinder 5, and the hydrogen gas enters the tube side of the shell-and-tube structure of the lower cylinder 5 as a gas feed 7 (that is, inside the inorganic membrane tube 6).
- the liquid feed 4 enters the upper cylinder 9 after being reduced in viscosity, and undergoes a hydrogenation reaction in the presence of the first hydrogenation catalyst 17 in the process of flowing through the upper cylinder 9 from bottom to top.
- the obtained partially hydrogenated reaction material can diffuse into the annular space 11 through the openings in the upper middle of the upper cylinder wall 19, or enter the annular space 11 through the area in the upper head that is connected to both the upper cylinder and the annular space.
- the reaction material entering the annular space 11 further undergoes hydrogenation reaction in the presence of the second hydrogenation catalyst 18 in the process of flowing through the annular space from top to bottom.
- the final reaction product 12 obtained at the bottom of the annular space 11 leaves the liquid phase reactor under the control of the discharge valve 13.
- the gas generated during the reaction and the dissolved gas separated are collected in the gas space 20 at the top of the outer cylinder of the reactor, and discharged as the exhaust gas 14 under the control of the exhaust valve 15.
- the feedstock oil 1 used in the comparative examples and examples of this application is a mixed wax oil feedstock, and the specific properties are shown in Table 1.
- the feedstock oil 2 is a vacuum residue feedstock, and the specific properties are shown in Table 2.
- the mixed wax oil raw materials shown in Table 1 are used as the hydrogenation reaction feed, and the conventional gas, liquid, and solid three-phase fixed-bed hydrogenation reactor is used for hydrogenation.
- the catalyst uses two beds, and the two beds have the same height. Each bed adopts the commercially available FZC protective agent/3936/3996 catalyst developed by Fushun Petrochemical Research Institute.
- the FZC protective agent is 14% of the total catalyst bed height. 3936 and 3996 catalysts each account for the total catalyst bed. 43% of height.
- the hydrogenation reaction conditions are as follows: the reaction temperature is 380-427°C, the reaction pressure is 15 MPaG, the liquid hourly volumetric space velocity is 0.72 h -1 , and the hydrogen-to-oil volume ratio at the reactor inlet is 400.
- the temperature distribution of the catalyst bed is shown in Table 3, and the properties of the liquid product are shown in Table 4.
- the mixed wax oil raw materials shown in Table 1 are used as the hydrogenation reaction feed, and the gas, liquid, and solid three-phase fixed-bed hydrogenation reactor is used for hydrogenation.
- the reactor adopts a sleeve structure and is divided into an outer cylinder and an inner cylinder.
- the inner cylinder is a straight cylinder, and the reaction feed enters from the inner cylinder and flows out from the outer cylinder.
- the diameter of the outer cylinder of the sleeve reactor is 300mm, and the diameter of the inner cylinder is 150mm.
- the hydrogenation catalyst filled in the inner cylinder is a commercial FZC protective agent/3996 catalyst developed by Fushun Petrochemical Research Institute
- the hydrogenation catalyst filled in the outer cylinder is a commercial FZC protective agent/3936 catalyst developed by Fushun Petrochemical Research Institute.
- the FZC protective agent in the outer cylinder is 12% of the total catalyst volume of the upper cylinder
- the FZC protective agent in the annular space is 12% of the total catalyst volume of the annular space.
- the amount of hydrogen contained in the bottom feed of the reactor is 9.10% of the mass of the feed oil (the corresponding hydrogen-to-oil volume ratio is 469).
- the reaction conditions of the inner cylinder of the reactor are as follows: the reaction temperature is 380-403°C, the reaction pressure is 15.2MPaG, the liquid hourly volumetric space velocity of the raw oil is 1.0h -1 ; the reaction conditions in the outer cylinder are as follows: the reaction temperature is 403- At 418°C, the reaction pressure is 14.9 MPaG, and the liquid hourly volumetric space velocity of the feed oil is 1.3 h -1 .
- the first hydrogenation catalyst filled in the upper cylinder of the liquid phase reactor adopts the commercially available FZC protective agent/3996 catalyst developed by Fushun Petrochemical Research Institute
- the second hydrogenation catalyst filled in the annular space adopts The commercially available FZC protective agent/3936 catalyst developed by Fushun Petrochemical Research Institute, in which the FZC protective agent in the upper cylinder is 14% of the total catalyst volume of the upper cylinder, and the FZC protective agent in the annular space is 14% of the total catalyst volume of the annular space .
- the amount of hydrogen contained in the liquid feed of the reactor is 2.0% of the mass of the feed oil (the sum of the fresh feed oil and the circulating oil); the hydrogen input in the lower cylinder of the reactor is the feed oil (the sum of the fresh feed oil and the circulating oil) ) 3.10% of the mass (the corresponding hydrogen oil volume ratio is 273); the circulation ratio (that is, the mass ratio of circulating oil to fresh feedstock oil) is 2.5.
- the reaction conditions in the upper cylinder of the reactor are as follows: the reaction temperature is 380-393°C, the reaction pressure is 15.0MPaG, the liquid hourly volumetric space velocity of the fresh raw oil is 1.2h -1 ; the reaction conditions in the annular space are as follows: the reaction temperature is The temperature is 393-402°C, the reaction pressure is 14.5MPaG, and the liquid hourly volumetric space velocity of the fresh feedstock oil is 1.6h -1 .
- the ratio of the maximum cross-sectional diameter of the upper cylinder of the reactor (that is, the diameter of the top plane) to the diameter of the reactor is 1:1.5, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 4:1; the upper part of the upper cylinder wall is away from the upper cylinder The distance from the bottom end is 2/3 of the total vertical height of the upper cylinder and the position is evenly opened
- the diameter of the circular hole is 85%; the ratio of the maximum cross-sectional diameter of the lower cylinder to the diameter of the reactor is 1:2.5, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 2.4:1.
- the first hydrogenation catalyst filled in the upper cylinder of the liquid phase reactor adopts the commercially available FZC protective agent/FF-26 catalyst developed by Fushun Petrochemical Research Institute
- the second hydrogenation catalyst filled in the annular space adopts the commercially available FZC protective agent/3996 catalyst developed by Fushun Petrochemical Research Institute, in which the FZC protective agent in the upper cylinder is 15% of the total catalyst volume of the upper cylinder, and the FZC protective agent in the annular space is the total catalyst volume of the annular space. 15%.
- the amount of hydrogen contained in the liquid feed of the reactor is 1.62% of the mass of the feed oil (the sum of the fresh feed oil and the circulating oil); the hydrogen input in the lower cylinder of the reactor is the feed oil (the sum of the fresh feed oil and the circulating oil) ) 3.30% of the mass (corresponding to the volume ratio of hydrogen to oil is 253); the circulation ratio is 2.0.
- the reaction conditions in the upper cylinder of the reactor are as follows: the reaction temperature is 380-393°C, the reaction pressure is 15.0MPaG, the liquid hourly volumetric space velocity of the fresh raw oil is 1.0h -1 ; the reaction conditions in the annular space are as follows: the reaction temperature is The temperature is 394-405°C, the reaction pressure is 14.5MPaG, and the liquid hourly volumetric space velocity of the fresh raw oil is 1.8h -1 .
- the ratio of the maximum cross-sectional diameter of the upper cylinder of the reactor to the diameter of the reactor is 1:2, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 3:1; the distance between the upper part of the upper cylinder wall and the bottom end of the upper cylinder is the upper cylinder Open evenly at positions 1/2 and above of the total vertical height
- the opening rate of the hole is 80%; the ratio of the maximum cross-sectional diameter of the lower cylinder to the reactor diameter is 1:2.5, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 2.4:1.
- the first hydrogenation catalyst filled in the upper cylinder of the liquid phase reactor adopts the commercially available FZC protective agent/FF-46 catalyst developed by Fushun Petrochemical Research Institute, and the second hydrogenation catalyst filled in the annular space
- the catalyst adopts the commercially available FZC protective agent/FF-26 catalyst developed by Fushun Petrochemical Research Institute, and the FZC protective agent in the upper cylinder and the annular space is 15% of the respective total catalyst volume.
- the amount of hydrogen contained in the liquid feed of the reactor is 1.60% of the mass of the feed oil (the sum of the fresh feed oil and the circulating oil); the hydrogen input in the lower cylinder of the reactor is the feed oil (the sum of the fresh feed oil and the circulating oil) ) 3.15% by mass (corresponding to the volume ratio of hydrogen to oil is 245); the circulation ratio is 2.0.
- the reaction conditions in the upper cylinder of the reactor are as follows: the reaction temperature is 378-390°C, the reaction pressure is 15.0MPaG, the liquid hourly volumetric space velocity of the fresh raw oil is 1.0h -1 ; the reaction conditions in the annular space are as follows: the reaction temperature is 391-400°C, the reaction pressure is 14.5MPaG, and the liquid hourly volumetric space velocity of the fresh raw material oil is 1.8h -1 .
- the ratio of the maximum cross-sectional diameter of the upper cylinder of the reactor to the diameter of the reactor is 1:1.5, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 4:1; the distance between the upper part of the upper cylinder wall and the bottom end of the upper cylinder is upper
- the positions of 2/3 and above of the total vertical height of the cylinder are evenly opened
- the diameter of the circular hole is 80%; the ratio of the maximum cross-sectional diameter of the lower cylinder to the reactor diameter is 1:3, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 2:1.
- the first hydrogenation catalyst filled in the upper cylinder of the liquid phase reactor adopts the commercially available FZC protective agent/FF-46 catalyst developed by Fushun Petrochemical Research Institute, and the second hydrogenation catalyst filled in the annular space
- the catalyst adopts the commercially available FZC protective agent/FF-26 catalyst developed by Fushun Petrochemical Research Institute, and the FZC protective agent in the upper cylinder and the annular space is 35% of the total catalyst volume of each.
- the amount of hydrogen contained in the liquid feed of the reactor is 4.20% of the mass of the feed oil (the sum of the fresh feed oil and the circulating oil); the hydrogen input in the lower cylinder of the reactor is the feed oil (the sum of the fresh feed oil and the circulating oil) ) 7.96% of the mass (corresponding to the volume ratio of hydrogen to oil is 410); the circulation ratio is 2.0.
- the reaction conditions in the upper cylinder of the reactor are as follows: the reaction temperature is 380-394°C, the reaction pressure is 15.0MPaG, the liquid hourly volumetric space velocity of the fresh raw oil is 2.5h -1 ; the reaction conditions in the annular space are as follows: the reaction temperature is The temperature is 393-406°C, the reaction pressure is 14.5MPaG, and the liquid hourly volumetric space velocity of the fresh raw oil is 0.5h -1 .
- the ratio of the maximum cross-sectional diameter of the upper cylinder of the reactor to the diameter of the reactor is 1:2, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 2.5:1; the distance between the upper part of the upper cylinder wall and the bottom end of the upper cylinder is upper The position of 1/2 and above of the total vertical height of the cylinder is evenly opened The diameter of the circular hole is 75%; the ratio of the maximum cross-sectional diameter of the lower cylinder to the reactor diameter is 1:2, and the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter is 2.5:1.
- the temperature rise of the catalyst in the upper cylinder that the temperature rise is greatly reduced, and the temperature rise in the reaction process is controlled to be more uniform, which can prevent the problems of concentrated heat release and coking on the surface of the catalyst.
- the reaction products in the upper cylinder can diffuse to the annular space in time after a certain residence time and a certain conversion rate. On the one hand, it can reduce the material on the surface of the catalyst.
- Excessive reaction can take away the reaction heat in time to prevent local hot spots; the lower cylinder not only has the effect of reducing viscosity, but also can improve the dissolution and dispersion of hydrogen in the feed oil and the uniformity of dispersion, and reduce the hydrogen-oil mass transfer interface Resistance to increase the hydrogenation reaction rate.
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Abstract
一种液相反应器及其应用,该反应器包括外筒体和沿反应器轴向设置的内筒体,外筒体包括上封头、直筒段(8)和下封头(10),内筒体和外筒体之间形成有环形空间(11),内筒体顶端敞口并与环形空间(11)连通;内筒体由上至下依次包括上筒(9)和下筒(5),其中上筒(9)位于直筒段(8)内,由上而下横截面积逐渐减小;下筒(5)位于下封头(10)内,由上而下横截面积逐渐增大;下筒(5)内设置有沿反应器轴向延伸的无机膜管(6),从而形成管壳式结构,无机膜管(6)的管壁上设置有供气体通过的孔道。
Description
相关申请的交叉引用
本申请要求申请人于2019年10月25日提交的申请号为201911020744.9、名称为“一种重油加氢反应器及加氢方法”的专利申请的优先权,其内容经此引用全文并入本文。
本申请涉及液相催化反应的领域,具体涉及一种液相反应器及其应用。
随着原油重质化、劣质化趋势的加氢,原油的组分越来越重,即重质原油的比例越来越高,因此重油加氢处理技术的进步成为加氢过程研究的关键之一。重油加氢反应器分为多种类型,如固定床加氢反应器、悬浮床加氢反应器、沸腾床加氢反应器等,以固定床加氢反应器的应用最为广泛,其中上流式固定床反应器能够处理多种类型的重质油品,在油品加氢过程中显示出了独特的优势,如劣质油品渣油、煤液化油中由于杂质含量高,容易造成加氢催化剂中毒或者催化剂孔道堵塞而快速失活,并且杂质可能堵塞床层使压降快速升高导致反应器工况变差,甚至无法正常操作,若采用上流式加氢反应过程使气液并流向上运动造成催化剂床层的膨胀,可以增加床层的空隙率,避免催化剂床层的堵塞。
在重油加氢工艺中,液相加氢工艺过程相比于传统的固定床气/液/固三相加氢工艺而言,具有加氢反应速率快、反应效率高、能耗低、投资少等诸多优势,得到广泛认可和应用,因此,上流式液相加氢反应过程综合了上流式加氢反应器和液相加氢反应工艺过程二者的优势,应用于加氢过程已经显示出了一定的优势。但是,重油液相加氢反应器及反应工艺中仍然存在如下问题:(1)重油黏度大,氢油传质速率低,导致反应速率低;(2)重油加氢过程的反应停留时间不易控制,停留短达不到反应要求的深度,而反应停留时间长副反应或裂解及催化剂结焦严重的问题。
CN 109306272A提出了一种重油加氢处理***,该重油加氢处理***包括主反应器和至少一个子反应器,主反应器包括第一筒体,第一筒体用于盛放物料,子反应器包括:混合单元,用于将物料和氢气混合,混合单元包括第二筒体,第二筒体上设置有物料入口、氢气入口和第一出口,物料入口与第一筒体的出口连通;强化装置,强化装置的入口与第二筒体的第一出口连通,强化装置的出口与第一筒体的容纳腔连通,强化装置用于给物料提供能量以使物料发生裂化反应。
CN 108659882 A提出了一种重油加氢方法及其加氢***,其中,所述重油加氢方法包括:将重油、循环油、硫化剂和催化剂混合,与氢气在第一反应器中进行加氢裂化,得到第一反应产物;将第一反应产物的部分物料返回第一反应器中,将其余物料在第二反应器中进行加氢裂化,得到第二反应产物;将第二反应产物分离为轻组分和重组分,将部分重组分返回第二反应器中,将其余重组分分离得到馏分油做为循环油;将轻组分在第三反应器中进行加氢精制得到轻油产品。该发明方法主要是为了提高传热、传质效率,保证物料在反应器内足够的停留时间,提高重油转化率和轻质油收率,但只是通过常规的加氢反应器结构,更不能有效的控制催化剂与原料的接触时间,也不能保证重油转化率和轻质油收率。
CN202063881U公开了一种液相加氢反应器,反应器顶部封头内设置混合器,混合器有混合油进料口和氢气入口,溶氢混合物出口和气体出口,混合物溶氢混合物出口插到反应器液相中。该专利的目的是通过混氢器在反应器内的结构,来增加气液相接触面积,使氢气溶解在混合油中,来提高加氢反应效率。
CN101632911B提出了一种上流式反应器及其应用,上流式反应器包括位于反应器底部的初始分布器和初始分布器上方的中间分布器,初始分布器由一个锥形折流板和一个位于其上方的筛板组成;中间分布器由开孔筛板和筛板板串结构组成,该发明所提供的上流式反应器的目的是实现气体均匀分布,从而提高催化剂的利用率。
综上所述,现有技术中的重质油加氢反应器及上流式液相加氢反应器,大多思路都是通过现有设备改进工艺、采用新的溶氢设备或多次溶氢等方法来提高加氢反应效率,没有解决重油液相加氢反应过程存在的反应速率低、转化深度不足、温升不均匀的问题,以及停留时 间长造成的液体收率低、副反应及裂解反应严重等问题。
发明内容
为克服现有技术的不足,本申请的目的是提供一种新型的液相反应器及其应用,所述反应器通过采用特殊设计的内、外双筒体结构,有利于降低液相反应物料的粘度,提高液相反应的传质推动力和反应速率,因而适用于高黏度液体物料的液相反应,特别是重油的液相催化加氢反应。
为了实现上述目的,本申请的一个方面提供了一种液相反应器,包括外筒体和沿反应器轴向设置的内筒体,所述外筒体包括上封头、直筒段和下封头,所述内筒体和外筒体之间形成有环形空间,所述内筒体顶端敞口并与所述环形空间连通,其特征在于:所述内筒体由上至下依次包括上筒和下筒,其中,
上筒位于所述直筒段内,由上而下横截面积逐渐减小,顶端敞口,底部与下筒顶部连通;
下筒位于所述下封头内,由上而下横截面积逐渐增大,底端与下封头内壁密闭连接,所述下筒内设置有沿反应器轴向延伸的无机膜管,从而形成管壳式结构,所述无机膜管的管壁上设置有供气体通过的孔道;
下封头设置有液体入口、气体入口和产物出口,液体入口和气体入口与所述下筒的底部连通,产物出口与所述环形空间的底部连通,其中所述液体入口与下筒的管壳式结构的壳侧或管侧中的一者连通,所述气体入口与所述管壳式结构的壳侧或管侧中的另一者连通。
优选地,所述液体入口与下筒的管壳式结构的壳侧连通,所述气体入口与所述管壳式结构的管侧连通。
优选地,所述上筒内装填有第一催化剂,所述环形空间内装填有与所述第一催化剂相同或不同的第二催化剂。
本申请的另一方面提供了使用根据本申请的液相反应器进行重油加氢的方法,包括如下步骤:
(1)将重油原料经由液体入口进料到下筒的管壳式结构的壳侧,并将氢气经由气体入口进料到所述管壳式结构的管侧,在所述下筒的顶部得到与所述重油原料相比黏度降低的包含氢气的反应物料,任选 地,所述重油原料中预先混合有氢气;
(2)使所述反应物料进入上筒底部,并使其在由下而上通过所述上筒的过程中在其中填装的第一加氢催化剂的存在下进行第一加氢反应,得到部分加氢的反应物料;
(3)使所述部分加氢的反应物料进入环形空间,并使其在由上而下通过所述环形空间的过程中在其中填装的第二加氢催化剂的存在下进行第二加氢反应,得到加氢反应产物,其中所述第二加氢催化剂与所述第一加氢催化剂相同或不同。
在本申请的液相反应器中,所述具有管壳式结构的下筒可以起到降低物料黏度的作用,其中气体物料经过无机膜管管壁上设置的孔道扩散进入液体物料中,对液体物料产生剪切,同时均匀地分散/溶解到液体物料中,从而降低其黏度。例如,当气体物料进入所述管壳式结构的管侧(即无机膜管内),而液体物料进入所述管壳式结构的壳侧(即无机膜管管壁与下筒筒壁之间的空间)时,气体物料可经由无机膜管管壁上设置的孔道由管内向管外的空间扩散,产生由内向外的推动力,而液体物料进入壳侧空间后,由于下筒的截面积自下往上逐渐缩小,产生了指向下筒顶端的中心的推动力,因此扩散的气体物料可对液体物料产生较大的剪切力,这一方面大幅度提高了气体物料在液体物料中的溶解分散量和分散均匀性,降低了所得反应物料的黏度,另一方面在扩散气体的作用下,使反应物料中的大分子和小分子之间的混合更加均匀,改善物料的流动性,也降低了物料黏度。此外,在本申请的液相反应器中,溶解分散了大量气体的反应物料进入上筒,在其内发生反应的过程中,由于横截面积逐渐增加,气体逐渐由液相主体内表面向外表面扩散,同样具有改善反应物料的流动性的作用。因此,采用本申请的反应器,可以在进料过程中和整个液相反应过程中保持降低反应物料黏度以及改善物料流动性的作用,从而有助于提高液相反应的传质过程推动力和反应速率。
本申请的重油加氢方法,通过在根据本申请的反应器的下筒内使反应物料黏度降低后依次经过上筒和环形空间发生催化加氢反应,可以提高重油液相加氢反应的传质过程推动力和反应速率,控制反应物料与催化剂(特别是不同活性催化剂)的接触时间,减缓催化剂表面结焦,减少轻质油深度裂解反应,提高重油液相加氢反应过程的液体 收率和重油脱杂质转化率。
附图是用来提供对本申请的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本申请,但并不构成对本申请的限制。在附图中:
图1是本申请的液相反应器和重油加氢方法的一种优选实施方式的示意图;
图2是图1所示反应器的下筒部分的局部放大的示意图;
图3是图1所示反应器的下筒部分的仰视示意图。
1为氢气,2为重油原料,3为氢油混合器,4为液体进料,5为下筒,6为无机膜管,7为气体进料,8为直筒段,9为上筒,10为下封头,11为环形空间,12为反应产物,13为出料阀,14为排放气,15为排气阀,16为格栅,17为第一加氢催化剂,18为第二加氢催化剂,19为上筒筒壁,20为气体空间,21为液相空间。
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本申请,并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值,而应当理解为还涵盖了接近该精确值的值,例如在该精确值±5%范围内的所有可能的数值。并且,对于所披露的数值范围而言,在该范围的端点值之间、端点值与范围内的具体点值之间,以及各具体点值之间可以任意组合而得到一个或多个新的数值范围,这些新的数值范围也应被视为在本文中具体公开。
除非另有说明,本文所用的术语具有与本领域技术人员通常所理解的相同的含义,如果术语在本文中有定义,且其定义与本领域的通常理解不同,则以本文的定义为准。
在本申请中,所谓的“上”和“下”是指沿反应器的轴向方向的上和下。
在本申请中,术语“无机膜管”具有本领域公知的含义,通常指由无机材料制成的管式半透膜,例如可以为无机陶瓷膜管。本申请对 所述无机膜管的直径和壁厚没有特别的限制,通常直径可以为约2-50mm,壁厚可以为约0.1-5mm,多根无机膜管可以集成为一个管束。
本申请中,除了明确说明的内容之外,未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且,本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合,由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分,而不应被视为是本文未曾披露或预期过的新内容,除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献,包括但不限于教科书和期刊文章等,均通过引用方式全文并入本文。
如上所述,在第一方面,本申请提供了一种液相反应器,包括外筒体和沿反应器轴向设置的内筒体,所述外筒体包括上封头、直筒段和下封头,所述内筒体和外筒体之间形成有环形空间,所述内筒体顶端敞口并与所述环形空间连通,其特征在于:所述内筒体由上至下依次包括上筒和下筒,其中,
上筒位于所述直筒段内,由上而下横截面积逐渐减小,顶端敞口,底部与下筒顶部连通;
下筒位于所述下封头内,由上而下横截面积逐渐增大,底端与下封头内壁密闭连接,所述下筒内设置有沿反应器轴向延伸的无机膜管,从而形成管壳式结构,所述无机膜管的管壁上设置有供气体通过的孔道;
下封头设置有液体入口、气体入口和产物出口,液体入口和气体入口与所述下筒的底部连通,产物出口与所述环形空间的底部连通,其中所述液体入口与下筒的管壳式结构的壳侧或管侧中的一者连通,所述气体入口与所述管壳式结构的壳侧或管侧中的另一者连通。
根据本申请,所述反应器的下筒具有管壳式结构,其管侧对应于所述无机膜管的内部空间,而其壳侧对应于所述无机膜管的管壁与所述下筒的筒壁之间的空间。
在优选的实施方式中,所述液相反应器的液体入口与下筒的管壳式结构的壳侧连通,所述液相反应器的气体入口与所述管壳式结构的管侧连通。
在本申请的液相反应器中,反应物料在上筒内由下而上移动,通 过上封头扩散至环形空间,而后在环形空间内由上而下移动。
在某些优选的实施方式中,所述上筒筒壁的中上部,优选在距上筒底端的距离为上筒总垂直高度的至少约1/3、优选约1/2的位置,设置有若干开孔,一般开孔部分的筒壁的开孔率为约30%-95%,优选约55%-75%。所述开孔的形状没有严格限制,例如可以为选自长方形、正方形、菱形、圆形、六角形等中的一种或多种的形状,优选为圆形。所述开孔的孔径大小(对于非圆形开孔为内切圆的直径)一般为约0.1mm-50mm,优选约5-15mm。在此类优选实施方式中,上筒内的部分反应物料可以通过上筒筒壁的开孔扩散至环形空间,从而一定程度上缩短反应物料在上筒内的停留时间,避免不希望的副反应。例如,当用在本申请的重油加氢方法中时,可以避免重油原料在上筒内填充的高活性催化剂表面的停留时间过长,从而既达到了所需的转化深度,又减少了副反应和裂解反应,进而可以提高液体收率。
在进一步优选的实施方式中,所述上筒的开孔部分的筒壁的垂直高度与上筒的总垂直高度之比为约1∶1.5至约1∶20,优选约1∶2至约1∶8。
在优选的实施方式中,所述上筒为由上至下横截面积逐渐减小的截头圆锥形,其最大横截面直径与反应器直径之比为约1∶1.05至约1∶50,优选约1∶1.5至约1∶5,最大横截面直径与最小横截面直径之比为约1∶1.1至约1∶30,优选约1∶2至约1∶10。
在进一步优选的实施方式中,所述下筒为由下至上横截面积逐渐减小的截头圆锥形,其最大横截面直径与反应器直径之比为约1∶1.05至约1∶50,优选约1∶1.15至约1∶5,最大横截面直径与最小横截面直径之比为约1∶1.1至约1∶30,优选约1∶2至约1∶10。
在本申请的液相反应器中,所述下筒可充当减黏组件,其管壳式结构的壳侧连通反应器的液体入口和气体入口中的一者,所述管壳式结构的管侧连通反应器的液体入口和气体入口中的另一者,其中所述无机膜管的管壁上设置有孔道,使得壳侧或管侧的气体可经由所述孔道向另一侧的空间扩散,从而降低位于另一侧的液体物料的黏度。优选地,所述无机膜管管壁上的孔道具有约0.5nm-200nm的平均孔径,使得经由所述孔道扩散出的气泡具有约10-1000nm,优选约50-500nm的平均尺寸。
在优选的实施方式中,所述上筒内和/或所述环形空间内装填有催 化剂。进一步优选地,所述上筒内装填有第一催化剂,例如第一加氢催化剂,所述环形空间内装填有第二催化剂,例如第二加氢催化剂,其中所述第一催化剂与所述第二催化剂可以相同或不同。特别优选地,所述第一催化剂的催化活性高于所述第二催化剂,例如所述第一加氢催化剂的加氢活性高于所述第二加氢催化剂。
在优选的实施方式中,所述反应器外筒体的顶部(即上封头内)设置有气体空间,且反应器上封头设置有气体出口(例如在上封头的最高点处),用于在反应过程中连续或间断地排出反应体系内的气体。
在优选的实施方式中,在所述反应器的上筒顶端和上封头之间的位置设置有格栅,用于固定上筒内的催化剂床层,阻挡催化剂进入上封头内的空间,但允许反应物料通过。本申请对所述格栅的具体结构没有特别的限制,只要其能够实现上述公开即可。在某些具体实施方式中,所述格栅可以是由格栅条或约翰逊网等构成的封板。
在第二方面,本申请提供了采用本申请的液相反应器进行重油加氢的方法,包括如下步骤:
(1)将重油原料经由液体入口进料到下筒的管壳式结构的壳侧,并将氢气经由气体入口进料到所述管壳式结构的管侧,在所述下筒的顶部得到与所述重油原料相比黏度降低的包含氢气的反应物料,任选地,所述重油原料中预先混合有氢气;
(2)使所述反应物料进入上筒底部,并使其在由下而上通过所述上筒的过程中在其中填装的第一加氢催化剂的存在下进行第一加氢反应,得到部分加氢的反应物料;
(3)使所述部分加氢的反应物料进入环形空间,并使其在由上而下通过所述环形空间的过程中在其中填装的第二加氢催化剂的存在下进行第二加氢反应,得到加氢反应产物,其中所述第二加氢催化剂与所述第一加氢催化剂相同或不同。
在优选的实施方式中,以体积计,步骤(1)中氢气的进料量(Nm
3/h)与重油原料的进料量(m
3/h)之比,在本申请中也称为氢油体积比或氢油比,为约1500∶1至约1∶1,优选约500∶1至约1∶1。
在某些优选实施方式中,通过反应器上部的液位控制反应器出料,以确保加氢反应过程为全液相加氢。
在优选的实施方式中,所述第一加氢反应的条件包括:反应温度 为约60-500℃,优选约320-460℃;反应压力为约0.5-20.0MPa,优选约6.0-15.0MPa;新鲜进料的液时体积空速为约0.01-10.0h
-1,优选为约0.1-2.0h
-1。
在进一步优选的实施方式中,所述第二加氢反应的条件包括:反应温度为约120-550℃,优选约350-500℃;反应压力为约0.5-20.0MPa,优选约6.0-15.0MPa;新鲜进料的液时体积空速为约0.1-10.0h
-1,优选约0.5-5.0h
-1。
根据本申请,所述的重油可以是各种类型的重质油品,例如可以是比重≥0.91、黏度大且流动性差的稠油,如减压渣油、蜡油、煤焦油、润滑油、蒽油、脱沥青油、生物柴油、动物油或植物油等油品。
根据本申请,所述预先混合有氢气的重油原料一般通过氢油混合器混合得到,如采用静态混合器、溶气泵、胶体磨、微孔板纳/微米氢分散组件、陶瓷膜纳/微米氢分散组件等具有气液混合功能的设备得到。在优选的实施方式中,在所述预先混合有氢气的重油原料中,氢气的质量含量一般为重油原料质量的约0.01wt%-20%,优选约2.0wt%-8.0wt%。
在优选的实施方式中,所述第一加氢催化剂的活性高于第二加氢催化剂,优选第一加氢催化剂的活性与第二加氢催化剂的活性之比为约1.05∶1至约10∶1。其中所述的活性高低是针对上筒和环形空间内发生的化学反应而言的,以每单位容积(或质量)催化剂在单位时间内转化原料反应物的数量来表示,催化活性的高低可以通过催化剂载体比表面积的大小、表面上活性中心的性质和单位表面积上活性中心的数量等进行选择或制备过程中进行调控。催化剂活性的评价方法如下:在相同的原料组成和反应条件下,同体积催化剂在同一套装置上进行加氢反应,经过相同的停留时间后测定产物组成数据,计算转化率比较大小,作为判断活性高低的依据。
根据本申请,所述第一和第二加氢催化剂可以根据反应的需要选择适宜的加氢催化剂,以实现不同的加氢目的。例如,所述第一和第二加氢催化剂可以各自独立地选自加氢精制催化剂、预加氢精制催化剂、加氢改质催化剂、选择性加氢催化剂、加氢处理催化剂、加氢裂化催化剂、补充加氢催化剂等,这些催化剂可以选择商品催化剂,也可以采用本领域常规使用的催化剂,或根据现有技术的方法制备。例 如,所述第一加氢催化剂和第二加氢催化剂可以相互独立地为现有重油加氢装置所用的催化剂,如抚顺石油化工研究院研制开发的3936、3996,FF-16、FF-24、FF-26、FF-36、FF-46、FF-56加氢处理、UOP公司的HC-K、HC-P催化剂、Topsoe公司的TK-555、TK-565催化剂、Akzo公司的KF-847、KF-848催化剂。
根据本申请,所述第一和第二加氢催化剂可以各自独立地包含载体和活性组分,例如以加氢催化剂的总重量计,载体含量可占约45-95wt%,活性组分可占约5-55wt%,其中所述活性组分优选选自第VIB族和第VIII族金属元素中的一种或多种,所述载体优选为氧化铝和/或含硅氧化铝。进一步优选地,所述第VIB族金属元素一般为Mo和/或W,第VIII族金属元素一般为Co和/或Ni。在特别优选的实施方式中,以氧化物计并以加氢催化剂的重量为基准,所述第一和第二加氢催化剂各自独立地包含约5-40wt%的第VIB族金属元素和约3-15wt%的第VIII族金属元素。
在优选的实施方式中,所述上筒内填装的第一加氢催化剂的活性高于所述环形空间内填装的第二加氢催化剂,且环形空间可以装填活性全部或部分低于上筒活性的加氢催化剂。
本申请的催化反应可以脱除部分或全部烃类原料中的硫、氮、氧、砷、金属、残碳等杂质,或饱和/部分饱和烯烃、芳烃、二烯烃,或发生烃类分子异构化、烷基化、环化、芳构化、裂化、裂解等反应。一般的重质油加氢反应过程具有以下特点:1)重质油具有密度大、粘稠大的特点,在加氢过程中由于氢油传质界面阻力大,存在反应速率低、脱杂质深度不足的缺点;2)如果重质油加氢反应过程的停留时间过短,往往达不到所需的转化深度,而停留时间过长,则会导致副反应及裂解反应严重、液体收率低;3)在加氢反应前期,基于原料中杂质组份浓度最高,加氢反应的推动力大;以及4)温度越高时,物料在催化剂表面越容易结焦,裂解反应越严重,而重质油加氢反应过程的温度尤其是后期温度非常高,导致反应后期的裂解反应非常严重。
本申请的重油加氢方法采用了具有特殊设计的液相反应器,使反应物料经过下筒降低黏度后,再依次经过上筒和环形空间发生加氢反应,由此提高重油液相加氢反应的传质过程推动力和反应速率。进一步地,通过在上筒中采用活性相对较高的加氢催化剂,而在环形空间 中采用活性相对较低的加氢催化剂,可以控制反应物料与不同活性催化剂的接触时间,由此减缓催化剂表面结焦,减少轻质油深度裂解反应,促进重质油的加氢转化率,提高重油液相加氢反应过程的液体收率和重质脱杂质转化率。
具体而言,在所述反应器中,下筒由下而上横截面积逐渐减小,其管壳式结构在降低物料黏度的同时,提高了氢气在原料油中的溶解分散量和分散均匀性,可以减小氢油传质界面阻力,提高加氢反应速率;上筒由下而上截面积逐渐增大,可以实现随着反应的进行,原料跟催化剂的接触呈逐渐接触,控制反应过程温升更加均匀,防止集中放热、催化剂表面结焦的问题;上筒筒壁的中上部开孔,使上筒中的反应产物在经过一定的停留时间、达到一定的转化率后,可以及时扩散至环形空间,一方面可以减少物料在催化剂表面的过度反应,另一方面可以及时带走反应热,防止出现局部热点;上筒填装高活性催化剂,可以在进料中杂质组份浓度高、物料黏度低的情况下,进一步提高反应前期的加氢反应速率;并且,环形空间填装低活性催化剂,可以在反应后期温度较高的情况下,减少物料在催化剂表面的结焦,从而减少裂解反应。
以下结合附图1说明本申请的液相反应器的一种优选实施方式,及采用其进行重油加氢方法的示意性流程:
如图1所示,在一优选实施方式中,本申请的液相反应器包括外筒体和沿反应器轴向设置的内筒体,所述外筒体包括上封头、直筒段8和下封头10,所述内筒体和外筒体之间形成有环形空间11,所述内筒体顶端敞口并与所述环形空间11连通,所述内筒体由上至下依次包括上筒9和下筒5。上筒9位于所述直筒段8内,由上而下横截面积逐渐减小,顶端敞口,底部与下筒5顶部连通。下筒5位于所述下封头10内,由上而下横截面积逐渐增大,底端与下封头10内壁密闭连接。所述下筒5内设置有沿反应器轴向延伸的无机膜管6,从而形成管壳式结构,所述无机膜管的管壁上设置有供气体通过的孔道。下封头10设置有液体入口、气体入口和产物出口,液体入口和气体入口与所述下筒5的底部连通,产物出口与所述环形空间11的底部连通,其中所述液体入口与下筒5的管壳式结构的壳侧或管侧中的一者(优选壳侧)连通,而所述气体入口与所述管壳式结构的壳侧或管侧中的另一者(优选管 侧)连通。在上筒9顶端与上封头之间的位置,如反应器上封头切线下部适当距离(尽量靠近上封头)处,设置有格栅16,其可以阻挡催化剂进入上封头内的空间并固定上筒内的催化剂床层,但允许反应物料通过。格栅16下部为催化剂,为了实现全液相反应,可以在反应器筒体的催化剂床层上部设置液位控制,使催化剂全部浸没在液相空间21之中。
如图2所示,在优选的实施方式中,在本申请反应器的下筒5内设置有多根沿着反应器轴向延伸的无机膜管6。所述无机膜管6的排布方式没有特别的限制,例如可以如图3所示那样呈环形排布。
在一优选实施方式中,当使用图1所示的液相反应器进行重油加氢时,重油原料2与氢气1经氢油混合器3混合后,作为液体进料4从液相反应器的底部进入下筒5的管壳式结构的壳侧,而氢气作为气体进料7进入下筒5的管壳式结构的管侧(即无机膜管6内)。液体进料4经减黏后进入上筒9,在由下而上流过上筒9的过程中在第一加氢催化剂17的存在下进行加氢反应。所得部分加氢的反应物料可以经由上筒筒壁19的中上部的开孔扩散至环形空间11,也可以经过上封头内与上筒和环形空间两者均连通的区域进入环形空间11。进入环形空间11的反应物料,在由上而下流过环形空间的过程中在第二加氢催化剂18的存在下进一步进行加氢反应。环形空间11底部得到的最终的反应产物12在出料阀13的控制下离开液相反应器。反应过程中生成的气体及分离出的溶解气汇聚在反应器外筒体顶部的气体空间20内,在排气阀15的控制下作为排放气14排出。
实施例
下面将结合实施例将对本申请予以进一步说明,但并不因此而限制本申请。
本申请对比例及实施例中采用的原料油1为混合蜡油原料,具体性质见表1;原料油2为减压渣油原料,具体性质见表2。
表1混合蜡油原料性质
表2减压渣油原料性质
分析项目 | 减压渣油 |
密度,g/m 3 | 991.4 |
粘度(100℃),mm 2/s | 611.3 |
残炭,%(wt) | 15.77 |
金属含量,μg/g | 288 |
族组成 | |
饱和烃,% | 22.45 |
芳烃,% | 35.16 |
胶质,% | 34.79 |
沥青质,% | 7.6 |
对比例1
以表1所示的混合蜡油原料作为加氢反应进料,采用常规气、液、固三相固定床加氢反应器进行加氢,催化剂采用2个床层,两个床层高度相同,每个床层均采用抚顺石油化工研究院开发的市售的FZC保护剂/3936/3996催化剂,其中的FZC保护剂为总催化剂床层高度的14%,3936和3996催化剂各占总催化剂床层高度的43%。
加氢反应条件如下:反应温度为380-427℃,反应压力为15MPaG,液时体积空速为0.72h
-1,反应器入口的氢油体积比为400。
催化剂床层温度分布见表3,液体产品性质见表4。
对比例2
以表1所示的混合蜡油原料作为加氢反应进料,采用气、液、固三相固定床加氢反应器进行加氢,反应器采用套筒式结构,分为外筒和内筒,内筒为直筒式,反应进料由内筒进入、外筒流出。套筒式反应器的外筒直径为300mm,内筒直径为150mm。内筒中装填的加氢催化剂为抚顺石油化工研究院开发的市售的FZC保护剂/3996催化剂,外 筒中装填的加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/3936催化剂,其中外筒中的FZC保护剂为上筒总催化剂体积的12%,环形空间中的FZC保护剂为环形空间总催化剂体积的12%
反应器的底部进料中含有的氢气量为原料油质量的9.10%(对应的氢油体积比为469)。
反应器内筒的反应条件如下:反应温度为380-403℃,反应压力为15.2MPaG,原料油的液时体积空速为1.0h
-1;外筒内的反应条件如下:反应温度为403-418℃,反应压力为14.9MPaG,原料油的液时体积空速为1.3h
-1。
以表1所示的混合蜡油为原料,外筒和内筒的催化剂温度分布见表3,液体产品性质见表5。
实施例1
采用图1所示的流程,液相反应器上筒中装填的第一加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/3996催化剂,环形空间中装填的第二加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/3936催化剂,其中上筒中的FZC保护剂为上筒总催化剂体积的14%,环形空间中的FZC保护剂为环形空间总催化剂体积的14%。反应器的液体进料中含有的氢气量为原料油(新鲜原料油与循环油之和)质量的2.0%;反应器下筒中氢气的通入量为原料油(新鲜原料油与循环油之和)质量的3.10%(对应的氢油体积比为273);循环比(即循环油与新鲜原料油的质量比)为2.5。
反应器上筒内的反应条件如下:反应温度为380-393℃,反应压力为15.0MPaG,新鲜原料油的液时体积空速为1.2h
-1;环形空间内的反应条件如下:反应温度为393-402℃,反应压力为14.5MPaG,新鲜原料油的液时体积空速为1.6h
-1。
反应器上筒的最大横截面直径(即顶部平面直径)与反应器直径之比为1∶1.5,最大横截面直径与最小横截面直径之比为4∶1;上筒筒壁上部距上筒底端距离为上筒总垂直高度的2/3及以上的位置均匀开设
的圆孔,开孔率为85%;下筒的最大横截面直径与反应器直径之比为1∶2.5,最大横截面直径与最小横截面直径之比为2.4∶1。
以表1所示的混合蜡油为原料,上筒和环形空间内的催化剂温度 分布见表3,液体产品性质见表5。
实施例2
采用图1所示的流程,液相反应器上筒中装填的第一加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/FF-26催化剂,环形空间中装填的第二加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/3996催化剂,其中上筒中的FZC保护剂为上筒总催化剂体积的15%,环形空间中的FZC保护剂为环形空间总催化剂体积的15%。反应器的液体进料中含有的氢气量为原料油(新鲜原料油与循环油之和)质量的1.62%;反应器下筒中氢气的通入量为原料油(新鲜原料油与循环油之和)质量的3.30%(对应的氢油体积比为253);循环比为2.0。
反应器上筒内的反应条件如下:反应温度为380-393℃,反应压力为15.0MPaG,新鲜原料油的液时体积空速为1.0h
-1;环形空间内的反应条件如下:反应温度为394-405℃,反应压力为14.5MPaG,新鲜原料油的液时体积空速为1.8h
-1。
反应器上筒的最大横截面直径与反应器直径之比为1∶2,最大横截面直径与最小横截面直径之比为3∶1;上筒筒壁上部距上筒底端距离为上筒总垂直高度的1/2及以上的位置均匀开设
的圆孔,开孔率为80%;下筒的最大横截面直径与反应器直径之比为1∶2.5,最大横截面直径与最小横截面直径之比为2.4∶1。
以表1所示的混合蜡油为原料,上筒和环形空间内的催化剂温度分布见表3,液体产品性质见表6。
实施例3
采用图1所示的流程,液相反应器上筒中装填的第一加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/FF-46催化剂,环形空间中装填的第二加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/FF-26催化剂,上筒和环形空间中的FZC保护剂为各自的总催化剂体积的15%。反应器的液体进料中含有的氢气量为原料油(新鲜原料油与循环油之和)质量的1.60%;反应器下筒中氢气的通入量为原料油(新鲜原料油与循环油之和)质量的3.15%(对应的氢油体 积比为245);循环比为2.0。
反应器上筒内的反应条件如下:反应温度为378-390℃,反应压力为15.0MPaG,新鲜原料油的液时体积空速为1.0h
-1;环形空间内的反应条件如下:反应温度为391-400℃,反应压力为14.5MPaG,新鲜原料油的液时体积空速为1.8h
-1。
反应器上筒的最大横截面直径与反应器的直径之比为1∶1.5,最大横截面直径与最小横截面直径之比为4∶1;上筒筒壁上部距上筒底端距离为上筒总垂直高度的2/3及以上的位置均匀开设
的圆孔,开孔率为80%;下筒的最大横截面直径与反应器直径之比为1∶3,最大横截面直径与最小横截面直径之比为2∶1。
以表1所示的混合蜡油为原料,上筒和环形空间内的催化剂温度分布见表3,液体产品性质见表7。
实施例4
采用图1所示的流程,液相反应器上筒中装填的第一加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/FF-46催化剂,环形空间中装填的第二加氢催化剂采用抚顺石油化工研究院开发的市售的FZC保护剂/FF-26催化剂,上筒和环形空间中的FZC保护剂为各自的总催化剂体积的35%。反应器的液体进料中含有的氢气量为原料油(新鲜原料油与循环油之和)质量的4.20%;反应器下筒中氢气的通入量为原料油(新鲜原料油与循环油之和)质量的7.96%(对应的氢油体积比为410);循环比为2.0。
反应器上筒内的反应条件如下:反应温度为380-394℃,反应压力为15.0MPaG,新鲜原料油的液时体积空速为2.5h
-1;环形空间内的反应条件如下:反应温度为393-406℃,反应压力为14.5MPaG,新鲜原料油的液时体积空速为0.5h
-1。
反应器上筒的最大横截面直径与反应器的直径之比为1∶2,最大横截面直径与最小横截面直径之比为2.5∶1;上筒筒壁上部距上筒底端距离为上筒总垂直高度的1/2及以上的位置均匀开设
的圆孔,开孔率为75%;下筒的最大横截面直径与反应器直径之比为1∶2,最大横截面直径与最小横截面直径之比为2.5∶1。
以表2所示的减压渣油为原料,上筒和环形空间内的催化剂温度 分布见表3,产品性质见表8。
表3对比例1-2和实施例1-4的催化剂温度分布
表4对比例1的液体产品性质
项目 | 方法 | 粗石脑油 | 柴油 | 尾油 |
实沸点切割范围 | <165℃ | 165-360℃ | >360℃ | |
收率(wt%) | 42.4 | 25.8 | 21.6 | |
比重(60°F/60°F) | ASTM D 1298 | 0.7575 | 0.8548 | 0.9029 |
总硫,wt-ppm | ASTM D 1266 | <55 | <350 | 1180 |
硫醇硫,wt-ppm | <50 | <50 | <50 | |
总氮,wt-ppm | <15 | <50 | 255 | |
馏程,℃ | ASTM | D 2892 | D 2892 | D 1160 |
IBP/10% | 60/83 | 175/200 | 345/377 | |
30%/50% | 95/105 | 247/280 | 408/451 | |
70%/90% | 114/132 | 295/308 | 505/564 | |
95% | 148 | 312 | 635 |
表4对比例2的液体产品性质
项目 | 方法 | 粗石脑油 | 柴油 | 尾油 |
实沸点切割范围 | <165℃ | 165-360℃ | >360℃ | |
收率(wt%) | 44.3 | 28.8 | 16.8 | |
比重(60°F/60°F) | ASTM D 1298 | 0.7573 | 0.8545 | 0.9026 |
总硫,wt-ppm | ASTM D 1266 | <30 | <200 | 800 |
硫醇硫,wt-ppm | <25 | <15 | <50 | |
总氮,wt-ppm | <15 | <30 | <150 | |
馏程,℃ | ASTM | D 2892 | D 2892 | D 1160 |
IBP/10% | 60/83 | 175/200 | 345/377 | |
30%/50% | 95/105 | 247/280 | 408/451 | |
70%/90% | 114/132 | 295/308 | 505/564 | |
95% | 145 | 317 | 638 |
表5实施例1的液体产品性质
项目 | 方法 | 粗石脑油 | 柴油 | 尾油 |
实沸点切割范围 | <165℃ | 165-360℃ | >360℃ | |
收率(wt%) | 47.7 | 35.8 | 11.2 | |
比重(60°F/60°F) | ASTM D 1298 | 0.7574 | 0.8548 | 0.9031 |
总硫,wt-ppm | ASTM D 1266 | <15 | <150 | <500 |
硫醇硫,wt-ppm | <10 | <10 | <10 | |
总氮,wt-ppm | <10 | <10 | <100 | |
馏程,℃ | ASTM | D 2892 | D 2892 | D 1160 |
IBP/10% | 60/85 | 175/208 | 345/380 | |
30%/50% | 97/108 | 254/288 | 406/457 | |
70%/90% | 110/135 | 298/308 | 512/564 | |
95% | 147 | 310 | 635 |
表6实施例2的液体产品性质
项目 | 方法 | 粗石脑油 | 柴油 | 尾油 |
实沸点切割范围 | <165℃ | 165-360℃ | >360℃ | |
收率(wt%) | 48.2 | 37.4 | 9.2 | |
比重(60°F/60°F) | ASTM D 1298 | 0.7573 | 0.8549 | 0.9028 |
总硫,wt-ppm | ASTM D 1266 | <15 | <150 | <500 |
硫醇硫,wt-ppm | <10 | <10 | <10 | |
总氮,wt-ppm | <10 | <10 | <100 | |
馏程,℃ | ASTM | D 2892 | D 2892 | D 1160 |
IBP/10% | 60/85 | 175/209 | 355/380 | |
30%/50% | 98/107 | 254/288 | 408/457 | |
70%/90% | 118/137 | 296/308 | 513/566 | |
95% | 148 | 311 | 634 |
表7实施例3的液体产品性质
项目 | 方法 | 粗石脑油 | 柴油 | 尾油 |
实沸点切割范围 | ASTM D 2892 | <165℃ | 165-360℃ | >360℃ |
收率(wt%) | 47.5 | 39.4 | 8.7 | |
比重(60°F/60°F) | ASTM D 1298 | 0.7573 | 0.8549 | 0.9028 |
总硫,wt-ppm | ASTM D 1266 | <15 | <150 | <500 |
硫醇硫,wt-ppm | <10 | <10 | <10 | |
总氮,wt-ppm | <10 | <10 | <100 | |
馏程,℃ | ASTM | D 2892 | D 2892 | D 1160 |
IBP/10% | 60/86 | 175/222 | 355/380 | |
30%/50% | 96/108 | 255/289 | 409/456 | |
70%/90% | 118/134 | 295/308 | 515/564 | |
95% | 148 | 311 | 635 |
表8实施例4的液体产品性质
由实施例1-3及对比例1-2的催化剂温度分布及加氢反应效果可以看出,采用本申请的液相反应器及重油加氢方法,使重油原料经过上筒微分散氢气减黏后再进行加氢反应,能够有效提高重油液相加氢反应的传质过程推动力和反应速率,且上筒为由下而上截面积逐渐增大的结构,可以达到随着反应的进行,原料与催化剂的接触面积逐渐增大,从上筒的催化剂温升可以看出,温升大幅度降低,控制反应过程温升更加均匀,可以防止集中放热、催化剂表面结焦的问题。另外,由于上筒筒壁的中上部开孔,使上筒内的反应产物在经过一定的停留时间、达到一定的转化率后,可以及时扩散至环形空间,一方面可以减少物料在催化剂表面的过度反应,另一方面可以及时带走反应热,防止出现局部热点;下筒不仅具有减黏作用,还能够提高氢气在原料油中的溶解分散量和分散均匀性,减小氢油传质界面阻力,提高加氢反应速率。
比较实施例1-3与对比例1-2的反应结果,可以看出在液体产品分布适当改善的情况下,实施例1-3所得产品中总硫、硫醇硫和总氮等杂质的含量大幅降低。由此表明,本申请的反应器和方法可以在产品分布更加优于现有技术的情况下,采用更加缓和的条件来达到所需的深度加氢转化率,而不会发生过多的裂解反应。从实施例4的反应结果可以看出,采用本申请的反应器和方法,可以在常规反应条件和更高空速下达到比较理想的脱金属效果和脱金属转化率。由此表明,采用本申请的反应器和方法,在达到与现有技术同等的脱金属转化率时, 可以采用更加缓和的反应条件,从而进一步减少裂解反应,提高液体产品收率。
Claims (13)
- 一种液相反应器,包括外筒体和沿反应器轴向设置的内筒体,所述外筒体包括上封头、直筒段和下封头,所述内筒体和外筒体之间形成有环形空间,所述内筒体顶端敞口并与所述环形空间连通,其特征在于:所述内筒体由上至下依次包括上筒和下筒,其中:上筒位于所述直筒段内,由上而下横截面积逐渐减小,顶端敞口,底部与下筒顶部连通;下筒位于所述下封头内,由上而下横截面积逐渐增大,底端与下封头内壁密闭连接,所述下筒内设置有沿反应器轴向延伸的无机膜管,从而形成管壳式结构,所述无机膜管的管壁上设置有供气体通过的孔道;下封头设置有液体入口、气体入口和产物出口,液体入口和气体入口与所述下筒的底部连通,产物出口与所述环形空间的底部连通,其中所述液体入口与下筒的管壳式结构的壳侧或管侧中的一者连通,所述气体入口与所述管壳式结构的壳侧或管侧中的另一者连通,优选地,所述液体入口与下筒的管壳式结构的壳侧连通,所述气体入口与所述管壳式结构的管侧连通。
- 根据权利要求1所述的液相反应器,其特征在于:所述上筒筒壁的中上部设置有若干开孔,开孔部分的筒壁的开孔率为约30%-95%,孔径大小为约0.1mm-50mm;优选地,开孔部分距上筒底端的垂直距离不小于上筒总垂直高度的约1/3,更优选不小于约1/2。
- 根据权利要求1或2所述的方法,其特征在于:所述上筒的开孔部分的筒壁的垂直高度与上筒的总垂直高度之比为约1∶1.5至约1∶20。
- 根据在先权利要求中任一项所述的液相反应器,其特征在于:所述上筒为由上至下横截面积逐渐减小的截头圆锥形,最大横截面直径与反应器直径之比为约1∶1.05至约1∶50,最小横截面直径与最大横截面直径之比为约1∶1.1至约1∶30。
- 根据在先权利要求中任一项所述的液相反应器,其特征在于:所述下筒为由下至上横截面积逐渐减小的截头圆锥形,最大横截面直径与反应器直径之比为约1∶1.05至约1∶50,最小横截面直径与最大横 截面直径之比为约1∶1.1至约1∶30。
- 根据在先权利要求中任一项所述的液相反应器,其特征在于:所述无机膜管管壁上的孔道具有约0.5nm-200nm的平均孔径,使得经由所述孔道扩散出的气泡尺寸为约10-1000nm。
- 根据在先权利要求中任一项所述的液相反应器,其特征在于:所述上筒内和/或所述环形空间内装填有催化剂,优选地,所述上筒内装填有第一催化剂,例如第一加氢催化剂,所述环形空间内装填有第二催化剂,例如第二加氢催化剂,所述第一催化剂与所述第二催化剂可以相同或不同,优选所述第一催化剂的催化活性高于所述第二催化剂。
- 使用根据权利要求7所述的液相反应器进行重油加氢的方法,包括如下步骤:(1)将重油原料经由液体入口进料到下筒的管壳式结构的壳侧,并将氢气经由气体入口进料到所述管壳式结构的管侧,在所述下筒的顶部得到与所述重油原料相比黏度降低的包含氢气的反应物料,任选地,所述重油原料中预先混合有氢气;(2)使所述反应物料进入上筒底部,并使其在由下而上通过所述上筒的过程中在其中填装的第一加氢催化剂的存在下进行第一加氢反应,得到部分加氢的反应物料;(3)使所述部分加氢的反应物料进入环形空间,并使其在由上而下通过所述环形空间的过程中在其中填装的第二加氢催化剂的存在下进行第二加氢反应,得到加氢反应产物,其中所述第二加氢催化剂与所述第一加氢催化剂相同或不同。
- 根据权利要求8所述的方法,其特征在于:以体积计,步骤(1)中氢气的进料量(Nm 3/h)与重油原料的进料量(m 3/h)之比为约1500∶1至约1∶1。
- 根据权利要求8或9所述的方法,其特征在于:所述第一加氢反应的条件包括:反应温度为约60-500℃,反应压力为约0.5-20.0MPa,新鲜进料的液时体积空速为约0.01-10.0h -1。
- 根据权利要求8-10中任一项所述的方法,其特征在于:所述第二加氢反应的条件包括:反应温度为约120-550℃,反应压力为约0.5-20.0MPa,新鲜进料的液时体积空速为约0.1-10.0h -1。
- 根据权利要求8-11中任一项所述的方法,其特征在于:所述的第一加氢催化剂的活性高于第二加氢催化剂的活性,优选第一加氢催化剂的活性与第二加氢催化剂的活性之比为约1.05∶1至约10∶1。
- 根据权利要求8-12中任一项所述的方法,其特征在于:所述第一和第二加氢催化剂各自独立地包含约45-95wt%的载体和约5-55wt%的活性组分,其中所述活性组分优选选自第VIB族和第VIII族金属元素中的一种或多种,所述载体优选选自氧化铝和含硅氧化铝;优选地,以氧化物计并以加氢催化剂的重量为基准,所述第一和第二加氢催化剂各自独立地包含约5-40wt%的第VIB族金属元素和约3-15wt%的第VIII族金属元素。
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