Gasoline selective hydrodesulfurization catalyst and preparation method and application thereof

Abstract

The invention discloses a gasoline selective hydrodesulfurization catalyst as well as a preparation method and application thereof. The catalyst comprises a hydrogenation metal component, an auxiliary agent component and a binder component, the hydrogenation metal component comprises at least one of a group VIB metal and a group VIII metal; on the basis of the weight of the catalyst, the content of the VIB group metal in terms of oxide is 50.0-65.0 wt%; the content of the group VIII metal in terms of oxide is 10.0 wt%-25.0 wt%; the content of the auxiliary agent component is 1.0 wt%-8.0 wt% in terms of oxide; the content of the binder component in terms of oxide is 10.0 wt%-30.0 wt%; the average pore diameter of the catalyst is 6.0 to 8.0 nm. The catalyst is suitable for FCC gasoline hydrodesulfurization, and can meet the production of clean gasoline with the sulfur content of not more than 10 mu g / g under the conditions of small octane number loss, high space velocity and low hydrogen-oil volume ratio.

Description

Technical Field

[0001] The present invention belongs to the field of hydrodesulfurization catalysts, and particularly relates to a gasoline selective hydrodesulfurization catalyst, a preparation method thereof, and an application thereof. Background Art

[0003] In the existing catalytic cracking gasoline desulfurization technologies, the French Prime-G + selective hydrodesulfurization process and the Szorb adsorption desulfurization process are mainly representative. The Prime-G + technology uses Mo-Co / Al 2 O 3 as a hydrodesulfurization catalyst, and adopts a process of full-fraction pre-hydrogenation, light and heavy gasoline fractionation, and heavy fraction gasoline hydrodesulfurization. When producing clean gasoline with a sulfur content of ≯10 μg / g, the octane number loss is relatively large. When producing national VI standard gasoline with an olefin content of ≯15.0 v%, the octane number loss of the product will be further increased due to the hydrogenation saturation of olefins. The Szorb technology uses NiO-ZnO as an adsorbent and adopts an adsorption-regeneration cycle process to treat full-fraction catalytic cracking gasoline. Compared with the raw material, the product has a significantly reduced sulfur content, a slight reduction in olefins, a slight increase in alkanes, and the loss of (RON+MON) / 2 is less than 1.0 unit. However, this method cannot significantly reduce the olefin content in gasoline products, and it cannot solve the problem of reducing olefins for catalytic cracking gasoline with a high olefin content.

[0004] CN103450935A discloses a method for producing ultra-low sulfur gasoline. This method uses a stepwise impregnation method to prepare a traditional selective hydrodesulfurization MoO 3 -CoO / Al 2 O 3 catalyst. The process includes: mixing pseudo-boehmite aluminum hydroxide powder, a lubricant such as carboxymethyl cellulose, and nitric acid aqueous solution and rolling them into a plastic powder, extruding the powder into strips, drying and calcining to prepare a catalyst support; impregnating and loading phosphorus and potassium on the catalyst support, drying and calcining to prepare a P 2 O 5 -K 2 O / Al 2 O 3 catalyst intermediate; impregnating and loading molybdenum and cobalt on the catalyst intermediate, drying and calcining to prepare a highly active MoO 3 -CoO-P 2 O 5 -K 2 O / Al 2 O 3 catalyst. When this hydrodesulfurization catalyst is used to produce gasoline meeting the national V standard in terms of sulfur content, the octane number loss is relatively large.

[0005] CN102309971B discloses a preparation method of a hydrotreating catalyst. By utilizing the characteristic of large liquid absorption amount of the powder of the hydrotreating catalyst support material before forming, the method obtains a hydrotreating catalyst with a high active metal content by using a one-step impregnation method. The disadvantages of this method are that alumina, as the main support component, needs to be pre-hydrothermally treated at a high temperature to stabilize its pore channels and reduce acidity, and it needs to go through multiple drying and calcination steps, with complex procedures; in particular, this method involves rolling and extrusion, resulting in unsmooth pore channels, which is not conducive to the diffusion of reactants and products on the surface and in the pores of the catalyst. The catalyst prepared by this method is suitable for use as a hydrotreating catalyst for heavy distillate oil, but not suitable for a gasoline selective hydrodesulfurization catalyst.

[0006] The hydrodesulfurization catalysts for the existing traditional technology of producing clean gasoline from sulfur- and olefin-containing inferior gasoline generally adopt a process scheme with a low hydro-metal content, high temperature, high hydrogen-oil volume ratio, and low space velocity to reduce the loss of the octane number of the hydrogenation product. Therefore, it causes a large amount of catalyst consumption and high energy consumption in the device. Especially under the conditions of a small reactor space and a small amount of hydrogen gas (such as without a recycle hydrogen compressor) in the device, it cannot meet the enterprise's need to produce national VI gasoline with a sulfur content of no more than 10 μg / g. Summary of the Invention

[0007] In view of the deficiencies in the prior art, the present invention provides a gasoline selective hydrodesulfurization catalyst, its preparation method, and application. This catalyst is applicable to the hydrodesulfurization of FCC gasoline and can meet the production of clean gasoline with a sulfur content of no more than 10 μg / g under the conditions of high space velocity and low hydrogen-oil volume ratio with a relatively small loss of octane number.

[0008] The first aspect of the present invention provides a gasoline selective hydrodesulfurization catalyst. The catalyst includes a hydro-metal component, an additive component, and a binder component.

[0009] According to the present invention, the hydro-metal component includes at least one metal from Group VIB and Group VIII. The metal from Group VIB is preferably W and / or Mo. The metal from Group VIII is preferably Ni and / or Co. The hydro-metal component is preferably W, Mo, Ni, and Co.

[0010] According to the present invention, based on the weight of the catalyst, the content of the metal from Group VIB in terms of its oxide is 50.0 wt% - 65.0 wt%, preferably 55.0 wt% - 60.0 wt%; the content of the metal from Group VIII in terms of its oxide is 10.0 wt% - 25.0 wt%, preferably 17.0 wt% - 22.0 wt%.

[0011] According to the present invention, preferably, based on the weight of the catalyst, the content of W in terms of oxide is 15.0 - 35.0 wt%; the content of Mo in terms of oxide is 20.0 - 45.0 wt%; the content of Ni in terms of oxide is 13.0 - 17.0 wt%; the content of Co in terms of oxide is 4.0 - 8.0 wt%.

[0012] According to the present invention, the promoter component includes at least one of K, Ca, P, Si, F, B, Ti, and Zr.

[0013] According to the present invention, further, based on the weight of the catalyst, the content of the promoter component in terms of oxide is 1.0 wt% - 8.0 wt%, preferably 3.0 wt% - 5.0 wt%.

[0014] According to the present invention, the binder component is one or more of alumina, titanium oxide, silicon oxide, and magnesium oxide.

[0015] According to the present invention, further, based on the weight of the catalyst, the content of the binder component in terms of oxide is 10.0 wt% - 30.0 wt%, preferably 15.0 wt% - 25.0 wt%.

[0016] According to the present invention, the specific surface area of the catalyst is 175 - 210 m 2 / g; the pore volume of the catalyst is 0.30 - 0.40 mL / g; the average pore diameter of the catalyst is 6.0 - 8.0 nm; the bulk density of the catalyst is 0.80 - 0.95 g / cm 3 .

[0017] The second aspect of the present invention provides a method for preparing the gasoline selective hydrodesulfurization catalyst. The method includes:

[0018] (1) Mixing a hydrogenation metal source, a promoter, and an acid solution to form a slurry, followed by spray drying to obtain microspheres;

[0019] (2) Mixing the microspheres and a binder, followed by shaping and calcination to obtain the catalyst.

[0020] According to the present invention, in step (1), the hydrogenation metal source is a compound containing a hydrogenation metal component, preferably at least one of a salt and a metal oxide. The promoter is a salt containing a promoter component. The binder is a salt and / or oxide containing a binder component, preferably at least one of pseudoboehmite and silica sol.

[0021] According to the present invention, the acid solution in step (1) is a nitric acid solution. The concentration of the nitric acid aqueous solution is 5.0 - 20.0 g / 100 mL. The addition amount of the nitric acid aqueous solution, calculated as nitric acid, accounts for 5.0 wt% - 10.0 wt% of the total amount of the hydrogenation metal source and the promoter, where the hydrogenation metal source is calculated as the oxide and the promoter is calculated as the oxide. Additionally, an appropriate amount of water can be added as needed. The liquid-solid mass ratio of the slurry is 2:1 - 6:1. The spray drying process is generally carried out in a spray drying device, such as a spray drying tower. The hot air inlet pressure of the spray drying device is 3.0 - 7.0 MPa, the inlet temperature is 300 - 400 °C, the outlet temperature is 120 - 200 °C, and microspheres are obtained through a cyclone separator.

[0022] According to the present invention, the diameter of the microspheres in step (1) is 20 - 50 μm particles; among them, the microspheres with a diameter of 30 - 40 μm account for 60 wt% - 95 wt%, preferably 80 wt% - 95 wt%, by mass.

[0023] According to the present invention, the shaping in step (2) is kneading shaping, preferably extrusion shaping. A nitric acid aqueous solution can also be added during the shaping process in step (2). Further, the concentration of the nitric acid aqueous solution is 5.0 - 20.0 g / 100 mL. The addition amount of the nitric acid aqueous solution, calculated as nitric acid, accounts for 5.0 wt% - 10.0 wt% of the total amount of the microspheres and the binder. An appropriate amount of water can be added as needed. The calcination conditions are: calcination at 400 - 600 °C for 3.0 - 6.0 hours. Drying can be carried out before calcination, and the drying conditions are: drying at 120 - 200 °C for 3.0 - 6.0 hours.

[0024] According to the present invention, the catalyst can be pre-sulfurized before application. The pre-sulfurization treatment method can adopt conventional methods. Preferably, the catalyst is pre-sulfurized in the presence of a sulfurizing agent and hydrogen. The pre-sulfurization conditions are: the pressure is 1.0 MPa - 4.5 MPa, the temperature is 200 °C - 400 °C, the sulfurization time is 5 - 15 hours, and the hydrogen-agent volume ratio (the volume ratio of hydrogen and the sulfurizing agent) is 10:1 - 100:1; the preferred sulfurization conditions: the pressure is 1.5 MPa - 3.0 MPa, the temperature is 260 °C - 330 °C, the hydrogen-agent volume ratio is 20:1 - 80:1, and the sulfurization time is 6 - 10 hours. The sulfurizing agent is a sulfide that can decompose into H 2 S. Preferably, the sulfurizing agent includes at least one of carbon disulfide (CS 2 2) and dimethyl disulfide (DMDS). Sulfurizing oil can also be added during the pre-sulfurization process. The sulfurizing oil is at least one of straight-run gasoline and hydrotreated naphtha. The distillation range of the sulfurizing oil is 40 - 180 °C. The liquid hourly space velocity of the sulfurizing oil is 2.0 h -1 -1 - 4.0 h -1 .

[0025] The third aspect of the present invention provides the application of the above gasoline selective hydrodesulfurization catalyst in gasoline hydrodesulfurization reaction.

[0026] According to the present invention, the method of the application can adopt a fixed-bed process.

[0027] According to the present invention, the gasoline is poor-quality gasoline. The poor-quality gasoline comes from the heavy fraction of catalytic cracking stabilized gasoline. The sulfur content of the gasoline is 20 - 300 μg / g, and the olefin content is 15.0 - 30.0 wt%; the initial boiling point of the gasoline is 60 - 80 °C, and the final boiling point is 190 - 205 °C.

[0028] According to the present invention, the conditions of the hydrodesulfurization reaction are as follows: the reaction pressure is 1.0 MPa - 4.5 MPa, the reaction temperature is 200 °C - 400 °C, the liquid hourly space velocity is 3.0 h -1 -10.0 h -1 , and the hydrogen-oil volume ratio is 10:1 - 100:1; the preferred reaction conditions: the reaction pressure is 1.5 MPa - 3.0 MPa, the reaction temperature is 250 °C - 300 °C, the liquid hourly space velocity is 5.0 h -1 -7.0 h -1 , and the hydrogen-oil volume ratio is 20:1 - 80:1.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] (1) The catalyst of the present invention comprises a hydrogenation metal component, a promoter component and a binder component; the hydrogenation metal component comprises at least one metal of Group VIB and Group VIII metals; preferably, based on the weight of the catalyst, the content of the Group VIB metal in terms of oxide is 50.0 wt% to 65.0 wt%; the content of the Group VIII metal in terms of oxide is 10.0 wt% to 25.0 wt%; the content of the promoter component in terms of oxide is 1.0 wt% to 8.0 wt%; the content of the binder component in terms of oxide is 10.0 wt% to 30.0 wt%; the average pore diameter of the catalyst is 6.0 to 8.0 nm. The hydrogenation metal component of the present invention adopts a high metal content, the content of the hydrogenation metal component in terms of oxide is above 60% and has an appropriate average pore diameter, compared with the traditional method using a low metal content (the content in terms of oxide is 15.0 wt% to 25.0 wt%). Further, the catalyst of the present invention also has an appropriate bulk density. The hydrodesulfurization catalyst is applied to the hydrodesulfurization of FCC gasoline, and can meet the production of clean gasoline with a sulfur content of ≤10 μg / g under the conditions of high space velocity and low hydrogen-oil volume ratio with a small loss of octane number; while the low hydrodesulfurization activity catalyst prepared by the traditional method can usually only meet the production of clean gasoline with a sulfur content of ≤10 μg / g under conventional process conditions, that is, low space velocity (liquid hourly space velocity is 2.0 h -1 ~4.0 h -1 ), high hydrogen-oil volume ratio (hydrogen-oil volume ratio is 200:1 to 300:1), and has a large loss of octane number.

[0031] In addition, in the prior art, alumina is used as the main carrier component, with a high content, and pre-high-temperature hydrothermal treatment is required to stabilize its pores and reduce acidity, and it needs to go through multiple drying and calcination steps, with complex steps; in the catalyst of the present invention, alumina is only used as a binder, with a small content and no special treatment is required. In the present invention, the hydrogenation metal component, the promoter component and the binder component work together to help improve the hydrodesulfurization performance of the catalyst.

[0032] (2) The preparation method of the catalyst of the present invention is to prepare the catalyst by first spray drying and then shaping and calcining. Compared with the prior art (for example, the prior art uses a powdered hydrotreating catalyst material to impregnate the active metal and then shaping treatment), the metal components of the present invention are more uniformly mixed and the pores are more unobstructed, which is more conducive to the diffusion of reactants and products such as sulfides and olefins on the surface and in the pores of the catalyst, reduces the residence time of olefins on the metal hydrogenation centers, and inhibits the over-hydrogenation saturation of olefins.

[0033] The method of the present invention can produce gasoline products meeting the National VI standard, in which the sulfur content is ≤10 μg / g and the research method octane number loss is ≤2.0.

[0034] (3) The catalyst of the present invention is applied to FCC gasoline hydrodesulfurization, and can meet the production of clean gasoline with a sulfur content of ≯10 μg / g under the conditions of high space velocity and low hydrogen-oil volume ratio with less octane number loss. Description of the Drawings

[0035] Figure 1 It is the scanning electron micrograph (SEM) of the microspheres prepared in Example 1;

[0036] Figure 2 It is the scanning electron micrograph (SEM) of the microspheres prepared in Example 2;

[0037] Figure 3 It is the scanning electron micrograph (SEM) of the microspheres prepared in Example 3;

[0038] Figure 4 It is the scanning electron micrograph (SEM) of the microspheres prepared in Example 4. Detailed Description of the Invention

[0039] The following further illustrates the solution and effects of the present invention with reference to the drawings and examples, but does not limit the protection scope of the present invention.

[0040] In the present invention, the specific surface area (S) is measured according to the standard of GB / T 5816, the pore volume (V) is measured according to the standard of Q / SH 361 913 (petrochemical industry standard), and the average pore diameter (D) is calculated according to D = 4V / S; the bulk density is measured according to the standard of Q / SH 361 928 (petrochemical industry standard).

[0041] Example 1

[0042] (1) Spray drying: Weigh 26.0 g of ammonium molybdate tetrahydrate containing MoO 3 , 30.0 g of ammonium metatungstate containing WO 3 , 15.0 g of nickel nitrate containing NiO, 5.0 g of basic cobalt carbonate containing CoO, and 4.0 g of potassium dihydrogen phosphate containing K 2 O, grind and mix them evenly, add 20 mL of nitric acid solution with a concentration of 20.0 g / 100 mL and deionized water to prepare a slurry. The liquid-solid mass ratio of the slurry is 5:1. Spray dry the slurry, the hot air inlet pressure of the spray drying equipment is 3.5 MPa, the inlet temperature is 350 °C, and the outlet temperature is 150 °C. Make microspheres through a cyclone separator, denoted as HMS-1. The SEM morphology is shown in Figure 1 . The diameter of the microspheres is 20 - 50 μm. Among them, the microspheres with a diameter of 30 - 40 μm account for 80 wt%.

[0043] (2) Extrusion molding: Mix 80.0 g of the above microspheres with 20.0 g of Al 2 O 3Pseudoboehmite, and grind and mix evenly. Add 79 mL of dilute nitric acid solution with a concentration of 10 g / 100 mL and appropriate deionized water to make a wet cake. Then extrude into strips and dry at 150 °C for 4 hours and calcine at 520 °C for 4 hours to make a strip catalyst, denoted as HMC-1. The catalyst composition is: MoO 3 (26.0 wt%)-WO 3 (30.0 wt%)-NiO(15.0 wt%)-CoO(5.0 wt%)-K 2 O(4.0 wt%) / Al 2 O 3 (20.0 wt%).

[0044] The properties of the catalyst are shown in Table 1. The hydrodesulfurization performance of the catalyst was investigated using feedstock gasoline-A and feedstock gasoline-B (properties are shown in Table 2) respectively. Before the test, the catalyst was pre-sulfurized. That is, the catalyst was loaded into a small fixed-bed hydrotreating reactor. The catalyst was pre-sulfurized first, and the sulfurizing oil was straight-run gasoline (boiling range 40 - 175 °C), and the mass concentration of CS 2 was 2.0%. The sulfurization reaction pressure was 1.6 MPa, the hydrogen-to-catalyst volume ratio was 20:1, the liquid hourly space velocity was 3.0 h -1 , and sulfurization was carried out at a temperature of 320 °C for 8 h.

[0045] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 20:1, the liquid hourly space velocity was 5.0 h -1 , the reaction temperature was 265 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0046] Using feedstock gasoline-B as the feedstock oil, desulfurized product-B was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 50:1, the liquid hourly space velocity was 5.0 h -1 , the reaction temperature was 270 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0047] Example 2

[0048] (1) Spray drying: Weigh 30.0 g of ammonium molybdate tetrahydrate containing MoO 3 , 26.0 g of ammonium metatungstate containing WO 3 , 15.0 g of nickel nitrate containing NiO, 5.0 g of basic cobalt carbonate containing CoO, 4.0 g of K 2Potassium dihydrogen phosphate of O was added and ground and mixed evenly. 20 mL of a nitric acid solution with a concentration of 20.0 g / 100 mL and deionized water were added to prepare a slurry. The liquid-solid mass ratio of the slurry was 4:1. The slurry was spray-dried. The hot air inlet pressure of the spray-drying equipment was 3.5 MPa, the inlet temperature was 350 °C, and the outlet temperature was 150 °C. Microspheres were made through a cyclone separator. The diameter of the microspheres was 20 - 50 μm, among which, the microspheres with a diameter of 30 - 40 μm accounted for 85 wt%.

[0049] (2) Extrusion molding: 80.0 g of the above microspheres were mixed with 20.0 g of Al 2 O 3 of pseudo-boehmite, and ground and mixed evenly. 93.0 mL of a dilute nitric acid solution with a concentration of 10 g / 100 mL and an appropriate amount of deionized water were added to make a wet cake. Then it was extrusion-molded and dried at 150 °C for 4 hours and calcined at 520 °C for 4 hours to make a bar-shaped catalyst. The catalyst composition was: MoO 3 (30.0 wt%) - WO 3 (26.0 wt%) - NiO (15.0 wt%) - CoO (5.0 wt%) - K 2 O (4.0 wt%) / Al 2 O 3 (20.0 wt%).

[0050] The properties of the catalyst are shown in Table 1. The hydrodesulfurization performance of the HMC-2 catalyst was investigated using feedstock gasoline-A and feedstock gasoline-B (properties are shown in Table 2) respectively. Before the test, the catalyst was pre-sulfurized first. That is, the catalyst was loaded into a small fixed-bed hydrotreating reactor. The catalyst was pre-sulfurized first. The sulfiding oil was straight-run gasoline (boiling range 40 - 175 °C), and the mass concentration of CS 2 was 2.0%. The sulfiding reaction pressure was 1.8 MPa, the hydrogen-to-catalyst volume ratio was 20:1, the liquid hourly space velocity was 3.0 h -1 , and it was sulfided at a reaction temperature of 320 °C for 8 h.

[0051] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 20:1, the liquid hourly space velocity was 6.0 h -1 , the reaction temperature was 270 °C, the reaction pressure was 1.8 MPa. After stable operation for 10 h, samples were taken for analysis, and the properties of the obtained gasoline product are shown in Table 3.

[0052] Using feedstock gasoline-B as the feedstock oil, desulfurized product-B was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 50:1, the liquid hourly space velocity was 6.0 h -1 , the reaction temperature was 275 °C, the reaction pressure was 1.8 MPa. After stable operation for 10 h, samples were taken for analysis, and the properties of the obtained gasoline product are shown in Table 3.

[0053] Example 3

[0054] (1) Spray drying: Weigh 35.0 g of ammonium tetramolybdate containing MoO 3 , 25.0 g of ammonium metatungstate containing WO 3 , 15.0 g of nickel nitrate NiO, 7.0 g of cobaltous carbonate CoO containing CoO, 3.0 g of potassium dihydrogen phosphate K 2 O. Grind and mix them evenly, add 34 mL of nitric acid with a concentration of 20.0 g / 100 mL and deionized water to prepare a slurry. The liquid-solid mass ratio of the slurry is 3:1. Spray dry the slurry. The hot air inlet pressure of the spray drying equipment is 3.5 MPa, the inlet temperature is 350 °C, and the outlet temperature is 150 °C. Make microspheres through a cyclone separator, denoted as HMS-3. The diameter of the microspheres is 20 - 50 μm. Among them, the microspheres with a diameter of 30 - 40 μm account for 85 wt%.

[0055] (2) Extrusion molding: Mix 85.0 g of the above microspheres with 15.0 g of pseudoboehmite containing Al 2 O 3 . Grind and mix them evenly, add 64 mL of a dilute nitric acid solution with a concentration of 10 g / 100 mL and an appropriate amount of deionized water to make a wet cake. Then extrude it into shape and dry it at 150 °C for 4 hours and calcine it at 520 °C for 4 hours to make a bar-shaped catalyst, denoted as HMC-3. The catalyst composition is: MoO 3 (35.0 wt%) - WO 3 (25.0 wt%) - NiO (15.0 wt%) - CoO (7.0 wt%) - K 2 O (3.0 wt%) / Al 2 O 3 (15.0 wt%).

[0056] The properties of the catalyst are shown in Table 1. Use raw gasoline-A and raw gasoline-B (properties are shown in Table 2) to investigate the hydrodesulfurization performance of the catalyst respectively. Before the test, pre-sulfurize the catalyst first. That is, load the catalyst into a small fixed-bed hydrotreating reactor. The catalyst is pre-sulfurized first. The sulfurizing oil is straight-run gasoline (boiling range 40 - 175 °C), and the mass concentration of CS 2 is 2.0%. The sulfurization reaction pressure is 1.6 MPa, the hydrogen-to-catalyst volume ratio is 20:1, the liquid hourly space velocity is 3.0 h -1 , and sulfurize at a reaction temperature of 320 °C for 8 h.

[0057] Use raw gasoline-A as the feedstock oil to obtain desulfurized product-A. The test conditions are: the hydrogen-to-oil volume ratio is 20:1, and the liquid hourly space velocity is 5.0 h -1, the reaction temperature was 265 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0058] Using raw gasoline - B as the feedstock, the desulfurized product - B was obtained. The test conditions were: the hydrogen - to - oil volume ratio was 50:1, the liquid hourly space velocity was 5.0 h -1 , the reaction temperature was 270 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0059] Example 4

[0060] (1) Spray drying: Weigh 40.0 g of ammonium molybdate tetrahydrate containing MoO 3 , 20.0 g of ammonium metatungstate containing WO 3 , 15.0 g of nickel nitrate NiO, 7.0 g of basic cobalt carbonate CoO, 3.0 g of potassium dihydrogen phosphate K 2 O. Grind and mix them evenly, add 34 mL of nitric acid with a concentration of 20.0 g / 100 mL and deionized water to prepare a slurry. The liquid - to - solid mass ratio of the slurry is 3:1. Spray - dry the slurry. The hot - air inlet pressure of the spray - drying equipment is 3.5 MPa, the inlet temperature is 350 °C, and the outlet temperature is 150 °C. Microspheres are formed through a cyclone separator, denoted as HMS - 3. The diameter of the microspheres is 20 - 50 μm. Among them, microspheres with a diameter of 30 - 40 μm account for 85 wt%.

[0061] (2) Extrusion molding: Mix the above 85.0 g of microspheres with 15.0 g of pseudo - boehmite containing Al 2 O 3 . Grind and mix them evenly, add 95 mL of dilute nitric acid solution with a concentration of 10 g / 100 mL and an appropriate amount of deionized water to make a wet cake. Then extrude it into a shape and dry it at 150 °C for 4 hours and calcine it at 520 °C for 4 hours to make a bar - shaped catalyst, denoted as HMC - 4. The catalyst composition is: MoO 3 (40.0 wt%) - WO 3 (20.0 wt%) - NiO(15.0 wt%) - CoO(7.0 wt%) - K 2 O(3.0 wt%) / Al 2 O 3 (15.0 wt%).

[0062] The properties of the catalyst are shown in Table 1. The hydrodesulfurization performance of the catalyst was investigated using feedstock gasoline-A and feedstock gasoline-B (properties shown in Table 2) respectively. Before the test, the catalyst was pre-sulfurized. That is, the catalyst was loaded into a small fixed-bed hydrotreating reactor. The catalyst was pre-sulfurized first, and the sulfurizing oil was straight-run gasoline (boiling range 40-175 °C), and the CS 2 mass concentration was 2.0%. The sulfurization reaction pressure was 1.6 MPa, the hydrogen-to-catalyst volume ratio was 20:1, the liquid hourly space velocity was 3.0 h -1 , and sulfurization was carried out at a reaction temperature of 320 °C for 8 h.

[0063] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 20:1, the liquid hourly space velocity was 5.0 h -1 , the reaction temperature was 265 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0064] Using feedstock gasoline-B as the feedstock oil, desulfurized product-B was obtained. The test conditions were: the hydrogen-to-oil volume ratio was 50:1, the liquid hourly space velocity was 5.0 h -1 , the reaction temperature was 270 °C, the reaction pressure was 1.6 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 3.

[0065] Comparative Example 1

[0066] A MoO 3 -CoO-K 2 O / Al 2 O 3 low-metal-content selective hydrodesulfurization catalyst was prepared by the stepwise impregnation method of CN103450935A.

[0067] Weigh 1000 g of pseudo-boehmite (Al 2 O 3 content is 78 wt%), add 5 wt% of the extrusion aid of sesbania powder based on Al 2 O 3 , add 5 wt% of a 10% aqueous nitric acid solution based on Al 2 O 3 . Mix and roll to form a plastic powder, and use an extrusion machine to prepare cylindrical bars with a diameter of 1.5 mm. Dry at 120 °C for 8 hours and calcine at 500 °C for 5 hours to prepare the catalyst support.

[0068] According to the K 2The O content is 2.0 wt%, a quantitative amount of potassium dihydrogen phosphate is taken, deionized water is added, and 120 mL of an impregnation solution is prepared. Then, it is sprayed onto 160 g of the above catalyst support. It is dried at 120 °C for 10 hours and calcined at 500 °C for 5 hours to prepare K 2 O / Al 2 O 3 catalyst intermediate.

[0069] According to the MoO 3 content on the catalyst being 13.0 wt% and the CoO content being 4.0 wt%, a quantitative amount of molybdenum oxide and cobalt basic carbonate are taken, deionized water is added, and 60 mL of an impregnation solution is prepared. Then, it is sprayed onto 80 g of the above catalyst intermediate. It is dried at 120 °C for 8 hours and calcined at 490 °C for 6 hours to prepare highly active MoO 3 (13.0 wt%)-CoO(4.0 wt%)-K 2 O(2.0 wt%) / Al 2 O 3 (81.0 wt%) catalyst.

[0070] The catalyst prepared in this example is the LM-R catalyst, and the properties of the LM-R catalyst are shown in Table 1. The hydrodesulfurization performance of the catalyst in Comparative Example-1 was investigated using feedstock gasoline-A and feedstock gasoline-B (properties are shown in Table 2) respectively. Before testing, the catalyst was pre-sulfurized. The pre-sulfurization method was the same as in Example 2.

[0071] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A was obtained. The test conditions were: hydrogen-oil volume ratio of 20:1, liquid hourly space velocity of 6.0 h -1 , reaction temperature of 270 °C, reaction pressure of 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 4.

[0072] Using feedstock gasoline-B as the feedstock oil for testing, desulfurized product-B was obtained. The test conditions were: hydrogen-oil volume ratio of 50:1, liquid hourly space velocity of 6.0 h -1 , reaction temperature of 275 °C, reaction pressure of 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 4.

[0073] The hydrodesulfurization performance of the catalyst in Comparative Example 1 was investigated using feedstock gasoline-A and feedstock gasoline-B (properties are shown in Table 2) respectively under conventional process conditions.

[0074] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A2 was obtained. The test conditions were: hydrogen-oil volume ratio of 200:1, liquid hourly space velocity of 4.0 h -1, the reaction temperature was 270 °C, the reaction pressure was 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 5.

[0075] Using raw material gasoline - B as the feedstock, the desulfurized product - B2 was obtained. The test conditions were: the hydrogen - to - oil volume ratio was 200:1, the liquid hourly space velocity was 3.0 h -1 , the reaction temperature was 275 °C, the reaction pressure was 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the obtained gasoline product are shown in Table 5.

[0076] Comparative Example 2

[0077] A hydrofining catalyst with a high metal content was prepared by the method of the prior art.

[0078] (1) Hydrothermal treatment: Using a vertical hydrothermal treatment device, 33.3 g of Al 2 O 3 pseudoboehmite was treated at 550 °C and a steam pressure of 1.0 MPa for 1 h to prepare modified alumina powder.

[0079] (2) Solution preparation: Weigh 30.0 g of ammonium molybdate tetrahydrate containing MoO 3 , 26.0 g of ammonium metatungstate containing WO 3 , 15.0 g of nickel nitrate containing NiO, 5.0 g of cobalt basic carbonate containing CoO, 4.0 g of potassium dihydrogen phosphate containing K 2 O, and grind and mix them evenly. Together with deionized water, it was stirred and heated to 80 °C and kept at a constant temperature for 5 h to prepare a 200 mL metal solution.

[0080] (3) Liquid - solid loading: The modified alumina powder obtained in step (1) was slurried and mixed with the metal solution obtained in step (2), the metal components were loaded onto the alumina, then filtration was carried out to form a wet cake, and it was dried at 120 °C for 4 h, then crushed, and sieved to obtain 100 - 200 mesh (74 - 150 μm).

[0081] (4) Extrusion molding: The metal - loaded hydro - metal powder obtained in step (3) was rolled for 30 minutes, then a 6 g / 100 mL dilute nitric acid solution accounting for 5 wt% of the mass of alumina in the metal - loaded hydro - metal powder was added, and it was continuously rolled into an extrudable paste, then extrusion molding was carried out, and it was dried at 150 °C for 4 h and calcined at 530 °C for 4 h to prepare a bar - shaped catalyst.

[0082] The catalyst prepared in this comparative example is simply referred to as the HM - R catalyst, and its composition is MoO 3 (30.0 wt%) - WO 3(26.0 wt%)-NiO(15.0 wt%)-CoO(5.0 wt%)-K 2 O(4.0 wt%) / Al 2 O 3 (20.0 wt%).

[0083] The properties of the HM-R catalyst are shown in Table 1. The hydrodesulfurization performance of the catalyst in this example was investigated using feedstock gasoline-A and feedstock gasoline-B (properties shown in Table 2), respectively. Before the test, the catalyst was pre-sulfurized. The pre-sulfurization method was the same as in Example 2.

[0084] Using feedstock gasoline-A as the feedstock oil, desulfurized product-A was obtained. The test conditions were: hydrogen-oil volume ratio of 20:1, liquid hourly space velocity of 6.0 h -1 , reaction temperature of 270 °C, reaction pressure of 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the gasoline product obtained are shown in Table 4.

[0085] Using feedstock gasoline-B as the feedstock oil, desulfurized product-B was obtained. The test conditions were: hydrogen-oil volume ratio of 50:1, liquid hourly space velocity of 6.0 h -1 , reaction temperature of 275 °C, reaction pressure of 1.8 MPa. After stable operation for 10 h, sampling and analysis were carried out, and the properties of the gasoline product obtained are shown in Table 4.

[0086] Table 1 Composition and properties of the catalysts obtained in each example

[0087] Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Catalyst Number HMC-1 HMC-2 HMC-3 HMC-4 LM-R HM-R Shape Cylindrical bar Cylindrical bar Cylindrical bar Cylindrical bar Cylindrical bar Cylindrical bar Diameter, mm 1.5 1.5 1.5 1.5 1.5 1.5 Length, mm 3.0～8.0 3.0～8.0 3.0～8.0 3.0～8.0 3.0～8.0 3.0～8.0 <![CDATA[Pore volume, mL·g -1 > 0.35 0.32 0.34 0.33 0.45 0.30 <![CDATA[Specific surface area, m 2 ·g -1 > 195.0 185.0 192.0 188.0 185.0 210.0 Average pore diameter, nm 7.2 6.9 7.1 7.0 9.7 5.7 <![CDATA[Bulk density, g·cm -3 > 0.85 0.90 0.87 0.89 0.78 1.0 Catalyst composition <![CDATA[MoO 3 ,wt%]]> 26.0 30.0 35.0 40.0 13.0 30.0 <![CDATA[WO 3 ,wt%]]> 30.0 26.0 25.0 20.0 / 26.0 NiO, wt% 15.0 15.0 15.0 15.0 / 15.0 CoO, wt% 5.0 5.0 7.0 7.0 4.0 5.0 <![CDATA[K 2 O, wt%]]> 4.0 4.0 3.0 3.0 2.0 4.0 <![CDATA[Al 2 O 3 ,wt%]]> 20.0 20.0 15.0 15.0 81.0 20.0

[0088] Table 2 Properties of feedstock gasoline

[0089]

[0090]

[0091] Table 3 Properties of gasoline products obtained in Examples 1-4

[0092]

[0093] Continued Table 3

[0094]

[0095]

[0096] Table 4 Properties of gasoline products obtained in Comparative Examples 1 and 2

[0097]

[0098] Table 5 Properties of products under conventional process conditions of gasoline feedstock in Comparative Example 1

[0099]

[0100]

[0101] It can be seen from the above table data that under the reaction conditions of low hydrogen-oil volume ratio and high space velocity, the hydrodesulfurization catalyst with high metal content prepared by the method of the present invention can produce gasoline products meeting the national VI standard, in which the sulfur content is not more than 10 μg / g and the research octane number loss is not more than 2.0; the hydrodesulfurization catalyst with low metal content prepared by the prior art cannot meet the requirement of producing gasoline with a sulfur content of not more than 10 μg / g; when the hydrodesulfurization catalyst with high metal content prepared by the prior art meets the requirement of producing gasoline with a sulfur content of not more than 10 μg / g, the loss of the research octane number (RON) of the product is relatively large.

Claims

1. A gasoline selective hydrodesulfurization catalyst, comprising a hydrogenation metal component, a promoter component, and a binder component; the hydrogenation metal component comprises at least one metal from Group VIB and Group VIII metals; Based on the weight of the catalyst, the content of the Group VIB metal calculated as the oxide is 50.0 wt% - 65.0 wt%; the content of the Group VIII metal calculated as the oxide is 10.0 wt% - 25.0 wt%; the content of the promoter component calculated as the oxide is 1.0 wt% - 8.0 wt; the content of the binder component calculated as the oxide is 10.0 wt% - 30.0 wt%; the average pore diameter of the catalyst is 6.0 - 8.0 nm.

2. The catalyst according to claim 1, characterized in that, based on the weight of the catalyst, the content of the Group VIB metal calculated as the oxide is 55.0 wt% - 60.0 wt%; the content of the Group VIII metal calculated as the oxide is 17.0 wt% - 22.0 wt%; the content of the promoter component calculated as the oxide is 3.0 wt% - 5.0 wt%; the content of the binder component calculated as the oxide is 15.0 wt% - 25.0 wt%.

3. The catalyst according to claim 1 or 2, characterized in that, The bulk density of the catalyst is 0.80 to 0.95 g / cm 3 .

4. The catalyst according to claim 1 or 2, characterized in that, the Group VIB metal is W and / or Mo; and / or, the Group VIII metal is Ni and / or Co; and / or, the promoter component comprises at least one of K, Ca, P, Si, F, B, Ti, and Zr; and / or, the binder component is one or more of alumina, titanium oxide, silicon oxide, and magnesium oxide.

5. A method for preparing the catalyst according to any one of claims 1 - 4, comprising: (1) Mixing a hydrogenation metal source, a promoter, and an acid solution to form a slurry, and spray-drying to obtain microspheres; (2) Mixing the microspheres and a binder, followed by shaping and calcination to obtain the catalyst.

6. The method according to claim 5, characterized in that, in step (1), the spray-drying is carried out in a spray-drying device; the hot air inlet pressure of the spray-drying device is 3.0 - 7.0 MPa, the inlet temperature is 300 - 400 °C, and the outlet temperature is 120 - 200 °C.

7. The method according to claim 5, characterized in that, in step (1), the diameter of the microspheres is 20 - 50 μm particles; among them, the microspheres with a diameter of 30 - 40 μm account for 60 wt% - 95 wt%, preferably 80 wt% - 95 wt%, by mass.

8. The method according to claim 5, characterized in that, in step (2), the calcination conditions are: calcination at 400 - 600 °C for 3.0 - 6.0 hours.

9. Use of the catalyst according to any one of claims 1 - 4 or the catalyst prepared by the method according to any one of claims 5 - 8 in gasoline hydrodesulfurization reaction.

10. The use according to claim 9, characterized in that, The gasoline is inferior gasoline, and the inferior gasoline is from the heavy fraction of catalytic cracking stabilized gasoline; preferably, the sulfur content of the gasoline is 20 to 300 μg / g, and the olefin content is 15.0 to 30.0 wt%; the initial boiling point of the gasoline is 60 to 80 °C, and the final boiling point is 190 to 205 °C.

11. According to the application described in claim 9, characterized in that The conditions for the hydrodesulfurization reaction are as follows: the reaction pressure is 1.0 MPa to 4.5 MPa, the reaction temperature is 200 °C to 400 °C, and the liquid hourly space velocity is 3.0 h -1 to 10.0 h -1 , and the hydrogen-oil volume ratio is 10:1 to 100:1; the preferred reaction conditions: the reaction pressure is 1.5 MPa to 3.0 MPa, the reaction temperature is 250 °C to 300 °C, and the liquid hourly space velocity is 5.0 h -1 to 7.0 h -1 , and the hydrogen-oil volume ratio is 20:1 to 80:1.

Images