CN114933916A

CN114933916A - Hydrodesulfurization module, catalytic distillation tower and catalytic distillation method

Info

Publication number: CN114933916A
Application number: CN202210504339.XA
Authority: CN
Inventors: 范煜; 石冈
Original assignee: China University of Petroleum Beijing
Current assignee: China University of Petroleum Beijing
Priority date: 2022-05-10
Filing date: 2022-05-10
Publication date: 2022-08-23
Anticipated expiration: 2042-05-10
Also published as: CN114933916B

Abstract

The invention provides a hydrodesulfurization module, a catalytic distillation tower and a catalytic distillation method, wherein the hydrodesulfurization module comprises a net body and a hydrodesulfurization catalyst filled in a cavity surrounded by the net body, and the net body comprises a plurality of layers of metal nets which are sequentially stacked; the hydrodesulfurization catalyst is prepared according to the process comprising the following steps: mixing a first metal source solution with alkyl primary amine and an organic aluminum source, reacting at 20-80 ℃ for 12-96 h, roasting the obtained solid product, and then loading a second metal component on the obtained catalyst precursor by adopting an impregnation method to obtain a catalyst; wherein the first metal source comprises at least one metal element from group VIB of the periodic Table of the elements and the second metal component comprises at least one metal element from group VIII of the periodic Table of the elements. The invention can improve the removal rate/conversion rate of non-ideal components such as sulfur compounds in oil products such as naphtha, gasoline and the like, and reduce the loss of octane number.

Description

Hydrodesulfurization module, catalytic distillation tower and catalytic distillation method

Technical Field

The invention relates to a hydrodesulfurization module, a catalytic distillation tower and a catalytic distillation method, and belongs to the field of catalytic hydrodesulfurization.

Background

With the development of technology, the environmental protection requirements for gasoline and other oils are higher and higher, for example, commercial gasoline in China is mainly catalytic cracking (FCC) gasoline, the quality standards of gasoline in China (a) (sulfur no more than 10mg/kg, olefin no more than 18 v%) are implemented in 2019, 1 and 1, and the quality standards of gasoline in China (b) (sulfur no more than 10mg/kg, olefin no more than 15 v%) are implemented in 2023, 1 and 1, while the environmental protection indexes such as aromatic hydrocarbon, benzene, vapor pressure, distillation range and density of gasoline are further limited. Therefore, the ultra-deep desulfurization, olefin reduction and octane number maintenance of the FCC gasoline and other oil products are key problems which need to be solved urgently in the clean gasoline production process.

The catalytic distillation technology makes the reaction and the product separation proceed in the same catalytic distillation tower, and the product and the reactant separation are realized while the reaction proceeds, in this kind of process, the catalyst is usually packaged and then packed in the catalytic distillation tower, for example, patent document cn02135488.x discloses a catalytic distillation element and a catalyst packing structure, in particular for the selective dehydrodiolefin of C4 fraction, the selective dehydroacetylene and diolefin reaction of C3 fraction, the element includes a catalyst basket, a packing and a basket frame with fixed function, the catalyst basket and the packing are arranged in the basket frame in a staggered way, the catalyst packing structure is composed of at least one such catalytic distillation element stacked on a grid in the catalytic distillation tower; patent document CN201610537448.6 discloses a catalytic distillation assembly, which uses two identical corrugated wire mesh sheets that are horizontal in the radial direction and are fastened and welded in a mirror image manner by using the bottom edges corresponding to the wave crests as the mirror image surface as catalyst bags, and uses corrugated plate strips with the same wave crest center distance to be clamped between the two corrugated wire mesh bags, so that a fixed corrugated gap is formed between the two corrugated wire mesh bags as a gas phase channel.

However, in the existing catalytic distillation process, on one hand, there are reports that the existing catalytic distillation process is effectively combined with a hydrodesulfurization catalyst to solve the problems of ultra-deep desulfurization, olefin reduction, octane number loss reduction and the like of petroleum products such as naphtha and gasoline, and on the other hand, the existing catalyst packaging structure has risks such as agent leakage and the like, and the catalytic distillation efficiency and the operation life are influenced.

Disclosure of Invention

Aiming at the defects, the invention provides a hydrodesulfurization module, a catalytic distillation tower and a catalytic distillation method, wherein the catalytic distillation process is applied to hydrodesulfurization of petroleum products such as naphtha, gasoline and the like, and the hydrodesulfurization catalyst prepared in a specific process and the hydrodesulfurization module formed by packaging the hydrodesulfurization catalyst are provided in a targeted manner, so that the problems of agent leakage and the like can be avoided, the removal rate/conversion rate of non-ideal components such as sulfur-containing compounds and the like in the petroleum products such as naphtha, gasoline and the like can be obviously improved, and the octane number loss is reduced.

In one aspect of the invention, a hydrodesulfurization module is provided, which comprises a net body and a hydrodesulfurization catalyst filled in a cavity surrounded by the net body, wherein the net body comprises a plurality of layers of metal nets which are sequentially stacked; the hydrodesulfurization catalyst is prepared according to the process comprising the following steps: dissolving a first metal source in a first solvent to obtain a first metal source solution; wherein the first metal source comprises at least one metal element from group VIB of the periodic Table of the elements; mixing the first metal source solution with alkyl primary amine and an organic aluminum source to obtain a mixed solution; reacting the mixed solution at 20-80 ℃ for 12-96 h, and then roasting the obtained solid product to obtain the catalyst precursor; loading a second metal component on the catalyst precursor by adopting an impregnation method to obtain the hydrodesulfurization catalyst; wherein the second metal component comprises at least one metal element from group VIII of the periodic Table of elements.

According to an embodiment of the present invention, the concentration of the first metal source solution is 0.005-0.1 mol/L; and/or mixing the first metal source with the first solvent at room temperature, and performing ultrasonic treatment until the first metal source is dissolved to obtain a first metal source solution; and/or the process of mixing the first metal source solution with alkyl primary amine and organic aluminum source comprises the following steps: adding alkyl primary amine into the first metal source solution, and stirring for 1-10 hours at 10-80 ℃ to obtain a suspension; adding the organic aluminum source into the suspension to obtain the mixed solution; and/or the roasting temperature is 400-550 ℃, and the roasting time is 5-15 h; and/or, the first metal source comprises molybdenum and/or tungsten; and/or, the alkyl primary amine comprises at least one of dodecyl amine, tetradecyl amine, hexadecyl amine, and octadecyl amine; and/or the organic aluminum source comprises at least one of aluminum isopropoxide, aluminum sec-butoxide and aluminum acetylacetonate; and/or, the first solvent comprises alcohol and/or water, the alcohol comprises at least one of methanol, ethanol, n-butanol and isopropanol; and/or the second metal component comprises cobalt and/or nickel; and/or the first metal source and the second metal component are respectively calculated by metal oxides, the organic aluminum source is calculated by aluminum oxide, based on the total mass of the first metal source, the second metal component and the organic aluminum source, the mass percent of the first metal source is 5-50%, the mass percent of the second metal component is l-30%, and the balance is the organic aluminum source.

According to one embodiment of the present invention, any two of the plurality of layers of metal mesh have different mesh numbers; and/or in the multilayer metal net, the mesh number of the metal net with the largest mesh number is 100-140, and the mesh number of the metal net with the smallest mesh number is 60-100; and/or, the metal mesh comprises a stainless steel mesh; and/or the hydrodesulfurization module further comprises at least one first filler sheet arranged in the cavity, and the at least one first filler sheet partitions the cavity into a plurality of spaces filled with the hydrodesulfurization catalyst; and/or the hydrodesulfurization module is in the shape of a regular or irregular polyhedron.

According to an embodiment of the present invention, the first packing sheets comprise loose sheets and/or structured packing, and the structured packing comprises at least one of windowed flow guide packing, plate corrugated packing, wire mesh corrugated packing, orifice plate corrugated packing, calendered orifice plate corrugated packing, and honeycomb packing; and/or the forming material of the first filler sheet comprises at least one of metal, plastic, ceramic and graphite.

In another aspect of the present invention, there is provided a packaging unit of the above hydrodesulfurization module, which includes a plurality of the hydrodesulfurization modules, a packing layer located between every two adjacent hydrodesulfurization modules, and a fixing band for fixing the plurality of hydrodesulfurization modules and the packing layer together.

According to an embodiment of the present invention, the packing layer comprises loose sheets and/or structured packing, and the structured packing comprises at least one of windowed flow guide packing, plate corrugated packing, wire mesh corrugated packing, orifice plate corrugated packing, calendered orifice plate corrugated packing, and honeycomb packing; and/or the forming material of the filler layer comprises at least one of metal, plastic, ceramic and graphite; and/or the fixing band is wound on the outer side of an arrangement structure consisting of the plurality of hydrodesulfurization modules and the filler layer positioned between every two adjacent hydrodesulfurization modules so as to bind, so that the plurality of hydrodesulfurization modules and the filler layer are fixed together; and/or, the securing strap may comprise a stainless steel strap.

In still another aspect of the present invention, there is provided a catalytic distillation column comprising at least one catalyst bed layer, wherein the catalyst bed layer comprises a plurality of sequentially arranged catalytic unit layers, each of the catalytic unit layers is formed by sequentially arranging a plurality of the packing units according to claim 5 or 6; in each two adjacent catalytic unit layers, a plurality of packaging units in one catalytic unit layer are transversely arranged, and a plurality of packaging units in the other catalytic unit layer are longitudinally arranged.

In still another aspect of the present invention, there is provided a catalytic distillation method comprising: the raw oil enters the catalytic distillation tower of claim 7, and catalytic distillation is carried out in a hydrogen environment, wherein hydrodesulfurization treatment is carried out under the action of a hydrodesulfurization catalyst in the hydrodesulfurization module, so as to obtain a purified oil product.

According to one embodiment of the present invention, after the hydrodesulfurization module is subjected to a sulfidation treatment, the feedstock oil is introduced into the catalytic distillation tower for catalytic distillation; and/or the operating conditions of the catalytic distillation column are: the tower pressure is 0.3-2.5 MPa, the tower top temperature is 60-280 ℃, and the tower bottom temperature is 150-350 ℃; and/or the raw oil comprises naphtha and/or gasoline; and/or the final distillation point of the raw oil is less than 250 ℃.

According to an embodiment of the present invention, the vulcanization process includes: contacting the hydrodesulfurization catalyst with a vulcanizing agent, and vulcanizing under the conditions of 1.5-2.0 MPa and 260-360 ℃; wherein the vulcanizing agent comprises dimethyl disulfide.

In the invention, a catalytic distillation process and a hydrodesulfurization process are combined, and hydrodesulfurization is carried out on petroleum products such as naphtha, gasoline and the like in a catalytic distillation mode, so that a specific hydrodesulfurization module is provided. Through the specific preparation process, the properties such as the pore structure, the specific surface area and the like of the carrier (alumina) in the prepared hydrodesulfurization catalyst can be improved, the dispersity of active components (a first metal component and a second metal component formed by a first metal source) on the carrier is improved, more active sites are provided for hydrodesulfurization reaction, the hydrodesulfurization/conversion efficiency is improved, olefin over-saturation can be avoided, and the octane number loss is reduced; in a hydrodesulfurization module formed by organically combining the hydrodesulfurization catalyst with a specific packaging structure (mesh body), the mesh body formed by a plurality of layers of metal meshes is adopted to package the catalyst (the catalyst is filled in a cavity surrounded by the mesh body), the mesh structure is favorable for the flow of components such as gas/liquid and the like, so that the components can be diffused in the catalyst, the mass transfer (especially radial mass transfer) and heat transfer efficiency between an oil phase and the catalyst are increased, the non-ideal components such as sulfur-containing compounds in oil products are efficiently removed/converted, and meanwhile, the mesh body is formed by sequentially stacking the plurality of layers of metal meshes, so that the risk of agent leakage and the like can be reduced.

Therefore, the invention has the advantages of high removal/conversion efficiency of non-ideal components such as sulfur-containing compounds (such as mercaptan, alkyl thiophene and the like), small octane number loss and the like, meets the requirements of deep desulfurization, olefin reduction, octane number loss reduction and the like on petroleum products such as naphtha, gasoline and the like, has wide application range, and can be suitable for treating the petroleum products such as naphtha, gasoline (such as FCC gasoline) and the like; in addition, the invention also has the advantages of long service life of the catalyst, low hydrogen consumption, low tower pressure, large gas-liquid flux and the like, and is beneficial to practical industrial application.

Drawings

FIG. 1 is a schematic view of a catalytic distillation column (first catalytic distillation column) according to an embodiment of the present invention;

fig. 2 is a schematic structural view of a catalytic distillation column (second catalytic distillation column) according to another embodiment of the present invention.

Description of the reference numerals: 1: a first preheater; 1': a second preheater; 2: a first catalytic distillation column; 2': second catalytic distillationA distillation column; 201: a hydrodesulfurization module; 202: a filler layer; 21: a first catalyst bed; 22: a second catalyst bed; 23: a third catalyst bed; 24: a fourth catalyst bed; 25: a fifth catalyst bed layer; 26: a column plate; 27: a tower kettle; 3: a first condenser; 3': a second condenser; 4: a first reboiler; 4': a second reboiler; a. a': raw oil; b: hydrogen gas; c: a first light fraction; c. C ₁ 、c ₂ : a portion of the first light fraction; c': a second light fraction; c. C ₁ '、c ₂ ': a portion of the second light fraction; d: a first heavy fraction; d ₁ 、d ₂ : a portion of the first heavy fraction; d': a second heavy fraction; d ₁ '、d ₂ ': a portion of the second heavy fraction.

Detailed Description

The present invention is described in further detail below in order to enable those skilled in the art to better understand the aspects of the present invention. The following detailed description is merely illustrative of the principles and features of the present invention, and the examples are intended to be illustrative of the invention and not limiting of the scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.

In the description of the present invention, the terms "first", "second", and the like are used for descriptive purposes only, for example, to distinguish various components for clarity of explanation/explanation of the technical solution, and are not to be interpreted as indicating or implying any number or order of the technical features indicated.

The invention provides a hydrodesulfurization module, which comprises a net body and a hydrodesulfurization catalyst filled in a cavity surrounded by the net body, wherein the net body comprises a plurality of layers of metal nets which are sequentially stacked; the hydrodesulfurization catalyst is prepared according to the process comprising the following steps: dissolving a first metal source in a first solvent to obtain a first metal source solution; wherein the first metal source comprises at least one metal element from group VIB of the periodic Table of the elements; mixing the first metal source solution with alkyl primary amine and an organic aluminum source to obtain a mixed solution; reacting the mixed solution at 20-80 ℃ for 12-96 h, and then roasting the obtained solid product to obtain a catalyst precursor; loading a second metal component on the catalyst precursor by adopting an impregnation method to obtain a hydrodesulfurization catalyst (a bimetallic supported hydrodesulfurization catalyst); wherein the second metal component comprises at least one metal element from group VIII of the periodic Table of the elements.

In general, after the above preparation process, the organic aluminum source forms a carrier (alumina) of the obtained hydrodesulfurization catalyst, the first metal source forms a first metal component supported on the carrier, and the first metal component and the second metal component are generally metal oxides respectively. According to the research of the inventor, the structure such as pore channels, specific surface area and the like of the carrier can be favorably regulated and controlled through the action of alkyl primary amine, and the dispersion of the first metal component and the second metal component is favorably realized, so that the prepared hydrodesulfurization catalyst has high dispersion degree of active components and is not easy to inactivate, the catalytic activity and the selectivity of the hydrodesulfurization catalyst are improved, and after the hydrodesulfurization catalyst is packaged by adopting the net body, the formed hydrodesulfurization module can be used for removing/converting non-ideal components such as sulfur-containing compounds (such as mercaptan, alkyl thiophene and the like) in petroleum products such as naphtha, gasoline and the like at high selectivity, and the octane number loss is reduced.

In some embodiments, the process of dissolving the first metal source in the first solvent may comprise: and mixing the first metal source with the first solvent at room temperature, carrying out ultrasonic treatment until the first metal source is completely dissolved to obtain a first metal source solution, and facilitating the improvement of the dissolving efficiency of the first metal source through ultrasonic treatment.

The concentration of the first metal source solution may be 0.005-0.1 mol/L, such as 0.005mol/L, 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.08mol/L, 0.1mol/L or any two of them.

Specifically, the first metal source comprises at least one metal element from group VIB of the periodic table, i.e. the metal of the first metal source comprises at least one from group VIB of the periodic table, exemplarily the metal of the first metal source comprises molybdenum (Mo) and/or tungsten (W).

Further, the first metal source may include a first metal compound, for example, a first metal salt including, for example, a metal acetylacetonate (first metal acetylacetonate complex), and/or a first metal oxide, and the like. In some embodiments, the first metal source comprises molybdenum acetylacetonate.

In general, the first metal source solution may be mixed with the alkyl primary amine and then mixed with the organic aluminum source, which is beneficial to further optimizing the performance of the hydrodesulfurization catalyst.

In some preferred embodiments, the process of mixing the first metal source solution with the primary alkyl amine, the organic aluminum source, comprises: adding alkyl primary amine into the first metal source solution, and stirring for 1-10 h at 10-80 ℃ to obtain a suspension; and adding an organic aluminum source into the suspension to obtain the mixed solution.

Specifically, the primary alkylamine is added to the first metal source solution, and then stirred until the primary alkylamine is uniformly dispersed, and for example, the stirring temperature may be 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, or any two of them, and the stirring time may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of them.

In some embodiments, the organic aluminum source may include at least one of aluminum isopropoxide, aluminum sec-butoxide, aluminum acetylacetonate.

In some embodiments, the alkyl primary amine can include at least one of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine. The alkyl group in the alkyl primary amine may be a branched alkyl group without a branch (i.e., the alkyl primary amine is a normal alkyl primary amine (e.g., a n-tetradecyl primary amine)), or may be an isomeric alkyl group with a branch (i.e., the alkyl primary amine is an isomeric alkyl primary amine).

In some embodiments, the first solvent may include alcohol and/or water, preferably including alcohol and water, such as a mixed solvent of alcohol and water.

The alcohol may include C1-C4 alcohol (i.e. alcohol having 1-4 carbon atoms), and preferably includes at least one of methanol, ethanol, n-butanol and isopropanol.

In the preparation process of the hydrodesulfurization catalyst, the mixed solution is reacted at 20-80 ℃ for 12-96 h, for example, the reaction temperature may be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or any two of them, and the reaction time may be 12h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 96h or any two of them. After the reaction is finished, filtering can be carried out, and the obtained solid product is sequentially washed, dried and roasted.

In some embodiments, the temperature of the firing is 400 to 550 ℃, such as 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃ or any two thereof, and the time of the firing is 5 to 15 hours, such as 5 hours, 8 hours, 10 hours, 12 hours, 15 hours or any two thereof.

Specifically, a second metal source may be mixed with a second solvent to make an impregnation solution; the catalyst precursor is impregnated with the impregnation liquid, for example, the catalyst precursor is placed in the impregnation liquid to be impregnated, to achieve the loading of the second metal component on the catalyst precursor. In specific embodiments, the second metal component may be supported on the catalyst precursor by an isovolumetric impregnation method.

The metal in the second metal source is the same as the metal in the second metal component, that is, the second metal source contains at least one metal element in group VIII of the periodic table, that is, the metal in the second metal source contains at least one metal in group VIII of the periodic table, and after the above preparation process, the second metal source forms the second metal component loaded on the carrier.

In some preferred embodiments, the metal in the second metal component comprises cobalt (Co) and/or nickel (Ni).

The second metal source may comprise a second metal compound, for example comprising a second metal salt and/or a second metal oxide and the like, and the second metal salt may comprise a second metal soluble salt (water soluble salt), for example comprising a nitrate, for example comprising nickel nitrate (Ni (NO) and the like ₃ ) ₂ ) And/or cobalt nitrate (Co (NO) ₃ ) ₂ ) The nitrates may in particular be in the form of hydrates, such as Ni (NO) ₃ ) ₂ ·6H ₂ O、Co(NO ₃ ) ₂ ·6H ₂ O, and the like.

In addition, the first metal source, the second metal source and the organic aluminum source are used in the following amounts: the first metal source and the second metal component (or the second metal source) are respectively calculated by metal oxides, the organic aluminum source is calculated by alumina, the mass percentage of the first metal source is 5-50%, such as 5%, 10%, 20%, 30%, 40%, 50% or the range composed of any two of the first metal source, the second metal component (or the second metal source), the mass percentage of the second metal component (or the second metal source) is l-30%, such as 1%, 5%, 10%, 15%, 20%, 25%, 30% or the range composed of any two of the second metal source, and the balance is the organic aluminum source based on the total mass of the first metal source, the second metal component (or the second metal source) and the organic aluminum source.

Correspondingly, in the prepared hydrodesulfurization catalyst, the mass content of the first metal component and the mass content of the second metal component in terms of metal oxides are respectively 5-50%, such as 5%, 10%, 20%, 30%, 40%, 50% or the range of any two of the metal oxides, the mass content of the second metal component is l-30%, such as 1%, 5%, 10%, 15%, 20%, 25%, 30% or the range of any two of the metal oxides, and the balance is carrier (alumina).

In the hydrodesulfurization module, the mesh numbers of any two of the plurality of metal meshes are different, that is, the mesh body is formed by sequentially stacking the plurality of metal meshes with different mesh numbers.

In some embodiments, the mesh number of the metal mesh with the largest mesh number in the multi-layer metal mesh is 100-140, such as 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh, etc., and the mesh number of the metal mesh with the smallest mesh number is 60-100, such as 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, etc.

Specifically, the metal mesh may include a stainless steel mesh.

In addition, the hydrodesulfurization module can further comprise at least one first packing sheet arranged in the cavity, and the at least one first packing sheet divides the cavity into a plurality of spaces filled with the catalyst. Through the arrangement of the first packing sheet, the gas-liquid flow conductivity can be improved, the flow resistance of a gas phase and a liquid phase in the catalytic distillation process is reduced, the mass transfer efficiency is improved, and the hydrodesulfurization reaction efficiency and the target product yield are further improved.

Preferably, the number of the first packing sheets is multiple, the cavity is divided into a plurality of spaces, and each space is filled with the hydrodesulfurization catalyst.

In particular, the first packing sheet may include a loose sheet and/or a structured packing, wherein the loose sheet may be a corrugated sheet, and the structured packing is assembled by a plurality of corrugated sheets, and in some embodiments, the structured packing includes at least one of a windowed flow guide packing, a plate corrugated packing, a wire mesh corrugated packing, a pore plate corrugated packing, a calendered pore plate corrugated packing, and a honeycomb packing.

Further, the forming material of the first filler pieces may include at least one of metal, plastic, ceramic, and graphite.

In addition, the hydrodesulfurization module may be in the shape of a regular or irregular polyhedron, for example, a rectangular parallelepiped or a cubic shape.

Specifically, the dictyosome is as holding hydrodesulfurization catalyst's shell, and it is formed by the range upon range of setting of multilayer (at least two-layer) metal mesh (this multilayer metal mesh specifically is along the direction of being stacked gradually the setting by the cavity inboard to the cavity outside), and this range upon range of setting of multilayer metal mesh forms the shell promptly, and this shell encloses and establishes into the cavity that holds hydrodesulfurization catalyst, and wherein, the edge (the hexahedral edge) combination department of metal mesh can weld, for example carries out laser welding to seal, form the cavity.

As shown in fig. 1 and fig. 2, the encapsulation unit of the hydrodesulfurization module provided by the present invention includes a plurality of hydrodesulfurization modules 201, a packing layer 202 located between every two adjacent hydrodesulfurization modules 201, and a fixing band for fixing the plurality of hydrodesulfurization modules 201 and the packing layer 202 together, such that every two hydrodesulfurization modules 201 are separated by the packing layer 202, and are fixed by the fixing band, which is beneficial to improving gas/liquid flow conductivity, reducing flow resistance of gas phase and liquid phase in the catalytic distillation process, and improving mass transfer efficiency, thereby improving hydrodesulfurization reaction efficiency and target product yield.

Wherein the number of filler layers 202 may be plural.

Specifically, packing layer 202 includes a second packing sheet, which may include a loose sheet and/or a structured packing, wherein the loose sheet may be a corrugated sheet, and the structured packing is assembled from a plurality of corrugated sheets, and in some embodiments, the structured packing includes at least one of a windowed flow guide packing, a plate corrugated packing, a wire mesh corrugated packing, a perforated plate corrugated packing, a calendered perforated plate corrugated packing, and a honeycomb packing. The forming material of the second filler pieces may include at least one of metal, plastic, ceramic, and graphite.

In the above packaging unit, the fixing band is wound around the outside of the arrangement structure composed of the plurality of hydrodesulfurization modules 201 and the filler layer 202 located between every two adjacent hydrodesulfurization modules 201 to bind, so as to fix the plurality of hydrodesulfurization modules 201 and the filler layer 202 together.

Wherein, the fixing band may comprise a stainless steel band.

The packaging unit can be specifically used for being filled in a catalytic distillation tower, so that catalytic distillation is carried out on petroleum products such as naphtha, gasoline and the like, during specific implementation, the fixing bands can be wound on the outer sides of the hydrodesulfurization modules 201 and the packing layers 202 according to the diameter of the maintenance manhole of the catalytic distillation tower and bound to form the packaging unit, then the packaging unit is filled into the catalytic distillation tower through the maintenance manhole of the catalytic distillation tower, and specifically, a plurality of packaging units can be filled into the catalytic distillation tower and arranged to form one catalytic unit layer 20.

In addition, parameters such as the size and the shape of the hydrodesulfurization module 201 can be adjusted according to parameters such as the diameter and the height of the catalytic distillation tower, and a proper number of hydrodesulfurization modules 201 and the packing layer 202 are bound into a packaging unit with a proper shape and size by using a fixing band.

As shown in fig. 1 and fig. 2, the catalytic distillation column of the present invention comprises at least one catalyst bed layer, the catalyst bed layer comprises a plurality of sequentially arranged catalytic unit layers, each catalytic unit layer is formed by sequentially arranging a plurality of packaging units; and in each two adjacent catalytic unit layers, a plurality of packaging units in one are transversely arranged, and a plurality of packaging units in the other are longitudinally arranged.

Specifically, in each catalytic unit layer, the length directions of the plurality of encapsulation units are the same, the length directions and lengths of the catalytic unit layers are the same as those of the encapsulation units forming the catalytic unit layers, one of the two adjacent catalytic unit layers is transversely arranged (i.e., the encapsulation units are transversely arranged), the other one is longitudinally arranged (i.e., the encapsulation units are longitudinally arranged), i.e., the catalytic unit layers are staggered at 90 degrees along the direction from one catalytic unit layer to the other catalytic unit layer (longitudinally).

In general, the catalytic distillation column is disposed longitudinally, i.e., the longitudinal direction as described above is the axial direction of the catalytic distillation column, and the transverse direction is the radial direction of the catalytic distillation column (perpendicular to the longitudinal direction/axial direction of the catalytic distillation column).

The catalytic distillation tower is provided with a plurality of catalyst beds, for example, 3-5 catalyst beds, and the plurality of catalyst beds are sequentially arranged along the longitudinal/axial direction of the catalytic distillation tower. Illustratively, as shown in fig. 1, the number of the catalyst beds is 3, that is, a first catalyst bed 21, a second catalyst bed 22 and a third catalyst bed 23 are sequentially arranged along the axial direction of the catalytic distillation column; as shown in fig. 2, the number of the catalyst beds is 5, that is, a first catalyst bed 21, a second catalyst bed 22, a third catalyst bed 23, a fourth catalyst bed 24 and a fifth catalyst bed 25 are sequentially stacked in the axial direction of the catalytic distillation column.

Specifically, the catalytic distillation column includes a reaction section and a column bottom located below the reaction section, the catalyst bed is disposed in the reaction section (i.e., the reaction section includes at least one catalyst bed), and the column bottom is used for containing distillate oil.

The catalytic distillation tower is provided with a raw oil inlet and a hydrogen inlet, the raw oil inlet is used for conveying raw oil to be subjected to catalytic distillation treatment to the reaction section/catalyst bed layer, and the hydrogen inlet is used for inputting hydrogen into the tower, so that the inside of the tower is in a hydrogen environment, and the raw oil entering the catalytic distillation tower through the raw oil inlet is contacted with the hydrogen to carry out hydrodesulfurization reaction in the hydrodesulfurization module. The raw oil inlet can be specifically arranged in the reaction section, for example, the raw oil inlet is arranged at the position 2/5-3/5 from bottom to top of the reaction section (namely, the bottom end of the reaction section is taken as the reference, the height of the raw oil inlet is 3/5 of the total height of the reaction section), and the hydrogen inlet is positioned below the reaction section and specifically can be arranged on distillate oil in a tower bottom.

In addition, the catalytic distillation tower can also comprise a preheater communicated with the raw oil inlet, so that the raw oil enters the preheater to be preheated and then enters the catalytic distillation tower to carry out catalytic distillation/hydrodesulfurization reaction.

In addition, the catalytic distillation tower is also provided with a light fraction outlet and a heavy fraction outlet, after the raw oil enters the catalytic distillation tower for catalytic distillation, the generated light fraction is output from the light fraction outlet, and the generated heavy fraction is output from the heavy fraction outlet, wherein the light fraction outlet is arranged at the top end of the catalytic distillation tower, and the heavy fraction outlet is arranged at the bottom end of the catalytic distillation tower.

In addition, the catalytic distillation tower can also comprise a condenser communicated with the light fraction outlet, and the light fraction is output from the light fraction outlet and then enters the condenser for condensation and liquefaction, so that a light fraction product is obtained.

In addition, the catalytic distillation tower can be also provided with a light fraction inlet, after the light fraction is output from the light fraction outlet, one part of the light fraction enters a product tank or a downstream treatment process as a product, and the rest part of the light fraction returns to the catalytic distillation tower from the light fraction inlet to form circulation. The light fraction inlet may be disposed at an upper portion of the catalytic distillation column, and may be specifically located above the reaction section (above the uppermost catalyst bed layer of the reaction section).

In addition, the catalytic distillation column may further comprise a reboiler in communication with the heavy fraction outlet.

In addition, the catalytic distillation tower can also be provided with a heavy fraction inlet, after the heavy fraction is output from the heavy fraction outlet, one part of the heavy fraction is used as a product to enter a product tank or a downstream treatment process, and the rest part of the heavy fraction enters a reboiler to be heated and then returns to the catalytic distillation tower to form circulation. Wherein, the heavy fraction inlet can be arranged at the lower part of the catalytic distillation tower, and particularly can be arranged below the reaction section (below the catalyst bed layer at the lowest layer of the reaction section).

The catalytic distillation process of the present invention comprises: and (3) feeding the raw oil into the catalytic distillation tower, and carrying out catalytic distillation/hydrodesulfurization reaction in a hydrogen environment, wherein the hydrodesulfurization treatment is carried out under the action of a hydrodesulfurization catalyst in the hydrodesulfurization module to obtain the purified oil product.

Specifically, raw oil can be preheated by a preheater, enters the catalytic distillation tower from a raw oil inlet, is mixed with hydrogen entering the catalytic distillation tower from a hydrogen inlet, enters a reaction section, is in contact with a hydrodesulfurization catalyst in a catalyst bed layer to carry out hydrodesulfurization reaction, and is subjected to distillation separation at the same time, a generated light fraction is output from a light fraction outlet and then enters a condenser for cooling, part of the light fraction is output as a light fraction product, and part of the light fraction returns to the catalytic distillation tower from a light fraction inlet to form circulation; and after the generated heavy fraction is output from the heavy fraction outlet, part of the heavy fraction is output as a heavy fraction product, and part of the heavy fraction enters a reboiler to be heated and then returns to the catalytic distillation tower from the heavy fraction inlet to form circulation.

Generally, before the catalytic distillation/hydrodesulfurization reaction, the hydrodesulfurization catalyst in the hydrodesulfurization module needs to be sulfided to convert the active metal components (the first metal component and the second metal component) therein from an oxidation state to a sulfided state, and then the catalytic distillation/hydrodesulfurization reaction is performed after the active metal components have hydrodesulfurization activity.

The hydrodesulfurization module can be in contact with a vulcanizing agent, and the vulcanization is carried out under the conditions of 1.5-2.0 MPa and 260-360 ℃, wherein the vulcanizing agent can comprise dimethyl disulfide (DMDS).

In specific implementation, the selective hydrodesulfurization effect can be further improved by adjusting and controlling appropriate operating conditions, and in some preferred embodiments, the operating conditions (catalytic distillation/hydrodesulfurization reaction conditions) of the catalytic distillation tower are as follows: a column pressure (column internal pressure) of 0.3 to 2.5MPa, for example, 0.3MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa or any two thereof, a column top temperature of 60 to 280 ℃, for example, 60 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 280 ℃ or any two thereof, and a column bottom temperature of 150 to 350 ℃, for example, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ or any two thereof.

In a specific embodiment, the catalytic distillation column includes a first catalytic distillation column 2, and accordingly, the catalytic distillation method includes a first catalytic distillation process performed in the first catalytic distillation column 2: preheating raw oil a by a first preheater 1, entering a first catalytic distillation tower 2 from a raw oil inlet of the first catalytic distillation tower 2, mixing with hydrogen b entering the first catalytic distillation tower 2 from a hydrogen inlet of the first catalytic distillation tower 2, entering a reaction section of the first catalytic distillation tower 2, contacting with a hydrodesulfurization catalyst (marked as a first hydrodesulfurization catalyst) in a catalyst bed layer of the first catalytic distillation tower 2, carrying out hydrodesulfurization reaction, simultaneously carrying out distillation separation, outputting a generated first light fraction c from a light fraction outlet of the first catalytic distillation tower, entering a first condenser 3 for cooling, and then partially outputting the first light fraction c ₁ Output as product (first light fraction product), part of the first light fraction c ₂ Returning the light fraction to the first catalytic distillation tower 2 from the light fraction inlet of the first catalytic distillation tower 2 to form a circulation; after the first heavy fraction d is output from the heavy fraction outlet of the first catalytic distillation tower 2, part of the first heavy fraction d ₁ As output of the product (first heavy fraction product), part of the first heavy fraction d ₂ And the heavy fraction is heated by the first reboiler 4 and then returned to the first catalytic distillation tower 2 from the heavy fraction inlet of the first catalytic distillation tower 2 to form circulation.

Specifically, there may be a tray 26 below the reaction section, the tray 26 being located between the reaction section and the column bottom 27.

Among them, the operating conditions of the first catalytic distillation column 2 may be: a column pressure of 0.3 to 1.0MPa, such as 0.3MPa, 0.5MPa, 0.8MPa, 1MPa or any combination thereof, a column top temperature of 60 to 100 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or any combination thereof, and a column bottom temperature of 150 to 200 ℃, such as 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or any combination thereof.

By the catalytic distillation process of the first catalytic distillation tower 2, sulfur-containing compounds such as mercaptan in the raw oil can be transferred into the first heavy fraction, simultaneously diene in the raw oil is selectively removed/converted, for example, mercaptan reacts with diene to generate thioether, and the thioether is transferred into the first heavy fraction, so that a clean first light fraction product is obtained, and the first light fraction output from the first catalytic distillation tower can be subjected to etherification and other treatments and then used as a gasoline blending component with a high octane number. Research shows that the removal/conversion rate of mercaptan in the raw oil is up to more than 98%, the removal/conversion rate of diene is up to more than 97%, and the octane number is basically not lost.

In another embodiment, the above catalytic distillation column comprises a second catalytic distillation column 2', and accordingly, the above catalytic distillation method comprises a second catalytic distillation process performed in the second catalytic distillation column 2': preheating raw oil a ' by a second preheater 1', then entering a second catalytic distillation tower 2' from a raw oil inlet of the second catalytic distillation tower 2', mixing with hydrogen b entering the second catalytic distillation tower 2' from a hydrogen inlet of the second catalytic distillation tower 2', entering a reaction section of the second catalytic distillation tower 2', contacting with a hydrodesulfurization catalyst (marked as a second hydrodesulfurization catalyst) in a catalyst bed layer of the second catalytic distillation tower 2', carrying out hydrodesulfurization reaction, simultaneously carrying out distillation separation, outputting a generated second light fraction c ' from a light fraction outlet of the second catalytic distillation tower 2', then entering a second condenser 3' for cooling, and then partially outputting the second light fraction c ₁ ' output as product (second light fraction product), part of the second light fraction c ₂ 'returning to the second catalytic distillation column from the light ends inlet of the second catalytic distillation column 2' forming a recycle; after the second heavy fraction d 'is output from the heavy fraction outlet of the second catalytic distillation column 2', part of the second heavy fraction d ₁ ' output as product (second heavy fraction product), part of the second heavy fraction d ₂ 'the heavy fraction heated by the second reboiler 4' is returned to the second catalytic distillation column 2 'from the heavy fraction inlet of the second catalytic distillation column 2', forming a cycle.

Wherein, the operating conditions of the second catalytic distillation column 2' may be: a column pressure of 1.5 to 2.5MPa, such as 1.5MPa, 1.8MPa, 2MPa, 2.2MPa, 2.5MPa or any combination thereof, a column top temperature of 150 to 280 ℃, such as 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 280 ℃ or any combination thereof, and a column bottom temperature of 250 to 350 ℃, such as 250 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃ or any combination thereof.

The sulfur-containing compounds in the first heavy fraction can be removed through the catalytic distillation process of the second catalytic distillation tower 2', so that the deep desulfurization of oil products is realized, and the total sulfur removal rate is improved. Research shows that the total sulfur removal rate can reach more than 99 percent, and the octane number loss is not higher than 0.4.

In specific implementation, the raw oil may be subjected to catalytic distillation in the first catalytic distillation tower alone, or may be subjected to catalytic distillation in the second catalytic distillation tower alone, or the first catalytic distillation tower and the second catalytic distillation tower may be connected in series, and the catalytic distillation may be performed in the first catalytic distillation tower and the second catalytic distillation tower in sequence.

In some preferred embodiments, the first heavy fraction and/or the first light fraction output from the first catalytic distillation tower can be used as the raw material oil of the second catalytic distillation tower, i.e. the raw material oil enters the first catalytic distillation tower to perform catalytic distillation, and then the first heavy fraction product output from the first catalytic distillation tower enters the second catalytic distillation tower to perform catalytic distillation, or the first heavy fraction product output from the first catalytic distillation tower and the first light fraction product are mixed and then enter the second catalytic distillation tower to perform catalytic distillation, and preferably the first heavy fraction product enters the second catalytic distillation tower to perform catalytic distillation. According to the research of the application, the effects of improving the desulfurization rate and reducing the octane number loss can be achieved.

And after the first heavy fraction product output by the first catalytic distillation tower enters a second catalytic distillation tower for catalytic distillation, the obtained second light fraction product and the second heavy fraction product can be mixed to be used as final purified oil products, or can be not mixed to be respectively used as a light fraction product and a heavy fraction product, and can be selected according to requirements during specific implementation.

It should be noted that the structures of the first catalytic distillation tower and the second catalytic distillation tower are the structures of the catalytic distillation towers described above, and are not described herein again, and for example, the first catalytic distillation tower has the structure shown in fig. 1, and the second catalytic distillation tower has the structure shown in fig. 2.

In addition, the composition/preparation process of the first hydrodesulfurization catalyst and the second hydrodesulfurization catalyst are within the scope of the composition/preparation process of the hydrodesulfurization catalyst, and are not repeated herein. Typically, the first hydrodesulfurization catalyst has a higher nickel content (higher than the second hydrodesulfurization catalyst) and the second hydrodesulfurization catalyst has a higher cobalt or molybdenum content (higher than the first hydrodesulfurization catalyst), and illustratively, the first hydrodesulfurization catalyst may not contain cobalt and the second hydrodesulfurization catalyst may not contain nickel, but is not limited thereto.

Specifically, the feedstock oil may include naphtha and/or gasoline, wherein the gasoline includes, for example, catalytic cracking (FCC) gasoline.

The final boiling point of the feed oil may be generally less than 250 ℃.

To make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

1. Preparation of the first hydrodesulfurization catalyst

(1-1) dissolving 13 parts of molybdenum acetylacetonate in a mixed solvent formed by mixing 2700 parts of ethanol and 300 parts of deionized water at room temperature by mass, and performing ultrasonic treatment until the molybdenum acetylacetonate is completely dissolved to obtain a first metal precursor solution (green solution);

(1-2) adding 18 parts by mass of n-tetradecyl primary amine into the first metal precursor solution, and stirring at 30 ℃ for 3 hours to obtain a white suspension;

(1-3) weighing 120 parts by mass of aluminum sec-butoxide, adding the aluminum sec-butoxide into the white suspension, reacting at 30 ℃ for 24 hours, filtering, washing the obtained solid product, drying at 120 ℃ in an oven for 24 hours, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor;

(1-4) 4.8 parts by mass of Ni (NO) was impregnated by an equal volume impregnation method ₃ ) ₂ ·6H ₂ O is loaded on the catalyst precursor to obtain the first hydrodesulfurization catalyst (NiMo/Al) ₂ O ₃ Catalyst a 1).

2. Encapsulation and loading of first hydrodesulfurization catalyst

(2-1)NiMo/Al ₂ O ₃ The catalyst A1 is filled in a cavity surrounded by the net body to form a cuboid or cubic hydrodesulfurization module; wherein, the net body is formed by sequentially laminating three layers of stainless steel nets with different meshes, a plurality of spaces are formed in the cavity by a plurality of first filler sheets at intervals, and NiMo/Al ₂ O ₃ The catalyst A1 is filled in the spaces;

(2-2) sequentially stacking a plurality of hydrodesulfurization modules, arranging a packing layer between every two adjacent hydrodesulfurization modules, and binding by using stainless steel bands to form a packaging unit;

(2-3) filling the packaging units into the catalytic distillation tower to form a plurality of catalyst bed layers, wherein the catalyst bed layers are sequentially distributed along the axial direction of the catalytic distillation tower, each catalyst bed layer comprises a plurality of sequentially arranged catalytic unit layers, each catalytic unit layer is formed by sequentially arranging a plurality of packaging units, the plurality of packaging units in one of every two connected catalytic unit layers are transversely arranged, and the plurality of packaging units in the other catalytic unit layer are longitudinally arranged (namely the upper layer and the lower layer in the two adjacent catalytic unit layers are staggered at 90 degrees);

after the filling, the first catalytic distillation tower is shown in fig. 1, and is provided with a raw oil inlet, a hydrogen inlet, a light fraction outlet, a light fraction inlet, a heavy fraction outlet, a heavy fraction inlet, a first preheater communicated with the raw oil inlet, a first condenser communicated with the light fraction outlet, and a first reboiler communicated with the heavy fraction outlet, wherein the raw oil inlet is arranged at 3/5 from bottom to top of the reaction section, the hydrogen inlet is arranged on distillate oil in the tower bottom, the light fraction outlet is arranged at the top end of the first catalytic distillation tower, the light fraction inlet is arranged at the upper part of the first catalytic distillation tower, the heavy fraction outlet is arranged at the bottom end of the first catalytic distillation tower, and the heavy fraction inlet is arranged at the lower part of the first catalytic distillation tower.

3. Catalytic distillation/hydrodesulfurization reaction

Under the conditions of 1.5-2.0 MPa and 260-360 ℃, vulcanizing the hydrodesulfurization module by using DMDS (dimethyl disulfide) so that active metal components in the hydrodesulfurization catalyst are converted from an oxidation state to a vulcanization state and have hydrodesulfurization activity;

then adjusting the pressure in the tower to be 0.4MPa, the temperature at the top of the tower to be 82 ℃ and the temperature at the bottom of the tower to be 194 ℃, and introducing the raw oil (catalytic gasoline) into a first catalytic distillation tower for catalytic distillation;

through detection, in the purified oil product (light fraction product) obtained after the catalytic distillation in the first catalytic distillation tower, the mercaptan removal/conversion rate is 98.5%, the diene removal/conversion rate is 97.2%, and the octane number is increased by 0.2%.

Example 2

The difference from example 1 is that: the heavy fraction product output from the first catalytic distillation tower in the embodiment 1 enters a second catalytic distillation tower for catalytic distillation;

1. preparation of the second hydrodesulfurization catalyst

The second hydrodesulfurization catalyst differs from the preparation of the first hydrodesulfurization catalyst in example 1 in that:

in the step (1-1), 11 parts of molybdenum acetylacetonate;

in the step (1-2), 20 parts of n-hexadecyl primary amine is adopted to replace 18 parts of n-tetradecyl primary amine;

in the step (1-4), 4.2 parts of Co (NO) is used ₃ ) ₂ ·6H ₂ Replacement of 4.8 parts of Ni (NO) by O ₃ ) ₂ ·6H ₂ O。

2. Encapsulation and packing of a second hydrodesulfurization catalyst

Referring to steps (2-1) to (2-3) in example 1, the second catalytic distillation column was packed with a second hydrodesulfurization catalyst;

after completion of the filling, the second catalytic distillation column is shown in fig. 2, which is different from the first catalytic distillation column in example 1 in that: the raw oil inlet is arranged at the position 2/5 from bottom to top of the reaction section.

3. Catalytic distillation/hydrodesulfurization reaction

The difference from the catalytic distillation/hydrodesulfurization reaction in example 1 is that: the second catalytic distillation column operating conditions were: the pressure in the column was 1.8MPa, the temperature at the top of the column was 262 ℃ and the temperature at the bottom of the column was 310 ℃ and the other conditions were the same as those of the catalytic distillation in example 1 using the first catalytic distillation column;

after detection, the total sulfur removal rate of the obtained purified oil product (mixture of light fraction products and heavy fraction products) after catalytic distillation in the second catalytic distillation tower is 99.4%, and the octane number loss is 0.4.

Comparative example 1

The difference from example 1 is that: the hydrodesulfurization catalyst is NiMo/Al prepared by the following process ₂ O ₃ Catalyst B1, the remaining conditions being the same as in example 1;

wherein, NiMo/Al ₂ O ₃ Catalyst B1 was prepared as follows: 6.9 parts by mass of ammonium heptamolybdate tetrahydrate and 4.8 parts by mass of Ni (NO) ₃ ) ₂ ·6H ₂ Dissolving O in deionized water, soaking in 40 parts of 20-40 mesh Al in equal volume ₂ O ₃ Putting the obtained sample on the particles, drying the sample in an oven at 120 ℃ for 24h, and roasting the dried sample at 500 ℃ for 4h to obtain NiMo/Al ₂ O ₃ Catalyst B1;

after detection and catalytic distillation/hydrodesulfurization reaction, the removal/conversion rate of mercaptan is 85.2%, the removal/conversion rate of diene is 86.7% and the octane number loss is 0.2 in the obtained purified oil product.

Comparative example 2

The difference from example 1 is that in step (1-3), 150 parts of aluminum chloride was used in place of 120 parts of aluminum sec-butoxide, and the other conditions were the same as in example 1;

through detection, the mercaptan removal/conversion rate is 87.3%, the diene removal/conversion rate is 88.5%, and the octane number loss is 0.2 in the obtained purified oil product through catalytic distillation/hydrodesulfurization reaction.

Comparative example 3

The difference from example 1 is that step (1-2) is eliminated, i.e., no addition of primary alkylamine is made during the preparation of the hydrodesulfurization catalyst, and the remaining conditions are the same as in example 1;

through detection, the removal/conversion rate of mercaptan is 80.5%, the removal/conversion rate of diene is 81.1% and the octane number loss is 0.4 in the obtained purified oil product through catalytic distillation/hydrodesulfurization reaction.

Comparative example 4

The difference from example 2 is that: the hydrodesulfurization catalyst is CoMo/Al prepared by the following process ₂ O ₃ Catalyst B2, the remaining conditions being the same as in example 2;

wherein, CoMo/Al ₂ O ₃ Catalyst B2 was prepared as follows: 5.9 parts by mass of ammonium heptamolybdate tetrahydrate and 4.2 parts by mass of Co (NO) ₃ ) ₂ ·6H ₂ Dissolving O in deionized water, soaking in 40 parts of 20-40 mesh Al in equal volume ₂ O ₃ Putting the obtained sample on the particles, drying the sample in an oven at 120 ℃ for 24h, and roasting the dried sample at 500 ℃ for 4h to obtain the CoMo/Al ₂ O ₃ Catalyst B2;

through detection, the total sulfur removal rate of the purified oil product obtained through catalytic distillation/hydrodesulfurization reaction is 88.7%, and the octane number loss is 1.5.

Comparative example 5

The difference from example 2 is that in step (1-3), 150 parts of aluminum chloride was used in place of 120 parts of aluminum sec-butoxide, and the other conditions were the same as in example 2;

through detection, the total sulfur removal rate of the purified oil product obtained through catalytic distillation/hydrodesulfurization reaction is 90.2%, and the octane number loss is 1.0.

Comparative example 6

The difference from example 2 is that step (1-2) is eliminated, i.e. no addition of primary alkylamine is made during the preparation of the hydrodesulfurization catalyst, and the remaining conditions are the same as in example 2;

through detection, the total sulfur removal rate of the purified oil product obtained through catalytic distillation/hydrodesulfurization reaction is 85.4%, and the octane number loss is 1.8.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A hydrodesulfurization module is characterized by comprising a net body and a hydrodesulfurization catalyst filled in a cavity surrounded by the net body, wherein the net body comprises a plurality of layers of metal nets which are sequentially stacked; the hydrodesulfurization catalyst is prepared according to the process comprising the following steps:

dissolving a first metal source in a first solvent to obtain a first metal source solution; wherein the first metal source comprises at least one metal element from group VIB of the periodic Table of the elements;

mixing the first metal source solution with alkyl primary amine and an organic aluminum source to obtain a mixed solution;

reacting the mixed solution at 20-80 ℃ for 12-96 h, and then roasting the obtained solid product to obtain the catalyst precursor;

loading a second metal component on the catalyst precursor by adopting an impregnation method to obtain the hydrodesulfurization catalyst; wherein the second metal component comprises at least one metal element from group VIII of the periodic Table of the elements.

2. The hydrodesulfurization module of claim 1,

the concentration of the first metal source solution is 0.005-0.1 mol/L;

and/or mixing the first metal source with the first solvent at room temperature, and performing ultrasonic treatment until the first metal source is dissolved to obtain a first metal source solution;

and/or the process of mixing the first metal source solution with alkyl primary amine and organic aluminum source comprises the following steps: adding alkyl primary amine into the first metal source solution, and stirring for 1-10 h at 10-80 ℃ to obtain a suspension; adding the organic aluminum source into the suspension to obtain the mixed solution;

and/or the roasting temperature is 400-550 ℃, and the roasting time is 5-15 h;

and/or, the first metal source comprises molybdenum and/or tungsten;

and/or, the alkyl primary amine comprises at least one of dodecyl amine, tetradecyl amine, hexadecyl amine, and octadecyl amine;

and/or the organic aluminum source comprises at least one of aluminum isopropoxide, aluminum sec-butoxide and aluminum acetylacetonate;

and/or, the first solvent comprises alcohol and/or water, the alcohol comprises at least one of methanol, ethanol, n-butanol and isopropanol;

and/or the second metal component comprises cobalt and/or nickel;

and/or the first metal source and the second metal component are respectively calculated by metal oxides, the organic aluminum source is calculated by aluminum oxide, and based on the total mass of the first metal source, the second metal component and the organic aluminum source, the mass percent of the first metal source is 5-50%, the mass percent of the second metal component is l-30%, and the balance is the organic aluminum source.

3. The hydrodesulfurization module of claim 1,

the mesh numbers of any two of the multilayer metal nets are different;

and/or in the multilayer metal nets, the mesh number of the metal net with the largest mesh number is 100-140, and the mesh number of the metal net with the smallest mesh number is 60-100;

and/or, the metal mesh comprises a stainless steel mesh;

and/or the hydrodesulfurization module further comprises at least one first filler sheet arranged in the cavity, and the at least one first filler sheet partitions the cavity into a plurality of spaces filled with the hydrodesulfurization catalyst;

and/or the hydrodesulfurization module is in the shape of a regular or irregular polyhedron.

4. The hydrodesulfurization module of claim 3,

the first packing sheet comprises loose sheets and/or regular packing, and the regular packing comprises at least one of windowed flow guide packing, plate corrugated packing, wire mesh corrugated packing, pore plate corrugated packing, calendered pore plate corrugated packing and honeycomb packing;

and/or the forming material of the first filler sheet comprises at least one of metal, plastic, ceramic and graphite.

5. An encapsulation unit of the hydrodesulfurization module according to any one of claims 1 to 4, comprising a plurality of the hydrodesulfurization modules, a filler layer between each two adjacent hydrodesulfurization modules, and a fixing band for fixing the plurality of hydrodesulfurization modules and the filler layer together.

6. Packaging unit according to claim 5,

the packing layer comprises scattered sheets and/or structured packing, and the structured packing comprises at least one of windowed flow guide packing, plate corrugated packing, wire mesh corrugated packing, pore plate corrugated packing, calendered pore plate corrugated packing and honeycomb packing;

and/or the forming material of the filler layer comprises at least one of metal, plastic, ceramic and graphite;

and/or the fixing belt is wound on the outer side of an arrangement structure consisting of the plurality of hydrodesulfurization modules and the filler layer positioned between every two adjacent hydrodesulfurization modules so as to bind the plurality of hydrodesulfurization modules and the filler layer together;

and/or, the securing strap may comprise a stainless steel strap.

7. A catalytic distillation tower, characterized by comprising at least one catalyst bed layer, wherein the catalyst bed layer comprises a plurality of sequentially arranged catalytic unit layers, and each catalytic unit layer is formed by sequentially arranging a plurality of packaging units as claimed in claim 5 or 6; in each two adjacent catalytic unit layers, a plurality of packaging units in one catalytic unit layer are transversely arranged, and a plurality of packaging units in the other catalytic unit layer are longitudinally arranged.

8. A catalytic distillation process, comprising: the raw oil enters the catalytic distillation tower of claim 7, and catalytic distillation is carried out in a hydrogen environment, wherein hydrodesulfurization treatment is carried out under the action of a hydrodesulfurization catalyst in the hydrodesulfurization module, so as to obtain a purified oil product.

9. A catalytic distillation process according to claim 8,

after the hydrodesulfurization module is subjected to vulcanization treatment, the raw oil enters the catalytic distillation tower for catalytic distillation;

and/or the operating conditions of the catalytic distillation column are: the tower pressure is 0.3-2.5 MPa, the tower top temperature is 60-280 ℃, and the tower bottom temperature is 150-350 ℃;

and/or the raw oil comprises naphtha and/or gasoline;

and/or the final distillation point of the raw oil is less than 250 ℃.

10. The catalytic distillation method according to claim 9, wherein the sulfidation process comprises: contacting the hydrodesulfurization catalyst with a vulcanizing agent, and vulcanizing under the conditions of 1.5-2.0 MPa and 260-360 ℃; wherein the vulcanizing agent comprises dimethyl disulfide.