WO2020155721A1 - 一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法 - Google Patents

一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法 Download PDF

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WO2020155721A1
WO2020155721A1 PCT/CN2019/115275 CN2019115275W WO2020155721A1 WO 2020155721 A1 WO2020155721 A1 WO 2020155721A1 CN 2019115275 W CN2019115275 W CN 2019115275W WO 2020155721 A1 WO2020155721 A1 WO 2020155721A1
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catalyst
hydrodesulfurization
rare earth
carrier
modified
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PCT/CN2019/115275
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English (en)
French (fr)
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赵亮
高金森
夏步田
董立霞
陈京业
张宇豪
徐春明
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中国石油大学(北京)
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Publication of WO2020155721A1 publication Critical patent/WO2020155721A1/zh
Priority to US17/390,820 priority Critical patent/US11998899B2/en

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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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    • C10G2400/02—Gasoline

Definitions

  • This application relates to petrochemical technology, in particular to a dual-functional catalyst for deep desulfurization and gasoline quality improvement, and a preparation method and application thereof.
  • Catalytic cracking (FCC) gasoline is the main blending component of my country's commercial gasoline, accounting for more than 75% of my country's commercial gasoline. These FCC gasolines contribute more than 90% of the sulfur content and more than 95% of olefins in the gasoline pool. Therefore, for our country, the key to reducing the sulfur content of commercial gasoline lies in the desulfurization of FCC gasoline.
  • Hydrodesulfurization (HDS) technology is currently the most mainstream and most widely used desulfurization technology in refineries.
  • One of the cores of HDS technology is the development of high-performance hydrodesulfurization catalysts.
  • the most widely used HDS catalyst in the clean production of gasoline is the presulfurized CoMo HDS catalyst, which is generally ⁇ -Al 2 O 3 as a carrier and loaded with active metal components Co and Mo.
  • the traditional CoMo-based HSD catalyst has the advantages of good thermal stability and low price.
  • the present application provides a hydrodesulfurization catalyst and a preparation method thereof.
  • the hydrodesulfurization catalyst can realize the deep desulfurization of feed oil with high sulfur content under relatively mild conditions and ensure that there is no large loss of octane number.
  • the present application also provides a gasoline hydrodesulfurization method. Due to the above-mentioned hydrodesulfurization catalyst, deep desulfurization of high-sulfur feedstock oil can be realized under milder conditions, and the octane number loss is small.
  • the present application provides a hydrodesulfurization catalyst comprising a modified catalyst carrier and a supported active metal, wherein the modified catalyst carrier is ⁇ -Al modified with rare earth elements 2 O 3 carrier, or, the modified catalyst carrier is a composite carrier prepared by mixing ⁇ -Al 2 O 3 and acid molecular sieve through a binder, and then modified by rare earth elements.
  • the interaction force between the active metal and the support is effectively reduced, so that the modified hydrodesulfurization catalyst is easier to be sulfided and reduced, thereby The hydrodesulfurization activity of the hydrodesulfurization catalyst is enhanced.
  • the introduction of rare earth elements can also change the acid properties of the carrier surface and form new B acid sites on the surface of the hydrodesulfurization catalyst.
  • the formation of B acid is conducive to the breaking of CS bonds in thiophene sulfides, thereby promoting direct desulfurization.
  • the occurrence of the reaction path (DDS) greatly improves the desulfurization efficiency of the hydrodesulfurization catalyst.
  • the hydrodesulfurization catalyst provided by the present application has excellent deep desulfurization capability, and is especially suitable for completing the deep hydrodesulfurization treatment of FCC gasoline with high sulfur content (sulfur content> 1500ppm) under relatively mild conditions. In addition, it will not significantly Reduce octane number.
  • Rare earth elements are the lanthanide elements in the periodic table of chemical elements, as well as 17 elements including yttrium (Y) and scandium (Sc).
  • the rare earth element used is selected from at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), and yttrium (Y), and in particular may be La and/or Ce.
  • the mass content of rare earth elements in the hydrodesulfurization catalyst is 0.5-5.0 wt%; preferably 0.5-3.0 wt%.
  • the rare earth element is selected as La
  • the mass content of La 2 O 3 in the hydrodesulfurization catalyst is 0.75 to 3%
  • the rare earth element is selected as Ce
  • CeO 2 The mass content in the hydrodesulfurization catalyst is 0.5-2% or 0.75-3%.
  • the hydrodesulfurization catalyst provided in the present application can be obtained by using an impregnation method to support the active metal on a modified catalyst carrier, and then aging, drying, and calcining.
  • the modified catalyst carrier is obtained by impregnation method, loading the rare earth compound on ⁇ -Al 2 O 3 , and then aging, drying and roasting.
  • ⁇ -Al 2 O 3 and acid molecular sieve are mixed and roasted through a binder to make a composite carrier, and then the rare earth compound is loaded on the composite carrier by the impregnation method, and then aged and dried. And calcining to obtain a modified catalyst carrier.
  • the impregnating solution containing rare earth compounds can be loaded on ⁇ -Al 2 O 3 or on a mixture of ⁇ -Al 2 O 3 and acid molecular sieve by an equal volume dipping method, and then at room temperature (20-25 It is aged for 6-12h at °C), dried at 100-160°C for 4-8h, and calcined at 500-700°C for 4-8h to obtain a modified catalyst carrier.
  • the above-mentioned rare earth compound may specifically be one or more of rare earth oxide, rare earth chloride and rare earth nitrate, such as lanthanum nitrate, cerium chloride and the like.
  • the firing atmosphere may specifically be nitrogen, argon, helium, or the like.
  • the modified catalyst support may be ⁇ -Al 2 O 3 modified with rare earth elements, or it may be ⁇ -Al 2 O modified with rare earth elements.
  • acidic molecular sieves refer to molecular sieves with acid catalytic function.
  • the acidic molecular sieves used in this application can be specifically selected from but not limited to the following molecular sieves: ZSM series molecular sieves, MCM series molecular sieves, SAPO series molecular sieves, Beta molecular sieves ( ⁇ molecular sieve, Beta Molecular sieve) one or more.
  • ZSM series molecular sieves can be one or more of ZSM-5, ZSM-8, ZSM-11, ZSM-35 molecular sieves, etc., preferably ZSM-5 molecular sieves;
  • MCM series molecular sieves can be MCM-22, MCM-36 , MCM-41 molecular sieve, etc., preferably MCM-41 molecular sieve;
  • SAPO series molecular sieve can be one or more of SAPO-5, SAPO-11, SAPO-34 molecular sieve, etc., preferably SAPO-34 Molecular sieve.
  • the mass ratio between ⁇ -Al 2 O 3 and acidic molecular sieve can generally be controlled at (9-1):1, preferably 4-8:1.
  • the supported active metal may be selected from at least two elements in the VIB and VIII groups of the periodic table, and in particular may include at least one VIB element and at least one VIII element.
  • the VIB group elements may be Cr, Mo, W, for example;
  • the VIII group elements may be Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, for example.
  • Mo and Co are usually selected as the metal activity together.
  • the molar ratio of VIB elements and VIII elements is usually controlled to be 1:0.1-0.6.
  • Mo and Co are used as active metals, where the atomic molar ratio of Mo to Co is 1:0.1-0.6 .
  • the active metal accounts for 3-25% of the total mass of the hydrodesulfurization catalyst, and further 10-25%.
  • Mo and Co are used as active metals
  • the mass fraction of MoO 3 in the hydrodesulfurization catalyst is 5-14%, preferably 10.5-14.0%
  • the mass fraction of CoO is 1-10%, preferably 3.0-4.0%.
  • This application also provides a method for preparing the aforementioned hydrodesulfurization catalyst, which includes the following steps:
  • the impregnation method is used to load the rare earth elements on ⁇ -Al 2 O 3 , and then the modified catalyst carrier is obtained by aging, drying and roasting; the impregnation method is used to load the active metal on the modified catalyst On the carrier, after aging, drying, and roasting, a hydrodesulfurization catalyst is obtained.
  • ⁇ -Al 2 O 3 and acid molecular sieve are mixed and roasted through a binder to form a composite carrier, and then the rare earth element is loaded on the composite carrier by the impregnation method, and then the modified material is obtained by aging, drying and roasting.
  • the catalyst carrier of sexual treatment adopting the impregnation method, the active metal is loaded on the modified catalyst carrier, and after aging, drying and roasting, the hydrodesulfurization catalyst is obtained.
  • the isometric impregnation method can be used to load the impregnating solution containing rare earth compounds on ⁇ -Al 2 O 3 or on a composite carrier, and then sequentially age at room temperature (20-25°C) for 6-12 hours. It is dried at 100-160°C for 4-8 hours and calcined at 500-700°C, preferably 540-700°C for 4-8 hours to obtain a carrier.
  • the above-mentioned rare earth compound may specifically be one or more of rare earth oxide, rare earth chloride and rare earth nitrate, such as lanthanum nitrate, cerium chloride and the like.
  • the firing atmosphere may specifically be nitrogen, argon, helium, or the like.
  • the binder used in the hydrodesulfurization catalyst is a composite carrier
  • the binder used can be a binder commonly used in the catalyst preparation process, such as amino trimethylene phosphonic acid (ATMP), Polyvinylpyrrolidone (PVP), Sesbania powder, etc.
  • ATMP amino trimethylene phosphonic acid
  • PVP Polyvinylpyrrolidone
  • Sesbania powder etc.
  • the isometric impregnation method is used to support the active metal on the modified catalyst support. Specifically, the impregnating liquid containing the active metal compound is loaded on the modified catalyst carrier, and then aging, drying, and roasting are performed to obtain the hydrodesulfurization catalyst.
  • the impregnating solution used for supporting the active metal contains water and an active metal compound as well as an organic complexing agent (or called an organic chelating agent).
  • the organic complexing agent is used to improve the dispersion of the active metal on the carrier, so as to reduce the interaction force between the active metal and the carrier, thereby improving the sulfidation degree and desulfurization effect of the hydrodesulfurization catalyst.
  • the organic complexing agent that meets the above requirements can be specifically selected from organic compounds that have two carboxyl groups in the molecular structure and are soluble in water, such as citric acid CA, tartrate TA, and ethylenediaminetetraacetic acid.
  • the mass ratio of organic complexing agent to water is usually controlled to be 1:1 ⁇ 3.
  • the molar ratio of the organic complexing agent to the group VIII element is generally controlled to be 0.3-2:1.
  • the molar ratio of organic complexing agent to metallic molybdenum is generally 0.5-2:1.
  • the above-mentioned active metal compounds may be metal salts such as carbonates and nitrates corresponding to the active metals.
  • the Co source may be, for example, basic cobalt carbonate and cobalt nitrate.
  • the Mo source can be, for example, ammonium heptamolybdate, molybdenum pentachloride and the like.
  • the mass fraction of MoO 3 in the impregnation solution is generally 7-20%, preferably 7-15%, based on oxide; the mass fraction of CoO in the impregnation solution is generally 1-8%, Preferably it is 2-8%.
  • the above-mentioned aging, drying and roasting can specifically be aged at room temperature for 6-12 hours, then dried at 80-120°C for 6-12 hours, and then roasted at 450-600°C for 4-8 hours to complete the active metal loading.
  • the hydrodesulfurization catalyst is obtained.
  • the firing atmosphere may specifically be one of nitrogen, argon, and helium.
  • the hydrodesulfurization catalyst of the present application can be extruded into a shape that meets the application environment, for example, can be prepared into clover, columnar, spherical, and other particles.
  • This application also provides a gasoline hydrodesulfurization method, which uses the aforementioned hydrodesulfurization catalyst.
  • the hydrodesulfurization catalyst can be presulfided first, and then the gasoline can be hydrodesulfurized.
  • the gasoline may be full-distillate gasoline or heavy-distillate gasoline, especially FCC gasoline with a sulfur content of more than 1500 ppm.
  • the reaction conditions for presulfurization can be: temperature 300 ⁇ 500°C, hydrogen partial pressure 1.5 ⁇ 2.5MPa, hydrogen to oil volume ratio (that is, the ratio of hydrogen volume to oil volume, abbreviated as H/O) 200 ⁇ 350, presulfide time 8 ⁇ 12h.
  • the optimal process conditions for gasoline hydrodesulfurization using the hydrodesulfurization catalyst are: temperature 250 ⁇ 300°C, hydrogen partial pressure 1.5 ⁇ 3.0MPa, hydrogen oil volume ratio 150 ⁇ 350, space velocity 3 ⁇ 8h -1 . Hydrodesulfurization under such mild conditions can not only achieve deep desulfurization, but also reduce the saturation of olefins to a certain extent and avoid a large loss of octane number.
  • this application provides a dual-functional catalyst for deep desulfurization and gasoline quality improvement, and its preparation method and application, which have the following beneficial effects:
  • the hydrodesulfurization catalyst provided by the present application through the introduction of rare earth elements, makes the hydrodesulfurization catalyst have excellent deep desulfurization ability.
  • relatively mild conditions temperature 260-300°C, hydrogen partial pressure 1.5-3.0 MPa
  • the high sulfur content (sulfur content>1500ppm) FCC gasoline is subjected to hydrodesulfurization, and the desulfurization rate can reach 98.5% or more, so that the sulfur content in the gasoline product obtained is below 40ppm, and even can reach below 10ppm, thereby achieving deep desulfurization.
  • the hydrodesulfurization catalyst has more excellent olefin protection function. During the hydrodesulfurization process, it is more inclined to the hydrodesulfurization reaction of sulfides, reducing the olefin saturation. . Therefore, while the hydrodesulfurization catalyst deeply desulfurizes high-sulfur FCC gasoline, the loss of octane number is less than 2.5 units or even lower, thus avoiding a large loss of octane number.
  • Figure 1 is a Py-FTIR diagram of the hydrodesulfurization catalyst provided in Examples 1-3 and Comparative Example 1;
  • Figure 2 is a Mo3d XPS diagram of the hydrodesulfurization catalyst provided in Examples 1-3 and Comparative Example 1;
  • Fig. 3 shows the results of the hydrogenation reaction of the hydrodesulfurization catalysts provided in Examples 1-3 and Comparative Example 1 on North China heavy fraction gasoline.
  • This embodiment provides a hydrodesulfurization catalyst, and the preparation steps are as follows:
  • This comparative example provides a CoMo/ ⁇ -Al 2 O 3 catalyst.
  • the preparation process is as follows: without any treatment on ⁇ -Al 2 O 3 , the preparation process of the active metal impregnation solution and the equal volume impregnation method are respectively the same as those of Example 1. Steps 2-3 are the same, and the catalyst composition is shown in Table 1.
  • This example provides a hydrodesulfurization catalyst.
  • the preparation steps are basically the same as those of Example 1, except that the loading of rare earth element Ce is increased by 50% compared to Example 1.
  • the resulting catalyst is named GZ-2 ,
  • the catalyst composition is shown in Table 1.
  • This embodiment provides a hydrodesulfurization catalyst.
  • the preparation steps are basically the same as those in Example 2. The difference is that the rare earth element Ce is changed to the rare earth element La, and the loading amount of the rare earth element La is basically the same as that in Example 2. Keeping the same, the prepared catalyst is named GZ-3.
  • This embodiment provides a rare earth element and acid molecular sieve modified hydrodesulfurization catalyst, and the preparation process is as follows:
  • Example 2 According to the steps of Example 1, the rare earth element Ce was impregnated on the composite support, and the Ce loading was controlled to be the same as in Example 1.
  • the prepared catalyst was named GZ-4.
  • Figure 1 is the Py-FTIR diagram of the hydrodesulfurization catalysts provided in the above Examples 1-3 and Comparative Example 1, wherein Figure 1(a) obtained at 200°C is used to calculate the total acid content of the hydrodesulfurization catalyst. Figure 1(b) obtained at 350°C is used to calculate the amount of medium-strong acid in the hydrodesulfurization catalyst.
  • the results of the hydrogenation reaction on the North China heavy fraction gasoline are shown in Figure 3.
  • the characteristic peaks near 1450 cm -1 and 1622 cm -1 are the characteristic absorption peaks of Lewis acid (L acid for short), and near 1542 cm -1
  • the characteristic absorption peak of acid (abbreviated as B acid).
  • the rare earth element La-modified hydrodesulfurization catalyst (GZ-3) has no obvious characteristic peak of B acid. It is speculated that the increase in hydrodesulfurization activity is mainly due to the decrease in the introduction of La The interaction between the support and the active metal is facilitated to form more MoS 2 active phases. It is precisely because the introduction of La's effect on the acidity of the hydrodesulfurization catalyst is mainly reflected in the reduction of the L acid content, which has no obvious effect on the formation of B acid, so the hydrodesulfurization performance of GZ-3 is not as good as that of the GZ-2 catalyst. Can be confirmed from Table 2.
  • the Mo3d spectrum of the sulfided catalyst contains the following three double peaks:
  • the double peaks with binding energy of 229.1 ⁇ 0.2 and 232.3 ⁇ 0.1eV are MoS 2
  • the characteristic peaks of the species; the double peaks with binding energies of 231.2 ⁇ 0.1 and 235.2 ⁇ 0.1eV represent the characteristic peaks of MoS x O y ; the double peaks with binding energies of 233.2 ⁇ 0.1 and 236 ⁇ 0.1eV are characteristic of Mo 6+ species peak.
  • the hydrodesulfurization catalyst modified by rare earth elements has a higher degree of sulfidation and has more MoS 2 active phases.
  • the content of MoS 2 active phase in the unmodified CoMo/ ⁇ -Al 2 O 3 catalyst in Comparative Example 1 is 45.2%, and the incompletely sulfurized product MoS x O y
  • the relative content of the species is the highest 25.1%; and in Example 3, the content of the MoS 2 active phase in the hydrodesulfurization catalyst modified by the rare earth element La is 61.9%, and the relative content of the MoS x O y species is 15.5%.
  • the introduction of rare earth elements can promote the sulfidation reduction of Mo species, which is conducive to the formation of more MoS 2 active phases, thereby enhancing the hydrodesulfurization effect of the hydrodesulfurization catalyst.
  • Example 4 it can be seen that when the rare earth element Ce and acid molecular sieve (ZSM-5 molecular sieve) are used to modify the catalyst at the same time, the octane protection capacity of the obtained GZ-4 catalyst is better than the other three. Examples, but the desulfurization effect is lower than other examples.
  • the obtained product oil has a high olefin content.
  • the hydrodesulfurization catalyst modified with rare earth elements has a better olefin protection function than the unmodified CoMo/ ⁇ -Al 2 O 3 catalyst, and it is more prone to hydrogenation of sulfides during the hydrodesulfurization process.
  • the removal reaction reduces the olefin saturation to a certain extent, thereby increasing the selectivity of the hydrodesulfurization reaction/olefin hydrogenation saturation reaction.
  • the hydrodesulfurization catalyst provided in the present application can meet the deep desulfurization of FCC gasoline with high sulfur content while reducing octane loss.
  • the octane loss caused by the unmodified CoMo/ ⁇ -Al 2 O 3 catalyst in Comparative Example 1 is as high as 3.5 units.
  • rare earth elements are used to modify The octane number loss caused by the hydrodesulfurization catalyst is less than 2.5 units, especially the octane number loss caused by the Ce-modified hydrodesulfurization catalyst (GZ-1 and GZ-2) is less than 2 units.
  • the hydrodesulfurization catalyst provided by the present application can achieve deep desulfurization of FCC gasoline with high sulfur content (sulfur content> 1500ppn) under relatively mild process conditions. After a hydrogenation reaction, the sulfur content can be reduced. To 40ppm or even below 10ppm, it also has a more excellent olefin protection function, and the final octane loss does not exceed 3.5 units, or even does not exceed 2 units.

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Abstract

提供一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法和应用。该双功能催化剂包含经改性处理的催化剂载体，以及负载的活性金属，其中，该经改性处理的催化剂载体为经稀土元素改性的γ-Al 2O 3载体，或者，该经改性处理的催化剂载体为γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧制备成的复合载体，再经稀土元素改性得到。深度脱硫与提高汽油品质的双功能催化剂，能够在较为缓和的条件下实现高硫含量催化裂化汽油的深度脱硫，并确保辛烷值无大幅度损失。

Description

一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法 技术领域
本申请涉及石油化工技术，具体涉及一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法和应用。
背景技术
近年来，机动车尾气排放造成了严重的大气污染，比如雾霾天气频发就与机动车排放的尾气有着密切的关系。已有研究表明，油品中的硫含量几乎决定了机动车排放的所有污染物水平。鉴于此，世界各国家和地区都制定了愈加严格的汽油质量标准，比如我国在2017年01月实施的国V标准中就要求汽油硫含量降至10ppm以下、烯烃降至≯25v％、芳烃≯40v％。而2019年实施的国VI车用汽油标准除了要求硫含量低至小于10ppm的前提下，还进一步要求烯烃含量降低至18v％以下，且辛烷值保持在92以上。另一方面，随着对原油的不断开采，原油质量越变越差，中硫原油(硫含量介于500ppm与2000ppm之间)和高硫原油(硫含量>2000ppm)的比例不断增加。在上述双重压力下，脱硫的重要性及严峻性便越来越突出，超低硫(硫含量≯10ppm)甚至无硫汽油的生产加工是世界范围内炼油及化工企业面临的巨大挑战。
催化裂化(FCC)汽油是我国商品汽油的主要调和组分，约占我国商品汽油的75％以上，这些FCC汽油贡献了汽油池中90％以上的硫含量和超过95％的烯烃。因此对我国而言，降低商品汽油硫含量的重点在于对FCC汽油的脱硫处理。
加氢脱硫(HDS)技术是目前炼油企业最主流、应用最广的脱硫技术，而HDS技术的核心之一就在于高性能加氢脱硫催化剂的研发。目前汽油清洁化生产中应用最广泛的HDS催化剂是经过预硫化处理的CoMo系HDS催化剂，其一般是以γ-Al 2O 3作为载体，负载有活性金属组分Co和Mo。传统的CoMo系HSD催化剂具有热稳定性好、价格低廉等优势，但不足之处在于，在处理硫含量较高(比如硫含量＞1500ppm)的原料油，尤其是催化裂化(FCC)汽油时，常规条件下难以实现深度脱硫，而提高加氢脱硫反应的苛刻度，又 会导致大量的烯烃饱和，进而带来较大的辛烷值损失。
综上，采用传统的加氢脱硫催化剂，难以获得满足当前汽油质量标准的高品质汽油产品。因此，开发一种新型的加氢脱硫催化剂，使其在较为缓和的条件下实现原料油、尤其是FCC汽油的深度脱硫，并确保辛烷值无较大损失，是目前有待解决的技术问题。
发明创造内容
针对上述缺陷，本申请提供一种加氢脱硫催化剂及其制备方法，该加氢脱硫催化剂能够在较为缓和的条件下实现高硫含量原料油的深度脱硫，并且确保辛烷值无较大损失。
本申请还提供一种汽油加氢脱硫方法，由于采用了上述加氢脱硫催化剂，因而能够在较为缓和的条件下实现高硫含量原料油的深度脱硫，且辛烷值损失较小。
为实现上述目的，本申请提供一种加氢脱硫催化剂，包含经改性处理的催化剂载体，以及负载的活性金属，其中，该经改性处理的催化剂载体为经稀土元素改性的γ-Al 2O 3载体，或者，该经改性处理的催化剂载体为γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧制备成的复合载体，再经稀土元素改性得到。
根据本申请提供的技术方案，通过在加氢脱硫催化剂中引入稀土元素，有效地降低了活性金属与载体之间的相互作用力，使改性后的加氢脱硫催化剂更容易被硫化还原，从而增强了加氢脱硫催化剂的加氢脱硫活性。并且，稀土元素的引入，还可以改变载体表面的酸性质，在加氢脱硫催化剂表面形成新的B酸位，而B酸的形成有利于噻吩类硫化物中C-S键的断裂，从而促进直接脱硫反应路径(DDS)的发生，大大提高了加氢脱硫催化剂的脱硫效率。因此，本申请提供的加氢脱硫催化剂具有优异的深度脱硫能力，尤其适合于在较为缓和的条件下完成高硫含量(硫含量＞1500ppm)FCC汽油的深度加氢脱硫处理，此外还不会显著降低辛烷值。
稀土元素是化学元素周期表中镧系元素以及钇(Y)和钪(Sc)共17种元素的统称。在本申请一些示例中，所使用的稀土元素选自镧(La)、铈(Ce)、镨(Pr)以及钇(Y)中的至少一种，尤其可以是La和/或Ce。
合理控制加氢脱硫催化剂中稀土元素的负载量，有利于进一步提高加氢脱硫催化剂的加氢脱硫活性及加氢脱硫效率。在本申请优选的实施方案中，以氧化物计，稀土元素在加氢脱硫催化剂中的质量含量为0.5～5.0wt％；优选0.5～3.0wt％。比如在本申请的一些示例中，稀土元素选择La，且La 2O 3在加氢脱硫催化剂中的质量含量为0.75～3％；在本申请的另一些示例中，稀土元素选择Ce，且CeO 2在加氢脱硫催化剂中的质量含量为0.5～2％或0.75～3％。
本申请中提供的加氢脱硫催化剂，具体可采用浸渍法，将活性金属负载于经改性处理的催化剂载体上，并经陈化、干燥、焙烧而得到。
其中，在本申请一些示例中，经改性处理的催化剂载体是采用浸渍法，将稀土化合物负载于γ-Al 2O 3上，再经陈化、干燥和焙烧得到。在本申请另一些示例中，是将γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧制成复合载体，然后采用浸渍法，将稀土化合物负载于复合载体上，再经陈化、干燥和焙烧，得到经改性处理的催化剂载体。
具体的，可通过等体积浸渍法，将含有稀土化合物的浸渍液负载到γ-Al 2O 3上或者负载到γ-Al 2O 3与酸性分子筛的混合物上，然后依次在室温(20～25℃)下陈化6～12h、在100～160℃下干燥4～8h、在500～700℃下焙烧4～8h，得到经改性处理的催化剂载体。
其中，上述稀土化合物具体可以是氧化稀土、氯化稀土和硝酸稀土中的一种或多种，比如硝酸镧、氯化铈等。焙烧气氛具体可以是氮气、氩气、氦气等。
如前述，本申请提供的加氢脱硫催化剂，其经改性处理的催化剂载体可以是经稀土元素改性的γ-Al 2O 3，或者也可以是经稀土元素改性的γ-Al 2O 3和酸性分子筛。其中，酸性分子筛是指具有酸催化功能的分子筛，本申请中所用的酸性分子筛，具体可以选自但不限于下列分子筛：ZSM系列分子筛、MCM系列分子筛、SAPO系列分子筛、贝塔分子筛(β分子筛、Beta分子筛)中的一种或多种。其中，ZSM系列分子筛可以为ZSM-5、ZSM-8、ZSM-11、ZSM-35分子筛等中的一种或多种，优选ZSM-5分子筛；MCM系列分子筛可以为MCM-22、MCM-36、MCM-41分子筛等中的一种或多种，优选MCM-41分子筛；SAPO系列分子筛可以为SAPO-5、SAPO-11、SAPO-34分子筛等中的 一种或多种，优选SAPO-34分子筛。
通过采用酸性分子筛作为γ-Al 2O 3的掺杂剂，不仅能够引入更多的酸中心，而且还能够调节加氢脱硫催化剂表面布朗斯台德(BAS)和路易斯酸位点(LAS)的比值，从而促进加氢脱硫反应的进行，提高脱硫率。
当载体中含有γ-Al 2O 3和酸性分子筛时，γ-Al 2O 3与酸性分子筛之间的质量比一般可控制在(9～1)：1，优选为4～8：1。
本申请提供的加氢脱硫催化剂，其负载的活性金属可以选自元素周期表中VIB和VIII族中的至少两种元素，尤其可以包括至少一种VIB族元素和至少一种VIII族元素。其中VIB族元素比如可以是Cr、Mo、W；VIII族元素比如可以是Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt。在本申请优选的实施方式中，通常选择Mo和Co共同作为金属活性。
合理调整活性金属中的元素组成，有利于进一步改善加氢脱硫催化剂的加氢脱硫效果。在本申请具体实施过程中，通常控制VIB族元素和VIII族元素的摩尔比为1：0.1～0.6，比如使用Mo和Co作为活性金属，其中Mo与Co的原子摩尔比为1：0.1～0.6。
在本申请一些示例中，以氧化物计，活性金属占加氢脱硫催化剂总质量的3～25％，进一步为10～25％。比如以Mo和Co作为活性金属，MoO 3在加氢脱硫催化剂中的质量分数为5～14％，优选10.5～14.0％，CoO的质量分数为1～10％，优选3.0～4.0％。
本申请还提供前述加氢脱硫催化剂的制备方法，包括如下步骤：
采用浸渍法，将稀土元素负载于γ-Al 2O 3上，再经陈化、干燥和焙烧，得到经改性处理的催化剂载体；采用浸渍法，将活性金属负载于经改性处理的催化剂载体上，并经陈化、干燥、焙烧，得到加氢脱硫催化剂。
或者，将γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧，制成复合载体，然后采用浸渍法，将稀土元素负载于复合载体上，再经陈化、干燥和焙烧，得到经改性处理的催化剂载体；采用浸渍法，将活性金属负载于经改性处理的催化剂载体上，并经陈化、干燥、焙烧，得到加氢脱硫催化剂。
具体的，可采用等体积浸渍法，将含有稀土化合物的浸渍液负载到γ-Al 2O 3上或者负载到复合载体上，然后依次在室温(20～25℃)下陈化6～12h、在100～160℃下干燥4～8h、在500～700℃、优选540～700℃下焙烧 4～8h，得到载体。
其中，上述稀土化合物具体可以是氧化稀土、氯化稀土和硝酸稀土中的一种或多种，比如硝酸镧、氯化铈等。焙烧气氛具体可以是氮气、氩气、氦气等。
当然，若加氢脱硫催化剂所用的经改性处理的催化剂载体为复合载体，则所用的粘结剂可以是催化剂制备过程中所常用的粘结剂，比如氨基三亚甲基膦酸(ATMP)、聚乙烯吡咯烷酮(PVP)、田菁粉等。通过加入适量的粘结剂，有利于制备得到性能优异、分布均匀、酸性适中的复合载体，比如粘结剂：γ-Al 2O 3+酸性分子筛＝1.5～3：1(质量比)。
本申请对于如何在经改性处理的催化剂载体上负载活性金属的具体方式不做特别限定，在本申请一些示例中，是采用等体积浸渍法，在经改性处理的催化剂载体上负载活性金属。具体是将将含有活性金属化合物的浸渍液负载到经改性处理的催化剂载体上，再经陈化、干燥、焙烧，得到加氢脱硫催化剂。
尤其是，负载活性金属所用浸渍液中除了包含水、活性金属化合物之外，还包含有机络合剂(或称为有机螯合剂)。该有机络合剂用于改善活性金属在载体上的分散度，以降低活性金属与载体之间的相互作用力，从而提高加氢脱硫催化剂的硫化度以及脱硫效果。满足上述要求的有机络合剂具体可以选自分子结构中带有两个羧基、且能够溶于水的有机化合物，比如柠檬酸CA、酒石酸TA和乙二胺四乙酸中的一种以上。
在配制浸渍液的过程中，通常控制有机络合剂与水的质量比为1：1～3。在本申请一些示例中，在配制浸渍液时，一般控制有机络合剂与VIII族元素的摩尔比为0.3～2：1。比如当选择Co和Mo共同作为活性金属时，一般有机络合剂与金属钼的摩尔比为0.5～2：1。
具体的，上述活性金属化合物，可以是活性金属所对应的碳酸盐、硝酸盐等金属盐，比如选择Co和Mo共同作为金属活性组分，则Co源比如可以是碱式碳酸钴、硝酸钴等，Mo源比如可以是七钼酸铵、五氯化钼等。在本申请具体实施过程中，以氧化物计，MoO 3在浸渍液中的质量分数一般为7～20％，优选7～15％；CoO在浸渍液中的质量分数一般为1～8％，优选2～8％。
上述陈化、干燥和焙烧，具体可在室温下陈化6～12h，然后在80～120 ℃下干燥6～12h，然后在450～600℃下焙烧4～8h，即完成活性金属的负载，得到加氢脱硫催化剂。焙烧气氛具体可以为氮气、氩气、氦气中的一种。
本申请的加氢脱硫催化剂，可以经挤条成型为满足应用环境的形状，例如可制备成三叶草、柱形、球形等颗粒。
本申请还提供一种汽油加氢脱硫方法，是采用前述加氢脱硫催化剂。
具体的，可首先对加氢脱硫催化剂进行预硫化，然后再对汽油实施加氢脱硫处理。该汽油可以是全馏分汽油，也可以是重馏分汽油，尤其可以是含硫量大于1500ppm的FCC汽油。预硫化的反应条件可以为：温度300～500℃，氢气分压1.5～2.5MPa，氢油体积比(即氢气体积与油品体积之比，简写为H/O)200～350，预硫化时间8～12h。
经进一步研究，使用该加氢脱硫催化剂对汽油进行加氢脱硫的最优工艺条件为：温度250～300℃，氢气分压1.5～3.0MPa，氢油体积比150～350，空速3～8h -1。在此温和的条件下进行加氢脱硫，不仅能够实现深度脱硫，而且能够在一定程度上减少烯烃饱和量，避免辛烷值的大量损失。
综上所述，本申请提供了一种深度脱硫与提高汽油品质的双功能催化剂及其制备方法和应用，具有以下有益效果：
本申请提供的加氢脱硫催化剂，通过引入稀土元素，使该加氢脱硫催化剂具有优异的深度脱硫能力，在较为缓和的条件(温度260～300℃，氢气分压1.5～3.0MPa)下，对高硫含量(硫含量＞1500ppm)FCC汽油进行加氢脱硫，脱硫率可达到98.5％以上，使得到的汽油产品中的硫含量在40ppm以下、甚至可达到10ppm以下，从而实现了深度脱硫。
此外，与未被稀土改性的催化剂相比，该加氢脱硫催化剂具有更加优异的烯烃保护功能，在加氢脱硫过程中，更倾向于硫化物的加氢脱除反应，减少了烯烃饱和量。因此，该加氢脱硫催化剂对高硫含量FCC汽油进行深度脱硫的同时，所造成的辛烷值损失小于2.5个单位甚至更低，因此避免了辛烷值的大量损失。
附图说明
图1为实施例1-3和对比例1中提供的加氢脱硫催化剂的Py-FTIR图；
图2为实施例1-3和对比例1中提供的加氢脱硫催化剂的Mo3d XPS图；
图3为实施例1-3和对比例1中提供的加氢脱硫催化剂对华北重馏分汽油的加氢反应结果。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1
本实施例提供一种加氢脱硫催化剂，其制备步骤如下：
1、用去离子水配制一定浓度的稀土元素浸渍液，然后采用等体积浸渍法将稀土元素浸渍液浸渍到γ-Al 2O 3上，浸渍过程中添加一定量的氨水以提高浸渍液的分散度。浸渍完成后室温陈化约12h，120℃干燥约8h、540℃焙烧约4h，获得稀土改性后的载体(命名为GZ载体)。
2、取适量水，开启搅拌加热至40℃，加入柠檬酸CA(CA/Co＝1.5)搅拌至完全溶解。再加入碳酸钴，搅拌反应至无气泡生成为止，将溶液缓慢升温至沸腾状态是物料全部溶解后(无气泡生成)，停止加热，降至室温后停搅拌。加入氨水至终体积的85％，再缓慢加入七钼酸铵搅拌至完全溶解，补加氨水至终体积，得到活性金属浸渍液，密封保存、备用。
3、将步骤2制得的活性金属浸渍液通过等体积浸渍法负载到步骤1制得的GZ复合载体上，饱和后再搅拌10min，室温下陈化12h，100℃下干燥8h，540℃下焙烧4h，得到稀土元素改性催化剂，命名为GZ-1。该催化剂组成见表1。
对比例1
本对比例提供一种CoMo/γ-Al 2O 3催化剂，其制备工艺为：对γ-Al 2O 3不做任何处理，活性金属浸渍液的配制过程以及等体积浸渍方法分别与实施例1中的步骤2-3相同，该催化剂组成见表1。
实施例2
本实施例提供一种加氢脱硫催化剂，其制备步骤与实施例1基本相同，不同之处仅为将稀土元素Ce的负载量相比实施例1提高了50％，所得催化剂命名为GZ-2，该催化剂组成见表1。
实施例3
本实施例提供一种加氢脱硫催化剂，其制备步骤与实施例2基本相同，不同之处为将稀土元素Ce改为稀土元素La，且稀土元素La的负载量与实施例2中的Ce基本保持一致，制得的催化剂命名为GZ-3。
实施例4
本实施例提供一种稀土元素和酸性分子筛改性加氢脱硫催化剂，其制备过程如下：
1、将γ-Al 2O 3和ZSM-5按照质量比约为8：1的比例混合，再加入PVP均匀混合，其中PVP的质量约为γ-Al 2O 3与ZSM-5质量和的2倍，然后经120℃干燥8h左右、500℃焙烧4h左右，获得γ-Al 2O 3/ZSM-5复合载体。
2、按照实施例1的步骤，将稀土元素Ce浸渍到复合载体上，控制Ce的负载量与实施例1相同，制得的催化剂命名为GZ-4。
图1为上述实施例1-3和对比例1中所提供的加氢脱硫催化剂的Py-FTIR图，其中200℃下得到的图1(a)用于计算加氢脱硫催化剂的总酸量，350℃下得到的图1(b)用于计算加氢脱硫催化剂的中强酸量。
取上述实施例1-3和对比例1中的加氢脱硫催化剂，放入内径为8mm的固定床反应器中，以3wt％CS 2溶液作为预硫化液对加氢脱硫催化剂进行预硫化，预硫化反应条件为：T＝340℃，P＝2.5MPa，H/O＝300，空速＝2h -1，预硫化时间为6h。取预硫化后反应前的加氢脱硫催化剂样品进行表征测试，所得XPS结果如图2所示。
预硫化反应完成后，分别以华北重馏分汽油(馏程102～194℃，硫含量1538ppm、研究法辛烷值RON＝88.9)、京博重馏分汽油(馏程104～185℃， 硫含量2276ppm、RON＝87.8)、格尔木重馏分汽油(馏程86～180℃，硫含量1854ppm、RON＝90.2)为原料测试加氢脱硫催化剂的加氢脱硫性能。反应工艺条件为：T＝260℃，P＝2MPa，H/O＝300，空速＝3.5h -1。其中对华北重馏分汽油的加氢反应结果如图3所示。
根据文献报道，在1450cm -1和1622cm -1附近的特征峰为Lewis酸(简称L酸)的特征吸收峰，在1542cm -1附近为
Figure PCTCN2019115275-appb-000001
酸(简称B酸)的特征吸收峰。由图1可知，实施例1-3中所提供的加氢脱硫催化剂，在物化性质上与对比例1中未改性的CoMo/γ-Al 2O 3催化剂相比有明显区别，尤其体现在，引入不同类型的稀土元素均会导致加氢脱硫催化剂的L酸特征峰的峰强发生明显的下降，原因可能是在加氢脱硫催化剂制备过程中，稀土元素会和载体表面的Al-OH发生反应，导致部分L酸被中和。
并且，采用稀土元素Ce对CoMo/γ-Al 2O 3催化剂进行改性后(GZ-1和GZ-2)，在200℃下得到的谱图中观察到了B酸的特征吸收峰，说明稀土元素Ce改性CoMo/γ-Al 2O 3催化剂表面同时分布着一定数量的L酸和B酸。而且与GZ-1相比，GZ-2具有更强的B酸中心。已有研究表明，B酸位的存在有利于噻吩类硫化物中C-S键的断裂，从而促进DDS(直接脱硫反应)路径的发生，有利于提高加氢脱硫反应效率。因此可据此推测GZ-2应具有比GZ-1更优的加氢脱硫性能，这点可从表2中得到证实。
另外，从图1可以看出，稀土元素La改性的加氢脱硫催化剂(GZ-3)没有出现明显的B酸的特征峰，推测其加氢脱硫活性的提高主要归因于La的引入降低了载体与活性金属之间的相互作用，从而有利于形成更多的MoS 2活性相。正是由于La的引入对加氢脱硫催化剂酸性的影响主要体现在降低L酸含量上，对B酸的形成无明显作用，因此GZ-3的加氢脱硫性能不如GZ-2催化剂，这点亦可从表2中得到证实。
如图2所示，从X射线光电子能谱分析XPS结果分析来看，硫化态催化剂的Mo3d光谱包含如下的三个双峰：结合能为229.1±0.2和232.3±0.1eV的双峰为MoS 2物种的特征峰；结合能为231.2±0.1和235.2±0.1eV的双峰代表MoS xO y物种的特征峰；结合能为233.2±0.1和236±0.1eV的双峰为Mo 6+物种的特征峰。由图2可知，在同样的预硫化条件下，稀土元素改性后的加氢脱硫催化剂的硫化程度更高，拥有更多的MoS 2活性相。以对比例1 和实施例3的对比情况为例，对比例1中未改性的CoMo/γ-Al 2O 3催化剂中MoS 2活性相的含量为45.2％，未完全硫化产物MoS xO y物种的相对含量为最高的25.1％；而实施例3中稀土元素La改性后的加氢脱硫催化剂中MoS 2活性相的含量为61.9％，MoS xO y物种的相对含量为15.5％。由此可推断，稀土元素的引入能够促进Mo物种的硫化还原，有利于形成更多的MoS 2活性相，从而增强加氢脱硫催化剂的加氢脱硫效果。
表1催化剂的组成(质量分数，wt％)
  γ-Al 2O 3 ZSM-5 La 2O 3 CeO 2 CoO MoO 3
对比例1 79.7 - - - 3.5 13.6
GZ-1 78.9 - - 0.75 3.7 13.4
GZ-2 78.1 - - 1.50 3.8 13.4
GZ-3 78.2 - 1.50 - 3.6 13.5
GZ-4 70.4 8.9 - 0.75 3.5 13.3
注释：“-”代表无；上述催化剂的组成总和小于100％是因为所用的工业级γ-Al 2O 3中有一定量的杂质。
表2不同催化剂的加氢反应性能
Figure PCTCN2019115275-appb-000002
表3不同催化剂上烯烃和辛烷值(RON)的变化
Figure PCTCN2019115275-appb-000003
由表2可知，采用本申请的方法，以稀土改性所获得的加氢脱硫催化剂对高硫含量(硫含量＞1500ppm)的FCC汽油具有非常优异的脱硫性能，在较为缓和的反应工艺条件下(T＝260℃，P＝2MPa)，脱硫率可达到98.5％以上，硫含量降低至35ppm以下，实现深度脱硫。
进一步对比GZ-1、GZ-2和GZ-3可以发现，稀土元素Ce改性后得到的GZ-1和GZ-2的加氢脱硫效果要优于稀土元素La改性后得到的GZ-3。而根据GZ-1和GZ-2的对比结果可知，改变稀土元素的含量对加氢脱硫效果的影响十分明显，适当提高稀土元素的负载量有利于汽油的深度脱硫，比如采用GZ-2可将汽油产品中硫含量降低至10ppm以下。
另外，根据实施例4的结果可以看出，当稀土元素Ce和酸性分子筛(ZSM-5分子筛)同时用于改性催化剂时，所得GZ-4催化剂的辛烷值保护能力要优于其余三个实施例，但脱硫效果低于其余实施例。
并且，如表3所示，从产品油的组成来看，采用实施例1-3中的加氢脱硫催化剂对高硫含量的FCC进行加氢脱硫后，所获得的产品油中的烯烃含量高于未改性的CoMo/γ-Al 2O 3催化剂。说明采用稀土元素改性后的加氢脱硫催化剂，具有比未改性CoMo/γ-Al 2O 3催化剂更加优异的烯烃保护功能，在加氢脱硫过程中，更倾向于发生硫化物的加氢脱除反应，这在一定程度上减少了烯烃饱和量，从而提高了加氢脱硫反应/烯烃加氢饱和反应的选择性。
结合表2和3以及图3可知，本申请提供的加氢脱硫催化剂对高硫含量 的FCC汽油满足深度脱硫的同时还可以减少辛烷值损失。以华北重馏分汽油为例，对比例1中未改性的CoMo/γ-Al 2O 3催化剂对其造成的辛烷值损失高达3.5个单位，实施例1-3中采用稀土元素改性后的加氢脱硫催化剂对造成的辛烷值损失小于2.5个单位，特别是采用Ce改性的加氢脱硫催化剂(GZ-1和GZ-2)造成的辛烷值损失小于2个单位。
综上所述，本申请提供的加氢脱硫催化剂，可在较缓和的工艺条件下实现高硫含量(硫含量＞1500ppn)FCC汽油的深度脱硫，经一次加氢反应后，可将硫含量降低至40ppm甚至10ppm以下，同时具有更加优异的烯烃保护功能，最终辛烷值损失不超过3.5个单位，甚至不超过2个单位。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种加氢脱硫催化剂，其特征在于，包含经改性处理的催化剂载体，以及负载的活性金属，
    其中，所述经改性处理的催化剂载体为经稀土元素改性的γ-Al 2O 3载体，或者，所述经改性处理的催化剂载体为γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧制备成的复合载体，再经稀土元素改性得到。
  2. 根据权利要求1所述的加氢脱硫催化剂，其特征在于，以氧化物计，所述稀土元素在加氢脱硫催化剂中的含量为0.5～5wt％。
  3. 根据权利要求1或2所述的加氢脱硫催化剂，其特征在于，所述稀土元素选自La、Ce、Pr和Y中的至少一种。
  4. 根据权利要求1-3任一项所述的加氢脱硫催化剂，其特征在于，所述加氢脱硫催化剂是采用浸渍法，将活性金属负载于所述经改性处理的催化剂载体上，并经陈化、干燥而得到。
  5. 根据权利要求1所述的加氢脱硫催化剂，其特征在于，所述γ-Al 2O 3与所述酸性分子筛之间的质量比为(9～1)：1；和/或，所述酸性分子筛选自ZSM-5、MCM-41、SAPO-34和Bata分子筛中的一种或多种。
  6. 根据权利要求1所述的加氢脱硫催化剂，其特征在于，所述活性金属选自元素周期表中VIB族和VIII族中的两种以上的元素。
  7. 一种权利要求1-6任一项所述加氢脱硫催化剂的制备方法，其特征在于，包括如下步骤：
    采用浸渍法，将稀土元素负载于γ-Al 2O 3上，再经陈化、干燥和焙烧，得到所述经改性处理的催化剂载体；或者，将γ-Al 2O 3与酸性分子筛通过粘结剂混合焙烧，制成复合载体，然后采用浸渍法，将稀土元素负载于所述复合载体上，再经陈化、干燥和焙烧，得到所述经改性处理的催化剂载体；
    采用浸渍法，将活性金属负载于所述经改性处理的催化剂载体上，并经陈化、干燥和焙烧，得到所述加氢脱硫催化剂。
  8. 根据权利要求7所述的制备方法，其特征在于，采用等体积浸渍法，将含有稀土化合物的浸渍液负载于γ-Al 2O 3上或者复合载体上，然后于室温下陈化6～12h、于100～160℃下干燥4～8h、于500～700℃下焙烧4～8h，得到所述经改性处理的催化剂载体；焙烧气氛为氮气、氩气或氦气。
  9. 根据权利要求7所述的制备方法，其特征在于，采用等体积浸渍法，将活性金属负载于所述经改性处理的催化剂载体上，且所用浸渍液中含有有机络合剂，所述有机络合剂选自柠檬酸、酒石酸和乙二胺四乙酸中的至少一种。
  10. 一种汽油加氢脱硫方法，其特征在于，采用了权利要求1-6任一项所述的加氢脱硫催化剂。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11998899B2 (en) 2019-02-01 2024-06-04 China University Of Petroleum-Beijing Bifunctional catalyst for deep desulfurization and gasoline quality improvement and preparation method therefor

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111298800B (zh) * 2020-03-26 2022-05-06 中国石油大学(北京) 一种加氢脱硫催化剂及其制备方法和应用
CN114029083B (zh) * 2021-12-03 2022-11-04 中国石油大学(北京) 一种加氢脱硫催化剂及其制备方法和应用
CN116328851A (zh) * 2021-12-23 2023-06-27 中国石油天然气股份有限公司 一种含b酸的加氢催化剂载体及其制备与应用
CN114768863B (zh) * 2022-06-02 2023-10-31 润和科华催化剂(上海)有限公司 一种重油加氢脱硫催化剂及其制备方法
CN117181306B (zh) * 2023-11-07 2024-03-15 明硕环境科技集团股份有限公司 一种高炉煤气用水解脱硫双功能催化剂的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998038265A1 (en) * 1997-02-28 1998-09-03 Exxon Research And Engineering Company Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams
CN101844088A (zh) * 2010-04-14 2010-09-29 中国科学院大连化学物理研究所 一种汽油选择性脱硫催化剂
CN101885983A (zh) * 2010-07-02 2010-11-17 中国石油大学(北京) 用于生产超低硫且高辛烷值汽油的高效耦合加氢改质方法
CN101898148A (zh) * 2009-05-27 2010-12-01 中国石油天然气股份有限公司 一种含l分子筛催化裂化汽油选择性加氢脱硫改质催化剂
WO2011095688A2 (en) * 2010-02-02 2011-08-11 Upm-Kymmene Corporation Process and apparatus for producing hydrocarbons
CN108479846A (zh) * 2018-02-08 2018-09-04 中国石油大学(北京) 一种芳构化催化剂及其制备方法和再生方法及芳构化方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3562987D1 (en) * 1984-10-30 1988-07-07 Eurecat Europ Retrait Catalys Method for presulfiding a catalyst for the treatment of hydrocarbons
KR20020061011A (ko) * 1999-12-28 2002-07-19 코닝 인코포레이티드 제올라이트/알루미나 촉매 지지체 조성물 및 이의 제조방법
CN101439293B (zh) * 2007-11-19 2011-03-16 中国石油天然气集团公司 含有介孔分子筛的选择性加氢脱硫催化剂及其制备方法
JP5468957B2 (ja) * 2010-03-29 2014-04-09 Ｊｘ日鉱日石エネルギー株式会社 水素化異性化触媒、その製造方法、炭化水素油の脱蝋方法、炭化水素の製造方法及び潤滑油基油の製造方法
US20120048778A1 (en) * 2010-08-25 2012-03-01 Catalytic Distillation Technologies Selective desulfurization of fcc gasoline
TWI604040B (zh) * 2012-11-08 2017-11-01 China Petrochemical Technology Co Ltd Hydrotreating catalyst, its manufacturing method and application thereof
CN104667956B (zh) * 2013-11-26 2017-02-15 中国石油化工股份有限公司 一种烃油加氢改质催化剂及其制备方法
CN106607096B (zh) * 2015-10-26 2019-05-21 中国石油化工股份有限公司 一种加氢催化剂及其制备方法
CN106890660A (zh) * 2015-12-17 2017-06-27 中国石油天然气股份有限公司 一种加氢脱硫催化剂及其制备方法
CN108421557B (zh) * 2017-02-15 2020-02-28 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998038265A1 (en) * 1997-02-28 1998-09-03 Exxon Research And Engineering Company Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams
EP0970163A1 (en) * 1997-02-28 2000-01-12 Exxon Research And Engineering Company Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams
CN101898148A (zh) * 2009-05-27 2010-12-01 中国石油天然气股份有限公司 一种含l分子筛催化裂化汽油选择性加氢脱硫改质催化剂
WO2011095688A2 (en) * 2010-02-02 2011-08-11 Upm-Kymmene Corporation Process and apparatus for producing hydrocarbons
CN101844088A (zh) * 2010-04-14 2010-09-29 中国科学院大连化学物理研究所 一种汽油选择性脱硫催化剂
CN101885983A (zh) * 2010-07-02 2010-11-17 中国石油大学(北京) 用于生产超低硫且高辛烷值汽油的高效耦合加氢改质方法
CN108479846A (zh) * 2018-02-08 2018-09-04 中国石油大学(北京) 一种芳构化催化剂及其制备方法和再生方法及芳构化方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAO, XIRUO: "Study on Catalyst Preparation And Process for Selective Hydrodesulfurization of FCC Gasoline", MASTER THESIS, 15 July 2016 (2016-07-15), pages 1 - 89, XP009522388 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11998899B2 (en) 2019-02-01 2024-06-04 China University Of Petroleum-Beijing Bifunctional catalyst for deep desulfurization and gasoline quality improvement and preparation method therefor

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