阅读说明：本技术 一种加氢催化剂及其制备方法 (Hydrogenation catalyst and preparation method thereof ) 是由 姚运海 刘丽 杨成敏 段为宇 李扬 郭蓉 周勇 孙进 郑步梅 丁莉 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种加氢催化剂及其制备方法。加氢催化剂包括加氢催化剂载体和加氢活性组分,以所述催化剂的总重量为基准,第VIB族金属硫化物为2.2wt%-33wt%,优选10wt%-20wt%,第VIII族金属氧化物计为0.2wt%-12wt%,优选3wt%-6wt%。制备方法如下：(1)用含第VIB族金属的浸渍液浸渍加氢催化剂载体,然后干燥处理,干燥后的物料进行硫化处理；(2)用含第族金属的浸渍液浸渍到步骤(1)硫化后的的物料,然后在惰性气氛下,进行干燥和焙烧,得到加氢催化剂。本发明催化剂具有较高的硫化度及高的II类活性中心数,本发明的催化剂可以应用在馏分油、渣油等油品加氢处理过程。(The invention discloses a hydrogenation catalyst and a preparation method thereof. The hydrogenation catalyst comprises a hydrogenation catalyst carrier and a hydrogenation active component, wherein the VIB group metal sulfide accounts for 2.2-33 wt%, preferably 10-20 wt%, and the VIII group metal oxide accounts for 0.2-12 wt%, preferably 3-6 wt%, based on the total weight of the catalyst. The preparation method comprises the following steps: (1) dipping a hydrogenation catalyst carrier by using dipping liquid containing VIB group metal, then drying, and vulcanizing the dried material; (2) by using a catalyst containing)

1. A hydrogenation catalyst comprises a hydrogenation catalyst carrier and a hydrogenation active component, and is characterized in that: the hydrogenation active components are VIB group metal sulfide and VIII group metal oxide, and the VIB group metal sulfide accounts for 2.2wt% -33wt%, preferably 10wt% -20wt%, and the VIII group metal oxide accounts for 0.2wt% -12wt%, preferably 3wt% -6wt%, based on the total weight of the catalyst.

2. The hydrogenation catalyst of claim 1, wherein: 10-20 wt% of VIB group metal sulfide and 3-6 wt% of VIII group metal oxide.

3. The hydrogenation catalyst of claim 1, wherein: the VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni.

4. The hydrogenation catalyst of claim 1, wherein: the catalyst is analyzed by XPS energy spectrum, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 60-90%.

5. The hydrogenation catalyst of claim 1, wherein: after the catalyst is vulcanized, XPS (X-ray diffraction spectroscopy) energy spectrum analysis is adopted, wherein the molar proportion of the +4 valence VIB metal content in the total VIB metal content is 65-100%, and the molar proportion of the interaction species content of the VIII metal and the VIB metal in the VIII metal content is 60-100%.

6. The hydrogenation catalyst of claim 1, wherein: the hydrogenation catalyst carrier is porous inorganic refractory oxide, and is selected from one or more of oxides of elements in II group, III group, IV group and IVB group in the periodic table.

7. The hydrogenation catalyst of claim 1, wherein: the hydrogenation catalyst carrier is one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide and aluminum magnesium oxide.

8. The hydrogenation catalyst of claim 1, wherein: the hydrogenation catalyst carrier is modified, the modified element is B, P or F or more, and the weight percentage of the modified element is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier.

9. A method for preparing a hydrogenation catalyst according to any one of claims 1 to 8, characterized by comprising: (1) dipping a hydrogenation catalyst carrier by using dipping liquid containing VIB group metal, then drying, and vulcanizing the dried material; (2) by using a catalyst containingAnd (2) impregnating the material vulcanized in the step (1) with an impregnation solution of the group metal, and then drying and roasting the material in an inert atmosphere to obtain the hydrogenation catalyst.

10. The method of claim 9, wherein: the mass concentration of the VIB group metal impregnation liquid in the step (1) is 0.1-2.0 g/mL, and an equal-volume impregnation mode is adopted.

11. The method of claim 9, wherein: the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.

12. The method of claim 9, wherein: the vulcanization treatment conditions in the step (1) are as follows: the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h; the vulcanizing agent is one or more of hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide.

13. The method of claim 9, wherein: the second step of (2)The mass concentration of the group metal impregnation liquid is 0.1 g/mL-1.0 g/mL, and an equal-volume impregnation mode is adopted.

14. The method of claim 9, wherein: the inert atmosphere in the step (2) is N₂And an inert gas; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

15. Use of the hydrogenation catalyst of any one of claims 1 to 9 in an oil hydrotreating process.

Technical Field

The invention relates to the technical field of oil product hydrogenation, in particular to a hydrogenation catalyst and a preparation method thereof.

Background

The sulfur compounds contained in diesel oil mainly include aliphatic sulfides, thioethers, Dibenzothiophenes (DBT), alkylbenzothiophenes, alkyldibenzothiophenes, and the like. The oil product desulfurization technology is divided into non-hydrodesulfurization and Hydrodesulfurization (HDS), wherein the non-hydrodesulfurization technology mainly comprises adsorption desulfurization, oxidation desulfurization, extraction desulfurization, biological desulfurization and the like. Although the non-hydrodesulfurization technology has great progress, especially the oxidative desulfurization has the best application prospect, the method has the defects of high operation cost, high oil product loss, high capital and equipment investment and the like, and the subsequent treatment of the oil product has certain difficulty, so that the industrialization is difficult to realize in a short time. The HDS technology adopts a desulfurization catalyst to react under the conditions of high temperature and high pressure to convert sulfide into H₂S, carrying out a separation process. Compared with other desulfurization technologies, HDS technology is mature. For oil products with high sulfur content, the technology can greatly reduce the sulfur content. Meanwhile, the HDS technology has flexible operation, high yield of refined oil and good color and luster, and can effectively remove sulfides such as thiophene and the like which are difficult to remove. With the increasingly strict requirements on the cleanness of diesel oil, the HDS technology becomes more and more important, becomes an important means for improving the product quality of oil refining enterprises, and makes a great deal of research work at home and abroad.

The more mature HDS technology in foreign countries is mostly centered on newly developed high-activity catalysts, such as STARS and NEBULA series catalysts of the American Abboto company, CENTINEL series catalysts of the American Standard company, TK series catalysts of the Denmark TopuSol company, HR series catalysts of the national Petroleum institute, and the like. The STARS catalyst technology (II type active reaction center) is suitable for producing low-sulfur or ultra-low-sulfur clean fuel with the sulfur mass fraction of less than 50 mu g/g, KF-757 taking Mo-Co as an active metal component and KF-848 catalyst taking Mo-Ni as an active metal component are mainly applied industrially, and the KF-757 and the KF-848 catalysts show very high hydrodesulfurization activity under different operating conditions. KF-757 is suitable for producing product with sulfur mass fraction less than 50 μ g/g under medium and low pressure, KF-848 is suitable for producing clean fuel with sulfur mass fraction less than 10 μ g/g under medium and high pressure.

The preparation method of the general II-Type active center catalyst is to introduce a chelating agent in the preparation process of the hydrofining catalyst, wherein the chelating agent has the effects of weakening the interaction between an active component and a carrier, improving the dispersion degree of the active component on the carrier, delaying the vulcanization of auxiliary metal (Co, Ni) and the like, and can promote the generation of a high-activity Type II Co-Mo-S phase.

CN102465005A discloses a start-up method of a II-type active center catalyst. The proposal requires introducing vulcanized oil at 135 ℃, which is beneficial to the generation of more II active centers by the catalyst. CN102443412A discloses a start-up method of an out-of-device presulfurization II-type active center hydrogenation catalyst. The temperature of the scheme is lower when the activated oil is introduced, and the constant temperature in the activation process is lower, so that the method has the advantage of forming more II-type active centers. CN201010222027.7 discloses a start-up vulcanization method for a class II active center hydrogenation catalyst, which has the advantages of simple process, convenient operation and more ideal vulcanization effect than the conventional method, thereby being beneficial to improving the number of class II active centers and further improving the activity of the catalyst. The method for improving the number of the active centers of the catalyst II in the patent mainly adopts a method for changing the vulcanization process to improve the activity of the catalyst.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst and a preparation method thereof. The catalyst has higher degree of vulcanization and high II-type activity center number, and can be applied to the hydrotreating process of distillate oil, residual oil and other oil products.

The hydrogenation catalyst comprises a hydrogenation catalyst carrier and hydrogenation active components, wherein the hydrogenation active components are VIB group metal sulfide and VIII group metal oxide, wherein the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni.

Based on the total weight of the catalyst, the VIB group metal sulfide accounts for 2.2wt% -33wt%, preferably 10wt% -20wt%, and the VIII group metal oxide accounts for 0.2wt% -12wt%, preferably 3wt% -6 wt%. The catalyst is analyzed by XPS energy spectrum, wherein the molar proportion of the +4 valence VIB group metal content in the total VIB group metal content is 60-90%.

The catalyst is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar proportion of the +4 valence VIB group metal content to the total VIB group metal content is 65-100%, and the molar proportion of the interaction species content of the VIII group metal and the VIB group metal content to the total VIII group metal content is 60-100%. The vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

The hydrogenation catalyst carrier is one or more of porous inorganic refractory oxides selected from the oxides of elements in groups II, III, IV and IVB in the periodic table, more preferably one or more selected from silica, alumina, magnesia, zirconia, titania, silica-alumina, magnesia-silica and alumina-magnesia, and further preferably alumina. The hydrogenation catalyst carrier can be modified according to the need, for example, modification elements such as B, P, F are adopted for modification, and the weight percentage of the modification elements is 0.5wt% -10wt% based on the weight of the modified hydrogenation catalyst carrier.

The preparation method of the hydrogenation catalyst comprises the following steps:

(1) dipping a hydrogenation catalyst carrier by using dipping liquid containing VIB group metal, then drying, and vulcanizing the dried material;

(2) by using a catalyst containingAnd (2) impregnating the material vulcanized in the step (1) with an impregnation solution of the group metal, and then drying and roasting the material in an inert atmosphere to obtain the hydrogenation catalyst.

In the method of the present invention, the preparation method of the group VIB metal immersion liquid in step (1) is well known to those skilled in the art, for example, a phosphate or ammonium salt solution is generally adopted, the mass concentration of the immersion liquid is 0.1 g/mL-2.0 g/mL, and an equal volume immersion mode can be adopted. The group VIB metal is preferably Mo and/or W.

In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.

In the method of the present invention, the vulcanization treatment in step (1) is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

In the method of the present invention, the second step of step (2)The preparation method of the dipping solution of the group metal is well known to those skilled in the art, for example, nitrate, acetate, sulfate solution and the like are generally adopted, the mass concentration of the dipping solution is 0.1 g/mL-1.0 g/mL, an equal-volume dipping mode can be adopted, and the second step isThe group metals are Ni and/or Co.

In the method of the invention, the inert atmosphere in the step (2) is N₂And an inert gas orA plurality of types; the drying temperature is 20-90 ℃, and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃, and the roasting time is 2-5 hours.

The hydrogenation catalyst of the invention is applied to the hydrogenation treatment process of distillate oil, residual oil and other oil products.

The hydrogenation catalyst of the invention needs to be vulcanized before application, and the general vulcanization conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.

Because the catalyst exists in an oxidation state before vulcanization, and the VIB metal is difficult to vulcanize the VIII metal and is easy to vulcanize, the VIII metal in a vulcanization state is easily wrapped by the VIB metal in a vulcanization state, so that the VIII metal cannot fully play a role of an auxiliary agent, a II active center is not easy to generate, and the activity of the catalyst is reduced. The inventor develops a new method, by the way of dipping and vulcanizing different active metals step by step, firstly dipping the VIB group metal on a carrier, then presulfurizing, and then dipping the VIB group metal on a sulfideGroup metals of the group IIIThe group metal covers the surface of the VIB group metal in a vulcanized state and gives full play toThe group metal auxiliary agent acts to create the condition of interaction between the group metal auxiliary agent and the group metal auxiliary agent, promote the generation of II active centers and further improve the activity of the catalyst.

Detailed Description

The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The catalyst composition provided by the invention can be prepared by inductively coupling plasmaBulk ICP and XPS spectra were combined and characterized by first characterizing the total group VIB metal content and the total group VIB metal content of the catalyst by ICPAnd (3) quantitatively characterizing the content of metal elements with different valence states in the catalyst by an XPS spectrometer. The catalyst provided by the invention has metal vulcanization degree of Mo⁴⁺Or W^{4 +}The content represents the degree of metal sulfidation of the catalyst. Using 30mL/min of H at 320 DEG C₂S sulfurizing for 2h, characterizing the metal valence state of the surface of the sample by an XPS PEAK spectrometer, respectively fitting and peak-splitting the energy spectrums of Mo3d, W4f, Co2p and Ni2p by adopting XPSPEAK version4.0, and calculating according to the peak area to obtain the metal sulfurization degree and the proportion of Co-Mo-S, Ni-Mo-S, Co-W-S, Ni-W-S.

Example 1

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂And adjusting the solution with ammonia water until ammonium molybdate is completely dissolved, fixing the volume with a 100mL volumetric flask, soaking the solution in an alumina carrier in the same volume, and drying the solution at 120 ℃ for 3 hours. Then using a catalyst containing 1.5% H₂Sulfurizing S hydrogen at 350 deg.C under 4.0MPa for 8 hr, and adding N₂Cooling to room temperature in the atmosphere to obtain MoS₂/Al₂O₃. 9.31g of Co (NO)₃)₂•6H₂O dissolved in 50mL of deionized water in N₂Equal volume of impregnation into MoS in atmosphere₂/Al₂O₃Then in N₂Drying at 90 deg.C for 4h, and calcining at 300 deg.C for 3h to obtain MoS₂-CoO/Al₂O₃Catalyst C-1.

Example 2

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂And adjusting the solution with ammonia water until ammonium molybdate is completely dissolved, fixing the volume with a 100mL volumetric flask, soaking the solution in an alumina carrier in the same volume, and drying the solution at 120 ℃ for 3 hours. Then using a catalyst containing 1.5% H₂Sulfurizing S hydrogen at 350 deg.C under 4.0MPa for 8 hr, and removing sulfurIn N₂Cooling to room temperature in the atmosphere to obtain MoS₂/Al₂O₃. 9.31g of Ni (NO)₃)₂•6H₂O dissolved in 50mL of deionized water in N₂Equal volume of impregnation into MoS in atmosphere₂/Al₂O₃Then in N₂Drying at 90 deg.C for 4h, and calcining at 300 deg.C for 3h to obtain MoS₂-NiO/Al₂O₃Catalyst C-2.

Example 3

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂And adjusting the solution with ammonia water until ammonium molybdate is completely dissolved, fixing the volume with a 100mL volumetric flask, soaking the solution in an alumina carrier in the same volume, and drying the solution at 120 ℃ for 3 hours. Then using a catalyst containing 1.5% H₂Sulfurizing S hydrogen at 350 deg.C under 4.0MPa for 8 hr, and adding N₂Cooling to room temperature in the atmosphere to obtain MoS₂/Al₂O₃. 5.11g of Ni (NO)₃)₂•6H₂O and 4.25Co (NO)₃)₂•6H₂O dissolved in 50mL of deionized water in N₂Equal volume of impregnation into MoS in atmosphere₂/Al₂O₃Then in N₂Drying at 90 deg.C for 4h, and calcining at 300 deg.C for 3h to obtain MoS₂-NiO-CoO/Al₂O₃Catalyst C-3.

Example 4

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂And O, adjusting with ammonia water until ammonium molybdate is completely dissolved, fixing the volume with a 100mL volumetric flask, soaking in the alumina carrier modified by the silica in the same volume, and drying at 120 ℃ for 3 hours. Then using a catalyst containing 1.5% H₂Sulfurizing S hydrogen at 350 deg.C under 4.0MPa for 8 hr, and adding N₂Cooling to room temperature in the atmosphere to obtain MoS₂/Al₂O₃. 9.31g of Co (NO)₃)₂•6H₂O dissolved in 50mL of deionized water in N₂Equal volume of impregnation into MoS in atmosphere₂/Al₂O₃Then in N₂Drying at 90 deg.C for 4h, and calcining at 300 deg.C for 3h to obtain MoS₂-CoO/SiO₂-Al₂O₃Catalyst C-4.

Example 5

12.6g of (NH)₄)₆Mo₇O₂₄•4H₂And O, adjusting by using ammonia water until ammonium molybdate is completely dissolved, then adding 10.2g of ammonium metatungstate, after the ammonium molybdate is completely dissolved, fixing the volume by using a 100mL volumetric flask, then soaking the alumina carrier modified by the silicon oxide in the volumetric flask in the same volume, and drying the alumina carrier for 3 hours at 120 ℃. Then using 3wt% CS₂Carrying out vulcanization treatment on the aviation kerosene at the airspeed of 1.0h^-1Hydrogen-oil volume ratio of 500:1, under 5.0MPa operating pressure, sulfurizing for 8h, then adding N₂Cooling to room temperature in the atmosphere to obtain MoS₂/Al₂O₃. 9.31g of Co (NO)₃)₂•6H₂O dissolved in 50mL of deionized water in N₂Equal volume of impregnation into MoS in atmosphere₂/Al₂O₃Then in N₂Drying at 90 deg.C for 4h, and calcining at 300 deg.C for 3h to obtain MoS₂-WS₂-CoO/Al₂O₃Catalyst C-5.

Comparative example 1

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂Adjusting the content of O in ammonia water until ammonium molybdate is completely dissolved, fixing the volume in a 100mL volumetric flask, soaking the solution into an alumina carrier in the same volume, drying the solution at 120 ℃ for 3h, and roasting the solution at 400 ℃ for 3h to obtain MoO₃/Al₂O₃. Then 9.31g of Co (NO)₃)₂•6H₂Dissolving O in 50mL of deionized water, and soaking in MoO in equal volume₃/Al₂O₃Then drying at 90 ℃ for 4h, and roasting at 300 ℃ for 3h to obtain MoO₃-CoO/Al₂O₃Catalyst DC-1.

Comparative example 2

17.6g of (NH)₄)₆Mo₇O₂₄•4H₂O, adjusted with phosphoric acid until ammonium molybdate was completely dissolved, and then 9.31g of Co (NO) was added₃)₂•6H₂O, finishAfter the whole solution is prepared, a 100mL volumetric flask is used for constant volume, then the solution is dipped into an alumina carrier in equal volume, and after the solution is dried for 3h at 120 ℃ and roasted for 3h at 400 ℃, MoO is obtained₃-CoO/Al₂O₃Catalyst DC-2

Example 6

This example demonstrates the hydrodesulfurization reaction performance of the catalyst provided by the present invention for diesel fuel.

The adopted evaluation raw oil is mixed diesel oil provided by a certain refinery of China Petroleum chemical.

And respectively carrying out hydrogenation reaction performance evaluation on the catalysts C-1 to C-5 and the comparative examples DC-1 to DC-2 by adopting a 200mL fixed bed liquid phase circulating hydrogenation device.

Presulfurizing conditions of the catalyst: using a catalyst containing 4wt% of CS₂The space velocity of the aviation kerosene is 1.0h^-1Presulfurizing the catalyst at an operating pressure of 5.0MPa with a hydrogen-oil volume ratio of 550: 1.

The prevulcanisation process is as follows: feeding pre-vulcanized oil at 120 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 150 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 230 ℃ at 6 ℃/h, vulcanizing at constant temperature for 10h, heating to 290 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 330 ℃ at 12 ℃/h, vulcanizing at constant temperature for 6h, naturally cooling to 200 ℃, and finishing the pre-vulcanization.

The evaluation reaction conditions were: the operating pressure is 11.0MPa, the reaction temperature is 360 ℃, the circulation ratio is 3, and the volume space velocity of the fresh raw material is 1.5h^-1The results of the three hydrogen mixtures are shown in Table 1.

TABLE 1 Properties of catalyst and evaluation results

The evaluation results in Table 3 can show that the active metal of the catalyst of the invention has higher sulfidation degree, and the catalyst of the invention is used in the liquid phase circulation hydrogenation reaction of diesel oil, and has the operating pressure of 11.0MPa, the reaction temperature of 360 ℃, the circulation ratio of 3 and the volume space velocity of fresh raw material of 1.5h^-1And under the process condition of tertiary hydrogen mixing, higher desulfurization performance is achieved.