CN106955724B

CN106955724B - Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN106955724B
Application number: CN201610012012.5A
Authority: CN
Inventors: 田辉平; 林伟; 王磊; 宋烨; 刘俊
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2016-01-08
Filing date: 2016-01-08
Publication date: 2019-12-27
Anticipated expiration: 2036-01-08
Also published as: CN106955724A

Abstract

The invention discloses a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2)3 to 35 wt% of a heat-resistant inorganic oxide; 3)5 to 40 wt% SiCN; 4)1 to 20 wt% of pillared interlayer clay; 5) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The hydrocarbon oil desulfurization catalyst has better stability, higher desulfurization activity, better abrasion resistance and longer service life.

Description

Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Technical Field

The present invention relates to a hydrocarbon oil desulfurization catalyst, a method for producing the same, and a method for desulfurizing a hydrocarbon oil, and more particularly, to a hydrocarbon oil desulfurization catalyst, a method for producing a hydrocarbon oil desulfurization catalyst, a hydrocarbon oil desulfurization catalyst obtained by the method, and a method for desulfurizing a hydrocarbon oil using the hydrocarbon oil desulfurization catalyst.

Background

With the increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures for improving air quality. Most of the sulfur in our country's gasoline products comes from thermally processed gasoline blending components, such as catalytically cracked gasoline. Therefore, the reduction of the sulfur content in the hot processing gasoline is beneficial to reducing the sulfur content of gasoline products in China. The current gasoline product standard GB 17930-2011 automotive gasoline requires that the sulfur content in a gasoline product must be reduced to 50 mu g/g by 12 months and 31 days in 2013. And future gasoline product quality standards will be more stringent. In this case, the catalytically cracked gasoline must be subjected to deep desulfurization in order to make the gasoline product meet the environmental requirements.

At present, the deep desulfurization method of oil products mainly comprises two methods of selective catalytic hydrodesulfurization and catalytic hydrogenation adsorption desulfurization. The catalytic hydrogenation adsorption desulfurization is realized by adsorbing and removing sulfides in hydrocarbon oil under certain temperature, pressure and hydrogen presence conditions, and the technology has the characteristics of low hydrogen consumption and low requirement on the purity of hydrogen, so that the technology has wide application prospect in the aspect of fuel oil desulfurization.

CN1355727A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, silica, alumina and nickel wherein the nickel is present in a substantially reduced valence state in an amount effective to remove sulfur from a stream of cracked-gasoline or diesel fuel which is contacted with said nickel-containing sorbent composition under desulfurization conditions. The composition is prepared by granulating a mixture of zinc oxide, silicon oxide and aluminum oxide to form granules, drying, calcining, impregnating with nickel or nickel-containing compound, drying, calcining, and reducing.

CN1382071A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein the cobalt is present in a substantially reduced valence state in an amount effective to remove sulfur from a stream of cracked-gasoline or diesel fuel which is contacted with said cobalt-containing sorbent composition under desulfurization conditions.

US6150300 discloses a process for the preparation of an adsorbent comprising the preparation of spherical particles: (a) mixing a silica-containing composition, a composition containing a metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding the first mixture; (b) the first mixture is pelletized to form particles having a diameter of 10-1000 mm. Wherein step (a) further comprises mixing with a metal promoter.

CN1422177A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, expanded perlite, alumina and a promoter metal, wherein said promoter metal is present in a substantially reduced valence state and in an amount which is capable of removing sulfur from a stream of cracked-gasoline or diesel fuel when contacted therewith under desulfurization conditions.

CN1627988A discloses a sorbent composition suitable for removing elemental sulfur and sulfur compounds from cracked-gasoline and diesel fuel, said sorbent composition comprising: zinc oxide, expanded perlite, aluminate salt and a promoter metal, wherein the promoter metal is present in an amount that will result in the removal of sulfur from a stream of cracked-gasoline or diesel fuel when the stream of cracked-gasoline or diesel fuel is contacted therewith under desulfurization conditions, and at least a portion of the promoter metal is present in a 0 valence state.

CN1856359A discloses a method for producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter to form a mixture thereof; b) drying the mixture to form a dried mixture; c) calcining the dried mixture to form a calcined mixture; d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence co-catalyst content therein, and e) recovering the modified composition. The promoter contains a plurality of metals selected from nickel and the like.

CN1871063A discloses a method for producing a composition, the method comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina to form a mixture thereof; b) drying the mixture to form a first dried mixture; c) calcining the first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto the first calcined mixture to form a promoted mixture; e) contacting the promoted mixture with an acid selected from the group consisting of citric acid, tartaric acid, and combinations thereof to form a contacted mixture; f) drying the contacted mixture to form a second dried mixture; g) calcining the second dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced-valence promoter content therein, and i) recovering said composition.

Although the disclosed adsorbent has certain desulfurization performance, the requirement on the sulfur content of the gasoline product is also strict with the improvement of the quality standard of the gasoline. 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 overcome the defects of low desulfurization activity, unstable structure and poor wear resistance of the adsorbent in the prior art, and provides a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method.

In order to achieve the above object, the present invention provides a hydrocarbon oil desulfurization catalyst comprising, based on the total weight of the hydrocarbon oil desulfurization catalyst: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2)3 to 35 wt% of a heat-resistant inorganic oxide; 3)5 to 40 wt% SiCN; 4)1 to 20 wt% of pillared interlayer clay; 5) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

The present invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst of the present invention, comprising: (1a) contacting SiCN, a heat-resistant inorganic oxide binder, water and an acidic liquid to form slurry, and mixing the slurry with pillared clay and at least one metal oxide selected from elements of groups IIB, VB and VIB to obtain carrier slurry; or (1b) contacting a heat-resistant inorganic oxide binder, water and an acidic liquid to form a slurry, and mixing the slurry with pillared clay, at least one metal oxide selected from group IIB, VB and VIB elements, and SiCN to obtain a carrier slurry; (2) molding, first drying and first roasting the carrier slurry to obtain a carrier; (3) introducing a precursor of a metal promoter into the carrier, and then carrying out second drying and second roasting to obtain a catalyst precursor; (4) and reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.

The invention also provides a hydrocarbon oil desulfurization catalyst prepared by the method.

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: under the hydrogen atmosphere, sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention are subjected to desulfurization reaction at 350-500 ℃ and 0.5-4 MPa.

The hydrocarbon oil desulfurization catalyst provided by the invention contains SiCN (silicon carbonitride) with stable chemical properties, reduces the related action with metal oxides such as zinc oxide and the like, and avoids the formation of zinc silicate substances, for example, a XRD spectrogram of the hydrocarbon oil desulfurization catalyst A1 obtained in example 1 shown in figure 1 after hydrothermal aging does not have a characteristic peak of zinc silicate. The hydrocarbon oil desulfurization catalyst provided by the invention has better stability and higher desulfurization activity, and can more effectively adsorb sulfur in hydrocarbon oil onto the hydrocarbon oil desulfurization catalyst in the process of hydrocarbon oil desulfurization to obtain hydrocarbon oil with lower sulfur content. The hydrocarbon oil desulfurization catalyst provided by the invention has better wear resistance, lower catalyst loss in the desulfurization process and longer service life.

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 pattern of a hydrocarbon oil desulfurization catalyst A1 obtained in example 1 before and after hydrothermal aging;

FIG. 2 is an XRD pattern of hydrocarbon oil desulfurization catalyst B1 obtained in comparative example 1 before and after hydrothermal aging.

Detailed Description

The following describes in detail specific embodiments of the present invention. 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.

The invention provides a hydrocarbon oil desulfurization catalyst, which comprises the following components in percentage by weight based on the total weight of the hydrocarbon oil desulfurization catalyst: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2)3 to 35 wt% of a heat-resistant inorganic oxide; 3)5 to 40 wt% SiCN; 4)1 to 20 wt% of pillared interlayer clay; 5) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

Preferably, the hydrocarbon oil desulfurization catalyst contains 25 to 70 wt% of the metal oxide, 6 to 25 wt% of the heat-resistant inorganic oxide, 10 to 30 wt% of SiCN, 2 to 15 wt% of the pillared clay, and 8 to 25 wt% of the metal promoter, based on the total weight of the hydrocarbon oil desulfurization catalyst.

More preferably, the hydrocarbon oil desulfurization catalyst contains 40 to 60 wt% of the metal oxide, 8 to 15 wt% of the heat-resistant inorganic oxide, 12 to 25 wt% of SiCN, 2 to 10 wt% of the pillared clay, and 12 to 20 wt% of the metal promoter, based on the total weight of the hydrocarbon oil desulfurization catalyst.

In the invention, the content of each component in the hydrocarbon oil desulfurization catalyst can be measured by an XRD crystal phase analysis method.

According to the invention, the hydrocarbon oil desulfurization catalyst has SiCN crystal phase peaks at 2 theta of 36.7 degrees and 60.0 degrees in a spectrogram obtained by XRD analysis.

The hydrocarbon oil desulfurization catalyst provided by the invention contains SiCN with a hexagonal crystal structure as a structural component, and the SiCN with the structure has high hydrothermal stability, so that zinc silicate substances can be effectively prevented from being formed in the composition of the catalyst in the process of hydrocarbon oil desulfurization, and the catalyst is ensured to have better desulfurization activity and stability. Preferably, the hydrocarbon oil desulfurization catalyst has no characteristic peaks of zinc silicate at 2 theta of 22.0, 25.54, 48.9 and 59.4 in an XRD spectrum after hydrothermal aging. The hydrothermal aging is carried out at the temperature of 500-700 ℃, the water vapor partial pressure of 10-30kPa, and the treatment time of 10-24 h.

According to the invention, the pillared interlayer clay is an interlayer mineral crystal and is formed by regularly and alternately arranging two single-layer mineral clay components, and the distance between the bottom surfaces of the pillared interlayer clay is not less than 1.7 nm. Preferably, the hydrocarbon oil desulfurization catalyst has a spectrum obtained by XRD analysis, wherein a characteristic peak of the pillared interlayer clay exists at a2 theta of 3.4 degrees. Preferably, examples of the pillared clay include, but are not limited to, at least one of rectorite, marmontite, bentonite, montmorillonite and smectite, and preferably, the pillared clay is rectorite.

According to the present invention, the at least one metal oxide selected from group IIB, VB and VIB elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide, and preferably, the metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide; more preferably, the metal oxide is zinc oxide.

According to the invention, preferably, the metal promoter is nickel and/or cobalt, and the hydrocarbon oil desulfurization catalyst can have higher desulfurization activity and regeneration performance; it may be further preferred that the metal promoter is nickel.

According to the present invention, preferably, the heat-resistant inorganic oxide is at least one of alumina, titanium dioxide, zirconium dioxide and tin dioxide. Preferably, the heat-resistant inorganic oxide provides a binding effect between the components of the hydrocarbon oil desulfurization catalyst. Wherein the alumina is at least one of gamma-alumina, eta-alumina, theta-alumina and chi-alumina; preferably, the alumina is gamma-alumina.

According to the invention, the SiCN used is selected to have a specific structure, so that the hydrocarbon oil desulfurization catalyst can have better wear resistance and desulfurization activity. Preferably, the SiCN has a hexagonal crystal structure, and is in a plate or column structure. Preferably, the particle size of SiCN is 1-20 μm, preferably 3-15 μm. Preferably, the specific surface area of SiCN is 1-30 m²(ii) in terms of/g. Preferably, the nitrogen adsorption pore volume of SiCN is 0.02-0.12 cm³(ii)/g; more preferably, the nitrogen adsorption pore volume of SiCN is 0.03-0.10 cm³/g。

In the preparation method of the present invention, the metal oxide may be added in the form of powder of the metal oxide, or may be added in the form of slurry after the metal oxide is mixed with water to form slurry.

In the invention, the at least one metal oxide selected from the group IIB, VB and VIB elements can be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide; preferably at least one of zinc oxide, molybdenum oxide and vanadium oxide; more preferably zinc oxide.

According to the present invention, as described above, the pillared clay is at least one of rectorite, marmontite, bentonite, montmorillonite and smectite; preferably rectorite.

According to the present invention, it is preferable that the heat-resistant inorganic oxide binder is selected from at least one of an alumina binder, a titania binder, a zirconia binder and a tin dioxide binder.

Preferably, the alumina binder may be alumina or converted to γ -Al under the conditions of the first firing₂O₃The substance of (1). Preferably, the alumina binder may be selected from at least one of SB powder, hydrated alumina, alumina sol, boehmite (boehmite), pseudoboehmite (pseudo boehmite), alumina trihydrate and amorphous aluminum hydroxide; preferably, the alumina binder is at least one of SB powder, pseudo-boehmite, and alumina sol.

Preferably, the titanium dioxide binder is a substance that is hydrolyzed in the acidic liquid and converted to anatase titanium dioxide under the first calcination conditions. Further, the titanium dioxide binder may be selected from at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide, and anatase titanium dioxide.

Preferably, the zirconia binder is a material that hydrolyzes in the acidic liquid and converts to zirconia under the first firing conditions. Further, the zirconia binder may be selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconia, and amorphous zirconia.

Preferably, the tin dioxide binder is a substance that is hydrolyzed in the acidic liquid and converted to tin dioxide under the first firing conditions. Further, the tin dioxide binder may be selected from at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide, and tin dioxide.

In the invention, the titanium dioxide binder, the zirconium dioxide binder and the tin dioxide binder are contacted with excessive acid solution and can be hydrolyzed to generate adhesive colloidal solution.

According to the invention, the acidic liquid may be an acid or an aqueous solution of an acid, the acid may be selected from water-soluble inorganic and/or organic acids, preferably the acid may be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

According to the present invention, the acidic liquid is preferably used in an amount such that the carrier slurry has a pH of 1 to 5, preferably 1.5 to 4.

In the present invention, the amount of water added in steps (1a) and (1b) 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 heat-resistant inorganic oxide binder is 5: 1-10: 1; or the weight ratio of the added water to the sum of the weights of the heat-resistant inorganic oxide binder and SiCN is 5: 1-10: 1.

in the present invention, the carrier slurry obtained may be in the form of a paste or slurry or the like. The carrier slurry may be thickened, dried and then shaped. More preferably, the carrier slurry is in the form of a slurry that can be spray dried to form microspheres having a particle size of 20 to 200 microns for molding purposes. To facilitate spray drying, the solid content of the carrier slurry before drying may be 10 to 50 wt%, preferably 20 to 50 wt%. 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.

In the present invention, the first drying method and conditions in step (2) are well known to those skilled in the art, and the drying method may be, for example, air drying, oven drying, or forced air drying. Preferably, the temperature of the first drying may be room temperature to 400 ℃, and preferably 100 to 350 ℃; the first drying time is more than 0.5h, preferably 0.5-100 h, and more preferably 2-20 h.

In the present invention, the first roasting condition in step (2) is also well known to those skilled in the art, and preferably, the temperature of the first roasting is 400 to 700 ℃, preferably 450 to 650 ℃; the first roasting time is at least 0.5h, preferably 0.5-100 h, and more preferably 0.5-10 h.

According to the invention, step (3) is used to add a metal promoter, as previously indicated. The precursor of the metal promoter is a material that can be converted to an oxide of the metal promoter under the second firing conditions; preferably, the precursor of the metal promoter may be selected from at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal promoter. Preferably, the precursor of the metal promoter may be at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of at least one of cobalt, nickel, iron and manganese; preferably at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel and/or cobalt; nickel nitrate and/or cobalt nitrate may be preferred; more preferably at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel; nickel nitrate is particularly preferred.

According to the present invention, the method of introducing the precursor of the metal promoter on the support is preferably impregnation or precipitation. The impregnation may be by impregnating the support with a solution or suspension of the precursor of the metal promoter; the precipitation may be by mixing a solution or suspension of the precursor of the metal promoter with the support and then precipitating the precursor of the metal promoter on the support by adding aqueous ammonia.

According to the invention, the temperature of the second drying is preferably 50-300 ℃, and is preferably 100-250 ℃; the second drying time is 0.5-8 h, preferably 1-5 h.

Preferably, the temperature of the second roasting is 300-800 ℃, and preferably 450-750 ℃; the second roasting time is more than 0.5h, and preferably 1-3 h. The second calcination may be carried out in the presence of oxygen or an oxygen-containing gas until volatile substances are removed and the precursor of the metal promoter is converted into an oxide form of the metal promoter to obtain a catalyst precursor.

According to the invention, in the step (4), the oxide of the metal promoter in the catalyst precursor is converted into the elemental metal, and the catalyst precursor can be reduced under the hydrogen-containing atmosphere, so that the metal promoter exists in a substantially reduced state, and the catalyst of the invention is obtained. The reducing conditions only convert the oxide of the metal promoter in the catalyst precursor to elemental metal, while the metal oxide in the support does not. Preferably, the reduction temperature is 300-600 ℃, and preferably 400-500 ℃; the reduction time is 0.5-6 h, preferably 1-3 h; the hydrogen content in the hydrogen-containing atmosphere is 10-60 vol%.

In the present invention, the reduction of the catalyst precursor in the step (4) may be carried out immediately after the catalyst precursor is produced, or may be carried out before the use (i.e., before the use for desulfurization adsorption). Since the metal promoter is readily oxidized and the metal promoter in the catalyst precursor is present in the form of an oxide, it is preferred that the reduction of the catalyst precursor in step (4) be carried out before desulfurization adsorption is carried out for ease of transportation. The reduction is such that the metal in the oxide of the metal promoter is substantially present in a reduced state, resulting in the desulfurization catalyst of the present invention.

According to the present invention, the heat-resistant inorganic oxide binder, SiCN, the metal oxide and the precursor of the metal promoter are preferably added in such amounts that the resulting hydrocarbon oil desulfurization catalyst contains 10 to 80 wt%, preferably 25 to 70 wt%, more preferably 40 to 60 wt% of the metal oxide, based on the total weight of the hydrocarbon oil desulfurization catalyst; 3 to 35 wt% of a heat-resistant inorganic oxide, preferably 6 to 25 wt%, more preferably 8 to 15 wt%; 5 to 40 wt% SiCN, preferably 10 to 30 wt%, more preferably 12 to 25 wt%; contains 1 to 20 wt% of pillared clay, preferably 2 to 15 wt%, more preferably 2 to 10 wt%; the metal promoter is contained in an amount of 5 to 30 wt%, preferably 8 to 25 wt%, and more preferably 12 to 20 wt%.

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: under the hydrogen atmosphere, carrying out desulfurization reaction on sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention at 350-500 ℃ and 0.5-4 MPa; preferably, the desulfurization reaction is carried out at 400 to 450 ℃ and 1.0 to 2.0 MPa. In this process, sulfur in the hydrocarbon oil is adsorbed onto the catalyst, thereby obtaining a hydrocarbon oil having a low sulfur content.

In the invention, the catalyst after reaction can be reused after regeneration. The regeneration is carried out under an oxygen atmosphere, and the regeneration conditions comprise: the regeneration pressure is normal pressure, the regeneration temperature is 400-700 ℃, and the optimal regeneration temperature is 500-600 ℃.

In the invention, before the hydrocarbon oil desulfurization is carried out again, the regenerated catalyst needs to be reduced under the hydrogen-containing atmosphere, and the reducing conditions of the regenerated catalyst comprise: the temperature is 350-500 ℃, preferably 400-450 ℃; the pressure is 0.2 to 2MPa, preferably 0.2 to 1.5 MPa.

In the present invention, the hydrocarbon oils include cracked-gasoline and diesel fuel, wherein "cracked-gasoline" means a hydrocarbon or any fraction thereof having a boiling range of 40 ℃ to 210 ℃, which is a product from a thermal or catalytic process that cracks larger hydrocarbon molecules into smaller molecules. 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, fluid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Thus, suitable catalytically cracked gasolines include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, fluid catalytically cracked gasoline, and heavy oil cracked-gasoline, and combinations thereof. In some instances, the cracked-gasoline when used as a hydrocarbon-containing fluid in the process of the present invention may be fractionated and/or hydrotreated prior to desulfurization. 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 represents any form of elemental sulfur such as organosulfur compounds commonly found in hydrocarbon-containing fluids such as cracked-gasoline or diesel fuel. The sulfur present in the hydrocarbon-containing fluids of the present invention includes, but is not limited to, Carbon Oxysulfide (COS), carbon disulfide (CS2), mercaptans or other thiopheneic compounds and the like, and combinations thereof, including, inter alia, thiophene, benzothiophene, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes, as well as higher molecular weight thiopheneic compounds commonly found in diesel fuel.

The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains SiCN component, the component is not easy to react with zinc oxide component in the process of multiple reactions and regeneration of the catalyst, and zinc silicate substance is not produced, so that the hydrocarbon oil desulfurization catalyst reduces desulfurization activity due to loss of zinc oxide. The catalyst of the invention has high desulfurization activity, and simultaneously has the property of obviously increasing the abrasion resistance of the catalyst, and can be suitable for the desulfurization process of repeated reaction and regeneration of catalytic cracking gasoline or diesel fuel.

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

The hydrocarbon oil desulfurization catalysts obtained in the examples and comparative examples were subjected to structural determination by obtaining an XRD spectrum using an X-ray diffractometer (Siemens's D5005 type), Cu target, Ka radiation, solid detector, tube voltage 40kV, and tube current 40 mA;

the SiCN used in the examples is SiCN-1, SiCN-2 and SiCN-3, which are provided by Nanjing division of China petrochemical catalyst Co., Ltd, and the specific structural characteristics are shown in Table 1,

TABLE 1

Structural features	SiCN-1	SiCN-2	SiCN-3
				Structure of the product	Hexagonal crystal, plate-like	Hexagonal crystal, columnar	Hexagonal crystal, plate-like
Average particle size (. mu.m)	9.5	3.6	15.0
				Specific surface area, m²/g	10.0	26.0	3.2
Pore volume of nitrogen adsorption in cm³/g	0.08	0.10	0.03

Measured by laser particle sizer (Mastersizer 2000 from malvern).

In the following examples and comparative examples, the composition of the hydrocarbon oil desulfurization catalyst was calculated in terms of the charge.

Example 1

This example illustrates the preparation of a hydrocarbon oil desulfurization catalyst according to the present invention.

(1) And (3) preparing a carrier. Mixing 4.43kg of zinc oxide powder (Headhorse, purity 99.7 wt%), 0.93kg of rectorite (catalyst Ziru division, containing 0.70kg of dry basis) and 6.57kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide and rectorite;

taking 1.33kg of pseudo-boehmite (catalyst Nanjing division, containing 1.00kg of dry basis) and 2.06kg of SiCN-1, stirring and mixing, then adding 4.6kg of deionized water, uniformly mixing to obtain slurry, then adding 360ml of 30 wt% hydrochloric acid (chemical purity, product of Beijing chemical plant) to make the pH of the slurry be 2.1, stirring and acidifying for 1h, heating to 80 ℃, aging for 2h, then adding mixed slurry of zinc oxide and rectorite, stirring for 1h to obtain carrier slurry;

the carrier slurry is adopted to be the Niro Bowen Nozle Tower^TMSpray drying with a spray dryer type at a spray drying pressure of 8.5 to 9.5MPa, an inlet temperature of 500 deg.C or less and an outlet temperature of about 150 deg.C. The microspheres obtained by spray drying are firstly dried for 1h at 180 ℃, and then roasted for 1h at 635 ℃ to obtain a carrier;

(2) preparing a catalyst precursor. Impregnating 3.2kg of carrier with 3.51kg of nickel nitrate hexahydrate (Beijing chemical reagent company, purity > 98.5 wt%) and 0.6kg of deionized water solution, drying the obtained impregnated substance at 180 ℃ for 4h, and roasting at 635 ℃ in air atmosphere for 1h to prepare a catalyst precursor;

(3) and (4) reducing. And reducing the catalyst precursor for 2h at 425 ℃ in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst A1.

The chemical composition of a1 is: the zinc oxide content was 44.3 wt%, the SiCN content was 20.6 wt%, the rectorite content was 7.0 wt%, the alumina content was 10.0 wt%, and the nickel content was 18.1 wt%.

Example 2

1.56kg of pseudo-boehmite (catalyst Nanjing division, containing 1.17kg of dry basis) and 1.50kg of SiCN-2 are stirred and mixed, then 8.2kg of deionized water is added and mixed evenly to form slurry, 260ml of 30 wt% 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 raised to 80 ℃ for aging for 2 h. After the temperature was lowered, 5.52kg of zinc oxide powder and 0.4kg of montmorillonite (0.3 kg of dry basis, available from catalyst Ziru division) were added and stirred for 1 hour to obtain a carrier slurry.

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 A2 was obtained after reduction.

The chemical composition of a2 is: the zinc oxide content was 55.2 wt%, the SiCN content was 15.0 wt%, the montmorillonite content was 3.0 wt%, the alumina content was 11.7 wt%, and the nickel content was 15.1 wt%.

Example 3

Mixing 4.93kg of zinc oxide powder, 0.66kg of rectorite (0.50 kg of catalyst, Qilu division, containing dry basis), 2.1kg of SiCN-3 and 8.8kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide, rectorite and SiCN;

1.80kg of pseudo-boehmite (product from Shandong aluminum plant, containing 1.36kg 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, rectorite and SiCN, and stirring for 1h to obtain carrier slurry.

The spray-dry molding of the carrier slurry was carried out by referring to the method of example 1.

Referring to the method of example 1, a catalyst precursor and a catalyst were prepared, except that a nickel nitrate and cobalt nitrate solution was used in place of the nickel nitrate hexahydrate-impregnated carrier, active components nickel and cobalt were introduced, and a hydrocarbon oil desulfurization catalyst a3 was obtained after reduction.

The chemical composition of a3 is: the zinc oxide content was 49.3 wt%, the SiCN content was 16.0 wt%, the rectorite content was 5.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.

Example 4

Mixing 4.93kg of zinc oxide powder, 0.66kg of rectorite (0.50 kg of catalyst, Qilu division, containing dry basis), 2.1kg of SiCN-1 and 8.8kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide, rectorite and SiCN;

1.80kg of pseudo-boehmite (1.36 kg of a product from Shandong aluminum plant) and 4.6kg of deionized water are uniformly mixed to obtain slurry, 300ml of 30 weight percent hydrochloric acid is added to ensure that the pH value of the slurry is 2.5, the mixture is stirred and acidified for 1h, and then the temperature is increased to 80 ℃ for aging for 2 h. And adding mixed slurry of zinc oxide, rectorite and SiCN, and stirring for 1h to obtain carrier slurry.

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 A4 was obtained after reduction.

The chemical composition of a4 is: the zinc oxide content was 49.3 wt%, the SiCN content was 16.0 wt%, the rectorite content was 5.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.

Example 5

2.4kg of titanium tetrachloride (Beijing chemical plant, analytical purity, 99 wt.%) was slowly added to 4.6kg of 5 wt.% dilute hydrochloric acid, and the mixture was slowly stirred to avoid the precipitation of titanium oxide crystals, thereby obtaining a pale yellow transparent titanium sol having a pH of 2.0;

mixing 4.43kg of zinc oxide powder (Headhorse, purity 99.7 wt%), 0.93kg of rectorite (catalyst Ziru division, containing 0.70kg of dry basis), 2.06kg of SiCN-1 and 8.80kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide, rectorite and SiCN; then adding the titanium sol, mixing and stirring for 1h to obtain carrier slurry;

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 A5 was obtained after reduction.

The chemical composition of a5 is: the zinc oxide content was 44.3 wt%, the SiCN content was 20.6 wt%, the rectorite content was 7.0 wt%, the titanium dioxide content was 10.0 wt%, and the nickel content was 18.1 wt%.

Example 6

Slowly adding 1.25kg (anatase type, containing 1.17kg of dry basis) of titanium dioxide into 3.8kg of 30 wt% hydrochloric acid (chemical pure, product of Beijing chemical plant) under stirring, wherein the pH value is 1.9, and stirring for reacting for 1h to obtain light yellow transparent titanium sol;

mixing 1.50kg of SiCN-2, 0.4kg of montmorillonite (catalyst, Qilu division, containing 0.30kg of dry basis), 5.52kg of zinc oxide powder and 10.0kg of deionized water under stirring to obtain mixed slurry of zinc oxide, montmorillonite and SiCN, adding the titanium sol, and stirring for 1 hour to obtain carrier slurry;

The chemical composition of a2 is: the zinc oxide content was 55.2 wt%, the SiCN content was 15.0 wt%, the titanium dioxide content was 11.7 wt%, the montmorillonite content was 3.0 wt%, and the nickel content was 15.1 wt%.

Example 7

Ethyl titanate (3.90 kg, analytical grade, 99 wt.%) was slowly added with stirring to a solution of 10 wt.% nitric acid (analytical grade, from beijing chemical plant) at pH 2.3 in 3.8kg, and stirred for 1h to give a pale yellow transparent titanium sol;

mixing 4.93kg of zinc oxide powder, 0.66kg of rectorite (0.50 kg of dry basis, available from catalyst Zillus division), 1.6kg of SiCN-3 and 10.8kg of deionized water, stirring for 30 minutes to obtain mixed slurry of zinc oxide, rectorite and SiCN, adding titanium sol, and stirring for 1 hour to obtain carrier slurry;

Referring to the method of example 1, a catalyst precursor and a catalyst were prepared, except that a nickel nitrate and cobalt nitrate solution was used in place of the nickel nitrate hexahydrate-impregnated carrier, active components nickel and cobalt were introduced, and a hydrocarbon oil desulfurization catalyst a7 was obtained after reduction.

The chemical composition of a7 is: the zinc oxide content was 49.3 wt%, the SiCN content was 16.0 wt%, the titania content was 13.5 wt%, the rectorite content was 5.0 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.

Example 8

mixing 4.93kg of zinc oxide powder, 1.6kg of SiCN-1, 0.66kg of rectorite (catalyst, Qilu division, containing 0.50kg of dry basis) and 10.8kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide, rectorite and SiCN; then adding titanium sol and stirring for 1h to obtain carrier slurry;

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 A8 was obtained after reduction.

The chemical composition of A8 is: the zinc oxide content was 49.3 wt%, the SiCN content was 16.0 wt%, the titanium dioxide content was 13.5 wt%, the rectorite content was 5.0 wt%, and the nickel content was 16.2 wt%.

Example 9

2.60kg of zirconium tetrachloride (99 wt% of analytical purity in Beijing chemical plant) was slowly added to 4.6kg of a5 wt% nitric acid solution, and the mixture was slowly stirred to prevent the zirconium oxide from crystallizing out, thereby obtaining a pale yellow transparent zirconium sol having a pH of 2.1;

mixing 4.43kg of zinc oxide powder (Headhorse, purity 99.7 wt%), 1.4kg of SiCN-2, 1.32kg of rectorite (catalyst Ziru division, containing 1.0kg of dry basis) and 6.57kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide and SiCN; then adding the zirconium sol, mixing and stirring for 1h to obtain carrier slurry;

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 A9 was obtained after reduction.

The chemical composition of a9 is: the zinc oxide content was 44.3 wt.%, the SiCN content was 14.0 wt.%, the rectorite content was 10.0 wt.%, the zirconium dioxide content was 13.6 wt.% and the nickel content was 18.1 wt.%.

Example 10

3.21kg of tin tetrachloride (SnCl)₄·5H₂O, Alfa, 99%) 4.6kg of a 5% by weight nitric acid solution was slowly added and stirred slowly to avoid tin oxide crystallization and to obtain colorlessThe pH of the clear tin sol was 2.1;

mixing 4.43kg of zinc oxide powder (Headhorse, purity 99.7 wt%), 1.40kg of SiCN-3, 1.32kg of rectorite (catalyst Ziru division, containing 1.0kg of dry basis) and 6.57kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide and SiCN; then adding the tin sol, mixing and stirring for 1h to obtain carrier slurry;

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 A10 was obtained after reduction.

The chemical composition of a10 is: the zinc oxide content was 44.3 wt%, the SiCN content was 14.0 wt%, the rectorite content was 10.0 wt%, the tin dioxide content was 13.6 wt%, and the nickel content was 18.1 wt%.

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 (catalyst Nanjing division, containing 1.36kg of dry basis) and 2.46kg of expanded perlite (catalyst Nanjing division, containing 2.40kg of dry basis), stirring and mixing, then adding 4.6kg of deionized water, uniformly mixing, adding 360ml of 30 wt% hydrochloric acid to make the pH of the slurry equal to 2.1, stirring and acidifying for 1h, heating to 80 ℃, aging for 2h, adding zinc oxide slurry, mixing, and stirring for 1h to obtain 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 B1.

The chemical composition of B1 is: 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 B2 is: 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;

taking 1.80kg of pseudo-boehmite (a product from Shandong aluminum plant and containing 1.35kg of dry basis) and 2.16kg of diatomite (world mining company and containing 2.10kg of dry basis) to be stirred and mixed, then adding 4.6kg of deionized water to be uniformly mixed, then adding 300ml of 30 weight percent hydrochloric acid to make the pH value of the slurry equal to 2.5, stirring and acidifying for 1h, and then heating to 80 ℃ and aging for 2 h. 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 B3 is: 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

1.80kg of pseudo-boehmite (which is produced by Shandong aluminum plant and contains 1.35kg of dry basis) and 2.84kg of kaolin (which is produced by Suzhou kaolin plant and contains 2.10kg of dry basis) are stirred and mixed, then 3.6kg 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 slurry 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 mixture was spray-dried and molded by the method of example 1, and an active component nickel was introduced and reduced to obtain a hydrocarbon oil desulfurization catalyst B4.

The chemical composition of B4 is: the zinc oxide content was 49.3 wt%, the kaolin content was 21.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.

Comparative example 5

According to the method of example 1, except that the ordered porous carbon silicon nitride material prepared according to example 2 of CN101774593A was substituted by 2.06kg of the ordered porous carbon silicon nitride material instead of 2.06kg of SiCN-1, a hydrocarbon oil desulfurization catalyst B5 was obtained.

The chemical composition of B5 is: the zinc oxide content was 44.3 wt%, the ordered porous silicon carbonitride material content was 20.6 wt%, the rectorite content was 7.0 wt%, the alumina content was 10.0 wt%, and the nickel content was 18.1 wt%.

Example 11

(1) And (4) evaluating the abrasion resistance. The abrasion resistance strength test was conducted on the hydrocarbon oil desulfurization catalysts A1-A10 and B1-B5. The straight tube abrasion method is adopted, the method is referred to RIPP 29-90 in petrochemical analysis method (RIPP) experimental method, and the results are shown in Table 2. The smaller the value obtained from the test, the higher the abrasion resistance. The attrition index in Table 2 corresponds to the percentage of fines generated when attrited under certain conditions.

(2) And (4) evaluating the desulfurization performance. A desulfurization evaluation experiment was conducted on the hydrocarbon oil desulfurization catalysts A1-A10 and B1-B5 by means of a fixed bed microreaction experimental apparatus, and 16 g 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 780ppm of sulfur concentration, the reaction pressure is 1.38MPa, 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. The sulfur removal activity is measured as the sulfur content in the gasoline product. 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 ℃. Will be provided withThe hydrocarbon oil desulfurization catalyst was subjected to desulfurization evaluation experiments, the activity of the catalyst was substantially stabilized after 6 cycles of regeneration, the activity of the catalyst was represented by the sulfur content in the product gasoline stabilized by the 6 th cycle of the catalyst, and the sulfur content in the stabilized product gasoline is shown in table 2.

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-.

TABLE 2

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 780ppm, a RON of 93.0 and a MON of 82.7.

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.

As can be seen from the result data in Table 2, the hydrocarbon oil desulfurization catalyst provided by the invention contains a SiCN component, and the hydrocarbon oil desulfurization catalyst can still well reduce the sulfur content of gasoline after repeated cyclic 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 the comparative example 5 contains the ordered porous silicon carbonitride material and does not contain the SiCN in the application, so that the abrasion index is far higher than that of the catalyst prepared in the example, which shows that the hydrocarbon oil desulfurization catalyst provided by the invention can have better abrasion resistance.

Example 12

Aging hydrocarbon oil desulfurization catalysts A1-A10 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 A1 and B1 before and after aging are analyzed, wherein XRD spectrograms of A1 before and after hydrothermal aging are shown in figure 1, and crystal phase peaks of SiCN exist at 2 theta of 36.7 degrees and 60.0 degrees for both the fresh agent and the aging agent; XRD spectra before and after hydrothermal aging of B1 are shown in FIG. 2. In fig. 1, the XRD spectrum of a1 after hydrothermal aging does not have characteristic peaks of zinc silicate of 22.0, 25.54, 48.9 and 59.4 in terms of 2 θ; in fig. 2, the XRD spectrum after hydrothermal aging of B1 shows the above characteristic peaks of zinc silicate. The XRD patterns of B1-B5 were analyzed quantitatively for the content of zinc silicate by the content of crystalline phase, and the results are shown in Table 3.

The desulfurization performance of A1-A10 and B1-B5 after aging was evaluated by the same evaluation method as in example 11, and the results are shown in Table 3.

TABLE 3

2.Δ MON represents the increase in product MON;

3.Δ RON represents the increase in product RON;

As can be seen from the results of Table 3, the hydrocarbon oil desulfurization catalysts obtained in the examples did not generate zinc silicate after the aging process, whereas the catalysts of comparative examples 1 to 4 generated zinc silicate with the silica-containing material, thereby decreasing the desulfurization activity of the catalysts.

It can be seen from the data of the product gasoline in tables 2 and 3 that the method provided by the invention can still obtain high product gasoline yield, and the octane number of the gasoline is not greatly changed.

Claims

1. A hydrocarbon oil desulfurization catalyst comprising, based on the total weight of the hydrocarbon oil desulfurization catalyst:

1)10 to 80% by weight of zinc oxide;

2)3 to 35 wt% of a heat-resistant inorganic oxide;

3)5 to 40 wt% SiCN;

4)1 to 20 wt% of pillared interlayer clay;

5) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese;

the SiCN has a hexagonal crystal structure and is of a sheet or columnar structure; the particle size of SiCN is 1-20 mu m; the specific surface area of SiCN is 1-30 m²(ii)/g; the nitrogen adsorption pore volume of SiCN is 0.02-0.12 cm³/g。

2. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein the hydrocarbon oil desulfurization catalyst comprises 40 to 60% by weight of the zinc oxide, 8 to 15% by weight of the heat-resistant inorganic oxide, 12 to 25% by weight of SiCN, and 2 to 10% by weight of the pillared clay, based on the total weight of the hydrocarbon oil desulfurization catalyst; 12 to 20 wt% of the metal promoter.

3. The hydrocarbon oil desulfurization catalyst according to claim 1 or 2, wherein a spectrum obtained by XRD analysis of the hydrocarbon oil desulfurization catalyst has crystal phase peaks of SiCN at 2 θ of 36.7 ° and 60.0 °.

4. The hydrocarbon oil desulfurization catalyst according to claim 1 or 2, wherein the heat-resistant inorganic oxide is at least one of alumina, titanium dioxide, zirconium dioxide, and tin dioxide.

5. A method for producing the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 4, comprising:

(1a) contacting SiCN, a heat-resistant inorganic oxide binder, water and an acidic liquid to form slurry, and mixing the slurry with pillared clay and zinc oxide to obtain carrier slurry;

or

(1b) Contacting heat-resistant inorganic oxide binder, water and acidic liquid to form slurry, and mixing the slurry with pillared interlayer clay, zinc oxide and SiCN to obtain carrier slurry;

(2) molding, first drying and first roasting the carrier slurry to obtain a carrier;

(3) introducing a precursor of a metal promoter into the carrier, and then carrying out second drying and second roasting to obtain a catalyst precursor;

(4) reducing the catalyst precursor in a hydrogen atmosphere to obtain a hydrocarbon oil desulfurization catalyst;

wherein the particle size of SiCN is 1-20 μm; the specific surface area of SiCN is 1-30 m²(ii)/g; the nitrogen adsorption pore volume of SiCN is 0.02-0.12 cm³/g。

6. The method of claim 5 wherein the SiCN has a hexagonal crystal structure, either a plate or a pillar structure.

7. The method of claim 5, wherein the SiCN particles have a particle size of 3 to 15 μm; the nitrogen adsorption pore volume of SiCN was 0.03cm³/g～0.10cm³/g。

8. The method of claim 5, wherein the refractory inorganic oxide binder is selected from at least one of an alumina binder, a titania binder, a zirconia binder, and a tin dioxide binder; the alumina binder is at least one selected from hydrated alumina, aluminum sol and amorphous aluminum hydroxide; the titanium dioxide binder is selected from at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide; the zirconium dioxide binder is selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconium oxide and amorphous zirconium dioxide; the tin dioxide binder is at least one selected from tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide.

9. The method of claim 8, wherein the hydrated alumina is selected from at least one of boehmite, pseudoboehmite, and alumina trihydrate.

10. The method of claim 5, wherein the pillared clay is at least one of rectorite, marmontite, bentonite, montmorillonite, and smectite.

11. The method of claim 5, wherein the precursor of the metal promoter is selected from at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate, and oxide of the metal promoter.

12. The method according to claim 5, wherein the acidic liquid is used in an amount such that the carrier slurry has a pH of 1 to 5; the acidic liquid is an acid or an aqueous acid solution, and the acid is selected from inorganic acid and/or organic acid which can be dissolved in water.

13. The method according to claim 5, wherein the temperature of the first drying is room temperature to 400 ℃, and the time of the first drying is 0.5 to 8 hours; the temperature of the first roasting is 400-700 ℃, and the time of the first roasting is more than 0.5 h; the temperature of the second drying is 50-300 ℃, and the time of the second drying is 0.5-8 h; the temperature of the second roasting is 300-800 ℃, and the time of the second roasting is 0.5-4 h; the reduction temperature is 300-600 ℃, the reduction time is 0.5-6 h, and the hydrogen content in the hydrogen atmosphere is 10-60 vol%.

14. A hydrocarbon oil desulfurization catalyst produced by the method of any one of claims 5 to 13.

15. A method for desulfurizing a hydrocarbon oil, comprising: in a hydrogen atmosphere, a sulfur-containing hydrocarbon oil is subjected to a desulfurization reaction with the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 4 and 14 at 350 to 500 ℃ and 0.5 to 4 MPa.