CN109718829B - Hydrocarbon oil desulfurization catalyst containing FAU structure molecular sieve, preparation method thereof and hydrocarbon oil desulfurization process - Google Patents

Hydrocarbon oil desulfurization catalyst containing FAU structure molecular sieve, preparation method thereof and hydrocarbon oil desulfurization process Download PDF

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CN109718829B
CN109718829B CN201711046525.9A CN201711046525A CN109718829B CN 109718829 B CN109718829 B CN 109718829B CN 201711046525 A CN201711046525 A CN 201711046525A CN 109718829 B CN109718829 B CN 109718829B
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hydrocarbon oil
oxide
molecular sieve
sulfur
oil desulfurization
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王磊
宋烨
田辉平
林伟
刘俊
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention relates to a hydrocarbon oil desulfurization catalyst containing FAU structure molecular sieve, a preparation method thereof and a hydrocarbon oil desulfurization process, wherein the hydrocarbon oil desulfurization catalyst contains 10-80 wt% of sulfur storage metal oxide calculated by oxide, 3-35 wt% of inorganic oxide binder calculated by oxide, 5-40 wt% of boron nitride calculated by oxide, 1-20 wt% of FAU structure molecular sieve calculated by dry basis and 5-30 wt% of metal promoter calculated by metal element, based on the weight of the hydrocarbon oil desulfurization catalyst or the total weight of the sulfur storage metal oxide, the inorganic oxide binder, the boron nitride, the FAU structure molecular sieve and the metal promoter. When the hydrocarbon oil desulfurization catalyst provided by the invention is applied to a hydrocarbon oil desulfurization process, the catalyst has the advantages of high stability, good desulfurization activity and good wear resistance.

Description

Hydrocarbon oil desulfurization catalyst containing FAU structure molecular sieve, preparation method thereof and hydrocarbon oil desulfurization process
Technical Field
The invention relates to a hydrocarbon oil desulfurization catalyst containing FAU structure molecular sieve, a preparation method thereof and a hydrocarbon oil desulfurization process.
Background
With the increasing scarcity of crude oil resources, how to effectively utilize limited resources to generate light products to the maximum becomes a goal pursued by oil refining technology developers. On the other hand, with the continuous improvement of environmental protection requirements, environmental protection regulations are becoming stricter, and the currently implemented gasoline quality standard GB17930-2013 requires that the sulfur content in gasoline must be lower than 10ppm from 1/2017. Therefore, a clean product production technology capable of simultaneously improving the yield of the target product becomes a choice of a plurality of oil refining enterprises.
In China, catalytic cracking is widely applied due to good operation flexibility, high gasoline yield and low one-time investment. However, the content of sulfur in the catalytic cracking raw material is continuously increased, so that the content of sulfur in gasoline which is a catalytic cracking product is relatively high, and the gasoline cannot reach the quality standard of clean oil products, and the gasoline needs to be subjected to post-treatment. However, the gasoline post-treatment desulfurization technology adopted at present is carried out in a high-pressure hydrogen atmosphere, and olefin in the gasoline is easy to be subjected to hydrogenation saturation, so that the octane number of the product gasoline is reduced.
Chinese patent CN 1355727a provides an adsorbent containing zinc oxide, silicon oxide, aluminum oxide and nickel or cobalt, and provides a preparation method of the adsorbent. The method firstly prepares a carrier containing zinc oxide, silicon oxide and aluminum oxide, and then introduces nickel or cobalt by impregnation. The adsorbent can be used for removing sulfur from cracked-gasoline or diesel fuel.
Chinese patent CN 1208124a prepared an adsorbent for removing sulfides in cracked gasoline by impregnating an adsorbent support comprising zinc oxide, expanded perlite and alumina with promoter metals such as cobalt and nickel, and then reducing the promoter at a suitable temperature. The adsorbent can eliminate sulfur from gasoline in the presence of hydrogen and reduce octane number caused by olefin saturation.
The disclosed adsorbent has certain desulfurization performance, but with the improvement of the quality standard of gasoline, the requirement on the sulfur content of the product gasoline is also strict. In addition, the catalyst is easy to wear in the use process, and the catalyst needs to be continuously supplemented, so that the operation cost is increased. It can thus be seen that there is a need to provide a novel catalyst having improved desulfurization activity and attrition resistance.
Disclosure of Invention
The invention aims to provide a hydrocarbon oil desulfurization catalyst containing a molecular sieve with an FAU structure, a preparation method thereof and a hydrocarbon oil desulfurization process.
In order to achieve the above object, the present invention provides a hydrocarbon oil desulfurization catalyst containing a molecular sieve of FAU structure, which contains, based on the weight of the hydrocarbon oil desulfurization catalyst, or based on the total weight of a sulfur-storing metal oxide, an inorganic oxide binder, boron nitride, a molecular sieve of FAU structure and a metal promoter, 10 to 80 wt% of the sulfur-storing metal oxide in terms of oxide, 3 to 35 wt% of the inorganic oxide binder in terms of oxide, 5 to 40 wt% of boron nitride, 1 to 20 wt% of the molecular sieve of FAU structure in terms of dry basis, and 5 to 30 wt% of the metal promoter in terms of metal element; wherein the sulfur storage metal oxide is at least one selected from group IIB metal oxides, group VB metal oxides and group VIB metal oxides; the metal element of the metal promoter is at least one selected from cobalt, copper, nickel, iron and manganese.
The invention also provides a preparation method of the hydrocarbon oil desulfurization catalyst, which comprises the following steps: a. mixing a sulfur-storing metal oxide and/or a sulfur-storing metal oxide precursor, a precursor of an inorganic oxide binder, boron nitride, a FAU-structured molecular sieve, water and an acidic liquid to obtain a carrier slurry; wherein the pH value of the carrier slurry is 1-5; b. sequentially carrying out spray drying molding, first drying and first roasting on the obtained carrier slurry to obtain a catalyst carrier; c. introducing a precursor of a metal promoter into the catalyst carrier, and then sequentially carrying out second drying and second roasting; optionally d, reducing the product obtained in the step c under hydrogen-containing atmosphere; obtaining the hydrocarbon oil desulfurization catalyst.
The invention also provides a process for desulfurizing hydrocarbon oil, which comprises the following steps: contacting sulfur-containing hydrocarbon oil with a hydrocarbon oil desulfurization catalyst and carrying out desulfurization reaction under the condition of hydrogen; wherein, the hydrocarbon oil desulfurization catalyst is the hydrocarbon oil desulfurization catalyst provided by the invention or the hydrocarbon oil desulfurization catalyst prepared by the method.
The hydrocarbon oil desulfurization catalyst provided by the invention contains boron nitride, so that the desulfurization catalyst has desulfurization and dehydrogenation performances and good abrasion resistance, and can be used for synergistically promoting reactions such as dehydrogenation and aromatization of naphthenes in hydrocarbon oil together with a molecular sieve to generate hydrogen and generate aromatic hydrocarbon components with high octane number, the consumption of additional hydrogen supply in a hydrocarbon oil desulfurization process is reduced, the operation and application cost of the process is reduced, and the quality of produced desulfurized gasoline is also improved. Compared with the desulfurization catalyst without using boron nitride, the catalyst has higher stability.
In addition, the use of hexagonal boron nitride can further improve the wear resistance and service life of the catalyst as compared to other boron nitrides.
The desulfurization catalyst provided by the invention has higher penetrating sulfur capacity and is suitable for hydrodesulfurization of hydrocarbon substances. The desulfurization catalyst containing the molecular sieve is used for desulfurization of cracked gasoline, has higher gasoline octane number than the existing desulfurization catalyst containing the molecular sieve, and the desulfurized gasoline can have higher aromatic hydrocarbon content.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD spectrum (abscissa 2. theta., unit) of a hydrocarbon oil desulfurization catalyst A1 prepared in example 1 of the present invention before and after hydrothermal aging.
FIG. 2 is an XRD spectrum (abscissa 2. theta., unit) of a hydrocarbon oil desulfurization catalyst B1 prepared in comparative example 1 of the present invention before and after hydrothermal aging.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Dry basis in the present invention refers to the product of the material after calcination at 650 c for 4 hours in an air atmosphere.
The invention provides a hydrocarbon oil desulfurization catalyst containing a FAU structure molecular sieve, which comprises 10-80 wt% of sulfur storage metal oxide calculated by oxide, 3-35 wt% of inorganic oxide binder calculated by oxide, 5-40 wt% of boron nitride, 1-20 wt% of FAU structure molecular sieve calculated by dry basis and 5-30 wt% of metal promoter calculated by metal element, based on the weight of the hydrocarbon oil desulfurization catalyst or based on the total weight of the sulfur storage metal oxide, the inorganic oxide binder, the boron nitride, the FAU structure molecular sieve and the metal promoter; preferably, the hydrocarbon oil desulfurization catalyst contains, based on the weight of the hydrocarbon oil desulfurization catalyst, 27 to 70 wt% of a sulfur-storing metal oxide in terms of oxide, 6 to 25 wt% of an inorganic oxide binder in terms of oxide, 10 to 30 wt% of boron nitride, 2 to 15 wt% of a FAU-structured molecular sieve in terms of dry basis, and 8 to 25 wt% of a metal promoter in terms of metal element, or the total weight of the sulfur-storing metal oxide, the inorganic oxide binder, boron nitride, the FAU-structured molecular sieve, and the metal promoter; further preferably, the hydrocarbon oil desulfurization catalyst contains 40 to 60% by weight, in terms of oxide, of the sulfur-storing metal oxide, 8 to 15% by weight, in terms of oxide, of the inorganic oxide binder, 12 to 25% by weight of boron nitride, 2 to 10% by weight, in terms of dry basis, of the FAU-structured molecular sieve, and 12 to 20% by weight, in terms of metallic element, of the sulfur-storing metal oxide, the inorganic oxide binder, boron nitride, the FAU-structured molecular sieve, and the metal promoter, based on the weight of the hydrocarbon oil desulfurization catalyst or the total weight of the sulfur-storing metal oxide, the inorganic oxide binder, the FAU-structured molecular sieve, and the metal promoter; wherein the sulfur storage metal oxide is at least one selected from group IIB metal oxides, group VB metal oxides and group VIB metal oxides; the metal element of the metal promoter is at least one selected from cobalt, copper, nickel, iron and manganese.
According to the present invention, the contents of the aforementioned components in the hydrocarbon oil desulfurization catalyst can be measured according to the following method (hereinafter sometimes referred to as XRD measurement method):
the hydrocarbon oil desulfurization catalyst sample is roasted for 4 hours at 650 ℃ in the air atmosphere, and stored for later use in the nitrogen atmosphere. 1g of the calcined catalyst sample was weighed and subjected to XRD spectrum measurement. Comparing the XRD spectrogram with a standard spectrogram of an inorganic crystal structure database, identifying each component, and further determining the strongest characteristic peak of each component. Then, the peak area of the strongest characteristic peak of a certain component is divided by the sum of the peak areas of all the strongest characteristic peaks, and the ratio is taken as the content of the component. In particular, the content of the metal promoter in terms of metal oxide obtained by this measurement method can be obtained by simple conversion.
The specific contents of the measurement of the contents of the components in the hydrocarbon oil desulfurization catalyst by the XRD method according to the present invention can be further referred to in "determination of chemical composition of S-Zorb adsorbent" of Q/SH 3360215-2009, which is incorporated herein by reference in its entirety.
The catalyst contains boron nitride, and has the following advantages:
1. the catalyst has good desulfurization effect, can reduce the use of sulfur-storing metal oxides and metal promoters, and reduces the cost of the catalyst;
2. the catalyst has good dehydrogenation effect, can cooperate with a molecular sieve to promote the reactions of naphthene dehydrogenation aromatization and the like in hydrocarbon oil, can generate aromatic hydrocarbon components with high octane number while generating hydrogen, reduces the consumption of hydrogen supply added in a hydrocarbon oil desulfurization process, reduces the cost of the process, and improves the quality of the produced desulfurized gasoline;
3. has improved catalyst antiwear performance.
According to the invention, when the hydrocarbon oil desulfurization catalyst is characterized by XRD, characteristic peaks of boron nitride can appear at diffraction angles 2 theta of 27.2 degrees +/-0.5 degrees, 41.5 degrees +/-0.5 degrees and 50.3 degrees +/-0.5 degrees. Boron nitride has various structures, and includes, for example, at least one selected from hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN), and wurtzite boron nitride (w-BN), and is preferably hexagonal boron nitride. The use of hexagonal boron nitride can further improve the wear resistance and life of the catalyst compared to other boron nitrides.
According to the present invention, an inorganic oxide binder is used for binding components of the catalyst, and for example, may be at least one selected from the group consisting of alumina, titania and tin dioxide, and the inorganic oxide may be introduced into the catalyst in the form of a precursor for improving the strength of the catalyst.
According to the present invention, the sulfur storage metal oxide may be at least one selected from the group consisting of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, and tungsten oxide, preferably at least one selected from the group consisting of zinc oxide, molybdenum oxide, and vanadium oxide, and more preferably zinc oxide.
According to the invention, the FAU-structured molecular sieve is an faujasite type molecular sieve which has three-dimensional twelve-membered ring channels with the pore diameter of
Figure BDA0001452312760000051
The FAU structure molecular sieve is mainly X-type and Y-type molecular sieves, generally SiO2/Al2O3The molar ratio of the X-type molecular sieve to the SiO 2.2-3.02/Al2O3The molecular sieve with the mole ratio more than 3.0 is a Y-type molecular sieve. The framework structures of the X-type molecular sieve and the Y-type molecular sieve belong to a hexagonal system, the space group structure is Fd3m, and the unit cell parameters of the X-type molecular sieve
Figure BDA0001452312760000052
Unit cell parameters of Y-type molecular sieve
Figure BDA0001452312760000053
According to the invention, the molecular sieve with FAU structure also comprises modified molecules with FAU structureAnd (4) screening. The modification method may include a hydrothermal method, a chemical treatment method (e.g., an inorganic acid treatment method, a silicofluoride alumino-silicofluoride method, and SiC 1)4Gas phase process) or hydrothermal combined with chemical treatment. The modified molecular sieve includes but is not limited to ultrastable Y-type molecular sieve (USY), rare earth element-containing REUSY, REHY and REY, phosphorus-containing PUSY, PREHY, PREY and the like. SiO of the molecular sieve with FAU structure2：Al2O3In a molar ratio of 1 to 4: 1; preferably, the SiO of the molecular sieve having FAU structure2：Al2O3In a molar ratio of 1.5 to 3: 1. preferably, the molecular sieve having the FAU structure is at least one of an X-type molecular sieve, a Y-type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, and PREY.
According to the present invention, the metal promoter may be at least one selected from cobalt, nickel, iron and manganese, preferably nickel.
The invention also provides a preparation method of the hydrocarbon oil desulfurization catalyst, which comprises the following steps: a. mixing a sulfur-storing metal oxide and/or a sulfur-storing metal oxide precursor, a precursor of an inorganic oxide binder, boron nitride, a FAU-structured molecular sieve, water and an acidic liquid to obtain a carrier slurry; wherein the pH value of the carrier slurry is 1-5; b. sequentially carrying out spray drying molding, first drying and first roasting on the obtained carrier slurry to obtain a catalyst carrier; c. introducing a precursor of a metal promoter into the catalyst carrier, and then sequentially carrying out second drying and second roasting; optionally d, reducing the product obtained in the step c under hydrogen-containing atmosphere; obtaining the hydrocarbon oil desulfurization catalyst.
According to the present invention, a precursor of the inorganic oxide binder is used to form the inorganic oxide binder after calcination, thereby binding the components of the catalyst, for example, the precursor of the inorganic oxide binder may be at least one of a titanium dioxide binder precursor, an alumina binder precursor, and a tin dioxide binder precursor. For example: the titania binder precursor is a titania sol, a gel of titania, and/or a substance that can be hydrolyzed in the acidic liquid to produce a cohesive colloid and that is converted into anatase titania under the first calcination condition, and may be, for example, at least one selected from titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrous titanium oxide, and anatase titania. The alumina binder precursor is an alumina sol, an alumina gel, and/or a substance that can be hydrolyzed in the acidic liquid to generate a cohesive colloid and is converted into alumina under the first calcination condition, and may be, for example, at least one selected from the group consisting of SB powder, hydrated alumina, an alumina sol, boehmite, pseudoboehmite, alumina trihydrate, and amorphous aluminum hydroxide. The tin dioxide binder precursor is a sol, a gel and/or a substance that can be hydrolyzed in the acidic liquid to generate a binding colloid of tin oxide and is converted into tin dioxide under the first baking condition, and may be, for example, at least one selected from tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide.
According to the invention, a precursor of the metal promoter is used to produce the metal promoter after calcination and optional reduction, and may be selected, for example, from at least one of the acetates, carbonates, nitrates, sulfates, thiocyanates and oxides of the metal in the metal promoter; preferably at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel and/or cobalt, more preferably nickel nitrate and/or cobalt nitrate, and further preferably nickel nitrate. The method of introducing the precursor of the metal promoter on the catalyst support may be impregnation or precipitation. The impregnation may be by impregnating the support with a solution or suspension of a precursor of the metal promoter; the precipitation may be mixing a solution or suspension of the precursor of the metal promoter with the catalyst support, and then adding ammonia to precipitate the precursor of the metal promoter on the catalyst support.
According to the present invention, an acidic liquid is used to bring the pH of the carrier slurry to 1 to 5, preferably 1.5 to 4, and for example, the acidic liquid may be an acid or an aqueous solution of an acid, and the acid may be a water-soluble inorganic acid and/or an organic acid, and for example, may be at least one selected from hydrochloric acid, nitric acid, phosphoric acid, and acetic acid.
According to the present invention, drying and calcination are well known to those skilled in the art for preparing a catalyst, and the drying method may be air drying, oven drying, forced air drying, etc., and calcination may be performed in a calcination furnace, for example, the conditions of the first drying may include: the temperature is 25-400 ℃, preferably 100-350 ℃, and the time is more than 0.5h, preferably 0.5-8h, and more preferably 2-20 h; the conditions of the first firing may include: the temperature is 400-700 ℃, preferably 450-650 ℃, and the time is more than 0.5h, preferably 0.5-100h, and more preferably 0.5-10 h; the conditions of the second drying may include: the temperature is 50-300 ℃, and the preferred temperature is 100-250 ℃; the time is 0.5 to 8 hours, preferably 1 to 5 hours; the conditions of the second firing may include: the temperature is 300-800 ℃, preferably 450-750 ℃, and the time is more than 0.5h, preferably 0.5-6h, and more preferably 1-3 h. The second firing may be performed in the presence of oxygen or an oxygen-containing gas. Optionally, the second calcination product may be reduced under an atmosphere containing hydrogen gas, so that the metal in the metal promoter exists in a substantially reduced state, preferably, the temperature of the reduction is 300-600 ℃, preferably 400-500 ℃; the reduction time is 0.5-6h, preferably 1-3 h; the hydrogen content of the hydrogen-containing atmosphere is 10 to 70% by volume. The reduction of the second calcined product may be carried out immediately after the second calcined product is produced, or may be carried out before use (i.e., before use in desulfurization adsorption).
According to the present invention, the mixing process in step a is not particularly limited, for example, in step a, the precursor of the inorganic oxide binder, boron nitride, water and acidic liquid are mixed first, and then mixed with the sulfur storage metal oxide and/or the sulfur storage metal oxide precursor and the FAU structure molecular sieve; or mixing the precursor of the inorganic oxide binder, water and acidic liquid, and then mixing with the sulfur storage metal oxide and/or the precursor of the sulfur storage metal oxide, boron nitride and the FAU structure molecular sieve. The amount of water added in the above mixing process may not be particularly limited as long as the carrier slurry can be obtained. For example, the weight ratio of the added water to the inorganic oxide binder is (5-10): 1; or the weight ratio of the added water to the sum of the weights of the inorganic oxide binder and the boron nitride is (5-10): 1. alternatively, the sulfur-storing metal oxide may be mixed with the other components in the form of a powder, or may be dispersed in water and then mixed with the other components in the form of a slurry.
In the present invention, the obtained carrier slurry may be in the form of a paste or slurry, and the carrier slurry may be thickened and then dried to be molded, and more preferably, the carrier slurry is in the form of a slurry, and microspheres having a particle size of 20 to 200 μm may be formed by spray drying to achieve the purpose of molding. To facilitate spray drying, the solids content of the carrier slurry before drying may be in the range of from 10 to 50% by weight, preferably from 20 to 50% by weight. The addition of water may be further included in the process of obtaining the carrier slurry, and the amount of water added is not particularly limited as long as the obtained carrier slurry satisfies the above solid content.
The invention also provides a process for desulfurizing hydrocarbon oil, which comprises the following steps: contacting sulfur-containing hydrocarbon oil with a hydrocarbon oil desulfurization catalyst and carrying out desulfurization reaction under the condition of hydrogen; wherein, the hydrocarbon oil desulfurization catalyst is the hydrocarbon oil desulfurization catalyst provided by the invention or the hydrocarbon oil desulfurization catalyst prepared by the method.
Desulfurization reactions according to the present invention are well known to those skilled in the art and will not be described further herein, for example, the conditions of the desulfurization reaction may include: the temperature is 350-500 ℃, preferably 400-450 ℃, and the pressure is 0.5-4MPa (absolute pressure), preferably 2-4 MPa.
According to the invention, the reacted catalyst can be reused after regeneration. The regeneration is carried out under an oxygen atmosphere, and the conditions of the regeneration can include: the regeneration pressure is normal pressure, and the regeneration temperature is 400-700 ℃, preferably 500-600 ℃.
According to the present invention, the regenerated catalyst may be further reduced under a hydrogen-containing atmosphere before the desulfurization reaction is carried out again, and the reducing conditions of the regenerated catalyst include: the temperature is 350-500 ℃, and preferably 400-450 ℃; the pressure is 0.2-2MPa, preferably 0.2-1.5 MPa.
One embodiment, the present invention specifically includes the following scheme:
1. a desulfurization catalyst comprising:
1) a sulfur-storing metal oxide, wherein the sulfur-storing metal is selected from one or more of a metal of group IIB of the periodic table, a metal of group VB of the periodic table, and a metal of group VIB of the periodic table, preferably from one or more of zinc, cadmium, niobium, tantalum, chromium, molybdenum, tungsten, and vanadium, more preferably from one or more of zinc, molybdenum, and vanadium, more preferably zinc;
2) an inorganic binder, preferably selected from one or more of heat-resistant inorganic oxides, more preferably selected from one or more of alumina, silica, titania and tin oxide, more preferably selected from one or more of alumina, titania and tin oxide;
3) a support component which is boron nitride (preferably hexagonal phase boron nitride) or a combination of said boron nitride with one or more selected from the group consisting of oxides, nitrides, carbides, oxynitrides, carbonitrides, oxycarbides and oxycarbonitrides of the element a selected from one or more of the group IVB metallic elements of the periodic table of the elements (other than boron nitride), boron, aluminium and silicon, more preferably said support component is selected from one or more of boron carbide, silicon nitride, silicon carbide, silica, aluminium nitride, aluminium carbide, aluminium oxide, titanium nitride, titanium carbide and titanium oxide, preferably boron nitride, more preferably hexagonal phase boron nitride;
4) an active metal component selected from one or more of the group consisting of a metal element of group VIII of the periodic table, an oxide of an iron-based element of the periodic table, a metal element of group IB of the periodic table, an oxide of a metal element of group IB of the periodic table, a metal element of group VIIB of the periodic table and an oxide of a metal element of group VIIB of the periodic table, preferably selected from one or more of iron, iron oxide, cobalt oxide, nickel oxide, copper oxide, manganese and manganese oxide, more preferably one or more of nickel, nickel oxide, cobalt and cobalt oxide, more preferably nickel, nickel oxide or a combination thereof; and
5) an acidic porous material, preferably selected from molecular sieves having the FAU structure (preferably selected from one or more of X molecular sieves, Y molecular sieves, USY molecular sieves, REUSY molecular sieves, REHY molecular sieves, REY molecular sieves, PUSY molecular sieves, PREHY molecular sieves, and PREY molecular sieves).
2. The desulfurization catalyst according to scheme 1, wherein the inorganic binder and/or the support component does not contain silicon element.
3. The desulfurization catalyst according to any one of claims 1-2, wherein the specific surface area of the boron nitride is 100-300m2G, preferably 120-260m2/g。
4. The desulfurization catalyst according to any one of embodiments 1-3, wherein the composition comprises:
10 to 80 wt% of the sulfur storage metal oxide (in terms of sulfur storage metal oxide), 3 to 35 wt% of the inorganic binder (in terms of oxide), 5 to 40 wt% of the support component (on a dry basis), 5 to 30 wt% of the active metal component (in terms of metal oxide), and 0 to 20 wt% of the acidic porous material (on a dry basis), relative to the total weight of the desulfurization catalyst, or relative to the total weight (as 100 wt%) of the component 1) to the component 5),
preferably, the sulfur storage metal oxide (in terms of sulfur storage metal oxide) is 25 to 70 wt%, the inorganic binder (in terms of oxide) is 6 to 25 wt%, the support component (on a dry basis) is 10 to 30 wt%, the active metal component (in terms of metal oxide) is 8 to 25 wt%, and the acidic porous material (on a dry basis) is 1 to 15 wt% with respect to the total weight of the desulfurization catalyst, or with respect to the total weight (as 100 wt%) of the component 1) to the component 5),
more preferably, the sulfur storage metal oxide (in terms of sulfur storage metal oxide) is 40 to 60 wt%, the inorganic binder (in terms of oxide) is 8 to 15 wt%, the support component (on a dry basis) is 12 to 25 wt%, the active metal component (in terms of metal oxide) is 12 to 20 wt%, and the acidic porous material (on a dry basis) is 2 to 10 wt%, relative to the total weight of the desulfurization catalyst, or relative to the total weight (as 100 wt%) of the component 1) to the component 5).
5. The desulfurization catalyst according to any one of claims 1 to 4, wherein the composition is a post-calcination composition, and the post-calcination composition refers to a composition measured after calcination at 650 ℃ for 4 hours under an air atmosphere.
6. The desulfurization catalyst according to any one of claims 1-5, wherein the composition further comprises at least one additive, preferably the additive is selected from one or more of alkali metal oxides (preferably selected from one or more of sodium oxide and potassium oxide), clays (preferably selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite), rare earth metal oxides (the rare earth metal is selected from one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, preferably from one or more of La, Pr and Nd), and antimony oxide.
7. A method for producing a desulfurization catalyst, comprising the steps of:
(1) a step of contacting at least the following components to obtain a catalyst precursor,
1) a sulfur-storing metal oxide and/or a precursor thereof, wherein the sulfur-storing metal is selected from one or more of the group IIB metals, the group VB metals and the group VIB metals of the periodic Table of the elements, preferably from one or more of zinc, cadmium, niobium, tantalum, chromium, molybdenum, tungsten and vanadium, more preferably from one or more of zinc, molybdenum and vanadium, more preferably zinc,
2) an inorganic binder and/or a precursor thereof, preferably the inorganic binder is selected from one or more of heat resistant inorganic oxides, more preferably from one or more of alumina, silica, titania and tin oxide, more preferably from one or more of alumina, titania and tin oxide,
3) a support component and/or a precursor thereof, wherein the support component is boron nitride (preferably hexagonal phase boron nitride) or a combination of the boron nitride with one or more of the oxides, nitrides, carbides, oxynitrides, carbonitrides, oxycarbides and oxycarbonitrides of an element A selected from one or more of the group IVB metal elements of the periodic Table of the elements (other than boron nitride), boron, aluminium and silicon, more preferably the support component is selected from one or more of boron carbide, silicon nitride, silicon carbide, silica, aluminium nitride, aluminium carbide, aluminium oxide, titanium nitride, titanium carbide and titanium oxide, preferably boron nitride, more preferably hexagonal phase boron nitride,
4) an active metal component and/or a precursor thereof, wherein the active metal component is selected from one or more of the group consisting of the elements of group VIII of the periodic Table of the elements, the oxides of the elements of the iron series of the periodic Table of the elements, the elements of group IB of the periodic Table of the elements, the elements of group VIIB of the periodic Table of the elements and the oxides of the elements of group VIIB of the periodic Table of the elements, preferably from one or more of iron, iron oxides, cobalt oxides, nickel oxides, copper oxides, manganese and manganese oxides, more preferably from one or more of nickel, nickel oxides, cobalt and cobalt oxides, more preferably from nickel, nickel oxides or combinations thereof,
5) an acidic porous material and/or a precursor thereof, preferably said acidic porous material is selected from molecular sieves having the structure of FAU (preferably selected from one or more of X molecular sieve, Y molecular sieve, USY molecular sieve, REUSY molecular sieve, REHY molecular sieve, REY molecular sieve, PUSY molecular sieve, PREHY molecular sieve and PREY molecular sieve), and
6) a contact medium, preferably water and/or an acidic liquid (preferably an acid or an aqueous acid solution),
(2) optionally after drying, a step of calcining the catalyst precursor to obtain the desulfurization catalyst, and
(3) optionally, a step of reducing the desulfurization catalyst.
8. The manufacturing method according to claim 7, wherein the step (1) includes the steps of:
(1-1) a step of contacting said component 1), said component 2), said component 3), optionally said component 5) and said component 6) to obtain a slurry,
(1-2) a step of calcining the slurry after optional drying to obtain a catalyst carrier, and
(1-3) a step of contacting the component 4) with the catalyst support to obtain the catalyst precursor.
9. The production process according to any one of aspects 7 to 8, wherein the relative charge ratio between the components is, by weight,
the component 1) (calculated as sulfur-storing metal oxide): the component 2) (calculated as oxides): the component 3) (dry basis based on carrier component): the component 4) (calculated as metal oxide): the component 5) (dry basis calculated on acidic porous material): water ═ water
(10-80): (3-35): (5-40): (5-30): (0-20): (50-500), the acid: the component 2) (calculated by oxide) is (0.01-1.0): 1,
it is preferable that the first and second liquid crystal layers are formed of,
the component 1) (calculated as sulfur-storing metal oxide): the component 2) (calculated as oxides): the component 3) (dry basis based on carrier component): the component 4) (calculated as metal oxide): the component 5) (dry basis calculated on acidic porous material): water ═ water
(25-70): (6-25): (10-30): (8-25): (1-15): (100-400), the acid: the component 2) (calculated by oxide) is (0.02-0.9): 1,
it is more preferable that the content of the organic compound,
the component 1) (calculated as sulfur-storing metal oxide): the component 2) (calculated as oxides): the component 3) (dry basis based on carrier component): the component 4) (calculated as metal oxide): the component 5) (dry basis calculated on acidic porous material): water ═ water
(40-60): (8-15): (12-25): (12-20): (2-10): (150-300), the acid: the component 2) (calculated by oxide) is (0.03-0.8): 1.
10. the production method according to any one of claims 7 to 9, wherein the conditions for the calcination include: the roasting temperature is 300-800 ℃, preferably 450-750 ℃, the roasting time is more than 0.5 hour, preferably 1-3 hours, under the oxygen-containing atmosphere; alternatively, the reducing conditions include: the reduction temperature is 300-600 ℃, preferably 400-500 ℃, the reduction time is 0.5-6 hours, preferably 1-3 hours, and the hydrogen-containing atmosphere (preferably the hydrogen content is 10-70 vol.%).
11. The production method according to any one of claims 7 to 10, wherein the conditions for drying include: the drying temperature is 25-400 ℃, preferably 100-350 ℃, and the drying time is more than 0.5 hour, preferably 2-20 hours; alternatively, the firing conditions include: the roasting temperature is 400-700 ℃, preferably 450-650 ℃, the roasting time is more than 0.5 hour, preferably 0.5-10 hours, and the roasting time is in oxygen-containing atmosphere.
12. The manufacturing method according to any one of claims 7 to 11, further comprising a step of introducing at least one additive, preferably, the additive is selected from one or more of alkali metal oxides (preferably selected from one or more of sodium oxide and potassium oxide) and/or precursors thereof, clays (preferably selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite) and/or precursors thereof, rare earth metal oxides (the rare earth metal is selected from one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, preferably from one or more of La, Pr and Nd) and/or precursors thereof, and antimony oxide and/or precursors thereof.
13. A desulfurization method comprising a step of contacting a sulfur-containing hydrocarbon oil (preferably crude oil or a petroleum fraction having a boiling range of not more than 450 ℃, particularly a petroleum fraction having a boiling range of from-42.1 ℃ to 350 ℃, more preferably one or more selected from the group consisting of liquefied petroleum gas, cracked gasoline, and diesel fuel) with the desulfurization catalyst according to any one of schemes 1 to 6 or the desulfurization catalyst manufactured according to the manufacturing method according to any one of schemes 7 to 12 under desulfurization reaction conditions.
14. The desulfurization method of claim 13, wherein said desulfurization reaction conditions comprise: under the hydrogen atmosphere, the reaction temperature is 350-500 ℃, preferably 400-450 ℃, the reaction pressure is 0.5-4MPa (absolute pressure), preferably 2-4MPa (absolute pressure), the volume ratio of hydrogen to oil is 0.1-0.5, preferably 0.15-0.4, and the mass space velocity is 2-6h-1Preferably 2.5 to 5h-1。
According to the present invention, the contents of the aforementioned components in the desulfurization catalyst can be measured according to the following method (hereinafter sometimes referred to as XRD measurement method):
the desulfurization catalyst sample was calcined at 650 ℃ for 4 hours in an air atmosphere and stored in a nitrogen atmosphere for future use. 1g of the calcined catalyst sample was weighed and subjected to XRD spectrum measurement. Comparing the XRD spectrogram with a standard spectrogram of an inorganic crystal structure database, identifying each component, and further determining the strongest characteristic peak of each component. Then, the peak area of the strongest characteristic peak of a certain component is divided by the sum of the peak areas of all the strongest characteristic peaks, and the ratio is taken as the content of the component. In particular, the content of the active metal component in terms of metal oxide obtained by this measurement method can be obtained by simple conversion thereof in terms of metal element.
Specific contents of the measurement of the contents of the components in the desulfurization catalyst by the XRD method according to the present invention can be further referred to in "determination of chemical composition of S-Zorb adsorbent" of Q/SH 3360215-2009, which is incorporated herein by reference in its entirety.
According to the present invention, the sulfur-containing hydrocarbon oils may include gasoline, preferably cracked gasoline, where "cracked gasoline" means hydrocarbons having a boiling range of 40 ℃ to 210 ℃, or any fraction thereof, which are the products of a thermal or catalytic process that cracks larger hydrocarbon molecules into smaller molecules, and diesel fuels. Suitable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like, and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, resid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Thus, suitable cracked-gasolines include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, resid catalytically cracked gasoline, and heavy oil cracked-gasoline, and combinations thereof. In some instances, the cracked-gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a sulfur-containing hydrocarbon oil in the process of the present invention. By "diesel fuel" is meant a liquid consisting of a mixture of hydrocarbons having a boiling range of from 170 ℃ to 450 ℃ or any fraction thereof. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oils, kerosene, straight-run diesel, hydrotreated diesel, and the like, and combinations thereof.
The term "sulfur" as used herein denotes elemental sulfur in any form, such as sulfur-containing hydrocarbon oils (fissured hydrocarbon oils)Gasoline or diesel fuel). The sulfur present in the sulfur-containing hydrocarbon oils of the present invention includes, but is not limited to, Carbon Oxysulfide (COS), carbon disulfide (CS)2) Thiol or other thiophenic compounds and the like and combinations thereof, for example, may include thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, and alkyldibenzothiophene, as well as the higher molecular weight thiophenic compounds commonly found in diesel fuel.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
The hydrocarbon oil desulfurization catalysts obtained in examples and comparative examples were subjected to structural determination by obtaining an XRD spectrum using an X-ray diffractometer (Siemens corporation, model D5005) under the following measurement conditions: cu target, Ka radiation, solid detector, tube voltage 40kV, tube current 40 mA.
Examples 1 to 7 are intended to illustrate the method for producing the hydrocarbon oil desulfurization catalyst of the present invention.
Example 1
2.38kg of titanium tetrachloride (Beijing chemical plant, analytical purity, 99 wt%) was slowly added with 4.6kg of 5 wt% diluted hydrochloric acid, and slowly stirred to avoid the precipitation of titanium oxide crystals, thereby obtaining a pale yellow transparent titanium sol with a pH of 2.0;
4.43kg of zinc oxide powder (Headhorse, purity 99.7% by weight) and 0.88kg of REY molecular sieve (Chinesemedicine catalyst, Qilu division, China) containing 0.70kg of dry basis, SiO2：Al2O3In a molar ratio of 2, a rare earth content of 16 wt%), 2.06kg of hexagonal boron nitride (purity)>99.0 percent, Qinhuang island Yinuo high new materials development Co., Ltd.) and 6.57kg of deionized water, stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride; then adding the titanium sol, mixing and stirring for 1h to obtain carrier slurry with the pH value of 3.5;
the resulting carrier slurry was used with a Niro Bowen Nozle TowerTMSpray drying is carried out by a spray dryer with the model of 8.5MPa of spray drying pressure and 150 ℃ of outlet temperature at 480 ℃ of spray drying gas inlet. The microspheres obtained by spray drying are first dried at 180 ℃ for 1h and thenRoasting at 635 ℃ for 1h to obtain a catalyst carrier;
impregnating 3.2kg of catalyst carrier with a solution containing 3.51kg of nickel nitrate hexahydrate (Beijing chemical reagent company, purity > 98.5 wt%) and 0.6kg of deionized water, drying the obtained impregnated matter at 180 ℃ for 4h, and roasting at 635 ℃ in air atmosphere for 1h to obtain a roasted product;
the calcined product was reduced in a hydrogen atmosphere (hydrogen content 70 vol%, balance nitrogen) at 425 ℃ for 2 hours to obtain a hydrocarbon oil desulfurization catalyst A1.
The hydrocarbon oil desulfurization catalyst A1 comprises the following chemical components: the zinc oxide content was 44.3 wt%, the hexagonal boron nitride content was 20.6 wt%, the REY molecular sieve content was 7.0 wt%, the titanium dioxide content was 10.0 wt%, and the nickel content was 18.1 wt%.
Example 2
1.56kg of pseudo-boehmite (Nanjing division of a petrochemical catalyst, China, containing 1.17kg of dry basis) and 1.50kg of hexagonal boron nitride (purity)>99.0 percent, qinhuang island yinuo high new materials development limited), then adding 8.2kg of deionized water, mixing evenly to obtain slurry, then adding 260ml of 30 weight percent hydrochloric acid to make the pH value of the slurry equal to 1.9, stirring and acidifying for 1h, then heating to 80 ℃ and aging for 2 h. After the temperature is reduced, 5.52kg of zinc oxide powder and 0.38kg of REY molecular sieve (0.3 kg of dry basis, SiO, available from Chinese petrochemical catalyst, Qilu division Co., Ltd.) are added2：Al2O3Was 2, rare earth content 16 wt%), and stirred for 1h to give a carrier slurry having a pH of 3.5.
Spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst a2 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A2 comprises the following chemical components: the zinc oxide content was 55.2 wt%, the hexagonal boron nitride content was 15.0 wt%, the REY molecular sieve content was 3.0 wt%, the alumina content was 11.7 wt%, and the nickel content was 15.1 wt%.
Example 3
4.83kg of zinc oxide powder and 1.26kg of REY molecular sieve (China petrochemical catalyst, Qilu division, containing dry basis)1.0kg，SiO2：Al2O3The molar ratio of 2, the rare earth content of 16 percent by weight), 1.2kg of hexagonal boron nitride and 8.8kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride;
ethyl titanate 3.90kg (Aldrich, analytical grade, 99 wt%) and deionized water 1.6kg were slowly added with stirring to a 10 wt% solution of nitric acid (analytical grade, ex beijing chemical plant) 3.8kg, pH 2.3, and stirred for 1h to obtain a pale yellow transparent titanium sol; and adding mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride, and stirring for 1h to obtain catalyst carrier slurry with the pH value of 3.5.
Referring to the preparation of the calcined product and the catalyst of example 1, except that the catalyst carrier impregnated with nickel nitrate hexahydrate was replaced with a solution of nickel nitrate and cobalt nitrate, active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst a3 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A3 comprises the following chemical components: the zinc oxide content was 48.3 wt%, the hexagonal boron nitride content was 12.0 wt%, the REY molecular sieve content was 10.0 wt%, the titanium dioxide content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.
Example 4
Mixing 4.83kg of zinc oxide powder, 1.26kg of REUSY molecular sieve (1.0 kg of dry basis, China petrochemical catalyst, Qilu division) and 1.2kg of hexagonal boron nitride with 8.8kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of the zinc oxide, the REUSY molecular sieve and the hexagonal boron nitride;
ethyl titanate 3.90kg (Aldrich, analytical grade, 99 wt%) and deionized water 1.6kg were slowly added with stirring to a 10 wt% solution of nitric acid (analytical grade, ex beijing chemical plant) 3.8kg, pH 2.3, and stirred for 1h to obtain a pale yellow transparent titanium sol; and adding mixed slurry of zinc oxide, REUSY molecular sieve and hexagonal boron nitride, and stirring for 1h to obtain carrier slurry with the pH value of 3.5.
Spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst a4 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A4 comprises the following chemical components: 48.3 wt% zinc oxide, 12.0 wt% hexagonal boron nitride, 10.0 wt% REUSY molecular sieve, 13.5 wt% titanium dioxide, and 16.2 wt% nickel.
Example 5
4.43kg of zinc oxide powder and 0.88kg of REY molecular sieve (China petrochemical catalyst, Qilu division, containing 0.70kg of dry basis, SiO)2：Al2O3The molar ratio of 2, the rare earth content of 16 percent by weight), 2.06kg of hexagonal boron nitride and 6.57kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride;
1.33kg of pseudo-boehmite (product from Shandong aluminum plant, containing 1.0kg of dry basis) and 4.6kg of deionized water are uniformly mixed to obtain slurry, 300ml of 30 wt% hydrochloric acid (chemical purity, product from Beijing chemical plant) is added to make the pH of the slurry equal to 2.5, the slurry is stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ for aging for 2 hours. And adding mixed slurry of zinc oxide, a molecular sieve and hexagonal boron nitride, and stirring for 1h to obtain carrier slurry.
Spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst a5 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A5 comprises the following chemical components: the zinc oxide content was 44.3 wt%, the hexagonal boron nitride content was 20.6 wt%, the REY molecular sieve content was 7.0 wt%, the alumina content was 10.0 wt%, and the nickel content was 18.1 wt%.
Example 6
4.43kg of zinc oxide powder and 0.88kg of REY molecular sieve (China petrochemical catalyst, Qilu division, containing 0.70kg of dry basis, SiO)2：Al2O3The molar ratio of 2, the rare earth content of 16 percent by weight), 2.06kg of hexagonal boron nitride and 6.57kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride;
2.35kg of tin tetrachloride (SnCl)4·5H2O, Alfa corporation, 99%) was slowly added with 3.6kg of deionized water, and 4.6kg of a5 wt% nitric acid solution, and slowly stirred to avoid tin oxide crystallization, to obtain a colorless and transparent tin sol having a pH of 2.1; and adding mixed slurry of zinc oxide, REY molecular sieve and hexagonal boron nitride, and stirring for 1h to obtain carrier slurry with the pH value of 3.5.
Spray-drying and molding the carrier slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst A6 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A6 comprises the following chemical components: the zinc oxide content was 44.3 wt%, the hexagonal boron nitride content was 20.6 wt%, the REY molecular sieve content was 7.0 wt%, the tin dioxide content was 10.0 wt%, and the nickel content was 18.1 wt%.
Example 7
2.38kg of titanium tetrachloride (Beijing chemical plant, analytical purity, 99 wt%) was slowly added with 4.6kg of 5 wt% diluted hydrochloric acid, and slowly stirred to avoid the precipitation of titanium oxide crystals, thereby obtaining a pale yellow transparent titanium sol with a pH of 2.0;
4.43kg of zinc oxide powder (Headhorse, purity 99.7% by weight) and 0.88kg of REY molecular sieve (Chinesemedicine catalyst, Qilu division, China) containing 0.70kg of dry basis, SiO2：Al2O3In a molar ratio of 2, a rare earth content of 16 wt%), 2.06kg of cubic boron nitride (purity)>99.0 percent, Qinhuang island Yinuo high new materials development Co., Ltd.) and 6.57kg of deionized water, stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and cubic boron nitride; then adding the titanium sol, mixing and stirring for 1h to obtain carrier slurry with the pH value of 3.5;
spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst a7 was obtained after reduction.
The hydrocarbon oil desulfurization catalyst A7 comprises the following chemical components: 44.3% by weight of zinc oxide, 20.6% by weight of cubic boron nitride, 7.0% by weight of REY molecular sieve, 10.0% by weight of titanium dioxide and 18.1% by weight of nickel.
Comparative example 1
Mixing 4.43kg of zinc oxide powder and 6.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;
taking 1.81kg of pseudo-boehmite (containing 1.36kg of dry basis of Nanjing division of a Chinese petrochemical catalyst) and 2.46kg of expanded perlite (containing 2.40kg of dry basis of Nanjing division of a Chinese petrochemical catalyst) to stir and mix, then adding 4.6kg of deionized water to mix uniformly, then adding 360ml of 30 weight percent hydrochloric acid to make the pH of the slurry equal to 2.1, stirring and acidifying for 1h, then heating to 80 ℃ to age for 2h, then adding zinc oxide slurry to mix, and stirring for 1h to obtain carrier slurry.
Spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst B1 was obtained after reduction.
The chemical composition of the hydrocarbon oil desulfurization catalyst B1 is as follows: the zinc oxide content was 44.3 wt.%, the expanded perlite content was 24.0 wt.%, the alumina content was 13.6 wt.%, and the nickel content was 18.1 wt.%.
Comparative example 2
1.56kg of pseudo-boehmite (which is produced by Shandong aluminum factory and contains 1.17kg of dry basis) and 1.85kg of diatomite (containing 1.80kg of dry basis) are stirred and mixed, then 8.2kg of deionized water is added and mixed uniformly, 260ml of 30 weight percent hydrochloric acid is added to make the pH value of the slurry equal to 1.9, the mixture is stirred and acidified for 1h, and then the temperature is increased to 80 ℃ for aging for 2 h. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.
Spray-drying and molding the carrier slurry and introducing an active component nickel in the carrier slurry by the method of example 1, and reducing the carrier slurry to obtain a hydrocarbon oil desulfurization catalyst B2.
The chemical composition of the hydrocarbon oil desulfurization catalyst B2 is as follows: the zinc oxide content was 55.2 wt.%, the diatomaceous earth content was 18.0 wt.%, the alumina content was 11.7 wt.%, and the nickel content was 15.1 wt.%.
Comparative example 3
Mixing 4.93kg of zinc oxide powder and 5.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;
1.80kg of pseudo-boehmite (a product from Shandong aluminum plant and containing 1.35kg of dry basis) and 2.16kg of diatomite (a product from world mining company and containing 2.10kg of dry basis) are stirred and mixed, then 4.6kg of deionized water is added and mixed uniformly, 300ml of 30 weight percent hydrochloric acid is added to make the pH value of slurry become 2.5, the mixture is stirred and acidified for 1 hour, and then the temperature is increased to 80 ℃ and the aging is carried out for 2 hours. And adding zinc oxide slurry, mixing and stirring for 1h to obtain carrier slurry.
The carrier slurry was spray-dried and formed by the method described in example 3, active components of nickel and cobalt were introduced, and the resultant was reduced to obtain a hydrocarbon oil desulfurization catalyst B3.
The chemical composition of the hydrocarbon oil desulfurization catalyst B3 is as follows: the zinc oxide content was 49.3 wt%, the diatomaceous earth content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.
Comparative example 4
Mixing 1.56kg of pseudo-boehmite (containing 1.17kg of dry basis from Nanjing division of a Chinese petrochemical catalyst) and 1.54kg of expanded perlite (containing 1.50kg of dry basis from Nanjing division of a Chinese petrochemical catalyst) under stirring, adding 8.2kg of deionized water, mixing uniformly to obtain slurry, adding 260ml of 30 wt% hydrochloric acid to adjust the pH of the slurry to 1.9, stirring and acidifying for 1h, and heating to 80 ℃ for aging for 2 h. After the temperature is reduced, 5.52kg of zinc oxide powder and 0.38kg of REY molecular sieve (0.3 kg of dry basis, SiO, available from Chinese petrochemical catalyst, Qilu division Co., Ltd.) are added2：Al2O3Was 2, rare earth content was 16 wt%), and stirred for 1 hour to obtain a carrier slurry.
Spray-drying and molding the carrier slurry and introducing an active component nickel in the carrier slurry by the method of example 1, and reducing the carrier slurry to obtain a hydrocarbon oil desulfurization catalyst B4.
The chemical composition of the hydrocarbon oil desulfurization catalyst B4 is as follows: 55.2% by weight of zinc oxide, 15.0% by weight of expanded perlite, 3.0% by weight of REY molecular sieve, 11.7% by weight of alumina and 15.1% by weight of nickel.
Comparative example 5
2.38kg of titanium tetrachloride (Beijing chemical plant, analytical purity, 99 wt%) was slowly added with 4.6kg of 5 wt% diluted hydrochloric acid, and slowly stirred to avoid the precipitation of titanium oxide crystals, thereby obtaining a pale yellow transparent titanium sol with a pH of 2.0;
4.43kg of zinc oxide powder (Headhorse, purity 99.7% by weight) and 0.88kg of REY molecular sieve (Chinesemedicine catalyst, Qilu division, China) containing 0.70kg of dry basis, SiO2：Al2O3In a molar ratio of 2, a rare earth content of 16 wt%), 2.06kg of silicon nitride (purity)>99.0 percent, Qinhuang island Yinuo high new materials development Co., Ltd.) and 6.57kg of deionized water, stirring for 30 minutes to obtain mixed slurry of zinc oxide, REY molecular sieve and silicon nitride; then adding the titanium sol, mixing and stirring for 1h to obtain carrier slurry with the pH value of 3.5;
spray-drying and molding the catalyst support slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst B5 was obtained after reduction.
The chemical composition of the hydrocarbon oil desulfurization catalyst B5 is as follows: the zinc oxide content was 44.3 wt%, the silicon nitride content was 20.6 wt%, the REY molecular sieve content was 7.0 wt%, the titanium dioxide content was 10.0 wt%, and the nickel content was 18.1 wt%.
Example 8
(1) And (3) evaluating the abrasion resistance of the hydrocarbon oil desulfurization adsorbent. The abrasion resistance strength test was conducted on the hydrocarbon oil desulfurization catalysts A1-A7 and B1-B5. The abrasion index of the catalyst was measured by a straight tube abrasion method with reference to RIPP 29-90 test method in petrochemical analysis method (RIPP) test method, and the results are shown in Table 1. The smaller the value obtained from the test, the higher the abrasion resistance. The attrition index in Table 1 corresponds to the percentage of fines generated when attrited under certain conditions.
(2) And (4) evaluating the desulfurization performance of the hydrocarbon oil desulfurization adsorbent. A desulfurization evaluation experiment was conducted on the hydrocarbon oil desulfurization catalysts A1-A7 and B1-B5 by means of a fixed bed microreaction experimental apparatus, and 16g of the hydrocarbon oil desulfurization catalyst was packed in a fixed bed reactor having an inner diameter of 30mm and a length of 1 m.
The raw material hydrocarbon oil is catalytic cracking gasoline with the sulfur content of 1000ppm, the reaction pressure is 2.1MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, the reaction temperature is 410 ℃, and the weight space velocity of the raw material hydrocarbon oil is 4h-1And carrying out desulfurization reaction on the sulfur-containing hydrocarbon oil to obtain the product gasoline.
The sulfur content in the gasoline product is used as a measure of the desulfurization activity of the hydrocarbon oil desulfurization catalyst. The sulfur content in the gasoline product was determined by an off-line chromatographic method using a GC6890-SCD instrument from agilent corporation.
In order to accurately represent the activity of the hydrocarbon oil desulfurization catalyst in industrial actual operation, the catalyst after the desulfurization evaluation experiment is regenerated in an air atmosphere at 550 ℃. A desulfurization evaluation experiment is carried out on the hydrocarbon oil desulfurization catalyst, the activity of the catalyst is basically stabilized after 6 cycles of regeneration, the sulfur content in the product gasoline after the 6 th cycle stabilization of the catalyst is used for representing the activity of the catalyst, and the sulfur content and the liquid yield of the stabilized product gasoline are shown in Table 1.
The penetration sulfur capacity for gasoline desulfurization of hydrocarbon oil desulfurization catalysts A1-A7 and B1-B5 was calculated, and the results are shown in Table 3. Wherein the breakthrough in the breakthrough sulfur capacity means that the sulfur content of the obtained gasoline is more than 10 mug/g from the beginning of the gasoline desulfurization. The breakthrough sulfur capacity refers to the content of sulfur co-adsorbed on the hydrocarbon oil desulfurization catalyst (based on the total weight of the hydrocarbon oil desulfurization catalyst) before breakthrough.
The Motor Octane Number (MON) and Research Octane Number (RON) of the gasoline before and after the stabilization of the sixth cycle were determined using GB/T503-.
The flow rates of the feed/exhaust gases in the hydrogenation reaction of catalysts A1-A7 and B1-B5 were measured, and the concentrations of hydrogen therein were analyzed by a QRD-1102A thermal conductivity hydrogen analyzer, and the amounts of hydrogen added (Q1) and discharged (Q2) were calculated and the difference in the amounts of hydrogen was determined, the results are shown in Table 1.
As can be seen from the result data in Table 1, the hydrocarbon oil desulfurization catalyst provided by the invention contains a boron nitride component, and the hydrocarbon oil desulfurization catalyst can still well reduce the sulfur content of gasoline after being subjected to multiple-cycle desulfurization, which indicates that the catalyst has better desulfurization activity and activity stability. And the wear index of the hydrocarbon oil desulfurization catalyst is lower, which shows that the catalyst has better abrasion resistance, so that the hydrocarbon oil desulfurization catalyst has longer service life. The hydrocarbon oil desulfurization catalyst in comparative example 4 contains the REY molecular sieve, but does not contain boron nitride of the present application, and therefore, the attrition index is much higher than that of the catalyst prepared in the examples, indicating that the hydrocarbon oil desulfurization catalyst provided by the present invention can have better attrition resistance. It can be seen from the comparison of the hydrocarbon oil desulfurization catalyst a1, the hydrocarbon oil desulfurization catalyst a7, and the hydrocarbon oil desulfurization catalyst B5 that the adsorbent containing hexagonal boron nitride having a layered structure has better abrasion resistance and octane number-improving performance, and although zinc silicate may not be generated from silicon nitride, the adsorbent can have higher abrasion resistance because the layered structure of hexagonal boron nitride can better interact with the binder, and silicon nitride does not have the octane number-improving effect and the effect of generating hydrogen.
Example 9
Aging hydrocarbon oil desulfurization catalysts A1-A7 and B1-B5 under the conditions that: the catalyst was treated for 16 hours at 600 ℃ under an atmosphere with a water vapor partial pressure of 20 kPa.
XRD spectrograms of the hydrocarbon oil desulfurization catalysts A1 and B1 before and after aging are analyzed, wherein XRD spectrograms of the hydrocarbon oil desulfurization catalyst A1 before and after hydrothermal aging are shown in figure 1, and the fresh agent and the aging agent have peaks at diffraction angles 2 theta of 27.2 degrees +/-0.5 degrees, 41.5 degrees +/-0.5 degrees and 50.3 degrees +/-0.5 degrees; XRD patterns of the hydrocarbon oil desulfurization catalyst B1 before and after hydrothermal aging are shown in FIG. 2.
In fig. 1, the XRD spectrum of the hydrocarbon oil desulfurization catalyst a1 after hydrothermal aging did not show characteristic peaks of zinc silicate of 2 θ of 22.0, 25.54, 48.9 and 59.4; in FIG. 2, the above-mentioned characteristic peaks of zinc silicate appear in the XRD spectrum of hydrocarbon oil desulfurization catalyst B1 after hydrothermal aging. The content of zinc silicate in the XRD spectrogram of the hydrocarbon oil desulfurization catalyst B1-B5 was quantitatively analyzed by using the crystal phase content, and the results are shown in Table 2.
The desulfurization performance of aged hydrocarbon oil desulfurization catalysts A1-A7 and aged hydrocarbon oil desulfurization catalysts B1-B5 was evaluated in the same manner as in example 8, and the results are shown in Table 2.
The penetration sulfur capacity of the aged hydrocarbon oil desulfurization catalysts A1-A7 and B1-B5 for gasoline desulfurization was calculated, and the results are shown in Table 3.
The flow rates of the feed/exhaust gases for the hydrogenation reaction of the aged catalysts A1-A7 and B1-B5 were measured by the same evaluation method as in example 8, and the hydrogen concentrations therein were analyzed by a QRD-1102A thermal conductivity analyzer, and the amount of hydrogen added (Q1) and the amount of hydrogen exhausted (Q2) were calculated and the difference in the amounts of hydrogen was determined, and the results are shown in Table 2.
As can be seen from the results of Table 2, the hydrocarbon oil desulfurization catalysts obtained in the examples did not produce zinc silicate after the aging process, whereas the catalysts of comparative examples 1 to 4 produced zinc silicate with the silica-containing material, thereby decreasing the desulfurization activity of the catalysts.
As can be seen from the data of the product gasoline in the tables 1-2, the method provided by the invention can still obtain high product gasoline yield, and has the advantage of obviously retaining the octane number of the gasoline.
As can be seen from Table 3, the breakthrough sulfur capacity for gasoline desulfurization using the hydrocarbon oil desulfurization catalyst of the present invention before aging was similar to that of the hydrocarbon oil desulfurization catalyst of the comparative example, and after the aging process, zinc silicate was not formed in the hydrocarbon oil desulfurization catalyst obtained in the examples, whereas zinc silicate was formed from the zinc oxide and the material containing silicon oxide in the catalysts of comparative examples 1 to 4, so that the breakthrough sulfur capacity of the catalyst was significantly decreased, and thus the desulfurization activity was also significantly decreased.
In addition, as can be seen from a comparison of hydrocarbon oil desulfurization catalyst a1 and hydrocarbon oil desulfurization catalyst B5, hydrocarbon oil desulfurization catalyst a1 containing boron nitride has better abrasion resistance, desulfurization performance, and octane number improvement performance than hydrocarbon oil desulfurization catalyst B5 containing silicon nitride.
TABLE 1
Figure BDA0001452312760000221
Note: the data on octane number in the table are the amount of change in octane number compared to the feed gasoline. Represents a reduction in octane number compared to the starting gasoline.
1. The feed gasoline had a sulfur content of 1000ppm, a RON of 93.8 and a MON of 83.1.
2.Δ MON represents the increase in product MON;
3.Δ RON represents the increase in product RON;
4. and delta (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.
5. The difference in the amount of hydrogen was the difference between the amount of discharged hydrogen (Q2) and the amount of added hydrogen (Q1) with respect to 1kg of hydrocarbon oil, with positive values indicating hydrogen generation and negative values indicating hydrogen consumption.
TABLE 2
Figure BDA0001452312760000231
Note: the data on octane number in the table are the amount of change in octane number compared to the feed gasoline. "-" indicates a reduction in octane number compared to the feed gasoline.
1. The feed gasoline had a sulfur content of 1000ppm, a RON of 93.8 and a MON of 83.1.
2.Δ MON represents the increase in product MON;
3.Δ RON represents the increase in product RON;
4. delta (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material;
5. the difference in the amount of hydrogen was the difference between the amount of discharged hydrogen (Q2) and the amount of added hydrogen (Q1) with respect to 1kg of hydrocarbon oil, with positive values indicating hydrogen generation and negative values indicating hydrogen consumption.
TABLE 3
Figure BDA0001452312760000241

Claims (14)

1. A hydrocarbon oil desulfurization catalyst containing a molecular sieve of FAU structure, which contains, based on the weight of the hydrocarbon oil desulfurization catalyst, or based on the total weight of a sulfur-storing metal oxide, an inorganic oxide binder, boron nitride, a molecular sieve of FAU structure, and a metal promoter, 10 to 80 wt% of the sulfur-storing metal oxide calculated as oxides, 3 to 35 wt% of the inorganic oxide binder calculated as oxides, 5 to 40 wt% of boron nitride, 1 to 20 wt% of the molecular sieve of FAU structure calculated on a dry basis, and 5 to 30 wt% of the metal promoter calculated as a metal element;
wherein the sulfur storage metal oxide is zinc oxide;
the metal element of the metal promoter is at least one selected from cobalt, copper, nickel, iron and manganese.
2. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein the hydrocarbon oil desulfurization catalyst contains 40 to 60% by weight, in terms of oxide, of the sulfur-storing metal oxide, 8 to 15% by weight, in terms of oxide, of the inorganic oxide binder, 12 to 25% by weight of boron nitride, 2 to 10% by weight, in terms of dry basis, of the FAU-structured molecular sieve, and 12 to 20% by weight, in terms of metallic element, of the sulfur-storing metal oxide, based on the weight of the hydrocarbon oil desulfurization catalyst, or based on the total weight of the sulfur-storing metal oxide, the inorganic oxide binder, boron nitride, the FAU-structured molecular sieve, and the metal promoter.
3. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein the hydrocarbon oil desulfurization catalyst, when characterized by XRD, exhibits peaks at diffraction angles 2 θ of 27.2 ° ± 0.5 °, 41.5 ° ± 0.5 ° and 50.3 ° ± 0.5 °.
4. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein the boron nitride comprises at least one selected from hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride, and wurtzite boron nitride;
the inorganic oxide binder is at least one selected from alumina, titanium dioxide and tin dioxide;
the FAU structure molecular sieve is at least one selected from X-type molecular sieve, Y-type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY and PREY.
5. The method for producing the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 4, which comprises:
a. mixing a sulfur-storing metal oxide and/or a sulfur-storing metal oxide precursor, a precursor of an inorganic oxide binder, boron nitride, a FAU-structured molecular sieve, water and an acidic liquid to obtain a carrier slurry; wherein the pH value of the carrier slurry is 1-5;
b. sequentially carrying out spray drying molding, first drying and first roasting on the obtained carrier slurry to obtain a catalyst carrier;
c. introducing a precursor of a metal promoter into the catalyst carrier, and then sequentially carrying out second drying and second roasting;
optionally d, reducing the product obtained in the step c under hydrogen-containing atmosphere;
obtaining the hydrocarbon oil desulfurization catalyst.
6. The production method according to claim 5, wherein the precursor of the inorganic oxide binder includes at least one selected from the group consisting of an alumina binder precursor, a titanium dioxide binder precursor, and a tin dioxide binder precursor;
the alumina binder precursor is at least one selected from the group consisting of SB powder, hydrated alumina, alumina sol, boehmite, pseudoboehmite, alumina trihydrate and amorphous aluminum hydroxide, the titanium dioxide binder precursor is at least one selected from the group consisting of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide, and the tin dioxide binder precursor is at least one selected from the group consisting of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide.
7. The production method according to claim 5, wherein the precursor of the metal promoter is at least one selected from acetates, carbonates, nitrates, sulfates, thiocyanates and oxides of the metal in the metal promoter.
8. The production method according to claim 5, wherein the acidic liquid is an acid or an aqueous acid solution, and the acid is a water-soluble inorganic acid and/or an organic acid.
9. The production method according to claim 5, wherein the conditions of the first drying include: the temperature is 25-400 ℃, and the time is 0.5-8 h;
the conditions of the first firing include: the temperature is 400-700 ℃, and the time is 0.5-100 h;
the conditions of the second drying include: the temperature is 50-300 ℃, and the time is 0.5-8 h;
the conditions of the second roasting include: the temperature is 300-;
the reduction treatment conditions include: the temperature is 300-600 ℃, the time is 0.5-6h, and the hydrogen content in the hydrogen-containing atmosphere is 10-70 volume percent.
10. The preparation method as claimed in claim 9, wherein the temperature of the first calcination is 450-650 ℃, and the temperature of the second calcination is 450-650 ℃.
11. The preparation method according to claim 5, wherein in step a, the precursor of the inorganic oxide binder, boron nitride, water and acidic liquid are mixed, and then mixed with the sulfur storage metal oxide and/or the sulfur storage metal oxide precursor and the FAU-structured molecular sieve; or
Mixing the precursor of the inorganic oxide binder, water and acidic liquid, and then mixing the mixture with the sulfur storage metal oxide and/or the precursor of the sulfur storage metal oxide, boron nitride and the FAU structure molecular sieve.
12. A process for the desulfurization of hydrocarbon oils, which process comprises: contacting sulfur-containing hydrocarbon oil with a hydrocarbon oil desulfurization catalyst and carrying out desulfurization reaction under the condition of hydrogen; wherein the hydrocarbon oil desulfurization catalyst is the hydrocarbon oil desulfurization catalyst of any one of claims 1 to 4 or the hydrocarbon oil desulfurization catalyst prepared by the method of any one of claims 5 to 11.
13. The process for desulfurizing hydrocarbon oil according to claim 12, wherein the conditions of the desulfurization reaction include: the temperature is 350 ℃ and 500 ℃, and the absolute pressure is 0.5-4 MPa.
14. The process for desulfurizing a hydrocarbon oil according to claim 12, wherein the sulfur-containing hydrocarbon oil is at least one selected from the group consisting of gasoline, light cycle oil, kerosene, straight-run diesel oil, and hydrotreated diesel oil.
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