CN111111754A

CN111111754A - Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN111111754A
Application number: CN201811285638.9A
Authority: CN
Inventors: 林伟; 宋烨; 王磊; 田辉平; 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: 2020-05-08
Anticipated expiration: 2038-10-31
Also published as: CN111111754B

Abstract

The invention discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method, wherein the desulfurization catalyst contains 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 molecular sieve with MFI structure and 5-30 wt% of active metal; and at least part of the silver oxide forms a general formula Ag with the zinc oxide_xZn_1‑xO, wherein x satisfies 0 < x ≦ 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 is_xZn_1‑xThe 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 adopting 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 exhaust gas of the automobile engine inhibits and irreversibly poisons the noble metal in the catalytic converter, thereby reducing the purification effect of the catalytic converter on the automobile exhaust gas. Unpurified automobile exhaust contains unburned non-methane hydrocarbons, nitrogen oxides and carbon monoxide, which are susceptible to photochemical smog formation under photocatalysis.

Most of sulfur in gasoline products in China comes from blending components of hot processed gasoline (such as catalytic cracking gasoline), so that the reduction of the sulfur content in the hot processed gasoline is beneficial to reducing the sulfur content of the gasoline products. The sulfur content in gasoline products limited in the current gasoline product standard GB17930-2011 motor gasoline in China must be reduced to 50 mu g/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 simultaneously, the octane number (including ROM and MON) of the gasoline is prevented from being reduced due to the change of the olefin content. The influence on the olefin content is generally due to the simultaneous hydrogenation reaction initiated by the removal of thiophenic compounds (including thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, and alkyldibenzothiophene). In addition, it is desirable to avoid desulfurization conditions that result in the loss of aromatics from catalytically cracked gasoline that may be saturated. It is therefore desirable to achieve desulfurization while maintaining the combustion properties of the gasoline product.

At present, two methods of hydrofining and adsorption desulfurization are mainly used as deep desulfurization methods of oil products, wherein the cost of hydrofining is high. S Zorb adsorption desulfurization belongs to adsorption desulfurization technology, which can realize the adsorption and removal of sulfide in hydrocarbon oil under certain temperature, pressure and hydrogen. 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.

CN104511282A discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method, wherein the desulfurization catalyst comprises 5-35 wt% of silicon oxide source, 5-35 wt% of alumina and 30-70 wt% of hydrocarbon oilZinc oxide, 2-15 wt% lead oxide and 5-30 wt% active metal; and at least part of the lead oxide is formed with zinc oxide and Pb_xZn_1-xO, x satisfies 0<x is less than or equal to 0.12; the active metal is at least one of cobalt, nickel, iron and manganese.

Although the catalysts disclosed in the above patents have a certain desulfurization performance, when processing raw gasoline with high sulfur content (average sulfur content is greater than 800 μ g/g) and large fluctuation, the sulfur content of the gasoline exceeds the standard and needs to be remitted.

Disclosure of Invention

The invention aims to overcome the problems of poor desulfurization activity and stability of the catalyst in the prior art, and provides a desulfurization catalyst with high desulfurization activity, low octane number loss, high stability, 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 silicon oxide 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 molecular sieve having an MFI structure, 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_xZn_1-xO, wherein x satisfies 0 < x ≦ 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 is_xZn_1-xThe 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 precipitator, and filtering, drying and roasting a mixture obtained by the precipitation reaction to obtain a precipitation product;

(2) contacting a silicon oxide source, an aluminum oxide source, a molecular sieve with an MFI structure, water and an acid solution to form a slurry, and mixing the precipitation product obtained in step (1) with the slurry to form a carrier mixture; then 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), drying and roasting to obtain a desulfurization catalyst precursor; the active metal is at least one of cobalt, nickel, iron and manganese;

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

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

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: and (2) carrying out contact reaction on the sulfur-containing hydrocarbon oil and a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst.

Through the technical scheme, at least part of silver oxide in the desulfurization catalyst provided by the invention is formed by the general formula Ag with zinc oxide_xZn_1-xThe zinc-silver composite metal oxide represented by O exists in a form, is used as a sulfur absorption component, stabilizes the crystal structure of ZnO, blocks the direct reaction of ZnO and a silicon source, and can still absorb and transfer hydrogen sulfide, 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 abrasion resistance, and the service life of the desulfurization catalyst can be prolonged. The desulfurization catalyst can absorb sulfur at lower temperature for oxidation regeneration. The sulfur content in the gasoline product treated by the desulfurization catalyst prepared by the invention 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, 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 shows the precipitation products C1-C3, ZnO and Ag₂XRD spectrum of O; wherein

2 theta values B representing diffraction peaks of (100), (002) and (101) planes of ZnO₁₀₀、B₀₀₂And B₁₀₁31.55 degrees, 34.21 degrees and 36.04 degrees respectively,

2 theta values A representing diffraction peaks of (100), (002) and (101) planes of ZnO in C1₁₀₀、A₀₀₂And A₁₀₁31.86 degrees, 34.53 degrees and 36.35 degrees respectively,

2 theta values A representing diffraction peaks of (100), (002) and (101) planes of ZnO in C2₁₀₀、A₀₀₂And A₁₀₁31.92 deg., 34.56 deg. and 36.39 deg. respectively,

2 theta values A representing diffraction peaks of (100), (002) and (101) planes of ZnO in C3₁₀₀、A₀₀₂And A₁₀₁31.88 °, 34.55 ° and 36.37 °, respectively;

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

FIG. 3 is an XRD spectrum of a 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 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 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 molecular sieve with MFI structure and 5-30 wt% of active metal, wherein the total weight of the desulfurization catalyst is taken as a reference; and at least part of the silver oxide forms a general formula Ag with the zinc oxide_xZn_1-xO, wherein x satisfies 0 < x ≦ 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 is_xZn_1-xZinc-silver complexes represented by OThe sulfur capacity of the metal oxide 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 keep 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 above general formula.

The desulfurization catalyst may be a catalyst containing silver oxide and zinc oxide all of which form a zinc-silver composite metal oxide represented by the above general formula; in addition to the zinc-silver composite metal oxide 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, for example, the entire silver oxide and the majority of zinc oxide may form a zinc-silver composite metal oxide. Preferably, the silver oxide and the zinc oxide contained in the desulfurization catalyst all form a zinc-silver composite metal oxide represented by the above general formula.

According to the present invention, after the silver oxide and the zinc oxide form the zinc-silver composite metal oxide, the lattice structure of the zinc oxide is not destroyed, but since the silver ions substitute for the zinc ions to enter the lattice, the diffraction angle of the characteristic peak characterizing ZnO in the XRD spectrogram of the desulfurization catalyst is changed, and thus 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 spectrum of the desulfurization catalyst a1 and the XRD spectrum of ZnO obtained under the same XRD measurement conditions as shown in fig. 2. In fig. 2, the individual characteristic peaks of silver oxide and zinc oxide do not appear, but characteristic peaks characterizing cubic crystals of zinc oxide with shifted peak positions appear, indicating that silver oxide and zinc oxide all form a zinc-silver composite metal oxide. Preferably, the desulfurization catalyst satisfies the following relationship: a. the₁₀₀-B₁₀₀0.3 ° to 0.5 °, a₁₀₀And B₁₀₀Respectively shows the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions, and represents the (100) plane of ZnO2 θ value of the diffraction peak of (2).

According to the present invention, preferably, the desulfurization catalyst satisfies the following relational expression: a. the₀₀₂-B₀₀₂0.3 ° to 0.5 °; a. the₀₀₂And B₀₀₂The XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions are respectively expressed as 2 θ values representing diffraction peaks of (002) plane of ZnO.

According to the present invention, preferably, the desulfurization catalyst satisfies the following relational expression: a. the₁₀₁-B₁₀₁0.3 ° to 0.5 °; a. the₁₀₁And B₁₀₁The XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions are respectively expressed as 2 θ values representing diffraction peaks of (101) plane of ZnO.

According to the present invention, it can be confirmed by the above XRD measurement that the desulfurization catalyst contains a zinc-silver composite metal oxide formed of silver oxide and zinc oxide, the molar ratio x of silver to zinc in the zinc-silver composite metal oxide can be measured by elemental analysis such as fluorescence spectrum analysis, and it can be confirmed that the zinc-silver composite metal oxide can be represented by the general formula Ag_xZn_1-xO, 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 silicon oxide source, 10 to 20% by weight of alumina, 35 to 50% by weight of zinc oxide, 5 to 12% by weight of silver oxide, 3 to 10% by weight of a molecular sieve having an MFI structure, 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 sulphur in the oxidised state to hydrogen sulphide, preferably the active metal is nickel.

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

Preferably, the alumina may be at least one of gamma alumina, η alumina, theta alumina, and chi alumina.

According to the invention, a typical representation of said molecular sieve with MFI structure is the ZSM-5 zeolite developed by Mobil corporation, USA, which is characterized by having

The ten-membered ring structure of (a). Preferably, the molecular sieve with MFI structure can be a ZSM-5 molecular sieve and/or a ZSM-5 molecular sieve modified with phosphorus or a transition metal; preferably, the molecular sieve having the MFI structure is at least one of ZSM-5, ZRP-1 and ZSP-3. SiO of the molecular sieve with MFI structure₂：Al₂O₃In a molar ratio of 15 to 100: 1; preferably, the SiO of the molecular sieve with MFI structure₂：Al₂O₃In a molar ratio of 20-40: 1.

the desulfurization catalyst formed by adopting the components has better activity and stable performance, and can effectively reduce the octane number loss of oil products.

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 precipitator, and filtering, drying and roasting a mixture obtained by the precipitation reaction to obtain a precipitation product; (2) contacting a silicon oxide source, an aluminum oxide source, a molecular sieve with an MFI structure, water and an acid solution to form a slurry, and mixing the precipitation product obtained in step (1) with the slurry to form a carrier mixture; then 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), drying and roasting to obtain a desulfurization catalyst precursor; the active metal is at least one of cobalt, nickel, iron and manganese; (4) and (4) reducing the desulfurization catalyst precursor obtained in the step (3) in a hydrogen-containing atmosphere to obtain the desulfurization catalyst.

In the preparation method of the desulfurization catalyst provided by the present invention, the zinc-silver composite metal oxide may be formed in step (1). By adopting the method, the sulfur capacity of the composite metal oxide formed by the silver oxide and the zinc oxide is higher, the desulfurization activity of the desulfurization catalyst is effectively improved, and the octane value loss of oil products is reduced.

According to the present invention, the amount of the silver-containing compound and the zinc-containing compound added in step (1) can be selected from a wide range as long as the general formula Ag can be formed_xZn_1-xA zinc-silver composite metal oxide represented by O. Preferably, the silver-containing compound and the zinc-containing compound are added in step (1) in such amounts that the resulting desulfurization catalyst contains silver oxide in an amount of 2 to 15 wt% and zinc oxide in an amount 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 such amounts that the resulting desulfurization catalyst contains silver oxide in an amount of 5 to 12 wt% and zinc oxide in an amount of 35 to 50 wt%, based on the total weight of the desulfurization catalyst.

According to the present invention, elemental analysis and XRD measurement are performed on the precipitation product obtained in step (1), and it can be judged from the results of the elemental analysis and XRD measurement that the precipitation product contains a zinc-silver composite metal oxide. Specifically, the precipitated product was first subjected to elemental analysis to determine that it contained silver and zinc. Then, the precipitated product was analyzed by XRD measurement, and as shown in fig. 1, it was concluded that a zinc-silver complex metal oxide was formed based on the characteristic peaks of the hexagonal system representing ZnO appearing in the XRD spectrum, but not the characteristic peaks of silver oxide. Because the zinc-silver composite metal oxide is formed by substituting silver for zinc into the lattice structure of zinc oxide, an independent silver oxide crystal structure is not available, so that the structural characteristics of ZnO crystals are still available in the XRD spectrogram of the zinc-silver composite metal oxide, but 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 technical oxide is shifted. Therefore, the XRD spectrum of the precipitated product can determine that the precipitated product contains the zinc-silver composite metal oxide.

According to the invention, the precipitation product preferably satisfies the following relation: a. the₁₀₀-B₁₀₀0.3 ° to 0.5 °, a₁₀₀And B₁₀₀Respectively show the 2 theta values of diffraction peaks of (100) planes of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

According to the invention, the precipitation product preferably satisfies the following relation: a. the₀₀₂-B₀₀₂0.3 ° to 0.5 °; a. the₀₀₂And B₀₀₂Respectively show the 2 theta values of diffraction peaks of (002) plane of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

According to the invention, the precipitation product preferably satisfies the following relation: a. the₁₀₁-B₁₀₁0.3 ° to 0.5 °; a. the₁₀₁And B₁₀₁Respectively show the 2 theta values of diffraction peaks of (101) plane of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

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

According to the present invention, the molar ratio of silver and 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 formula_xZn_1-xA zinc-silver composite metal oxide represented by O, wherein x satisfies 0 < x.ltoreq.0.24, and x represents an atomic molar ratio. In the formed zinc-silver composite metal oxide represented by the general formula, silver and zinc are matched according to the atomic mole ratio, so that ZnO crystals can have better crystal structure stability in high-temperature environments in the processes of sulfur absorption and oxidation regeneration, and the desulfurization catalyst containing the zinc-silver composite metal oxide can be further ensured to have better desulfurization activity.

According to the invention, the silver-containing compound in step (1) can be various water-soluble silver-containing compounds, preferably 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 precipitating agent used in the precipitation reaction in step (1) may be urea and/or aqueous ammonia. The precipitant can make the precipitation reaction more complete and is favorable for the generation of the zinc-silver composite metal oxide.

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

According to the present invention, the drying and firing may serve to convert the mixture coprecipitated in step (1) into a zinc-silver composite metal oxide. In order to obtain a zinc-silver composite metal oxide that can be represented by the above general formula, it is preferable that the drying conditions in step (1) include: the drying temperature is 100-; the roasting conditions comprise: the roasting temperature is 400-700 ℃, and the roasting time is 0.5-3 h.

According to the step (2) in the preparation method of the desulfurization catalyst, a silicon oxide source, an aluminum oxide source, a molecular sieve with an MFI structure and the precipitation product obtained in the step (1) are used for preparing the carrier. Preferably, the silicon oxide source, the molecular sieve with MFI structure and the aluminum oxide source are added in such amounts that the content of the silicon oxide source, the content of the aluminum oxide and the content of the molecular sieve with MFI structure in the obtained desulfurization catalyst are 5-35 wt%, 5-35 wt% and 1-20 wt%, respectively, based on the total weight of the desulfurization catalyst; preferably, the silicon oxide source, the molecular sieve with MFI structure and the aluminum oxide source are added in amounts such that the resulting desulfurization catalyst contains 12 to 20 wt% of the silicon oxide source, 10 to 20 wt% of the aluminum oxide source and 3 to 10 wt% of the molecular sieve with MFI structure, based on the total weight of the desulfurization catalyst.

According to the present invention, preferably, the alumina source may be a substance that can be converted into alumina under the condition of the calcination in step (2). Preferably, the alumina source is hydrated alumina and/or an aluminum 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 a binding effect between the components of the desulfurization catalyst. Preferably, the silica source is silica or a natural ore having a silica content greater than 45% by weight. Preferably, the silica source may be at least one of pillared clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica and silica gel.

It should be noted that, although the above-mentioned silica source may contain alumina, 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 only includes 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 silica source. Although the molecular sieve having an MFI structure contains alumina, the amount of alumina contained in the molecular sieve having an MFI structure is still counted as the amount of the molecular sieve having an MFI structure not included in the alumina. Namely, the content of each component in the desulfurization catalyst prepared by the method provided by the invention is calculated according to the feeding amount.

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

In the present invention, the amount of water added in step (2) may not be particularly limited as long as the slurry described in step (2) can be obtained. For example, water is added in an amount 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 mixture, a paste mixture, a dough, or a slurry. By the shaping, the support mixture can be shaped into extrudates, tablets, pellets, spheres or microspheroidal particles. For example, where the support mixture is a dough or paste mixture, the support mixture may be shaped (preferably extruded) 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 are then dried and calcined. If the carrier mixture is in the form of a wet mixture, the mixture may be thickened, dried and shaped. More preferably, the carrier mixture is in the form of a slurry that is spray dried to form microspheres having a particle size of 20 to 200 microns for shaping purposes. To facilitate spray drying, the slurry may have a solids content of from 10 to 50% by weight, preferably from 20 to 50% by weight, before drying.

In the present invention, the drying method and conditions of the carrier mixture 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, in the step (2), the drying temperature may be between room temperature and 400 ℃, preferably 100-350 ℃; the drying time is at least 0.5 hour, preferably 0.5 to 60 hours.

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

In step (3) of the present invention, the amount of the active metal-containing compound added is such that the content of the active metal in the obtained desulfurization catalyst is 5 to 30 wt% based on the total weight of the desulfurization catalyst; preferably 10-20 wt%. Wherein the active metal-containing substance may be a substance that is converted into an oxide of the active metal under the calcination conditions in 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 the 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 achieved by various methods. For example, impregnation or precipitation methods known to those skilled in the art may be used. The impregnation method is to impregnate the carrier with a solution or suspension of an active metal-containing compound; the precipitation method is to mix a solution or suspension of an active metal-containing compound with the carrier, and then to precipitate the active metal on the carrier by adding aqueous ammonia. The impregnation method is preferred.

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

The reduction of the desulfurization catalyst precursor in the step (4) of the present invention may be carried out immediately after the desulfurization catalyst precursor is produced, or may be carried out 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 a reduced state, resulting in the desulfurization catalyst of the present invention. Preferably, the conditions for reducing the desulfurization catalyst precursor 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; the temperature of the reduction is preferably 400-500 ℃ and the time of the reduction is preferably 1-3 hours.

The invention also provides the 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 in detail herein.

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: and (2) carrying out contact reaction on sulfur-containing hydrocarbon oil and a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst 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 in a hydrogen atmosphere under the reaction conditions including: the reaction temperature can be 350-500 ℃, preferably 360-430 ℃; the pressure of the reaction can be 0.5-4 MPa; preferably 1-2 MPa.

According to the present invention, the method for desulfurizing a hydrocarbon oil may further comprise: and regenerating the reacted desulfurization catalyst after the reaction. The conditions for regeneration include: regeneration is carried out in an oxygen atmosphere (the oxygen content may be 10-80 vol%); the regeneration temperature is 450-600 ℃, preferably 480-520 ℃; the regeneration pressure 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 reduction conditions include: the reduction is carried out under a hydrogen atmosphere (the hydrogen content may be 30 to 60% by volume); the temperature of the reduction can be 350-500 ℃, preferably 400-450 ℃; the pressure of the reduction may be 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 ℃ and 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 oil, kerosene, straight-run diesel, catalytic cracking diesel, hydrotreated diesel, and the like, and combinations thereof.

As used herein, the term "sulfur" is intended to represent 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 (CS)₂) Thiol or other thiophenic compounds and the like and combinations thereof including, inter alia, thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, and alkyldibenzothiophene, as well as higher molecular weight thiophenic compounds commonly found in diesel fuel.

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

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

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

Polycrystalline X-ray diffraction (XRD) the structure of the desulfurization adsorbent composition was measured using an X-ray diffractometer (Siemens D5005 type), Cu target, K α radiation, solid detector, tube voltage 40kV, and tube current 40 mA.

Example 1

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

(1) A precipitated product was prepared. 10.9 kg of zinc acetate dihydrate powder (from Beijing chemical plant, analytical grade), 0.72 kg of anhydrous silver acetate (national chemical reagent Co., analytical grade) and 18 kg of deionized water were mixed, stirred for 30 minutes and completely dissolved. Adding 1.8 kg of ammonia water to obtain a precipitate, filtering, drying at 150 ℃ for 2 hours, and then roasting at 500 ℃ for 1 hour to obtain a precipitate C1.

The precipitated product C1 was subjected to fluorescence analysis and XRD measurement. No Ag is present in the XRD spectrum (see figure 1)₂Diffraction peak of O and standard diffraction peak of ZnO appears to be shifted to right, wherein A₁₀₀-B₁₀₀＝0.31°，A₀₀₂-B₀₀₂＝0.32°，A₁₀₁-B₁₀₁0.31 °, indicating Ag in precipitated product C1₂O and ZnO form a zinc-silver composite metal oxide with a chemical composition of Ag_0.087Zn_0.913O。

(2) And (3) preparing a carrier. 1.60 kg of alumina (from Shandong aluminum plant, containing 1.20 kg of dry basis) and 3.0 kg of kaolin (containing 2.50 kg of dry basis) (from Qilu petrochemical catalyst plant) were mixed with 1.0 kg of ZSP-3 molecular sieve (from catalyst Nanjing division, containing 0.7 kg of dry basis) under stirring, 3.6 kg of deionized water was added and mixed uniformly, 300 ml of 30 wt% hydrochloric acid (chemical purity, from Beijing chemical plant) was added, stirred and acidified for 1 hour, and then heated to 80 ℃ for aging for 2 hours. The precipitated product C1 was added thereto and mixed, followed by stirring for 1 hour to obtain a carrier mixture.

The carrier mixture adopts 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 first dried at 150 ℃ for 1 hour and then calcined at 480 ℃ for 1 hour to obtain the catalyst carrier.

(3) A desulfurization catalyst precursor is prepared. 6.4 kg of the catalyst carrier obtained in the step (2) was spray-impregnated with 7.0 kg of nickel nitrate hexahydrate and 1.10 kg of a deionized water solution in two passes, and the resulting mixture was dried at 150 ℃ for 4 hours and then calcined at 480 ℃ for 1 hour to obtain a desulfurization catalyst precursor.

(4) And preparing the 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 desulfurization catalyst A1.

The composition of the desulfurization catalyst A1 is calculated according to the feeding amount as follows: 40.0 percent of zinc oxide, 5.0 percent of silver oxide, 12.0 percent of alumina, 18.0 percent of kaolin, 7 percent of ZSP-3 molecular sieve and 18.0 percent of nickel.

The XRD measurement result of the desulfurization catalyst a1 is shown in fig. 2. Corresponding to the XRD spectrum of the precipitated product C1, the 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, which indicates that the structure of the zinc-silver composite metal oxide exists in the desulfurization catalyst prepared by adopting the zinc-silver composite metal oxide as the raw material.

Example 2

(1) A precipitated product was prepared. Mixing 14.0 kg of zinc nitrate hexahydrate (product of Beijing chemical plant, analytically pure), 1.76 kg of silver nitrate powder (national chemical reagent company, analytically pure) and 18 kg of deionized water, stirring for 30 minutes, adding 2.0 kg of urea, heating to 80 ℃, treating for 2 hours to obtain white precipitate, filtering, drying at 150 ℃ for 2 hours, and roasting at 500 ℃ for 1 hour to obtain a precipitate product C2.

The precipitated product C2 was subjected to XRD measurement. No Ag is present in the XRD spectrum (see figure 1)₂Diffraction peak of O and standard diffraction peak of ZnO appears to be shifted to right, wherein A₁₀₀-B₁₀₀＝0.37°，A₀₀₂-B₀₀₂＝0.35°，A₁₀₁-B₁₀₁0.35 °, indicating Ag in precipitated product C2₂O and ZnO form a zinc-silver composite metal oxide with a chemical composition of Ag_0.22Zn_0.78O。

(2) And (3) preparing a carrier. 2.40 kg of alumina (produced by Shandong aluminum plant, containing 1.8 kg of dry base), 1.54 kg of expanded perlite (catalyst Nanjing division, containing 1.80 kg of dry base) and 0.40 kg of ZRP-1 molecular sieve (catalyst Nanjing division, containing 0.3 kg of dry base) are mixed under stirring, 4.8 kg of deionized water is added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (chemical purity, produced by Beijing chemical plant) is added, stirred and acidified for 1 hour, and then heated to 80 ℃ for aging for 2 hours. The precipitated product C2 was added thereto and mixed, followed by stirring for 1 hour to obtain a carrier mixture.

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

(3) A desulfurization catalyst precursor is prepared. A desulfurization catalyst precursor was obtained by the method of step (3) of reference example 1.

(4) And preparing the desulfurization catalyst. A desulfurization catalyst A2 was obtained by the method described in step (4) of example 1.

The composition of the desulfurization catalyst A2 is calculated according to the feeding amount as follows: 38.0 percent of zinc oxide, 12.0 percent of silver oxide, 18.0 percent of alumina, 15.0 percent of expanded perlite, 3 percent of ZRP-1 molecular sieve and 14.0 percent of nickel.

Example 3

(1) A precipitated product was prepared. 13.6 kg of zinc acetate dihydrate powder (from Beijing chemical plant, analytical grade), 1.03 kg of silver nitrate (national chemical reagent Co., analytical grade) and 20 kg of deionized water were mixed, stirred for 30 minutes and completely dissolved. White precipitate obtained after 2.0 kg of urea was added and treated by heating to 80 ℃ for 2 hours. After filtration, the product is dried for 2 hours at 150 ℃ and then roasted for 1 hour at 500 ℃ to obtain a precipitated product C3.

The precipitated product C3 was subjected to XRD measurement. No Ag is present in the XRD spectrum (see figure 1)₂Diffraction peak of O and standard diffraction peak of ZnO appears to be shifted to right, wherein A₁₀₀-B₁₀₀＝0.33°，A₀₀₂-B₀₀₂＝0.34°，A₁₀₁-B₁₀₁0.33 °, indicates Ag in precipitated product C3₂O and ZnO form a zinc-silver composite metal oxide with a chemical composition ofAg_0.10Zn_0.90O。

(2) And (3) preparing a carrier. 2.13 kg of alumina (from Shandong aluminum plant, containing 1.6 kg of dry base) and 1.34 kg of diatomaceous earth (from catalyst Nanjing division, containing 1.3 kg of dry base) were mixed under stirring, 4.8 kg of deionized water was added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (chemical purity, from Beijing chemical plant) was added, stirred and acidified for 1 hour, and then heated to 80 ℃ for aging for 2 hours. The precipitated product C3 was added thereto and mixed, followed by stirring for 1 hour to obtain a carrier mixture.

(4) And preparing the desulfurization catalyst. A desulfurization catalyst A3 was obtained by the method described in step (4) of example 1.

The composition of the desulfurization catalyst A3 is calculated according to the feeding amount as follows: 47.0 percent of zinc oxide, 7.0 percent of silver oxide, 16.0 percent of alumina, 13.0 percent of diatomite, 5.0 percent of ZRP-1 molecular sieve and 12.0 percent of nickel.

Example 4

This example is different from example 3 in that: when preparing the desulfurization catalyst precursor, cobalt nitrate solution is used to replace nickel nitrate hexahydrate to impregnate the carrier, and active component cobalt is introduced. The rest was the same as in example 3, and desulfurization catalyst A4 was finally obtained.

The composition of the desulfurization catalyst A4 is calculated according to the feeding amount as follows: 47.0 percent of zinc oxide, 7.0 percent of silver oxide, 16.0 percent of alumina, 13.0 percent of diatomite, 5.0 percent of ZRP-1 molecular sieve and 12.0 percent of cobalt.

Comparative example 1

This comparative example illustrates the preparation of a desulfurization catalyst by a prior art preparation method.

4.55 kg of zinc oxide powder (from Beijing chemical plant, containing 4.5 kg of dry matter) and 6.9 kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry.

1.60 kg of alumina (from Shandong aluminum plant, containing 1.20 kg of dry basis) and 3.0 kg of kaolin (containing 2.50 kg of dry basis) (from Qilu petrochemical catalyst plant) were mixed under stirring, then 3.6 kg of deionized water was added and mixed uniformly, 300 ml of 30 wt% hydrochloric acid (chemical purity, from Beijing chemical plant) was added and stirred for acidification for 1 hour, and then the mixture was heated to 80 ℃ and aged for 2 hours. Then adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

Spray drying and impregnation of the carrier mixture with the active component nickel introduced thereto were carried out in accordance with the procedure of example 1 to obtain desulfurization catalyst B1.

The composition of the desulfurization catalyst B1 is calculated according to the feeding amount as follows: 45.0 percent of zinc oxide, 12.0 percent of alumina, 25.0 percent of kaolin and 18.0 percent of nickel.

Comparative example 2

5.06 kg of zinc oxide powder (product of Beijing chemical plant, containing 5.0 kg of dry base) and 7.8 kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry.

2.40 kg of alumina (produced by Shandong aluminum plant and containing 1.8 kg of dry base) and 1.85 kg of expanded perlite (produced by catalyst Nanjing division and containing 1.80 kg of dry base) are mixed under stirring, 4.8 kg of deionized water is added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (chemical purity, produced by Beijing chemical plant) is added, stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ and aged for 2 hours. Then adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

Spray drying and impregnation of the carrier mixture with the active component nickel introduced thereto were carried out in accordance with the procedure of example 1 to obtain desulfurization catalyst B2.

The composition of the desulfurization catalyst B2 is calculated according to the feeding amount as follows: 50.0 percent of zinc oxide, 18.0 percent of alumina, 18.0 percent of expanded perlite and 14.0 percent of nickel.

Comparative example 3

5.76 kg of zinc oxide powder (from Beijing chemical plant, containing 5.7 kg of dry matter) and 7.8 kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry.

2.13 kg of alumina (from Shandong aluminum plant, containing 1.6 kg of dry base) and 1.55 kg of diatomaceous earth (from catalyst Nanjing division, containing 1.50 kg of dry base) were mixed under stirring, 4.8 kg of deionized water was added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (chemical purity, from Beijing chemical plant) was added, stirred and acidified for 1 hour, and then heated to 80 ℃ for aging for 2 hours. Then adding zinc oxide slurry, mixing and stirring for 1 hour to obtain a carrier mixture.

Spray drying and impregnation of the carrier mixture with the active component nickel introduced thereto were carried out in accordance with the procedure of example 1 to obtain desulfurization catalyst B3.

The composition of the desulfurization catalyst B3 is calculated according to the feeding amount as follows: 57.0% by weight of zinc oxide, 16.0% by weight of alumina, 15.0% by weight of diatomaceous earth, and 12.0% by weight of nickel.

Comparative example 4

3.84 kg of zinc oxide powder (from Beijing chemical plant, containing 3.8 kg of dry basis), 1.21 kg of silver oxide powder (national chemical reagent company, analytical purity) 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 (produced by Shandong aluminum plant and containing 1.8 kg of dry base) and 1.85 kg of expanded perlite (produced by catalyst Nanjing division and containing 1.80 kg of dry base) are mixed under stirring, 4.8 kg of deionized water is added and mixed uniformly, 275 ml of 30 wt% hydrochloric acid (chemical purity, produced by Beijing chemical plant) is added, stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ and aged for 2 hours. Then adding zinc oxide and silver paste oxide, mixing and stirring for 1 hour to obtain a carrier mixture.

Spray drying and impregnation of the carrier mixture with the active component nickel introduced thereto were carried out in accordance with the procedure of example 1 to obtain desulfurization catalyst B4.

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

Test example 1

(1) And (4) evaluating the abrasion resistance. The desulfurization catalysts A1-A4 and B1-B4 are evaluated by a straight pipe abrasion method, the evaluation method refers to a method of RIPP 29-90 in petrochemical engineering analysis method (RIPP) experimental method, and the smaller the numerical value, the higher the abrasion resistance. The results are shown in Table 1.

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

Evaluation conditions for desulfurization reaction: the desulfurization adsorption composition A1 of 16 g is filled in a fixed bed reactor with the inner diameter of 30mm and the length of 1m, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, the reaction temperature is 380 ℃, and the feeding of the adsorption reaction raw material is the weight space velocity of 4h^-1And carrying out desulfurization reaction on the sulfur-containing hydrocarbon oil.

Carrying out desulfurization reaction by taking catalytic cracking gasoline as a raw material: 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 characterize the activity of the desulfurization catalyst A1 in the actual industrial operation, the desulfurization catalyst A1 was subjected to regeneration treatment after the reaction was completed, and the regeneration treatment was carried out under an air atmosphere at 480 ℃. The activity of the desulfurization catalyst A1 was substantially stabilized after 6 cycles of reaction and regeneration, and the sulfur content in the product gasoline after the desulfurization catalyst A1 was stabilized represented the activity of the desulfurization catalyst A1, and the results are shown in Table 1. Evaluation of desulfurization performance of the desulfurization adsorbent composition using A2-A4 and B1-B4 was also conducted, 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.

Motor Octane Number (MON) and Research Octane Number (RON) of the catalytically cracked gasoline as the reaction raw material and the gasoline as the product after the desulfurization catalyst was stabilized were measured by GB/T503-.

The breakthrough sulfur capacity for gasoline desulfurization of hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 was calculated and shown in Table 3. Wherein, the penetration in the penetrating sulfur capacity means: the gasoline desulfurization is carried out from the beginning until the sulfur content of the obtained gasoline breaks through 10 mug/g. The breakthrough sulfur capacity means: the co-adsorbed sulfur content on the gasoline desulfurization catalyst (based on the total weight of the gasoline desulfurization catalyst) prior to breakthrough.

Carrying out desulfurization reaction by using simulated hydrocarbon oil as a raw material: 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:

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

2.△ MON indicates an increased value of product MON;

3.△ RON indicates an increased value of product RON;

4.△ (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.

It can be seen from the results of examples 1-4 and table 1 that the desulfurization catalyst a1-a4 provided by the present invention contains a zinc-silver composite metal oxide, and the hydrocarbon oil desulfurization catalyst can still achieve a good reduction in the sulfur content of gasoline after being subjected to multiple cycles of desulfurization, and has better desulfurization activity and activity stability. The desulfurization catalyst has better abrasion resistance, so that the desulfurization catalyst has longer service life.

In addition, the desulfurization catalyst can absorb sulfur at 380 ℃ and perform oxidative regeneration at 480 ℃ at lower temperature.

Test example 2

Aging hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 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.

In fig. 3, the XRD spectrum of a1 after hydrothermal aging shows no characteristic peaks of zinc silicate, i.e., 22.0, 25.54, 48.9 and 59.4; in fig. 4, the XRD spectrum after hydrothermal aging of B1 shows the above characteristic peaks of zinc silicate. The XRD patterns of B1-B4 were analyzed quantitatively for the content of zinc silicate by the content of crystalline phase, and the results are shown in Table 2.

The desulfurization performance of aged A1-A4 and B1-B4 was evaluated under the desulfurization reaction evaluation conditions (catalytically cracked gasoline) as in test example 1, and the results are shown in Table 2.

The penetration sulfur capacity of the aged hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 for gasoline desulfurization was calculated, and the results are shown in Table 3.

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 1000ppm, a RON of 93.0 and a MON of 82.7.

2.△ MON indicates an increased value of product MON;

3.△ RON indicates an increased value of product RON;

TABLE 3

TABLE 4

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

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

It can be seen from the data of the product gasoline in tables 1 and 2 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.

As can be seen from table 3, the breakthrough sulfur capacity of gasoline desulfurization using the gasoline desulfurization catalyst of the present invention before aging was similar to that of the gasoline desulfurization catalyst of the comparative example, and after the aging process, since the breakthrough sulfur capacity of the zinc-silver composite metal oxide was higher and no zinc silicate was produced in the hydrocarbon oil desulfurization catalyst obtained in the examples, whereas the breakthrough sulfur capacity of the catalyst was significantly decreased and the desulfurization activity was also significantly decreased in the catalysts of the comparative examples 1 to 4 since the breakthrough sulfur capacity of zinc oxide was lower than that of the zinc-silver composite metal oxide and zinc silicate was produced with a material containing silicon oxide.

As can be seen from the data of the results in Table 4, with respect to the simulated hydrocarbon oils, the hydrocarbon oil desulfurization catalysts provided in examples 1 to 4 were subjected to desulfurization reactions, and the product oils obtained were reduced in the content of naphthenes (methylcyclohexane) and olefins (1-heptene), increased in the content of aromatization products such as toluene, and increased in the content of isomerization products (dimethylpentane), as compared with the composition of the simulated hydrocarbon oil feedstock. It can be shown that the use of the hydrocarbon oil desulfurization catalyst of the present invention affects the composition of the product oil obtained by the desulfurization reaction, and thus the octane number in Table 2 is less lowered. The hydrocarbon oil desulfurization catalyst provided by the invention can enhance the dehydrogenation aromatization reaction of the hydrocarbon oil while performing hydrocarbon oil desulfurization, and can effectively make up the octane number loss caused by olefin hydrogenation in the desulfurization process.

The hydrocarbon oil desulfurization catalyst provided by the invention contains a specific composition, and can effectively remove sulfides in hydrocarbon oil, promote isomerization and dehydroaromatization reactions of the hydrocarbon oil in the desulfurization process, increase components for compensating octane number, and generate aromatic hydrocarbons which do not exceed the limit of national standard.

Claims

1. The desulfurization catalyst contains 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 molecular sieve with MFI structure and 5-3 wt% of zeolite based on the total weight of the desulfurization catalyst0 wt% of a reactive metal; and at least part of the silver oxide forms a general formula Ag with the zinc oxide_xZn_1-xO, wherein x satisfies 0 < x ≦ 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 is_xZn_1-xThe sulfur capacity of the zinc-silver composite metal oxide represented by O is more than or equal to 30 percent.

2. The desulfurization catalyst of claim 1 wherein said desulfurization catalyst satisfies the following relationship: a. the₁₀₀-B₁₀₀0.3 ° to 0.5 °, a₁₀₀And B₁₀₀The XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions are respectively expressed as 2 θ values representing diffraction peaks of (100) plane of ZnO.

3. The desulfurization catalyst of claim 1 wherein said desulfurization catalyst satisfies the following relationship: a. the₀₀₂-B₀₀₂0.3 ° to 0.5 °; a. the₀₀₂And B₀₀₂The XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions are respectively expressed as 2 θ values representing diffraction peaks of (002) plane of ZnO.

4. The desulfurization catalyst of claim 1 wherein said desulfurization catalyst satisfies the following relationship: a. the₁₀₁-B₁₀₁0.3 ° to 0.5 °; a. the₁₀₁And B₁₀₁The XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO obtained under the same XRD measurement conditions are respectively expressed as 2 θ values representing diffraction peaks of (101) plane of ZnO.

5. The desulfurization catalyst of any one of claims 1 to 4, wherein the desulfurization catalyst comprises 12 to 20 wt% of a silicon oxide source, 10 to 20 wt% of alumina, 35 to 50 wt% of zinc oxide, 5 to 12 wt% of silver oxide, 3 to 10 wt% of a molecular sieve having an MFI structure, and 10 to 20 wt% of an active metal, based on the total weight of the desulfurization catalyst.

6. The desulfurization catalyst of any one of claims 1-4, wherein said active metal is nickel.

7. The desulfurization catalyst of any one of claims 1-4, wherein said silica source is silica or a natural ore having a silica content of more than 45 wt.%.

8. The desulfurization catalyst of any one of claims 1-4, wherein said molecular sieve having MFI structure is ZSM-5 molecular sieve, and/or ZSM-5 molecular sieve modified with phosphorus or a transition metal.

9. A method of preparing a desulfurization catalyst, the method comprising:

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

10. The preparation method according to claim 9, wherein the silver-containing compound and the zinc-containing compound are added in step (1) in such amounts that the resulting desulfurization catalyst contains silver oxide in an amount of 2 to 15 wt% and zinc oxide in an amount of 30 to 70 wt%, based on the total weight of the desulfurization catalyst.

11. The production method according to claim 9, wherein the precipitation product satisfies the following relational expression: a. the₁₀₀-B₁₀₀0.3 ° to 0.5 °, a₁₀₀And B₁₀₀Respectively show the 2 theta values of diffraction peaks of (100) planes of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

12. The production method according to claim 9, wherein the precipitation product satisfies the following relational expression: a. the₀₀₂-B₀₀₂0.3 ° to 0.5 °; a. the₀₀₂And B₀₀₂Respectively show the 2 theta values of diffraction peaks of (002) plane of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

13. The production method according to claim 9, wherein the precipitation product satisfies the following relational expression: a. the₁₀₁-B₁₀₁0.3 ° to 0.5 °; a. the₁₀₁And B₁₀₁Respectively show the 2 theta values of diffraction peaks of (101) plane of ZnO in the XRD spectrum of the precipitation product and the XRD spectrum of ZnO obtained under the same XRD measurement conditions.

14. The method according to any one of claims 9 to 13, wherein the precipitated product contains at least partially Ag_xZn_1-xA zinc-silver composite metal oxide represented by O, wherein x satisfies 0 < x.ltoreq.0.24, and x represents an atomic molar ratio.

15. The production method according to claim 9 or 10, wherein the silver-containing compound is silver nitrate and/or silver acetate.

16. The production method according to claim 9 or 10, wherein the zinc-containing compound is at least one of zinc acetate, zinc chloride, and zinc nitrate.

17. The process according to claim 9, wherein the precipitating agent used in the precipitation reaction in step (1) is urea and/or aqueous ammonia.

18. The method according to claim 9, wherein the mixture in step (1) has a pH of 9 to 13.

19. The production method according to claim 9, wherein the drying conditions in step (1) include: the drying temperature is 100-; the roasting conditions comprise: the roasting temperature is 400-700 ℃, and the roasting time is 0.5-3 h.

20. The production method according to claim 9, wherein the silica source, the alumina source, the molecular sieve having an MFI structure, and the active metal-containing compound are added in amounts such that the resulting desulfurization catalyst contains 5 to 35 wt% of the silica source, 5 to 35 wt% of the alumina source, 1 to 20 wt% of the molecular sieve having an MFI structure, and 5 to 30 wt% of the active metal, based on the total weight of the desulfurization catalyst.

21. The production method according to claim 9, wherein the alumina source is a substance that can be converted into alumina under the condition of the calcination in step (2).

22. The production method according to claim 21, 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.

23. The production method according to claim 9, 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.

24. A desulfurization catalyst obtained by the production method according to any one of claims 9 to 23.

25. A method for desulfurizing a hydrocarbon oil, the method comprising: a sulfur-containing hydrocarbon oil is subjected to a contact reaction with a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst according to any one of claims 1 to 7 and 24.