CN111111768B

CN111111768B - Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN111111768B
Application number: CN201811285661.8A
Authority: CN
Inventors: 宋烨; 林伟; 田辉平; 王磊; 刘俊
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-10-31
Filing date: 2018-10-31
Publication date: 2023-07-11
Anticipated expiration: 2038-10-31
Also published as: CN111111768A

Abstract

The invention discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method, wherein the desulfurization catalyst comprises 5-35 wt% of a silicon oxide source, 5-35 wt% of alumina, 30-70 wt% of zinc oxide, 2-15 wt% of silver oxide, 1-20 wt% of a phosphorus-aluminum molecular sieve and 5-30 wt% of active metal based on the total weight of the desulfurization catalyst; and at least part of the silver oxide forms a general formula Ag with the zinc oxide _x Zn _1‑x The zinc-silver composite metal oxide represented by O exists in a form, wherein x is more than 0 and less than or equal to 0.24, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese, and the Ag _x Zn _1‑x The sulfur capacity of the zinc-silver composite metal oxide represented by O is more than or equal to 30 percent. The desulfurization catalyst prepared by the proportion has the characteristics of high desulfurization activity, high stability, long service life and good wear resistance.

Description

Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Technical Field

The invention relates to a desulfurization catalyst for hydrocarbon oil, in particular to a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method.

Background

Sulfur in the tail gas of the automobile engine can inhibit noble metal in the catalytic converter and irreversibly poison the noble metal, so that the purifying effect of the catalytic converter on the tail gas of the automobile is reduced. The raw automobile exhaust contains unburned non-methane hydrocarbons, nitrogen oxides and carbon monoxide, and these gases are prone to photochemical smog under photocatalysis.

The majority of sulfur in the gasoline products of China comes from the blending components of the hot processed gasoline (such as the catalytic cracking gasoline), so the reduction of sulfur content in the hot processed gasoline helps to reduce the sulfur content of the gasoline products. The sulfur content in the limited gasoline products in the current gasoline product standard GB 17930-2011 "motor gasoline" in China must be reduced to 50 mug/g, and the quality standard of future gasoline products is stricter.

In order to ensure the combustion performance of the automobile fuel, the sulfur content of the automobile fuel is reduced, and meanwhile, the octane number (comprising ROM and MON) of the gasoline is prevented from being reduced as much as possible due to the change of the olefin content in the gasoline. The impact on olefin content is generally due to the simultaneous initiation of hydrogenation reactions to remove thiophenes (including thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes). In addition, it is desirable to avoid desulfurization conditions that would saturate aromatics in the catalytically cracked-gasoline. The most desirable approach is therefore to achieve desulfurization while maintaining the combustion performance of the gasoline product.

At present, the deep desulfurization method of the oil product mainly comprises two methods of hydrofining and adsorption desulfurization, wherein the hydrofining cost is high. S Zorb adsorption desulfurization belongs to adsorption desulfurization technology, which realizes adsorption removal of sulfide in hydrocarbon oil under certain temperature, pressure and hydrogen conditions. 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 desulfurization.

CN1355727a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein the nickel is present in a substantially reduced valence state in an amount that is capable of removing sulfur from a cracked-gasoline or diesel fuel stream contacted with the nickel-containing adsorbent composition under desulfurization conditions. The composition is obtained by granulating a mixture of zinc oxide, silicon oxide and aluminum oxide to form granules, drying, calcining, impregnating with nickel or a nickel-containing compound, drying, calcining, and reducing.

CN1382071a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, 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 cracked-gasoline or diesel fuel stream contacted with the cobalt-containing adsorbent composition under desulfurization conditions.

US6150300 discloses a method of preparing an adsorbent comprising preparing 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 formed into spheres having a diameter of 10-1000 mm. Wherein step (a) further comprises mixing with a metal promoter.

CN1422177a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, expanded perlite, alumina and promoter metal, wherein the promoter metal is present in a substantially reduced valence state and in an amount that will remove sulfur from the cracked-gasoline or diesel fuel stream 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, and promoter metal, wherein the promoter metal is present in an amount that will result in desulfurization from a stream of cracked-gasoline or diesel fuel when the cracked-gasoline or diesel fuel stream is contacted therewith under desulfurization conditions, and at least a portion of the promoter metal is present in the 0-valent state.

CN1856359a discloses a method of producing a composition comprising: a) Mixing the liquid, the zinc-containing compound, the silica-containing material, alumina, and the 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 cocatalyst content therein, and e) recovering the composition. The promoter comprises a plurality of metals selected from nickel and the like.

CN1871063a discloses a method of producing a composition, the method comprising: a) Mixing a liquid, a zinc-containing compound, a silica-containing material, and 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 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 the second calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having reduced valence promoter content therein, and i) recovering the composition.

CN104511282a discloses a desulfurization catalyst, a method for preparing the same, and a method for desulfurizing hydrocarbon oil, wherein the desulfurization catalyst comprises 5-35 wt% of a silica source, 5-35 wt% of alumina, 30-70 wt% of zinc oxide, 2-15 wt% of lead oxide, and 5-30 wt% of an active metal; and at least part of the lead oxide forming with zinc oxide Pb at the same time _x Zn _1-x O represents zinc-lead solid solution, and x is 0<x is less than or equal to 0.12; the active metal is at least one of cobalt, nickel, iron and manganese.

The catalysts disclosed in the above patents have certain desulfurization performance, but when raw gasoline with high sulfur content (average sulfur content is more than 800 mug/g) and large fluctuation is processed, the condition that the sulfur content of the gasoline exceeds the standard can occur, and the reversion is needed.

Disclosure of Invention

The invention aims to solve the problems of poor desulfurization activity and stability in the prior art, and provides a desulfurization catalyst with high desulfurization activity, low octane number loss, high stability, reduced octane number loss of oil products, long service life and good wear resistance, a preparation method thereof and a hydrocarbon oil desulfurization method.

In order to achieve the above object, the present invention provides a desulfurization catalyst comprising 5 to 35% by weight of a silica source, 5 to 35% by weight of alumina, 30 to 70% by weight of zinc oxide, 2 to 15% by weight of silver oxide, 1 to 20% by weight of a phosphorus-aluminum molecular sieve, and 5 to 30% by weight of an active metal, based on the total weight of the desulfurization catalyst; and at least part of the silver oxide forms a general formula Ag with the zinc oxide _x Zn _1-x The zinc-silver composite metal oxide represented by O exists in a form, wherein x is more than 0 and less than or equal to 0.24, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese, and the Ag _x Zn _1-x The sulfur capacity of the zinc-silver composite metal oxide represented by O is more than or equal to 30 percent.

The invention also provides a preparation method of the desulfurization catalyst, which comprises the following steps: (1) Carrying out precipitation reaction on a mixed solution obtained by mixing a silver-containing compound, a zinc-containing compound and a precipitant, and filtering, drying and roasting a mixture obtained by the precipitation reaction to obtain a precipitation product; (2) Contacting a silica source, an alumina source, a phosphorus-aluminum molecular sieve, water, and an acid solution to form a slurry, and mixing the precipitated product obtained in step (1) with the slurry to form a carrier mixture; forming, drying and roasting the carrier mixture to form a carrier; (3) Introducing a compound containing active metal to the carrier obtained in the step (2), and drying and roasting to obtain a desulfurization catalyst precursor; the active metal is at least one of cobalt, nickel, iron and manganese; (4) And (3) reducing the desulfurization catalyst precursor obtained in the step (3) in a hydrogen-containing atmosphere to obtain the desulfurization catalyst.

The invention also provides a desulfurization catalyst obtained by the preparation method provided by the invention.

The invention also provides a method for desulfurizing hydrocarbon oil, which comprises the following steps: and (3) carrying out contact reaction on sulfur-containing hydrocarbon oil and a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst.

Through the technical scheme, the desulfurization catalyst provided by the invention is at least partially formed by silver oxide and zinc oxide and has the general formula Ag _x Zn _1-x The zinc-silver composite metal oxide represented by O exists as a sulfur absorbing component, stabilizes the crystal structure of ZnO, and blocks the direct reaction of ZnO and a silicon source, so that the desulfurization catalyst provided by the invention has better desulfurization activity and activity stability.

The desulfurization catalyst prepared by the invention also has better wear resistance, and can prolong the service life of the desulfurization catalyst. The desulfurization catalyst can absorb sulfur at lower temperature for oxidation regeneration. The sulfur content in the gasoline treated by the desulfurization catalyst can be reduced to 4-8ppm, and the octane number loss of the oil product can be reduced.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:

FIG. 1 is a diagram of precipitated products C1-C3, znO and Ag ₂ XRD spectrum of O; wherein the method comprises the steps of

2 theta value B of diffraction peak of (100), (002) and (101) planes of ZnO ₁₀₀ 、B ₀₀₂ And B ₁₀₁ 31.55 deg., 34.21 deg. and 36.04 deg. respectively,

2 theta value A of diffraction peaks of (100), (002) and (101) planes representing ZnO in C1 ₁₀₀ 、A ₀₀₂ And A ₁₀₁ 31.86 deg., 34.53 deg. and 36.35 deg. respectively,

2 theta value A of diffraction peaks of (100), (002) and (101) planes representing ZnO in C2 ₁₀₀ 、A ₀₀₂ And A ₁₀₁ 31.92 °, 34.56 ° and 36.39 °,

2 theta value A of diffraction peaks of (100), (002) and (101) planes representing ZnO in C3 ₁₀₀ 、A ₀₀₂ And A ₁₀₁ 31.88 °, 34.55 ° and 36.37 °, respectively;

FIG. 2 is an XRD spectrum of desulfurization catalyst A1;

FIG. 3 is an XRD spectrum of desulfurization catalyst A1 before and after aging;

fig. 4 is an XRD spectrum before and after aging of the desulfurization catalyst B1.

Detailed Description

The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

The invention provides a desulfurization catalyst, which comprises 5-35 wt% of silicon oxide source, 5-35 wt% of alumina, 30-70 wt% of zinc oxide, 2-15 wt% of silver oxide, 1-20 wt% of phosphorus-aluminum molecular sieve and 5-30 wt% of active metal based on the total weight of the desulfurization catalyst; and at least part of the silver oxide forms a general formula Ag with the zinc oxide _x Zn _1-x The zinc-silver composite metal oxide represented by O exists in a form, wherein x is more than 0 and less than or equal to 0.24, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese, and the Ag _x Zn _1-x The sulfur capacity of the zinc-silver composite metal oxide represented by O is more than or equal to 30 percent.

According to the present invention, the desulfurization catalyst contains silver oxide and zinc oxide, and the desulfurization catalyst may contain a zinc-silver composite metal oxide formed of silver oxide and zinc oxide. The zinc-silver composite metal oxide can stabilize the lattice structure of zinc oxide and maintain the activity of zinc oxide components. The amount of silver oxide contained in the desulfurization catalyst and the amount of zinc oxide contained in the desulfurization catalyst may be such that the desulfurization catalyst contains a zinc-silver composite metal oxide represented by the general formula.

The desulfurization catalyst may be a zinc-silver composite metal oxide containing silver oxide and zinc oxide all of which form a zinc-silver composite represented by the above general formula; the desulfurization catalyst may contain a small amount of zinc oxide in addition to the zinc-silver composite metal oxide represented by the general formula. Preferably, the desulfurization catalyst contains silver oxide and zinc oxide, both of which form a zinc-silver composite metal oxide represented by the above general formula.

According to the present invention, after the zinc silver composite metal oxide is formed by the silver oxide and the zinc oxide, the lattice structure of the zinc oxide is not destroyed, but since silver ions replace zinc ions to enter the lattice, diffraction angles of characteristic peaks representing ZnO in an XRD spectrum of the desulfurization catalyst are changed, so that the presence of the zinc silver composite metal oxide in the desulfurization catalyst can be determined by measuring the desulfurization catalyst by XRD. The XRD pattern of the desulfurization catalyst A1 and the XRD pattern of ZnO obtained under the same XRD measurement conditions as shown in fig. 2. In fig. 2, individual characteristic peaks of silver oxide and zinc oxide are not present, but characteristic peaks of cubic crystals of zinc oxide characterizing a shift in peak position are present, indicating that silver oxide and zinc oxide all form a zinc-silver composite metal oxide. Preferably, the desulfurization catalyst satisfies the following relationship: a is that ₁₀₀ -B ₁₀₀ =0.2° to 0.5 °, a ₁₀₀ And B ₁₀₀ The 2 theta values of diffraction peaks of the (100) plane of ZnO are represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO, respectively, obtained under the same XRD measurement conditions.

According to the present invention, the desulfurization catalyst preferably satisfies the following relationship: a is that ₀₀₂ -B ₀₀₂ =0.2° to 0.5 °; a is that ₀₀₂ And B ₀₀₂ The 2 theta value of the diffraction peak of the (002) plane of ZnO is represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO, which are obtained under the same XRD measurement conditions, respectively.

According to the present invention, the desulfurization catalyst preferably satisfies the following relationship: a is that ₁₀₁ -B ₁₀₁ =0.2° to 0.5 °; a is that ₁₀₁ And B ₁₀₁ The 2 theta value of the diffraction peak of the (101) plane of ZnO is represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions, respectively.

According to the invention, by XRD as described aboveIt can be determined that the desulfurization catalyst contains a zinc-silver composite metal oxide formed of silver oxide and zinc oxide, and that the molar ratio x of silver to zinc in the zinc-silver composite metal oxide can be determined by elemental analysis such as fluorescence spectroscopy, and that the zinc-silver composite metal oxide can be obtained by using a catalyst having the general formula Ag _x Zn _1-x O represents, wherein x satisfies 0 < x.ltoreq.0.24, and x represents an atomic molar ratio.

According to the present invention, the desulfurization catalyst preferably contains 12 to 20% by weight of a silica source, 10 to 20% by weight of alumina, 35 to 50% by weight of zinc oxide, 5 to 12% by weight of silver oxide, 1 to 20% by weight of a phosphorus-aluminum molecular sieve, and 10 to 20% by weight of an active metal, based on the total weight of the desulfurization catalyst.

According to the invention, the active metal may be any metal capable of reducing sulfur in the oxidized state to hydrogen sulfide, preferably the active metal is nickel.

According to the present invention, the silica source may provide adhesion between the components of the desulfurization catalyst. Preferably, the silica source may be silica or natural ore having a silica content of greater than 45 wt.%. Preferably, the silica source may be at least one of a layered clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica, and silica gel.

According to the present invention, the alumina may provide a bond between the components of the desulfurization catalyst. Preferably, the alumina may be at least one of gamma-alumina, eta-alumina, theta-alumina and chi-alumina.

According to the present invention, the molecular sieve is used in cracking and shape-selective hydrocarbon oil desulfurizing catalyst to raise the octane number of hydrocarbon oil, and may be, for example, crystalline silicoaluminophosphate with Si introduced into aluminum phosphate skeleton comprising PO ₄ ⁺ 、AlO ₄ ^- SiO (silicon oxide) ₂ Tetrahedral composition. The SAPO molecular sieve comprises 13 three-dimensional microporous framework structures, and the pore size of the three-dimensional microporous framework structures is

Pore volume of 0.18-0.48cm ³ And/g. Preferably, the SAPO molecular sieve may be at least one selected from the group consisting of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20, and the pore sizes of the SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieves are respectively->

(12 membered ring), ->

(10 membered ring), ->

(10 membered ring), ->

(8 membered ring) and->

(6 membered ring); pore volumes of 0.31cm respectively ³ /g、0.18cm ³ /g、0.42cm ³ /g、0.42cm ³ Per g and 0.40cm ³ And/g. Preferably, the SAPO molecular sieve is at least one of SAPO-11, SAPO-31 and SAPO-34.

In the preparation method of the desulfurization catalyst provided by the invention, the zinc-silver composite metal oxide can be formed in the step (1).

The amounts of the silver-containing compound and the zinc-containing compound added in step (1) can be selected within a wide range according to the present invention, so long as the silver-containing compound and the zinc-containing compound can be formed using the general formula Ag _x Zn _1-x The zinc-silver composite metal oxide represented by O is only needed. Preferably, the silver-containing compound and zinc-containing compound in step (1) are added in amounts such that the resulting desulfurization catalyst has a silver oxide content of 2 to 15 wt% and a zinc oxide content of 30 to 70 wt% based on the total weight of the desulfurization catalyst; preferably, the silver-containing compound and the zinc-containing compound are added in amounts such that the resulting desulfurization catalyst has a silver oxide content of 5 to 12 wt% and a zinc oxide content of 35 to 50 wt% based on the total weight of the desulfurization catalyst.

According to the present invention, the precipitated product obtained in the step (1) is subjected to elemental analysis and XRD measurement, and it can be determined that the precipitated product contains zinc-silver composite metal oxide based on the elemental analysis and XRD measurement results. Specifically, the precipitated product is first subjected to elemental analysis to determine that it contains elemental silver and elemental zinc. Next, the precipitate was subjected to XRD measurement analysis, and as shown in fig. 1, it was inferred that a zinc-silver composite metal oxide was formed from the characteristic peaks characterizing the hexagonal system of ZnO, but not the characteristic peaks of silver oxide, which appear in the XRD spectrum. Because the zinc-silver composite metal oxide is formed by substituting silver for zinc into the lattice structure of zinc oxide, the independent silver oxide crystal structure is not available, so that in the XRD spectrum of the zinc-silver composite metal oxide, the structural characteristics of ZnO crystals are still available, and the structural characteristics of silver oxide crystals are not available. But the position of the crystalline phase peak of ZnO in the zinc-silver composite oxide is shifted. Therefore, the precipitated product can be judged to contain zinc-silver composite metal oxide by XRD spectrum of the precipitated product.

According to the invention, the precipitated product preferably satisfies the following relationship: a is that ₁₀₀ -B ₁₀₀ =0.2° to 0.5 °, a ₁₀₀ And B ₁₀₀ The 2 theta value of the diffraction peak of the (100) plane of ZnO is represented in the XRD spectrum of the precipitate and the XRD spectrum of ZnO, respectively, obtained under the same XRD measurement conditions.

According to the invention, the precipitated product preferably satisfies the following relationship: a is that ₀₀₂ -B ₀₀₂ =0.2° to 0.5 °; a is that ₀₀₂ And B ₀₀₂ The 2 theta value of the diffraction peak of the (002) plane of ZnO is represented in the XRD spectrum of the precipitate and the XRD spectrum of ZnO, respectively, obtained under the same XRD measurement conditions.

According to the invention, the precipitated product preferably satisfies the following relationship: a is that ₁₀₁ -B ₁₀₁ =0.2° to 0.5 °; a is that ₁₀₁ And B ₁₀₁ The 2 theta value of the diffraction peak of the (101) plane of ZnO is represented in the XRD spectrum of the precipitate and the XRD spectrum of ZnO, respectively, obtained under the same XRD measurement conditions.

In the present invention, the 2 θ value according to the diffraction peak of ZnO crystal appearing in the XRD spectrum of the precipitated product satisfies the above-described relational expression. It can be determined that the precipitated product obtained by the preparation method provided by the invention contains zinc-silver composite metal oxide.

According to the present invention, the molar ratio of silver to zinc in the formed zinc-silver composite metal oxide can be determined by elemental analysis and XRD measurement of the precipitated product. Preferably, the precipitated product obtained in step (1) contains Ag of the general formula _x Zn _1-x O represents zinc-silver composite metal oxide, wherein x is more than 0 and less than or equal to 0.24, and x represents atomic mole ratio. In the formed zinc-silver composite metal oxide represented by the general formula, silver and zinc are matched according to the atomic molar ratio, so that ZnO crystals can be provided with better crystal structure stability in a high-temperature environment in the processes of sulfur absorption and oxidation regeneration, and better desulfurization activity of a desulfurization catalyst containing the zinc-silver composite metal oxide can be further ensured.

According to the present invention, the silver-containing compound in step (1) may be various water-soluble silver-containing compounds, and preferably the silver-containing compound is silver nitrate and/or silver acetate. The silver-containing compound used in the present invention may also be in the form of a hydrated compound containing water of crystallization.

According to the present invention, the zinc-containing compound in step (1) may be various water-soluble zinc-containing compounds, and preferably, the zinc-containing compound is at least one of zinc acetate, zinc chloride and zinc nitrate. The zinc-containing compound used in the present invention may also be in the form of a hydrated compound containing water of crystallization.

According to the invention, the precipitation reaction in step (1) is used to co-precipitate silver and zinc from the mixed solution to obtain a mixture containing silver and zinc. Preferably, the precipitant used in the precipitation reaction in step (1) may be urea and/or ammonia. The use of the precipitant can make the precipitation reaction more complete and is beneficial to the formation of zinc-silver composite metal oxide.

According to the invention, the pH of the mixture in step (1) is preferably from 9 to 13. When the mixture obtained by the precipitation reaction in the step (1) is in the above pH range, it is ensured that silver and zinc contained in the mixed solution are more completely co-precipitated, and the formation of zinc-silver composite metal oxide is facilitated.

According to the invention, the drying and firing may function to convert the mixture co-precipitated in step (1) into a zinc silver composite metal oxide. In order to obtain a zinc-silver composite metal oxide which can be represented by the above general formula, preferably, the drying conditions in step (1) include: drying at 100-200deg.C for 0.5-3 hr; the roasting conditions include: the roasting temperature is 400-700 ℃, and the roasting time is 0.5-3h.

According to the step (2) in the preparation method of the desulfurization catalyst provided by the invention, the step is used for preparing a silicon oxide source, an aluminum oxide source and the precipitation product obtained in the step (1) into a carrier. Preferably, the silica source and the alumina source are added in amounts such that the resulting desulfurization catalyst has a silica source content of 5 to 35 wt% and an alumina content of 5 to 35 wt% based on the total weight of the desulfurization catalyst; preferably, the silica source and the alumina source are added in amounts such that the resulting desulfurization catalyst has a silica source content of 12 to 20 wt%, an alumina content of 10 to 20 wt%, and a phosphorus-aluminum molecular sieve content of 2 to 10 wt%, based on the total weight of the desulfurization catalyst.

According to the present invention, the alumina source may preferably be a substance capable of being converted into alumina under the firing conditions of step (2). Preferably, the alumina source is hydrated alumina and/or an alumina sol; the hydrated alumina is at least one of boehmite, pseudo-boehmite, alumina trihydrate and amorphous aluminum hydroxide.

According to the present invention, the silica source may provide adhesion between the components of the desulfurization catalyst. Preferably, the source of silica is silica or a natural ore having a silica content of greater than 45 wt.%. Preferably, the silica source may be at least one of a layered clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica, and silica gel.

Although alumina may be contained in the above-mentioned silica source, the content of alumina in the present invention does not include the amount of alumina contained in the above-mentioned silica source, and the content of alumina includes only the amount of alumina formed from the alumina source. The amount of alumina contained in the silica source is still calculated as the amount of the silica source. The content of each component in the desulfurization catalyst prepared by the method is calculated according to the feeding amount.

In the present invention, in step (2), the acid solution may be used in such an amount that the pH of the carrier mixture is 1 to 5, preferably 1.5 to 4. The acid solution may be selected from inorganic and/or organic acids soluble in water, and may be, for example, at least one of hydrochloric acid, nitric acid, phosphoric acid, and acetic acid.

In the present invention, the amount of water to be added in step (1) is not particularly limited as long as the mixed solution in step (1) can be obtained. For example, the weight ratio of the amount of water added to the sum of the weights of the silver-containing compound and the zinc-containing compound is 5-10:1.

In the present invention, the amount of water to be added in the step (2) is not particularly limited as long as the slurry described in the step (2) can be obtained. For example, the amount of water added is such that the resulting slurry has a solids content of 15 to 40% by weight.

In step (2) of the present invention, the carrier mixture may be in the form of a wet mix, a paste mix, a dough or slurry, or the like. By means of the shaping, the carrier mixture can be shaped into extrudates, tablets, pellets, spheres or microspheroidal particles. For example, when the carrier mixture is a dough or paste mixture, the carrier mixture may be shaped (preferably extrusion molded) to form granules, preferably cylindrical extrudates having a diameter of 1.0 to 8.0mm and a length of 2.0 to 5.0mm, and the resulting extrudates may then be dried and calcined. If the carrier mixture is in the form of a wet mixture, the mixture may be thickened and shaped after drying. More preferably, the carrier mixture is in the form of a slurry and is spray dried to form microspheres having a particle size of 20-200 microns for shaping purposes. To facilitate spray drying, the solids content of the slurry before drying may be from 10 to 50% by weight, preferably from 20 to 50% by weight.

In the present invention, the drying method and conditions of the carrier mixture are well known to those skilled in the art, and for example, the drying method may be air drying, or air drying. Preferably, in step (2), the temperature of drying may be from room temperature to 400 ℃, preferably from 100-350 ℃; the drying time is at least 0.5 hours, preferably 0.5 to 60 hours.

In the present invention, the calcination conditions of the carrier mixture may also be known to those skilled in the art, and in general, the calcination temperature is 400 to 700 ℃, preferably 450 to 650 ℃; the calcination time is at least 0.5 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.

In the step (3) of the present invention, the active metal-containing compound is added in an amount such that the content of the active metal in the resulting desulfurization catalyst is 5 to 30% by weight based on the total weight of the desulfurization catalyst; preferably 10-20% by weight. Wherein the active metal-containing material may be a material that is converted to an oxide of the active metal under the firing conditions of step (3). The active metal-containing compound may be selected from at least one of an acetate, a carbonate, a nitrate, a sulfate, a thiocyanate, and an oxide of an active metal. The active metal may be at least one of cobalt, nickel, iron and manganese; preferably the active metal may be nickel.

In the present invention, the introduction of the active metal-containing compound onto the support can be accomplished by a variety of methods. For example, it may be achieved by impregnation or precipitation methods known to those skilled in the art. The impregnation method is to impregnate the support with a solution or suspension of an active metal-containing compound; the precipitation method is to mix a solution or suspension of the active metal-containing compound with the carrier, and then add ammonia water to precipitate the active metal on the carrier. The impregnation method is preferred.

The drying and calcination in step (3) of the present invention may be to remove volatile matters on the support to which the active metal-containing compound is introduced and to convert the active metal into an oxide of the active metal, resulting in a desulfurization catalyst precursor. The drying conditions may include a drying temperature of about 50 to 300 c, preferably 100 to 250 c, for a period of about 0.5 to 8 hours, preferably about 1 to 5 hours. The calcination conditions may include the presence of oxygen or an oxygen-containing gas, and the calcination temperature may be about 300 to 800 ℃, preferably 400 to 750 ℃, and the calcination time may be about 0.5 to 4 hours, preferably 1 to 3 hours.

The reduction of the desulfurization catalyst precursor in step (4) of the present invention may be performed immediately after the preparation of the desulfurization catalyst precursor, or may be performed before use (i.e., before use in desulfurization adsorption). Since the active metal is easily oxidized and the active metal in the desulfurization catalyst precursor exists in the form of an oxide, it is preferable that the step (4) of reducing the desulfurization catalyst precursor is performed before the desulfurization adsorption is performed for the convenience of transportation. The reduction is such that the metal in the oxide of the active metal is substantially present in the reduced state, resulting in the desulfurization catalyst of the present invention. Preferably, the conditions under which the desulfurization catalyst precursor is reduced under a hydrogen atmosphere include: the hydrogen content is 10-60 vol%, the reduction temperature is 300-600 ℃, and the reduction time is 0.5-6 hours; preferably, the temperature of the reduction is 400-500 ℃ and the time of the reduction is 1-3 hours.

The invention also provides a desulfurization catalyst obtained by the preparation method provided by the invention. The desulfurization catalyst has the composition, content and structural characteristics of the desulfurization catalyst, and is not described herein.

The invention also provides a method for desulfurizing hydrocarbon oil, which comprises the following steps: and carrying out contact reaction on sulfur-containing hydrocarbon oil and a desulfurization catalyst, wherein the desulfurization catalyst is provided by the invention.

According to the present invention, in the method for desulfurizing hydrocarbon oil, the sulfur-containing hydrocarbon oil and the desulfurization catalyst may be reacted under a hydrogen atmosphere, and the reaction conditions include: the temperature of the reaction may be 350-500 ℃, preferably 360-430 ℃; the pressure of the reaction can be 0.5-4MPa; preferably 1-2MPa.

According to the present invention, the method for desulfurizing hydrocarbon oil may further include: and regenerating the desulfurization catalyst after the reaction. The regeneration conditions included: regeneration is carried out under an oxygen atmosphere (the oxygen content may be 10-80% by volume); the regeneration temperature is 450-600 ℃, preferably 480-520 ℃; the pressure of regeneration is normal pressure.

In the present invention, the method for desulfurizing hydrocarbon oil may further include: the regenerated desulfurization catalyst is reduced before reuse. The conditions for the reduction include: the reduction is carried out under a hydrogen atmosphere (the hydrogen content may be 30-60 vol%); the temperature of the reduction may be 350-500 ℃, preferably 400-450 ℃; the pressure of the reduction may be 0.2 to 2MPa, preferably 0.2 to 1.5MPa.

In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons having a boiling range of 40 to 210 ℃ or any fraction thereof, 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 and heavy oil catalytic cracking, among others, and combinations thereof. Thus, suitable catalytically cracked gasolines include, but are not limited to, coker gasolines, thermally cracked gasolines, visbreaker gasolines, fluid catalytic cracked gasolines, and heavy oil cracked gasolines, and combinations thereof. In some cases, the cracked-gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention. By "diesel fuel" is meant a liquid composed of a mixture of hydrocarbons having a boiling range of 170 ℃ to 450 ℃ or any fraction thereof. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight run diesel, catalytically cracked diesel, hydrotreated diesel, and the like, and combinations thereof.

In the present invention, the term "sulfur" is used to represent any form of elemental sulfur such as organosulfur compounds commonly found in hydrocarbon-containing fluids such as cracked-gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluid of the present invention includes, but is not limited to, carbon Oxysulfide (COS), carbon disulfide (CS) ₂ ) Mercaptans or other thiophenes, and the like, and combinations thereof, including, inter alia, thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes, as well as the higher molecular weight thiophenes commonly found in diesel fuels.

In the present invention, the pressures involved are gauge pressures.

The present invention will be described in detail by examples.

In the following examples and comparative examples, the composition of the desulfurization absorbing composition was calculated as a charge.

Polycrystalline X-ray diffraction (XRD) was performed using an X-ray diffractometer (Siemens company model D5005) to determine the structure of the desulfurization absorbing composition, cu target, ka radiation, solid detector, tube voltage 40kV, tube current 40mA.

Example 1

This example is intended to illustrate the preparation method of the desulfurization catalyst of the present invention.

(1) The precipitated product was prepared. 10.9 kg of zinc acetate dihydrate powder (analytically pure from Beijing chemical Co., ltd.), 0.72 kg of anhydrous silver acetate (analytical pure from Country chemical reagent Co.) and 18 kg of deionized water were mixed and stirred for 30 minutes to be completely dissolved. 1.8 kg of ammonia water was added to obtain a precipitated product, which was dried at 150℃for 2 hours after filtration, and then calcined at 500℃for 1 hour to obtain a precipitated product C1.

The precipitated product C1 was subjected to fluorescence analysis and XRD measurement. XRD pattern (see FIG. 1) without Ag ₂ The diffraction peak of O, and the standard diffraction peak of ZnO appears right shifted, wherein A ₁₀₀ -B ₁₀₀ ＝0.31°，A ₀₀₂ -B ₀₀₂ ＝0.32°，A ₁₀₁ -B ₁₀₁ =0.31°, indicating Ag in the precipitated product C1 ₂ O and ZnO all form zinc-silver composite metal oxide, and the chemical composition of the zinc-silver composite metal oxide is Ag _0.087 Zn _0.913 O。

(2) Preparing a carrier. 1.60 kg of alumina (obtained from Shandong aluminum factory, containing 1.20 kg of dry basis) and 3.0 kg of kaolin (obtained from Qilu petrochemical catalyst factory, containing 2.50 kg of dry basis) were mixed with 1.0 kg of SAPO-11 (obtained from Nanjing division, catalyst, containing 0.7 kg of dry basis) under stirring, 3.6 kg of deionized water was added to the mixture, and after the mixture was uniformly mixed, 300 ml of 30 wt% hydrochloric acid (obtained from chemical purity, beijing chemical factory) was added to the mixture, stirred and acidified for 1 hour, and then the mixture was heated to 80℃for aging for 2 hours. The precipitated product C1 was added and mixed, followed by stirring for 1 hour to obtain a carrier mixture.

The carrier mixture adopts Niro Bowen Nozzle Tower ^TM Spray drying is carried out by a model spray dryer, the spray drying pressure is 8.5-9.5 MPa, the inlet temperature is below 500 ℃, and the outlet temperature is about 150 ℃. The microspheres obtained by spray drying were dried at 150℃for 1 hour and then calcined at 480℃for 1 hour to obtain a catalyst support.

(3) Preparing a desulfurization catalyst precursor. 6.4 kg of the catalyst support obtained in the step (2) was impregnated with 7.0 kg of nickel nitrate hexahydrate and 1.10 kg of deionized water solution in two sprays, and the resultant mixture was dried at 150℃for 4 hours and then calcined at 480℃for 1 hour to obtain a desulfurization catalyst precursor.

(4) Preparing a desulfurization catalyst. And (3) reducing the desulfurization catalyst precursor obtained in the step (3) in a hydrogen atmosphere at 400 ℃ for 3 hours to obtain a desulfurization catalyst A1.

The composition of the desulfurization catalyst A1 is calculated according to the feeding amount: 40.0 wt% of zinc oxide, 5.0 wt% of silver oxide, 12.0 wt% of aluminum oxide, 18.0 wt% of kaolin, 7 wt% of SAPO-11 molecular sieve and 18.0 wt% of nickel.

The results of fluorescence analysis and XRD measurement of the desulfurization catalyst A1 are shown in FIG. 2. Corresponding to the XRD spectrum of the precipitated product C1, diffraction peaks of ZnO in the XRD spectrum of the desulfurization catalyst A1 are respectively 31.75 degrees, 34.42 degrees and 36.24 degrees, and the peak positions are consistent with the ZnO peak positions appearing in the XRD spectrum of the precipitated product C1, so that the structure of the zinc-silver composite metal oxide in the desulfurization catalyst prepared by adopting the zinc-silver composite metal oxide as a raw material is shown.

Example 2

(1) The precipitated product was prepared. 14.0 kg of zinc nitrate hexahydrate (manufactured by Beijing chemical factory, analytical grade), 1.76 kg of silver nitrate powder (manufactured by national chemical reagent company, analytical grade) and 18 kg of deionized water were mixed, stirred for 30 minutes, 2.0 kg of urea was added and heated to 80 ℃ for 2 hours to obtain white precipitate, and after filtration, the white precipitate was dried at 150 ℃ for 2 hours and then calcined at 500 ℃ for 1 hour to obtain precipitate C2.

The precipitated product C2 was subjected to fluorescence analysis and XRD measurement. XRD pattern (see FIG. 1) without Ag ₂ The diffraction peak of O, and the standard diffraction peak of ZnO appears right shifted, wherein A ₁₀₀ -B ₁₀₀ ＝0.37°，A ₀₀₂ -B ₀₀₂ ＝0.35°，A ₁₀₁ -B ₁₀₁ =0.35°, indicating Ag in the precipitated product C2 ₂ O and ZnO all form zinc-silver composite metal oxide, and the chemical composition of the zinc-silver composite metal oxide is Ag _0.22 Zn _0.78 O。

(2) Preparing a carrier. 2.40 kg of alumina (obtained from Shandong aluminum factory, containing 1.8 kg of dry basis) and 1.85 kg of expanded perlite (obtained from Nanjing division, catalyst, containing 1.80 kg of dry basis) were mixed with 0.43 kg of SAPO-31 (obtained from Nanjing division, catalyst, containing 0.3 kg of dry basis) under stirring, then 4.8 kg of deionized water was added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (obtained from Beijing chemical factory) was added, stirred and acidified for 1 hour, and then the mixture was aged at 80℃for 2 hours. The precipitated product C2 was added and mixed and stirred for 1 hour to obtain a carrier mixture.

The carrier mixture was spray-dried, molded and calcined by the method of example 1 to obtain a carrier.

(3) Preparing a desulfurization catalyst precursor. The desulfurization catalyst precursor was obtained by the method of step (3) of example 1.

(4) Preparing a desulfurization catalyst. The desulfurization catalyst A2 was obtained by the method of step (4) of example 1.

The composition of the desulfurization catalyst A2 is calculated according to the feeding amount: 38.0% of zinc oxide, 12.0% of silver oxide, 18.0% of aluminum oxide, 15.0% of expanded perlite, 3% of SAPO-31 molecular sieve and 14.0% of nickel.

Example 3

(1) The precipitated product was prepared. 13.6 kg of zinc acetate dihydrate powder (analytically pure from Beijing chemical Co., ltd.), 1.03 kg of silver nitrate (analytical pure from Country chemical reagent Co.) and 20 kg of deionized water were mixed and stirred for 30 minutes to be completely dissolved. After addition of 2.0 kg of urea and treatment by heating to 80℃for 2 hours, a white precipitate is obtained. After filtration, the mixture was dried at 150℃for 2 hours and then calcined at 500℃for 1 hour to give a precipitated product C3.

The precipitated product C3 was subjected to fluorescence analysis and XRD measurement. XRD pattern (see FIG. 1) without Ag ₂ The diffraction peak of O, and the standard diffraction peak of ZnO appears right shifted, wherein A ₁₀₀ -B ₁₀₀ ＝0.33°，A ₀₀₂ -B ₀₀₂ ＝0.34°，A ₁₀₁ -B ₁₀₁ =0.33°, indicating Ag in the precipitated product C3 ₂ O and ZnO all form zinc-silver composite metal oxide, and the chemical composition of the zinc-silver composite metal oxide is Ag _0.10 Zn _0.90 O。

(2) Preparing a carrier. 2.13 kg of alumina (obtained from Shandong aluminum factory, including 1.6 kg of dry basis) and 1.34 kg of kieselguhr (obtained from Nanjing division, catalyst, including 1.5 kg of dry basis) were mixed with 0.6 kg of SAPO-34 (obtained from Nanjing division, catalyst, including 0.5 kg of dry basis) under stirring, then 4.8 kg of deionized water was added to the mixture, and after the mixture was uniformly mixed, 275 ml of 30 wt% hydrochloric acid (obtained from Beijing chemical factory) was added, stirred and acidified for 1 hour, and then the mixture was aged at 80℃for 2 hours. The precipitated product C3 was added and mixed and stirred for 1 hour to obtain a carrier mixture.

(4) Preparing a desulfurization catalyst. The desulfurization catalyst A3 was obtained by the method of step (4) of example 1.

The composition of the desulfurization catalyst A3 is calculated according to the feeding amount: 47.0 wt% of zinc oxide, 7.0 wt% of silver oxide, 16.0 wt% of aluminum oxide, 13.0 wt% of kieselguhr, 5.0 wt% of SAPO-34 molecular sieve and 12.0 wt% of nickel.

Example 4

This embodiment differs from embodiment 3 in that: when preparing the desulfurization catalyst precursor, the solution of cobalt nitrate is used for replacing a nickel nitrate hexahydrate impregnated carrier, and the active component cobalt is introduced. The procedure of example 3 was followed except that desulfurization catalyst A4 was finally obtained.

The composition of the desulfurization catalyst A4 is calculated according to the feeding amount: 47.0 wt% of zinc oxide, 7.0 wt% of silver oxide, 16.0 wt% of aluminum oxide, 13.0 wt% of kieselguhr, 5.0 wt% of SAPO-34 molecular sieve and 12.0 wt% of cobalt.

Comparative example 1

This comparative example is used to illustrate the preparation of desulfurization catalysts by prior art preparation methods.

4.55 kg of zinc oxide powder (4.5 kg of dry basis) and 6.9 kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry.

Mixing 1.60 kg of alumina (obtained from Shandong aluminum factory, containing 1.20 kg of dry basis) and 3.0 kg of kaolin (obtained from Qilu petrochemical catalyst factory, containing 2.50 kg of dry basis) under stirring, adding 3.6 kg of deionized water, uniformly mixing, adding 300 ml of 30 wt% hydrochloric acid (obtained from chemical pure, beijing chemical factory), stirring, acidifying for 1 hour, and heating to 80 ℃ for aging for 2 hours. And adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

The desulfurization catalyst B1 was obtained by performing spray-drying of the support mixture and impregnating the active component-introduced nickel by the method of example 1.

The composition of the desulfurization catalyst B1 is calculated according to the feeding amount: 45.0% by weight of zinc oxide, 12.0% by weight of aluminum oxide, 25.0% by weight of kaolin and 18.0% by weight of nickel.

Comparative example 2

5.06 kg of zinc oxide powder (5.0 kg of dry basis) and 7.8 kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry.

2.40 kg of alumina (obtained from Shandong aluminum factory, containing 1.8 kg of dry basis) and 1.85 kg of expanded perlite (obtained from Nanjing division, catalyst, containing 1.80 kg of dry basis) are mixed under stirring, then 4.8 kg of deionized water is added, after uniform mixing, 275 ml of 30 wt% hydrochloric acid (obtained from chemical purity, beijing chemical factory) is added, stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ for aging for 2 hours. And adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

The desulfurization catalyst B2 was obtained by spray-drying and impregnating the support mixture with the active ingredient nickel by the method of example 1.

The composition of the desulfurization catalyst B2 is calculated according to the feeding amount: 50.0% by weight of zinc oxide, 18.0% by weight of aluminum oxide, 18.0% by weight of expanded perlite and 14.0% by weight of nickel.

Comparative example 3

5.76 kg of zinc oxide powder (5.7 kg of dry basis) and 7.8 kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry.

2.13 kg of alumina (obtained from Shandong aluminum factory, containing 1.6 kg of dry basis) and 1.55 kg of kieselguhr (obtained from Nanjing division, catalyst, containing 1.50 kg of dry basis) are mixed under stirring, 4.8 kg of deionized water is added, after mixing uniformly, 275 ml of 30 wt% hydrochloric acid (obtained from chemical purity, obtained from Beijing chemical factory) is added, stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ for aging for 2 hours. And adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

The support mixture was spray-dried and impregnated with the active component nickel by the method of example 1 to obtain a desulfurization catalyst B3.

The composition of the desulfurization catalyst B3 is calculated according to the feeding amount: 57.0% by weight of zinc oxide, 16.0% by weight of aluminum oxide, 15.0% by weight of diatomite and 12.0% by weight of nickel.

Comparative example 4

3.84 kg of zinc oxide powder (3.8 kg of dry basis, obtained from Beijing chemical Co., ltd.), 1.21 kg of silver oxide powder (analytical grade, national chemical reagent Co.) and 7.8 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed slurry of zinc oxide and silver oxide.

2.40 kg of alumina (obtained from Shandong aluminum factory, containing 1.8 kg of dry basis) and 1.85 kg of expanded perlite (obtained from Nanjing division, catalyst, containing 1.80 kg of dry basis) are mixed under stirring, then 4.8 kg of deionized water is added, after uniform mixing, 275 ml of 30 wt% hydrochloric acid (obtained from chemical purity, beijing chemical factory) is added, stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ for aging for 2 hours. And adding zinc oxide and silver oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

The desulfurization catalyst B4 was obtained by spray-drying and impregnating the support mixture with the active ingredient nickel by the method of example 1.

The composition of the desulfurization catalyst B4 is calculated according to the feeding amount: 38.0% of zinc oxide, 12.0% of silver oxide, 18.0% of aluminum oxide, 18.0% of expanded perlite and 14.0% of nickel.

Test example 1

(1) And (5) evaluating the abrasion resistance strength. The desulfurization catalysts A1-A4 and B1-B4 are evaluated by adopting a straight pipe abrasion method, and the evaluation method refers to the method of RIPP 29-90 in the petrochemical analysis method (RIPP) experimental method, and the smaller the numerical value is, the higher the abrasion resistance is. The results are shown in Table 1.

(2) And (5) evaluating desulfurization performance. The desulfurization catalysts A1 to A4 and B1 to B4 were evaluated by using a fixed bed micro-reaction experimental apparatus, and the adsorption reaction raw material was catalytically cracked gasoline and simulated hydrocarbon oil having a sulfur concentration of 1000ppm (composition see Table 4).

Desulfurization reaction evaluation conditions: 16 g of desulfurization adsorbing composition A1 was charged in a fixed bed reactor having an inner diameter of 30mm and a length of 1m, a reaction pressure of 1.38MPa, a hydrogen flow rate of 6.3L/h, a gasoline flow rate of 80mL/h, a reaction temperature of 380℃and a feed rate of adsorption reaction raw materials of 4h by weight space velocity ^-1 Desulfurizing the sulfur-containing hydrocarbon oil.

The desulfurization reaction is carried out by taking catalytic cracking gasoline as raw material: the desulfurization activity is measured by the sulfur content in the gasoline product. The sulfur content in the gasoline product is measured by an off-line chromatographic analysis method by adopting a GC6890-SCD instrument of the Anjeam company. In order to accurately characterize the activity of the desulfurization catalyst A1 in industrial practice, the desulfurization catalyst A1 was subjected to a regeneration treatment after completion of the reaction, the regeneration treatment being carried out under an air atmosphere at 480 ℃. The activity of the desulfurization catalyst A1 is basically stabilized after the desulfurization catalyst A1 is subjected to reaction regeneration for 6 cycles, and the sulfur content in the gasoline product after the stabilization of the desulfurization catalyst A1 represents the activity of the desulfurization catalyst A1, and the result is shown in Table 1. Desulfurization performance evaluation of the desulfurization absorbing compositions using A2 to A4 and B1 to B4 was performed similarly, and the results are shown in Table 1.

Meanwhile, the product gasoline is weighed to calculate the yield. The results are shown in Table 1.

The Motor Octane Number (MON) and Research Octane Number (RON) of the catalytic cracking gasoline as a reaction raw material and the gasoline as a product after the desulfurization catalyst was stabilized were measured by GB/T503-1995 and GB/T5487-1995, respectively, and the results are shown in Table 1.

The breakthrough sulfur capacities for gasoline desulfurization with hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 were calculated and are shown in Table 3. Wherein, the penetration in penetrating sulfur capacity means: the sulfur content of the obtained gasoline breaks through 10 mug/g from the start of gasoline desulfurization. Penetration sulfur capacity refers to: the co-adsorbed sulfur content on the gasoline desulfurization catalyst prior to breakthrough (based on the total weight of the gasoline desulfurization catalyst).

The simulated hydrocarbon oil is used as a raw material for desulfurization reaction: the effect of the desulfurization reaction on the composition in the simulated hydrocarbon oil was evaluated and the results are shown in table 4.

TABLE 1

Note that:

1. the sulfur content of the feed gasoline was 1000ppm, RON was 93.7 and MON was 83.6.

2. Delta MON represents the added value of product MON;

3. delta RON represents the increased value of RON of the product;

4. 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 results of examples 1-4 and Table 1, the desulfurization catalysts A1-A4 provided by the invention contain zinc-silver composite metal oxide, and the sulfur content of gasoline can be well reduced after the hydrocarbon oil desulfurization catalyst is subjected to multiple-cycle desulfurization, and the desulfurization catalyst has better desulfurization activity and activity stability. The desulfurization catalyst has better abrasion resistance strength, so that the desulfurization catalyst has longer service life.

In addition, the desulfurization catalyst can be oxidized and regenerated at 380 ℃ and 480 ℃ at a lower temperature.

Test example 2

The hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 are aged under the following conditions: the catalyst was placed under an atmosphere of 600℃and a water vapor partial pressure of 20kPa for 16 hours.

In fig. 3, no characteristic peaks of 2θ=22.0, 25.54, 48.9 and 59.4 of zinc silicate appear in the XRD spectrum after A1 hydrothermal aging; in fig. 4, the above characteristic peaks of zinc silicate appear in the XRD spectrum after B1 hydrothermal aging. The XRD patterns of B1-B4 were quantitatively analyzed for zinc silicate content by using the crystalline phase content, and the results are shown in Table 2.

The desulfurization performance of A1 to A4 and B1 to B4 after aging was evaluated by the desulfurization reaction evaluation conditions (catalytically cracked gasoline) in test example 1, and the results are shown in Table 2.

The breakthrough sulfur capacities of the aged hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 for gasoline desulfurization were calculated and the results are shown in Table 3.

TABLE 2

Note that: the data in the table on octane number is the amount of change in octane number compared to the feed gasoline. "-" means a decrease in octane number as compared to the feed gasoline.

1. The sulfur content of the feed gasoline was 1000ppm, RON was 93.0 and MON was 82.7.

2. Delta MON represents the added value of product MON;

3. Delta RON represents the increased value of RON of the product;

TABLE 3 Table 3

TABLE 4 Table 4

Note that: n-heptane, 1-heptene, methylcyclohexane, dimethylpentane, toluene (Acros Organics, 99.9%) were all monomeric hydrocarbon model compounds.

As can be seen from the results of Table 2, zinc silicate was not formed in the hydrocarbon oil desulfurization catalysts obtained in examples, but zinc silicate was formed with the silica-containing material in the catalysts of comparative examples 1 to 4 after the aging process, thereby reducing the desulfurization activity of the catalysts.

It can also be seen from the data of the gasoline products in tables 1 and 2 that the method provided by the invention can still obtain high gasoline yield, and the octane number of the gasoline is not greatly changed.

As can be seen from Table 3, the penetrating sulfur capacity of gasoline desulfurization using the gasoline desulfurization catalyst of the present invention is similar to that of the gasoline desulfurization catalyst of the comparative example before aging, and after aging, zinc-silver complex metal oxide is higher in penetrating sulfur capacity, and zinc silicate is not formed in the hydrocarbon oil desulfurization catalyst obtained in the examples, whereas the catalyst of comparative examples 1 to 4 has zinc oxide penetrating sulfur capacity lower than that of zinc-silver complex metal oxide, and zinc oxide forms zinc silicate with the silicon oxide-containing material, so that the penetrating sulfur capacity of the catalyst is significantly reduced, and thus desulfurization activity is also significantly reduced.

As can be seen from the data of the results in table 4, for the simulated hydrocarbon oil, the hydrocarbon oil desulfurization catalysts provided in examples 1 to 4 were subjected to desulfurization reaction to obtain product oils in which the content of naphthenes (methylcyclohexane) and olefins (1-heptenes) was reduced, and the content of aromatization products such as toluene was increased and the content of isomerization products (dimethylpentanes) was increased, as compared with the composition of the simulated hydrocarbon oil feedstock. It can be explained that the use of the hydrocarbon oil desulfurization catalyst of the present invention can affect the composition of the product oil obtained by the desulfurization reaction, and thus the octane number reduction in table 2 is less. The hydrocarbon oil desulfurization catalyst provided by the invention enhances the dehydrogenation aromatization reaction of hydrocarbon oil while carrying out hydrocarbon oil desulfurization, and can effectively compensate octane number loss caused by olefin hydrogenation in the desulfurization process.

The hydrocarbon oil desulfurization catalyst provided by the invention contains specific components, sulfide in hydrocarbon oil can be effectively removed by using the catalyst, simultaneously, isomerization and dehydroaromatization reactions of the hydrocarbon oil in a desulfurization process are promoted, components for making up octane number are increased, and the generated aromatic hydrocarbon does not exceed the limit of national standards.

Claims

1. A desulfurization catalyst comprising, based on the total weight of the desulfurization catalyst, 5-35 wt% of a silica source, 5-35 wt% of alumina, 30-70 wt% of zinc oxide, 2-15 wt% of silver oxide, 1-20 wt% of a phosphorus-aluminum molecular sieve, and 5-30 wt% of an active metal; and at least part of the silver oxide forms a general formula Ag with the zinc oxide _x Zn _1-x The zinc-silver composite metal oxide represented by O exists in a form, wherein x is more than 0 and less than or equal to 0.24, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese, and the Ag _x Zn _1-x The sulfur capacity of the zinc-silver composite metal oxide represented by O is more than or equal to 30 percent;

wherein the desulfurization catalyst satisfies the following relationship: a is that ₁₀₀ -B ₁₀₀ =0.31° to 0.5 °, a ₁₀₀ And B ₁₀₀ The 2 theta value of the diffraction peak of the (100) plane of ZnO is represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions;

wherein the desulfurization catalyst satisfies the following relationship: a is that ₀₀₂ -B ₀₀₂ =0.32° to 0.5 °; a is that ₀₀₂ And B ₀₀₂ The 2 theta value of the diffraction peak of the (002) plane of ZnO is represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions, respectively;

wherein the desulfurization catalyst satisfies the following relationship: a is that ₁₀₁ -B ₁₀₁ =0.31° to 0.5 °; a is that ₁₀₁ And B ₁₀₁ The 2 theta value of the diffraction peak of the (101) plane of ZnO is represented in the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions, respectively.

2. The desulfurization catalyst of claim 1, wherein the desulfurization catalyst comprises 12-20 wt.% silica source, 10-20 wt.% alumina, 35-50 wt.% zinc oxide, 5-12 wt.% silver oxide, 2-10 wt.% aluminophosphate molecular sieve, and 10-20 wt.% active metal, based on the total weight of the desulfurization catalyst.

3. The desulfurization catalyst according to claim 1 or 2, wherein the active metal is nickel.

4. The desulfurization catalyst of claim 1, wherein the silica source is silica or a natural ore having a silica content of greater than 45 wt%.

5. The desulfurization catalyst of claim 1, wherein the phosphoaluminous molecular sieve is at least one of SAPO-11, SAPO-31, SAPO-34, and SAPO-20.

6. A process for preparing the desulfurization catalyst as claimed in any one of claims 1 to 5, which comprises:

(1) Carrying out precipitation reaction on a mixed solution obtained by mixing a silver-containing compound, a zinc-containing compound and a precipitant, and filtering, drying and roasting a mixture obtained by the precipitation reaction to obtain a precipitation product;

(2) Contacting a silica source, an alumina source, a phosphorus-aluminum molecular sieve, water, and an acid solution to form a slurry, and mixing the precipitated product obtained in step (1) with the slurry to form a carrier mixture; forming, drying and roasting the carrier mixture to form a carrier;

(3) Introducing a compound containing active metal to the carrier obtained in the step (2), and drying and roasting to obtain a desulfurization catalyst precursor; the active metal is at least one of cobalt, nickel, iron and manganese;

(4) And (3) reducing the desulfurization catalyst precursor obtained in the step (3) in a hydrogen-containing atmosphere to obtain the desulfurization catalyst.

7. The production process according to claim 6, wherein the silver-containing compound and the zinc-containing compound are added in such an amount that the content of silver oxide is 2 to 15% by weight and the content of zinc oxide is 30 to 70% by weight based on the total weight of the desulfurization catalyst in the resulting desulfurization catalyst in step (1).

8. The production method according to claim 6 or 7, wherein the silver-containing compound is silver nitrate and/or silver acetate.

9. The production method according to claim 6 or 7, wherein the zinc-containing compound is at least one of zinc acetate, zinc chloride and zinc nitrate.

10. The process according to claim 6, wherein the precipitant used in the precipitation reaction in step (1) is urea and/or ammonia.

11. The process according to claim 6, wherein the pH of the mixture in step (1) is 9 to 13.

12. The production method according to claim 6, wherein the drying conditions in step (1) include: drying at 100-200deg.C for 0.5-3 hr; the roasting conditions include: the roasting temperature is 400-700 ℃, and the roasting time is 0.5-3h.

13. The production method according to claim 6, wherein the silica source, the alumina source and the active metal-containing compound are added in amounts such that the resulting desulfurization catalyst has a silica source content of 5 to 35 wt%, an alumina content of 5 to 35 wt%, a phosphorus-aluminum molecular sieve content of 1 to 20 wt% and an active metal content of 5 to 30 wt%, based on the total weight of the desulfurization catalyst.

14. The production method according to claim 6, wherein the alumina source is a substance capable of being converted into alumina under the firing condition of step (2).

15. The method of claim 14, wherein the alumina source is hydrated alumina and/or an alumina sol; the hydrated alumina is at least one of boehmite, pseudo-boehmite, alumina trihydrate and amorphous aluminum hydroxide.

16. The production method according to claim 6, wherein the active metal-containing compound in step (3) is at least one of an acetate, a carbonate, a nitrate, a sulfate, a thiocyanate, and an oxide of the active metal.

17. A desulfurization catalyst obtained by the production process according to any one of claims 6 to 16.

18. A process for desulfurizing a hydrocarbon oil, the process comprising: contacting a sulfur-containing hydrocarbon oil with a desulfurization catalyst, wherein the desulfurization catalyst is a desulfurization catalyst as claimed in any one of claims 1-5 and 17.