CN104511309B - A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil - Google Patents

Abstract

The invention discloses a desulfurization catalyst. Based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-30% by weight of silicon oxide source, 5-30% by weight of aluminum oxide, and 30-70% by weight of zinc oxide , 2-15% by weight of lead oxide, 1-20% by weight of aluminum phosphorus molecular sieve and 5-30% by weight of active metals; and at least part of the lead oxide to form the general formula Pb _x Zn _1- Exist in the form of zinc-lead solid solution represented by _x O, wherein x satisfies 0<x≤0.12, and x represents the atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese. The invention also provides a preparation method of the desulfurization catalyst and a method for desulfurization of hydrocarbon oil. The desulfurization catalyst provided by the invention has better desulfurization activity and activity stability.

Description

A kind of desulfurization catalyst and its preparation method and the method for hydrocarbon oil desulfurization

technical field

The present invention relates to a kind of desulfurization catalyst and its preparation method and the method of hydrocarbon oil desulfurization, specifically, relate to a kind of desulfurization catalyst, a kind of preparation method of desulfurization catalyst and the desulfurization catalyst obtained by this method, and desulfurization catalyst in hydrocarbon oil desulfurization method applied in .

Background technique

As people pay more and more attention to environmental protection, environmental regulations are becoming stricter, and reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures to improve air quality, because sulfur in fuel will affect the performance of automotive catalytic converters produce adverse effects. The sulfur present in the exhaust of automobile engines will inhibit the precious metals in the converter and cause irreversible poisoning, reducing the effect of the converter on the purification of automobile exhaust. Unpurified vehicle exhaust contains unburned non-methane hydrocarbons, nitrogen oxides, and carbon monoxide, which are catalyzed by sunlight to form photochemical smog.

Most of the sulfur in my country's gasoline products comes from thermally processed gasoline blending components, such as catalytic cracking gasoline. Therefore, the reduction of sulfur content in thermally processed gasoline will help reduce the sulfur content of gasoline products in my country. my country's current gasoline product standard GB17930-2011 "Motor Gasoline" requires that by December 31, 2013, the sulfur content in gasoline products must be reduced to 50 μg/g. And the quality standards of gasoline products in the future will be stricter. In this case, FCC gasoline must undergo deep desulfurization to make gasoline products meet environmental protection requirements.

In order to ensure the combustion performance of automobile fuel, while reducing the sulfur content of automobile fuel, it should also try to avoid the change of olefin content in gasoline to reduce its octane number (including ROM and MON). The impact on olefin content is generally due to the simultaneous initiation of hydrogenation reactions that remove thiophenes, including thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes. In addition, it is also necessary to avoid desulfurization conditions that may cause the aromatics of FCC gasoline to be saturated and lost. Therefore, the most ideal method is to achieve desulfurization while maintaining the combustion performance of gasoline products.

At present, there are mainly two methods for deep desulfurization of oil products: hydrofining and adsorption desulfurization, and the cost of hydrofining is relatively high. S Zorb adsorption desulfurization belongs to adsorption desulfurization technology, which realizes the adsorption and removal of sulfide in hydrocarbon oil under certain temperature, pressure and hydrogen exposure conditions. This technology has the characteristics of low hydrogen consumption and low requirement on the purity of hydrogen, which makes this technology have broad application prospects in fuel desulfurization.

CN1355727A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein nickel exists in a reduced valence state substantially, and its presence can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the nickel-containing sorbent composition under desulfurization conditions. The composition is obtained by granulating the mixture of zinc oxide, silicon oxide and aluminum oxide to form particles, drying, calcining, impregnating with nickel or a compound containing nickel, drying, calcining and reducing.

CN1382071A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein cobalt exists in a substantially reduced valence state, and its existing amount can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the cobalt-containing sorbent composition under desulfurization conditions.

US6150300 discloses a method for preparing an adsorbent, including preparing spherical particles: (a) mixing a composition containing silicon dioxide, a composition containing metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding said first mixture; (b) spherical said first mixture to form particles having a diameter of 10-1000 mm. Wherein step (a) also includes mixing with a metal accelerator.

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

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

CN1856359A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina and a cocatalyst to form a mixture thereof; b) drying the mixture to form a dried the 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 cocatalyst content having a reduced valence state therein the composition of the material, and e) the recovery composition. The cocatalyst contains various metals selected from nickel and the like.

CN1871063A discloses a method of producing a composition 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 second a dried mixture; c) calcining said first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto said first calcined mixture to form a promoted mixture; e ) contacting the accelerated 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) drying the second calcining the dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under appropriate conditions to produce a composition comprising reduced valence promoter content therein, and i) The composition is recovered.

Although the disclosed adsorbents have a certain desulfurization performance, due to the desulfurization in the hydrogen-facing state, the hydrogenation of olefins inevitably occurs, resulting in the loss of octane number. And with the improvement of gasoline quality standards, the requirements for the sulfur content of product gasoline are also becoming stricter. It can be seen that there is a need to provide a new catalyst with higher desulfurization activity and capable of improving the octane number of product gasoline.

Contents of the invention

The object of the present invention is to provide a desulfurization catalyst, a preparation method thereof and a method for desulfurization of hydrocarbon oil in order to overcome the problem of reduced activity of adsorbents in the prior art.

In order to achieve the above object, the present invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-30% by weight of silica source, 5-30% by weight of alumina, 30-70% by weight % of zinc oxide, 2-15% by weight of lead oxide, 1-20% by weight of aluminum phosphorus molecular sieve and 5-30% by weight of active metals; and at least part of the lead oxide is formed with the zinc oxide. The zinc-lead solid solution represented by the formula Pb _x Zn _1-x O exists in the form of a zinc-lead solid solution, wherein x satisfies 0<x≤0.12, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese.

The present invention also provides a method for preparing a desulfurization catalyst, the method comprising: (1) performing a precipitation reaction on a mixed solution obtained by mixing a lead-containing compound, a zinc-containing compound and water, and filtering, drying and Roasting to obtain a precipitated product; (2) contacting a silicon oxide source, an alumina source, aluminum phosphorus 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; Then shape, dry and roast the carrier mixture to form a carrier; (3) introduce a compound containing an active metal into the carrier obtained in step (2) and dry and roast to obtain a desulfurization catalyst precursor; the active metal is cobalt , at least one of nickel, iron and manganese; (4) reducing the desulfurization catalyst precursor obtained in step (3) in an atmosphere containing hydrogen to obtain a desulfurization catalyst.

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

The present invention also provides a method for desulfurizing hydrocarbon oil, the method comprising: contacting and reacting sulfur-containing hydrocarbon oil with a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst provided by the present invention.

Through the above technical scheme, at least part of the lead oxide in the desulfurization catalyst provided by the present invention exists in the form of a zinc-lead solid solution represented by the general formula Pb _x Zn _1-x O formed with zinc oxide, as a sulfur absorbing component, so that the present invention provides The desulfurization catalyst has better desulfurization activity and activity stability. Moreover, the desulfurization catalyst also has better wear resistance strength, which can increase the service life of the desulfurization catalyst. In addition, the desulfurization catalyst can also absorb sulfur at a lower temperature and carry out oxidative regeneration. In the prior art, the temperature for absorbing sulfur is 410°C, and the temperature for oxidative regeneration is 550°C. The desulfurization catalyst A1 in Example 1 has a zinc-lead solid solution with a chemical composition of Pb _0.044 Zn _0.956 O, and the wear index is 5.6; in Example 4, the desulfurization catalyst A1 can treat the raw material at 380°C to reduce the sulfur content of the product gasoline 9 μg/g, and the regeneration temperature is 480°C. In Comparative Example 4, although the desulfurization catalyst B4 containing lead oxide and zinc oxide was obtained, no zinc-lead solid solution was formed, and the sulfur content of the product gasoline obtained by treating the raw materials at 380° C. was as high as 28 μg/g.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the XRD spectrogram of precipitation product C1-C3, ZnO and PbO; Wherein

The 2θ values B ₁₀₀ , B ₀₀₂ and B ₁₀₁ of the diffraction peaks representing the (100) plane, (002) plane and (101) plane of ZnO are 31.55°, 34.21° and 36.04°, respectively,

The 2θ values A ₁₀₀ , A ₀₀₂ and A ₁₀₁ of the diffraction peaks representing the (100) plane, (002) plane and (101) plane of ZnO in C1 are 31.75°, 34.42° and 36.24°, respectively,

The 2θ values A ₁₀₀ , A ₀₀₂ and A ₁₀₁ of the diffraction peaks representing the (100) plane, (002) plane and (101) plane of ZnO in C2 are 31.80°, 34.45° and 36.28°, respectively,

The 2θ values A ₁₀₀ , A ₀₀₂ and A ₁₀₁ of the diffraction peaks representing the (100) plane, (002) plane and (101) plane of ZnO in C3 are 31.78°, 34.43° and 36.26°, respectively;

Figure 2 is the XRD spectrum of the desulfurization catalyst A1.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-30% by weight of silicon oxide source, 5-30% by weight of aluminum oxide, 30-70% by weight of zinc oxide, 2-15% by weight of lead oxide, 1-20% by weight of aluminum phosphorus molecular sieve and 5-30% by weight of active metal; and at least part of said lead oxide is formed with said zinc oxide with the general formula Pb _x Zn _{1 -x} O exists in the form of a zinc-lead solid solution, where x satisfies 0<x≤0.12, and x represents an atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese.

According to the present invention, the desulfurization catalyst contains lead oxide and zinc oxide, and the desulfurization catalyst may contain zinc-lead solid solution formed by lead oxide and zinc oxide. The zinc-lead solid solution can stabilize the lattice structure of zinc oxide and maintain the activity of zinc oxide components. The amount of lead 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-lead solid solution represented by the above general formula. The desulfurization catalyst may contain lead oxide and zinc oxide that all form a zinc-lead solid solution represented by the above general formula; it may also contain lead oxide and/or zinc oxide in addition to the zinc-lead solid solution represented by the above general formula , For example, all the lead oxide and most of the zinc oxide form a zinc-lead solid solution, and the desulfurization catalyst contains a small amount of zinc oxide in addition to the zinc-lead solid solution. It is preferable that all lead oxide and zinc oxide contained in the desulfurization catalyst form a zinc-lead solid solution represented by the above general formula.

According to the present invention, after lead oxide and zinc oxide form a zinc-lead solid solution, the lattice structure of zinc oxide is not destroyed, but because lead ions replace zinc ions and enter the lattice, so the XRD spectrum of the desulfurization catalyst represents ZnO The diffraction angle of the characteristic peaks will change, so the determination of the desulfurization catalyst by XRD can confirm that there is a zinc-lead solid solution in the desulfurization catalyst. As shown in Figure 2, the XRD spectrum of the desulfurization catalyst A1 and the XRD spectrum of ZnO obtained under the same XRD measurement conditions. In Figure 2, there are no individual characteristic peaks of lead oxide and zinc oxide, but characteristic peaks of cubic crystals of zinc oxide with shifted peak positions appear, indicating that lead oxide and zinc oxide all form a zinc-lead solid solution. Preferably, the desulfurization catalyst satisfies the following relational formula: A ₁₀₀ -B ₁₀₀ =0.2° to 0.3°, A ₁₀₀ and B ₁₀₀ respectively represent the XRD spectrum and the desulfurization catalyst obtained under the same XRD measurement conditions In the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (100) plane of ZnO is represented.

According to the present invention, preferably, the desulfurization catalyst satisfies the following relational formula: A ₀₀₂ -B ₀₀₂ =0.2° to 0.3°; A ₀₀₂ and B ₀₀₂ respectively represent the desulfurization catalyst obtained under the same XRD measurement conditions The XRD spectrum and the XRD spectrum of ZnO represent the 2θ value of the diffraction peak of the (002) plane of ZnO.

According to the present invention, preferably, the desulfurization catalyst satisfies the following relational formula: A ₁₀₁ -B ₁₀₁ =0.2° to 0.3°; A ₁₀₁ and B ₁₀₁ respectively represent the desulfurization catalyst obtained under the same XRD measurement conditions The XRD spectrum and the XRD spectrum of ZnO represent the 2θ value of the diffraction peak of the (101) plane of ZnO.

According to the present invention, it can be determined that the desulfurization catalyst contains zinc-lead solid solution formed by lead oxide and zinc oxide through the above-mentioned XRD measurement, and the molar ratio x of lead and zinc in the zinc-lead solid solution can be determined by element analysis such as fluorescence spectrum analysis, and can be determined The zinc-lead solid solution can be represented by the general formula Pb _x Zn _1-x O, wherein x satisfies 0<x≤0.12, and x represents an atomic molar ratio.

According to the present invention, the desulfurization catalyst preferably, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 10-20% by weight of silica source, 10-20% by weight of alumina, 35-54% by weight of Zinc oxide, 5-12% by weight of lead oxide, 2-10% by weight of aluminum phosphorus molecular sieve and 10-20% by weight of active metal.

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

According to the present invention, the silicon oxide source can provide bonding between the components in the desulfurization catalyst. Preferably, the silicon oxide source may be silicon oxide or natural ore with a silicon oxide content greater than 45% by weight. Preferably, the silicon oxide source may be at least one of layered clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica and silica gel.

According to the present invention, the alumina can provide bonding between components in the desulfurization catalyst. Preferably, the alumina may be at least one of γ-alumina, η-alumina, θ-alumina and χ-alumina.

According to the present invention, the aluminum phosphorus molecular sieve (SAPO molecular sieve for short) is a close-body silicoaluminophosphate, which is obtained by introducing silicon into the aluminum phosphate framework, and the framework is composed of PO ⁴⁺ , AlO ^4- and SiO ₂ tetrahedrons, Including 13 three-dimensional microporous skeleton structures. Preferably, the pore size of the aluminum phosphorus molecular sieve is 3-8 , the pore volume is 0.18-0.48cm ³ /g. Preferably, the aluminum phosphorus molecular sieve is at least one of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieves. The pore sizes of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieves are 8 (12-membered ring), 6 (10 rings), 7 (10 rings), 4.3 (8 member ring) and 3 (6-membered ring), the pore volumes are 0.31, 0.18, 0.42, 0.42 and 0.40 cm ³ /g, respectively. More preferably, the aluminum phosphorus molecular sieve is at least one of SAPO-11, SAPO-31 and SAPO-34 molecular sieves.

The present invention also provides a method for preparing a desulfurization catalyst, the method comprising: (1) performing a precipitation reaction on a mixed solution obtained by mixing a lead-containing compound, a zinc-containing compound and water, and filtering, drying and Roasting to obtain a precipitated product; (2) contacting a silicon oxide source, an alumina source, aluminum phosphorus 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; Then shape, dry and roast the carrier mixture to form a carrier; (3) introduce a compound containing an active metal into the carrier obtained in step (2) and dry and roast to obtain a desulfurization catalyst precursor; the active metal is cobalt , at least one of nickel, iron and manganese; (4) reducing the desulfurization catalyst precursor obtained in step (3) in an atmosphere containing hydrogen to obtain a desulfurization catalyst.

In the preparation method of the desulfurization catalyst provided by the present invention, step (1) can form a zinc-lead solid solution.

According to the present invention, the addition amount of the lead-containing compound and the zinc-containing compound described in step (1) can be selected within a wide range, as long as a zinc-lead solid solution that can be represented by the general formula Pb _x Zn _1-x O can be formed, namely Can. Preferably, the amount of the lead-containing compound and the zinc-containing compound in step (1) is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of lead oxide is 2-15% by weight. The content of zinc is 30-70% by weight; preferably, the amount of the lead-containing compound and the zinc-containing compound is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of lead oxide is 5-12% % by weight, the content of zinc oxide is 35-54% by weight.

According to the present invention, the precipitated product obtained in step (1) is subjected to elemental analysis and XRD measurement, and according to the elemental analysis and XRD measurement results, it can be determined that the precipitated product contains zinc-lead solid solution. Specifically, firstly, the precipitated product is subjected to elemental analysis to determine that it contains lead and zinc elements. Secondly, the precipitated product was subjected to XRD measurement and analysis, as shown in Figure 1, according to the characteristic peaks of the hexagonal crystal system of ZnO in the XRD spectrum, without the characteristic peaks of lead oxide, it can be inferred that a zinc-lead solid solution was formed. Because the formation of zinc-lead solid solution is that lead replaces zinc and enters the lattice structure of zinc oxide, and the independent lead oxide crystal structure is gone. In this way, in the XRD spectrum of zinc-lead solid solution, there are still structural features of ZnO crystals, but there is no lead oxide. Structural features of crystals. However, the position of the crystal phase peak of ZnO in the Zn-Pb solid solution shifts. Therefore, it can be determined that the precipitated product contains zinc-lead solid solution through the XRD spectrum of the precipitated product.

According to the present invention, preferably, the precipitation product satisfies the following relational formula: A ₁₀₀ -B ₁₀₀ =0.2° to 0.3°, and A ₁₀₀ and B ₁₀₀ respectively represent the properties of the precipitation product obtained under the same XRD measurement conditions. The XRD spectrum and the XRD spectrum of ZnO represent the 2θ value of the diffraction peak of the (100) plane of ZnO.

According to the present invention, preferably, the precipitation product satisfies the following relational formula: A ₀₀₂ -B ₀₀₂ =0.2° to 0.3°; A ₀₀₂ and B ₀₀₂ respectively represent the properties of the precipitation product obtained under the same XRD measurement conditions The XRD spectrum and the XRD spectrum of ZnO represent the 2θ value of the diffraction peak of the (002) plane of ZnO.

According to the present invention, preferably, the precipitation product satisfies the following relational formula: A ₁₀₁ -B ₁₀₁ =0.2° to 0.3°; A ₁₀₁ and B ₁₀₁ respectively represent the properties of the precipitation product obtained under the same XRD measurement conditions. The XRD spectrum and the XRD spectrum of ZnO represent the 2θ value of the diffraction peak of the (101) plane of ZnO.

In the present invention, according to the 2θ value of the diffraction peak of the ZnO crystal appearing in the XRD spectrum of the precipitation product satisfies the above relational formula. It can be judged that the precipitation product obtained by the preparation method provided by the present invention contains zinc-lead solid solution.

According to the present invention, elemental analysis and XRD measurement can be performed on the precipitated product to determine the molar ratio of lead and zinc in the formed zinc-lead solid solution. Preferably, according to XRD analysis, the precipitated product obtained in step (1) contains a zinc-lead solid solution represented by the general formula Pb _x Zn _1-x O, wherein x satisfies 0<x≤0.12, and x represents an atomic molar ratio. In the formed zinc-lead solid solution represented by the above general formula, lead and zinc are matched according to the above-mentioned atomic molar ratio, which can provide ZnO crystals with better crystal structure stability in the high-temperature environment of the sulfur absorption and oxidation regeneration process, so that further Ensure that the desulfurization catalyst containing zinc-lead solid solution has better desulfurization activity.

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

According to the present invention, the zinc-containing compound in step (1) can be various water-soluble zinc-containing compounds, 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 crystal water.

According to the present invention, the precipitation reaction in step (1) is used to co-precipitate lead and zinc from the mixed solution to obtain a mixture containing lead and zinc. Preferably, the precipitation agent used in the precipitation reaction in step (1) can be urea and/or ammonia water. The use of the above-mentioned precipitating agent can make the precipitation reaction more complete, and is conducive to the formation of zinc-lead solid solution.

According to the present invention, preferably, the pH of the mixture in step (1) is 9-13. When the mixture obtained by the precipitation reaction in step (1) is in the above pH range, it can ensure that the lead and zinc contained in the mixed solution are co-precipitated more completely, and it is conducive to the formation of zinc-lead solid solution.

According to the present invention, the drying and roasting can transform the co-precipitated mixture in step (1) into a zinc-lead solid solution. In order to obtain the zinc-lead solid solution that can be represented by the above general formula, preferably, the drying conditions in step (1) include: the drying temperature is 100-200°C, and the drying time is 0.5-3h; the roasting The conditions include: the calcination temperature is 400-700°C, and the calcination time is 0.5-3h.

According to the step (2) in the preparation method of the desulfurization catalyst provided by the present invention, this step is used to prepare the carrier by preparing the silica source, the alumina source, the phosphorus-aluminum molecular sieve and the precipitated product obtained in the step (1). Preferably, the added amount of the silica source, the alumina source and the aluminum phosphorus molecular sieve is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of the silica source is 5- 30% by weight, the content of alumina is 5-30% by weight, and the content of aluminum-phosphorus molecular sieve is 1-20% by weight; preferably, the addition amount of the silicon oxide source, the alumina source and the aluminum-phosphorus molecular sieve In the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of silicon oxide source is 12-25% by weight, the content of aluminum oxide is 10-25% by weight, and the content of aluminum phosphorus molecular sieve is 2-10% by weight. weight%.

In the present invention, the weight ratio of the silicon oxide source to the aluminum oxide may be 0.4-2:1; preferably, it may be 0.6-1.5:1.

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

According to the present invention, the silicon oxide source can provide bonding between the components in the desulfurization catalyst. Preferably, the silicon oxide source is silicon oxide or a natural ore with a silicon oxide content greater than 45% by weight. Preferably, the silicon oxide source may be at least one of layered 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 amount of alumina. The amount of alumina contained in the silica source is still counted as the amount of the silica source. The phosphorus-aluminum molecular sieve added in step (2) is the same as that described above, and will not be repeated here. Although the aluminum phosphorus molecular sieve contains alumina, the amount of aluminum oxide contained in the aluminum phosphorus molecular sieve is still counted as the amount of the aluminum phosphorus molecular sieve and not included in the alumina. That is, 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 step (2), the acid solution is used in an amount such that the pH of the carrier mixture is 1-5, preferably 1.5-4. The acid solution may be selected from water-soluble inorganic and/or organic acids, such as 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 weight ratio of the amount of water added to the sum of the weight of the lead-containing compound and the zinc-containing compound is 5-10:1.

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

In step (2) of the present invention, the carrier mixture may be in the form of wet mixture, paste mixture, dough or slurry. By said 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 pasty mixture, the carrier mixture can be molded (preferably extruded) to form granules, preferably cylindrical extrusions with a diameter of 1.0-8.0 mm and a length of 2.0-5.0 mm. The extrudates are then dried and calcined. If the carrier mixture is in the form of a wet mixture, the mixture can be thickened, dried and shaped. More preferably, the carrier mixture is in the form of a slurry, which is spray-dried to form microspheres with a particle size of 20-200 microns to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the slurry before drying may be 10-50% by weight, preferably 20-50% by weight.

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

In the present invention, the calcination conditions of the carrier mixture can also be known to those skilled in the art. Generally speaking, the calcination temperature is 400-700°C, preferably 450-650°C; the calcination time is at least 0.5 hours, preferably 0.5-100 hours, more preferably 0.5-10 hours.

In the step (3) of the present invention, the amount of the compound containing the active metal is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of the active metal is 5-30% by weight; preferably 10 -20% by weight. Wherein, the active metal-containing substance may be converted into an oxide of the active metal under the calcination conditions of step (3). The active metal-containing compound may be selected from at least one of acetates, carbonates, nitrates, sulfates, thiocyanates and oxides of active metals. 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 through various methods. For example, it can be realized by impregnation method or precipitation method known to those skilled in the art. The impregnation method is to impregnate the carrier with the solution or suspension of the compound containing the active metal; the precipitation method is to mix the solution or suspension of the compound containing the active metal with the carrier, and then add ammonia to precipitate the active metal on the carrier. The impregnation method is preferred.

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

The reduction of the desulfurization catalyst precursor in step (4) of the present invention can be carried out immediately after the desulfurization catalyst precursor is prepared, or can be carried out before use (that is, before being used for desulfurization adsorption). Since the active metals are easy to oxidize, and the active metals in the desulfurization catalyst precursor exist in the form of oxides, for the convenience of transportation, the step (4) of reducing the desulfurization catalyst precursor is preferably carried out before desulfurization adsorption. The reduction means that the metal in the active metal oxide basically exists in a reduced state to obtain 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% by volume, the reduction temperature is 300-600°C, and the reduction time is 0.5-6 hours; the preferred reduction temperature is 400-500°C, the reduction time is 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 features of the aforementioned desulfurization catalyst, which will not be repeated here.

The present invention also provides a method for desulfurizing hydrocarbon oil, the method comprising: contacting and reacting sulfur-containing hydrocarbon oil with a desulfurization catalyst, wherein the desulfurization catalyst is the desulfurization catalyst provided by the present invention.

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

According to the present invention, the method for desulfurizing hydrocarbon oil may further include: regenerating the reacted desulfurization catalyst after the reaction. Regeneration conditions include: regeneration under oxygen atmosphere (oxygen content can be 10-80% by volume); regeneration temperature is 450-600°C, preferably 480-520°C; regeneration pressure is normal pressure.

In the present invention, the method for desulfurizing hydrocarbon oil may further include: reducing the regenerated desulfurization catalyst before reuse. Reduction conditions include: reduction under hydrogen atmosphere (hydrogen content can be 30-60% by volume); reduction temperature can be 350-500°C, preferably 400-450°C; reduction pressure can be 0.2-2MPa, preferably 0.2-1.5MPa.

In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons with a boiling range of 40 to 210°C or any fraction thereof, which are derived from the cracking of larger hydrocarbon molecules into smaller molecules Product of thermal or catalytic processes. Applicable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, etc., 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. Accordingly, suitable catalytically cracked gasoline includes, but is not limited to, coker gasoline, thermally cracked gasoline, visbroken gasoline, fluid catalytically cracked gasoline, and heavy oil cracked gasoline, 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. The term "diesel fuel" means a liquid composed of a hydrocarbon mixture or any fraction thereof with a boiling range of 170°C to 450°C. 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 organic sulfur compounds commonly present in hydrocarbon-containing fluids such as cracked gasoline or diesel fuel. The 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 thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often 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 adsorption composition is calculated according to the feed.

Polycrystalline X-ray Diffraction (XRD) X-ray diffractometer (Siemens D5005 type) was used to determine the structure of the desulfurization adsorption composition, Cu target, Kα radiation, solid detector, tube voltage 40kV, tube current 40mA.

Example 1

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

(1) Prepare the precipitated product. Mix 10.9 kg of zinc acetate dihydrate powder (produced by Beijing Chemical Plant, analytically pure), 0.86 kg of lead acetate trihydrate (Sinopharm Chemical Reagent Company, analytically pure) and 18 kg of deionized water, and dissolve completely after stirring for 30 minutes. The precipitated product obtained by adding 1.8 kg of ammonia water was filtered, dried at 150° C. for 2 hours, and then calcined at 500° C. for 1 hour to obtain the precipitated product C1.

The precipitated product C1 was subjected to fluorescence analysis and XRD determination. In the XRD spectrum (see Figure 1) there is no diffraction peak of PbO, and the standard diffraction peak of ZnO shifts to the right, where A ₁₀₀ -B ₁₀₀ =0.2°, A ₀₀₂ -B ₀₀₂ =0.21°, A ₁₀₁ -B ₁₀₁ = 0.2°, indicating that PbO and ZnO in the precipitated product C1 all form a zinc-lead solid solution, and its chemical composition is Pb _0.044 Zn _0.956 O.

(2) Prepare the carrier. Take 1.60 kg of alumina (produced by Shandong Aluminum Factory, including 1.20 kg on a dry basis), 2.16 kg of kaolin (including 1.80 kg on a dry basis) (obtained from Qilu Petrochemical Catalyst Factory) and 1.0 kg of SAPO-11 (catalyst Nanjing Branch, including 0.7 kg on a dry basis) and mix under stirring, then add 3.6 kg of deionized water and mix evenly, add 300 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 1 hour, then heat up to 80 ° C for 2 hours of aging . The precipitated product C1 was added and stirred for 1 hour to obtain a carrier mixture.

The carrier mixture is spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray-drying pressure is 8.5 to 9.5 MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 150° C. for 1 hour, and then calcined at 480° C. for 1 hour to obtain a catalyst carrier.

(3) Preparation of desulfurization catalyst precursor. 6.4 kg of the catalyst carrier obtained in step (2) was spray-impregnated twice with 7.0 kg of nickel nitrate hexahydrate and 1.10 kg of deionized aqueous solution, and the resulting mixture was dried at 150°C for 4 hours and then calcined at 480°C for 1 hour to obtain Desulfurization catalyst precursor.

(4) Preparation of desulfurization catalyst. The desulfurization catalyst precursor obtained in step (3) was reduced in a hydrogen atmosphere at 400°C for 3 hours to obtain desulfurization catalyst A1.

The composition of the desulfurization catalyst A1 is calculated according to the feed amount: 40.0% by weight of zinc oxide, 5.0% by weight of lead oxide, 12.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of SAPO-11 molecular sieve, and 18.0% by weight 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, the diffraction peaks of ZnO in the XRD spectrum of the desulfurization catalyst A1 are at 31.75°, 34.42° and 36.24° respectively, which are the same as the ZnO peaks in the XRD spectrum of the precipitated product C1 The phase coincidence indicates that the structure of zinc-lead solid solution exists in the desulfurization catalyst prepared by using zinc-lead solid solution as raw material.

Example 2

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

(1) Prepare the precipitated product. Mix 14.0 kg of zinc nitrate hexahydrate (produced by Beijing Chemical Plant, analytically pure), 1.80 kg of lead nitrate powder (Sinopharm Chemical Reagent Company, analytically pure) and 18 kg of deionized water, stir for 30 minutes, add 2.0 kg of urea and heat to After treatment at 80°C for 2 hours, a white precipitate was obtained. After filtration, it was first dried at 150°C for 2 hours, and then calcined at 500°C for 1 hour to obtain the precipitated product C2.

The precipitated product C2 was subjected to fluorescence analysis and XRD determination. In the XRD spectrum (see Figure 1) there is no diffraction peak of PbO, and the standard diffraction peak of ZnO appears to shift to the right, where A ₁₀₀ -B ₁₀₀ =0.25°, A ₀₀₂ -B ₀₀₂ =0.24°, A ₁₀₁ -B ₁₀₁ = 0.24°, indicating that PbO and ZnO in the precipitated product C2 all form a zinc-lead solid solution, and its chemical composition is Pb _0.1 Zn _0.9 O.

(2) Prepare the carrier. Take 2.40 kg of alumina (produced by Shandong Aluminum Plant, including 1.8 kg on a dry basis), 1.54 kg of expanded perlite (from the Catalyst Nanjing Branch, including 1.50 kg on a dry basis) and 0.43 kg of SAPO-31 (from the Catalyst Nanjing Branch, including a dry Base 0.3 kg) and mix under stirring, then add 4.8 kg of deionized water and mix evenly, add 275 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 1 hour, then heat up to 80 ° C for 2 hours of aging. The precipitated product C2 was added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and calcined to obtain the carrier.

(3) Preparation of desulfurization catalyst precursor. Referring to the method in step (3) of Example 1, the desulfurization catalyst precursor was obtained.

(4) Preparation of desulfurization catalyst. The desulfurization catalyst A2 was obtained by referring to the method in step (4) of Example 1.

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

Example 3

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

(1) Prepare the precipitated product. Mix 13.6 kg of zinc acetate dihydrate powder (produced by Beijing Chemical Factory, analytically pure), 1.05 kg of lead nitrate (Sinopharm Chemical Reagent Company, analytically pure) and 20 kg of deionized water, and dissolve completely after stirring for 30 minutes. After adding 2.0 kg of urea and heating to 80°C for 2 hours, a white precipitate was obtained. After filtration, it was first dried at 150°C for 2 hours, and then calcined at 500°C for 1 hour to obtain the precipitated product C3.

The precipitated product C3 was subjected to fluorescence analysis and XRD determination. In the XRD spectrum (see Figure 1) there is no diffraction peak of PbO, and the standard diffraction peak of ZnO shifts to the right, where A ₁₀₀ -B ₁₀₀ =0.23°, A ₀₀₂ -B ₀₀₂ =0.22°, A ₁₀₁ -B ₁₀₁ = 0.22°, indicating that PbO and ZnO in the precipitated product C3 all form a zinc-lead solid solution, and its chemical composition is Pb _0.07 Zn _0.93 O.

(2) Prepare the carrier. Take 2.13 kg of alumina (produced by Shandong Aluminum Plant, including 1.6 kg on a dry basis), 1.03 kg of diatomite (from Nanjing Branch of Catalyst, including 1.0 kg on a dry basis) and 0.6 kg of SAPO-34 (from Nanjing Branch of Catalyst, including 1.0 kg on a dry basis) Base 0.5 kg) and mix under stirring, then add 4.8 kg of deionized water and mix evenly, add 275 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 1 hour, then heat up to 80 ° C for 2 hours of aging. The precipitated product C3 was added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and calcined to obtain the carrier.

(3) Preparation of desulfurization catalyst precursor. Referring to the method in step (3) of Example 1, the desulfurization catalyst precursor was obtained.

(4) Preparation of desulfurization catalyst. Referring to the method of step (4) of Example 1, desulfurization catalyst A3 was obtained.

The composition of the desulfurization catalyst A3 is calculated according to the feed amount: 50.0% by weight of zinc oxide, 7.0% by weight of lead oxide, 16.0% by weight of aluminum oxide, 10.0% by weight of diatomite, 5.0% by weight of SAPO-34 molecular sieve, and 12.0% by weight of nickel.

Comparative example 1

This comparative example is used to illustrate the preparation method of the prior art to prepare the desulfurization catalyst.

Mix 4.55 kg of zinc oxide powder (produced by Beijing Chemical Plant, including 4.5 kg on a dry basis) with 6.9 kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry.

Take 1.60 kg of alumina (produced by Shandong Aluminum Factory, including 1.20 kg on a dry basis) and 3.0 kg of kaolin (including 2.50 kg on a dry basis) (obtained from Qilu Petrochemical Catalyst Factory) and mix them under stirring, then add 3.6 kg of deionized water to mix After uniformity, 300 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added, stirred and acidified for 1 hour, then heated to 80° C. for 2 hours of aging. Zinc oxide slurry was added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and impregnated to introduce nickel as an active component to obtain desulfurization catalyst B1.

The composition of the desulfurization catalyst B1 is calculated according to the feed 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

Mix 5.06 kg of zinc oxide powder (produced by Beijing Chemical Plant, including 5.0 kg on a dry basis) and 7.8 kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry.

Take 2.40 kg of alumina (produced by Shandong Aluminum Factory, including 1.8 kg on dry basis) and 1.85 kg of expanded perlite (catalyst Nanjing Branch, including 1.80 kg on dry basis) and mix them under stirring, then add 4.8 kg of deionized water and mix well Finally, 275 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added, stirred and acidified for 1 hour, and then heated to 80° C. for 2 hours of aging. Zinc oxide slurry was added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and impregnated to introduce nickel as an active component to obtain desulfurization catalyst B2.

The composition of the desulfurization catalyst B2 is calculated according to the feed 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

Mix 5.76 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 5.7 kg on a dry basis) with 7.8 kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry.

Take 2.13 kg of alumina (produced by Shandong Aluminum Factory, containing 1.6 kg on a dry basis) and 1.55 kg of diatomite (catalyst Nanjing Branch, containing 1.50 kg on a dry basis) and mix them under stirring, then add 4.8 kg of deionized water and mix well Finally, 275 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added, stirred and acidified for 1 hour, and then heated to 80° C. for 2 hours of aging. Zinc oxide slurry was added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and impregnated to introduce nickel as an active component to obtain desulfurization catalyst B3.

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

Comparative example 4

Mix 3.84 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 3.8 kg on a dry basis), 1.21 kg of lead oxide powder (Sinopharm Chemical Reagent Company, analytically pure) and 7.8 kg of deionized water, and stir for 30 minutes to obtain zinc oxide and oxide Lead mixed slurry.

Take 2.40 kg of alumina (produced by Shandong Aluminum Factory, including 1.8 kg on dry basis) and 1.85 kg of expanded perlite (catalyst Nanjing Branch, including 1.80 kg on dry basis) and mix them under stirring, then add 4.8 kg of deionized water and mix well Finally, 275 ml of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added, stirred and acidified for 1 hour, and then heated to 80° C. for 2 hours of aging. Zinc oxide and lead oxide slurries were added and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and impregnated to introduce nickel as an active component to obtain desulfurization catalyst B4.

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

Example 4

(1) Evaluation of abrasion resistance. The desulfurization catalysts A1-A3 and B1-B4 are evaluated by the straight pipe wear method. The evaluation method refers to the method of RIPP29-90 in the "Petrochemical Analysis Method (RIPP) Experimental Method". The smaller the value, the higher the wear resistance strength . The results are shown in Table 1.

(2) Evaluation of desulfurization performance. The desulfurization catalysts A1-A3 and B1-B4 were evaluated using a fixed-bed micro-reactor experimental device, and the raw material for the adsorption reaction was FCC gasoline with a sulfur concentration of 960ppm. Pack 16 grams of desulfurization adsorption composition A1 into a fixed-bed reactor with an inner diameter of 30 mm and a length of 1 m, the reaction pressure is 1.38 MPa, the hydrogen flow rate is 6.3 L/h, the gasoline flow rate is 80 mL/h, and the reaction temperature is 380 °C, the feed of the raw material for the adsorption reaction is at a weight space velocity of 4h ^-1 , and the desulfurization reaction of the sulfur-containing hydrocarbon oil is carried out. The desulfurization activity is measured by the sulfur content in the product gasoline. The sulfur content in the product gasoline was determined by off-line chromatographic analysis method using Agilent's GC6890-SCD instrument. In order to accurately characterize the activity of the desulfurization catalyst A1 in actual industrial operation, the desulfurization catalyst A1 was regenerated after the reaction was completed, and the regeneration treatment was carried out under an air atmosphere of 480°C. The activity of the desulfurization catalyst A1 was basically stabilized after 6 cycles of reaction and regeneration. The activity of the desulfurization catalyst A1 was represented by the sulfur content in the product gasoline after the stabilization of the desulfurization catalyst A1. The results are shown in Table 1. The desulfurization performance evaluation of the desulfurization adsorption composition using A2-A3 and B1-B4 was also carried out, and the results are shown in Table 1.

At the same time, the product gasoline is weighed to calculate its yield. The results are shown in Table 1.

Using GB/T503-1995 and GB/T5487-1995 to measure the motor octane number (MON) and research octane number (RON) of the reaction raw material catalytic cracking gasoline and the product gasoline after the desulfurization catalyst is stabilized, the results are shown in Table 1 .

Table 1

Note:

1. The sulfur content of raw gasoline is 960ppm, RON is 93.7, and MON is 83.6.

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

3. △RON represents the added value of the product RON;

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

From the result data of Examples 1-4 and Table 1, it can be seen that the desulfurization catalysts A1-A3 provided by the present invention contain zinc-lead solid solution, and the desulfurization catalysts have better desulfurization activity and activity stability. The desulfurization catalyst has better wear resistance strength, so that the desulfurization catalyst has a longer service life.

In addition, the desulfurization catalyst can absorb sulfur at a lower temperature of 380°C and oxidize and regenerate at 480°C.

Claims (22)

1. A desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 5-30% by weight of silicon oxide source, 5-30% by weight of aluminum oxide, 30-70% by weight of zinc oxide, 2 - 15% by weight of lead oxide, 1-20% by weight of aluminum phosphorus molecular sieve and 5-30% by weight of active metal; and at least part of said lead oxide to form the general formula Pb _x Zn _1-x O with said zinc oxide It exists in the form of zinc-lead solid solution, where x satisfies 0<x≤0.12, and x represents the atomic molar ratio; the active metal is at least one of cobalt, nickel, iron and manganese. 2. The desulfurization catalyst according to claim 1, wherein, the desulfurization catalyst satisfies the following relational formula: A ₁₀₀ -B ₁₀₀ =0.2° to 0.3°, A ₁₀₀ and B ₁₀₀ respectively represent that obtained under the same XRD measurement conditions In the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (100) plane of ZnO; B ₁₀₀ =31.55°. 3. The desulfurization catalyst according to claim 1, wherein the desulfurization catalyst satisfies the following relational formula: A ₀₀₂ -B ₀₀₂ = 0.2° to 0.3°; A ₀₀₂ and B ₀₀₂ respectively represent that they are obtained under the same XRD measurement conditions In the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (002) plane of ZnO; B ₀₀₂ =34.21°. 4. The desulfurization catalyst according to claim 1, wherein, the desulfurization catalyst satisfies the following relational formula: A ₁₀₁ -B ₁₀₁ =0.2° to 0.3°; A ₁₀₁ and B ₁₀₁ respectively represent that they are obtained under the same XRD measurement conditions In the XRD spectrum of the desulfurization catalyst and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (101) plane of ZnO; B ₁₀₁ =36.04°. 5. The desulfurization catalyst according to any one of claims 1-4, wherein, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains 10-20% by weight of a silicon oxide source, 10-20% by weight of Aluminum oxide, 35-54% by weight of zinc oxide, 5-12% by weight of lead oxide, 2-10% by weight of aluminum phosphorus molecular sieve and 10-20% by weight of active metal. 6. The desulfurization catalyst according to any one of claims 1-4, wherein the active metal is nickel. 7. The desulfurization catalyst according to any one of claims 1-4, wherein the silicon oxide source is silicon oxide or a natural ore with a silicon oxide content greater than 45% by weight. 8. desulfurization catalyst according to claim 1, wherein, the pore size of described aluminum phosphorus molecular sieve is The pore volume is 0.18-0.48 cm ³ /g. 9. The desulfurization catalyst according to claim 1 or 8, wherein the aluminum phosphorus molecular sieve is at least one of SAPO-11, SAPO-31, SAPO-34 and SAPO-20. 10. A preparation method of a desulfurization catalyst, the method comprising: (1) performing a precipitation reaction on a mixed solution obtained by mixing a lead-containing compound, a zinc-containing compound and water, and filtering, drying and roasting the mixture obtained by the precipitation reaction to obtain a precipitated product; (2) Contact the silica source, alumina source, aluminum phosphorus molecular sieve, water and acid solution to form a slurry, and mix the precipitated product obtained in step (1) with the slurry to form a carrier mixture; then the carrier mixture Shaping, drying and firing to form a carrier; (3) introducing a compound containing an active metal onto the carrier obtained in 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) reducing the desulfurization catalyst precursor obtained in step (3) under a hydrogen-containing atmosphere to obtain a desulfurization catalyst; Wherein, the amount of the lead-containing compound and the zinc-containing compound in the step (1) is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the content of lead oxide is 2-15% by weight, and the content of zinc oxide The content is 30-70% by weight; The precipitation product at least partially contains a zinc-lead solid solution represented by the general formula Pb _x Zn _1-x O, wherein x satisfies 0<x≤0.12, and x represents an atomic molar ratio; The drying conditions include: the drying temperature is 100-200°C, and the drying time is 0.5-3h; the roasting conditions include: the roasting temperature is 400-700°C, and the roasting time is 0.5-3h; The added amount of the silicon oxide source, the aluminum oxide source, the aluminum phosphorus molecular sieve and the compound containing the active metal is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, the amount of the silicon oxide source The content is 5-30% by weight, the content of alumina is 5-30% by weight, the content of aluminum phosphorus molecular sieve is 1-20% by weight and the content of active metal is 5-30% by weight. 11. The preparation method according to claim 10, wherein, the precipitated product satisfies the following relational formula: A ₁₀₀ -B ₁₀₀ =0.2° to 0.3°, A ₁₀₀ and B ₁₀₀ respectively represent that they are obtained under the same XRD measurement conditions In the XRD spectrum of the precipitated product and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (100) plane of ZnO is represented; B ₁₀₀ =31.55°. 12. The preparation method according to claim 10, wherein the precipitated product satisfies the following relational formula: A ₀₀₂ -B ₀₀₂ = 0.2° to 0.3°; A ₀₀₂ and B ₀₀₂ respectively represent that they are obtained under the same XRD measurement conditions In the XRD spectrum of the precipitated product and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (002) plane of ZnO; B ₀₀₂ =34.21°. 13. The preparation method according to claim 10, wherein, the precipitated product satisfies the following relational formula: A ₁₀₁ -B ₁₀₁ =0.2° to 0.3°; A ₁₀₁ and B ₁₀₁ respectively indicate that they are obtained under the same XRD measurement conditions In the XRD spectrum of the precipitated product and the XRD spectrum of ZnO, the 2θ value of the diffraction peak representing the (101) plane of ZnO is represented; B ₁₀₁ =36.04°. 14. The preparation method according to claim 10, wherein the lead-containing compound is lead nitrate and/or lead acetate. 15. The preparation method according to claim 10, wherein the zinc-containing compound is at least one of zinc acetate, zinc chloride and zinc nitrate. 16. The preparation method according to claim 10, wherein the precipitation agent used in the precipitation reaction in step (1) is urea and/or ammoniacal liquor. 17. The preparation method according to claim 10, wherein the pH of the mixture in step (1) is 9-13. 18. The preparation method according to claim 10, wherein the alumina source is a substance that can be transformed into alumina under the conditions of the calcination in step (2). 19. The preparation method according to claim 18, wherein, the alumina source is hydrated alumina and/or aluminum sol; the hydrated alumina is boehmite, pseudoboehmite, trihydrate At least one of alumina and amorphous aluminum hydroxide. 20. The preparation method according to claim 10, wherein the compound containing active metal described in step (3) is acetate, carbonate, nitrate, sulfate, thiocyanate and oxidation of active metal. at least one of the 21. The desulfurization catalyst obtained by the preparation method according to any one of claims 10-20. 22. A method for desulfurizing hydrocarbon oil, the method comprising: contacting sulfur-containing hydrocarbon oil with a desulfurization catalyst, characterized in that the desulfurization catalyst is the desulfurization catalyst described in any one of claims 1-9 and 21 .