A gasoline selective hydrodesulfurization catalyst, its preparation method and application

Abstract

The application discloses a gasoline selective hydrodesulfurization catalyst and a preparation method and application thereof. The catalyst comprises a hydrogenation metal component, an auxiliary component and a binder component; the hydrogenation metal component comprises at least one of a group VIB metal and a group VIII metal; the content of the group VIB metal in the form of an oxide is 50.0wt%-65.0wt% based on the weight of the catalyst; the content of the group VIII metal in the form of an oxide is 10.0wt%-25.0wt%; the content of the auxiliary component in the form of an oxide is 1.0wt%-8.0wt%; the content of the binder component in the form of an oxide is 10.0wt%-30.0wt%; and the average pore diameter of the catalyst is 6.0-8.0nm. The catalyst is suitable for FCC gasoline hydrodesulfurization, can meet the requirement of producing clean gasoline with a sulfur content ≯10μg / g under the condition of high space velocity and low hydrogen / oil volume ratio with a small octane loss.

Description

TECHNICAL FIELD

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

[0002] Among the existing catalytic cracking gasoline desulfurization technologies, the Prime-G + and the Szorb adsorption desulfurization process are representative. The Prime-G + technology uses Mo-Co / Al2O3 as a hydrodesulfurization catalyst, and adopts a process of full-range pre-hydrogenation, light and heavy gasoline fractionation, and heavy fraction gasoline hydrodesulfurization. When the technology is used to produce clean gasoline with a sulfur content of ≯10 µg / g, the octane number loss is relatively large. When the technology is used to produce national VI standard gasoline with an olefin content of ≯15.0 v%, the further increase of the product octane number loss is caused by the hydrogenation saturation of the olefin. The Szorb technology uses NiO-ZnO as an adsorbent, and adopts an adsorption-regeneration circulation process to treat full-range catalytic cracking gasoline. Compared with the raw material, the product has a significantly reduced sulfur content, a slightly reduced olefin content, a slightly increased alkane content, and a (RON+MON) / 2 loss of less than 1.0 unit. However, the method cannot significantly reduce the olefin content in the gasoline product, and cannot solve the problem of reducing the olefin content for catalytic cracking gasoline with a relatively high olefin content.

[0003] CN103450935A discloses a method for producing ultra-low sulfur gasoline. The method uses a step-by-step impregnation method to prepare a traditional selective hydrodesulfurization MoO3-CoO / Al2O3 catalyst, and the process includes: mixing pseudo-boehmite powder, sesbania powder, and nitric acid aqueous solution, and rolling and mixing into a plastic powder, drying and calcining the extruded strip to prepare a catalyst carrier; impregnating and loading phosphorus and potassium on the catalyst carrier, and then drying and calcining to prepare a P2O5-K2O / Al2O3 catalyst intermediate; impregnating and loading molybdenum and cobalt on the catalyst intermediate, and then drying and calcining to prepare a high-activity MoO3-CoO-P2O5-K2O / Al2O3 catalyst. The hydrodesulfurization catalyst has a relatively large octane number loss when used to produce gasoline with a sulfur content meeting the national V standard.

[0004] CN102309971B discloses a preparation method of a hydroprocessing catalyst. The method uses the large liquid absorption amount of the hydroprocessing catalyst carrier material powder before molding, and adopts a one-time impregnation method to obtain a hydroprocessing catalyst with high active metal content. The method has the following disadvantages: the alumina as the main carrier component needs to be pre-high-temperature hydrothermally treated to stabilize the pore and reduce the acidity, and needs to be dried and calcined for multiple times, which is complex; in particular, the method uses rolling and extruding, and the pore is not smooth, which is not conducive to the diffusion of reactants and products on the surface and in the pore of the catalyst. The catalyst prepared by the method is suitable for being used as a heavy distillate oil hydroprocessing catalyst, and is not suitable for being used as a gasoline selective hydrodesulfurization catalyst.

[0005] The existing hydrogenation desulfurization catalyst for producing clean gasoline from conventional sulfur-containing and olefin-containing poor gasoline generally adopts a process scheme of low hydrogenation metal content, high temperature, high hydrogen oil volume ratio and low space velocity, so as to reduce the loss of octane number of hydrogenation products, and therefore, the catalyst consumption of the device is large, the energy consumption is high, and especially under the conditions of small device reactor space and small hydrogen amount (such as no circulating hydrogen compressor), the device cannot meet the needs of enterprises to produce national VI gasoline with sulfur content≯10µg / g. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application provides a gasoline selective hydrodesulfurization catalyst, a preparation method and application thereof. The catalyst is suitable for use in FCC gasoline hydrodesulfurization, and can meet the needs of producing clean gasoline with sulfur content≯10µg / g under the conditions of high space velocity and low hydrogen oil volume ratio with small octane number loss.

[0007] The first aspect of the present application provides a gasoline selective hydrodesulfurization catalyst. The catalyst comprises a hydrogenation metal component, an auxiliary component and a binder component.

[0008] According to the present application, the hydrogenation metal component comprises at least one of a Group VIB metal and a Group VIII metal. The Group VIB metal is preferably W and / or Mo. The Group VIII metal is preferably Ni and / or Co. The hydrogenation metal component is preferably W, Mo, Ni and Co.

[0009] According to the present application, the content of the Group VIB metal as calculated based on the oxide is 50.0wt% to 65.0wt%, preferably 55.0wt% to 60.0wt%, and the content of the Group VIII metal as calculated based on the oxide is 10.0wt% to 25.0wt%, preferably 17.0wt% to 22.0wt%, based on the weight of the catalyst.

[0010] According to the present application, preferably, the content of W in terms of oxide is 15.0-35.0 wt% based on the weight of the catalyst; the content of Mo in terms of oxide is 20.0-45.0 wt% based on the weight of the catalyst; the content of Ni in terms of oxide is 13.0-17.0 wt% based on the weight of the catalyst; and the content of Co in terms of oxide is 4.0-8.0 wt% based on the weight of the catalyst.

[0011] According to the present application, the auxiliary component comprises at least one of K, Ca, P, Si, F, B, Ti and Zr.

[0012] According to the present application, further, the content of the auxiliary component in terms of oxide is 1.0 wt%-8.0 wt% based on the weight of the catalyst, preferably 3.0 wt%-5.0 wt%.

[0013] According to the present application, the binder component is one or more of alumina, titania, silica and magnesia.

[0014] According to the present application, further, the content of the binder component in terms of oxide is 10.0 wt%-30.0 wt% based on the weight of the catalyst, preferably 15.0 wt%-25.0 wt%.

[0015] According to the present application, 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; and the bulk density of the catalyst is 0.80-0.95 g / cm 3 .

[0016] The present application provides a preparation method of the gasoline selective hydrodesulfurization catalyst.

[0017] (1) mixing a hydrogenation metal source, an auxiliary agent and an acid solution to form a slurry, spray drying to obtain microspheres;

[0018] (2) mixing the microspheres and a binder, shaping treatment, and calcining to obtain the catalyst.

[0019] According to the present application, the hydrogenation metal source in step (1) is a compound containing a hydrogenation metal component, preferably at least one of a salt and a metal oxide. The auxiliary agent is a salt containing an auxiliary component. The binder is a salt and / or oxide containing a binder component, preferably at least one of boehmite and silica sol.

[0020] According to the present application, the acid solution in step (1) is nitric acid solution. The concentration of the aqueous nitric acid solution is 5.0-20.0 g / 100 mL. The amount of the aqueous nitric acid solution added is 5.0wt%-10.0wt% of the total amount of the hydrogenation metal source and the additive, wherein the hydrogenation metal source is calculated as an oxide and the additive is calculated as an oxide. In addition, 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℃, the outlet temperature is 120-200℃, and the microspheres obtained after cyclone separation.

[0021] According to the present application, the diameter of the microspheres in step (1) is 20-50 µm particles; wherein the microspheres with a diameter of 30-40 µm account for 60wt%-95wt%, preferably 80wt%-95wt%, by mass.

[0022] According to the present application, the shaping in step (2) is kneading shaping, preferably extrusion strip shaping. An aqueous nitric acid solution can also be added during the shaping process in step (2). Further, the concentration of the aqueous nitric acid solution is 5.0-20.0 g / 100 mL. The amount of the aqueous nitric acid solution added is 5.0wt%-10.0wt% of the total amount of the microspheres and the binder, calculated as nitric acid. An appropriate amount of water can also be added as needed. The calcination conditions are: calcination at 400-600℃ for 3.0-6.0 hours. Drying can be carried out before calcination, and the drying conditions are: drying at 120-200℃ for 3.0-6.0 hours.

[0023] According to the present application, the catalyst can be subjected to a presulfurization treatment before use. The method of presulfurization treatment can use conventional methods. Preferably, the catalyst is presulfurized in the presence of a sulfiding agent and hydrogen. The presulfurization conditions are: pressure 1.0 MPa-4.5 MPa, temperature 200℃-400℃, sulfidation time 5-15 hours, hydrogen agent volume ratio (volume ratio of hydrogen to sulfiding agent) 10:1-100:1; preferred sulfidation conditions: pressure 1.5 MPa-3.0 MPa, temperature 260℃-330℃, hydrogen agent volume ratio 20:1-80:1, sulfidation time 6-10 hours. The sulfiding agent is a sulfide that can decompose into H2S. Preferably, the sulfiding agent includes at least one of carbon disulfide (CS2) and dimethyl disulfide (DMDS). A sulfiding oil can also be added during the presulfurization process. The sulfiding oil is at least one of straight-run gasoline and hydrogenated naphtha. The distillation range of the sulfiding oil is 40-180℃. The liquid hourly space velocity of the sulfiding oil is 2.0 h -1 -4.0 h -1 .

[0024] The third aspect of the present application provides the use of the above-mentioned gasoline selective hydrodesulfurization catalyst in a gasoline hydrodesulfurization reaction.

[0025] According to the present application, the method of the use can adopt a fixed bed process.

[0026] According to the present application, the gasoline is a poor-quality gasoline. The poor-quality gasoline is from a heavy fraction of a catalytically cracked 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.

[0027] According to the present application, the conditions of the hydrodesulfurization reaction are as follows: the reaction pressure is 1.0-4.5 MPa, the reaction temperature is 200-400 °C, the liquid hourly space velocity is 3.0-10.0 h -1 ~10.0 h -1 , and the hydrogen to oil volume ratio is 10:1-100:1; the preferred reaction conditions are: the reaction pressure is 1.5-3.0 MPa, the reaction temperature is 250-300 °C, the liquid hourly space velocity is 5.0-7.0 h -1 ~7.0 h -1 , and the hydrogen to oil volume ratio is 20:1-80:1.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] (1) The catalyst of the present application comprises a hydrogenation metal component, an auxiliary component, and a binder component; the hydrogenation metal component comprises at least one of a Group VIB metal and a Group VIII metal; preferably, the content of the Group VIB metal, calculated as an oxide, is 50.0-65.0 wt% based on the weight of the catalyst; the content of the Group VIII metal, calculated as an oxide, is 10.0-25.0 wt%; the content of the auxiliary component, calculated as an oxide, is 1.0-8.0 wt%; the content of the binder component, calculated as an oxide, is 10.0-30.0 wt%; and the average pore diameter of the catalyst is 6.0-8.0 nm. The hydrogenation metal component of the present application has a high metal content, the content of the hydrogenation metal component, calculated as an oxide, is more than 60%, and has a suitable average pore diameter, compared with the traditional method which uses a low metal content (15.0-25.0 wt% calculated as an oxide). Further, the catalyst of the present application also has a suitable bulk density, and the hydrodesulfurization catalyst is used in an FCC gasoline hydrodesulfurization reaction, can meet the requirement of producing clean gasoline with a sulfur content ≯ 10 µg / g under the conditions of high space velocity and low hydrogen to oil volume ratio with a small loss of octane number; while the low hydrodesulfurization activity catalyst prepared by the traditional method can only be used in a conventional process, i.e. under the conditions of low space velocity (2.0-4.0 h -1 ~4.0 h-1 The catalyst can meet the requirement of producing clean gasoline with sulfur content ≯ 10 µg / g and large octane loss under the condition of high hydrogen to oil volume ratio (hydrogen to oil volume ratio is 200:1-300:1).

[0030] In addition, in the prior art, alumina is used as a main carrier component, and the content is high, and pre-high-temperature hydrothermal treatment is needed to stabilize the pore and reduce the acidity, and the catalyst needs to be dried and calcined for many times, and the steps are complex; in the catalyst, the alumina is only used as a binder, and the content is small, and no special treatment is needed. The hydrogenation metal component, the auxiliary component and the binder component in the catalyst work together to improve the hydrogenation desulfurization performance of the catalyst.

[0031] (2) The catalyst is prepared by the method of the present application, which comprises the steps of: spraying and drying, and then shaping and calcining. Compared with the prior art (for example, the prior art adopts a powdered hydrogenation treatment catalyst material to impregnate active metals, and then shaping treatment), the metal components in the catalyst of the present application are more uniformly mixed, the pore is more unobstructed, and the diffusion of the reactants such as sulfides and olefins and the products in the surface and the pore of the catalyst is more favorable, the residence time of the olefins on the metal hydrogenation center is reduced, and the excessive hydrogenation saturation of the olefins is inhibited.

[0032] The method of the present application can produce gasoline products meeting the national VI standard, wherein the sulfur content is ≯ 10 µg / g, and the research octane number loss is ≯ 2.0.

[0033] (3) The catalyst of the present application is applied to the hydrogenation desulfurization of FCC gasoline, and can meet the requirement of producing clean gasoline with sulfur content ≯ 10 µg / g under the condition of high space velocity and low hydrogen to oil volume ratio with small octane loss. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a scanning electron microscope (SEM) image of the microspheres prepared in Example 1;

[0035] Figure 2 is a scanning electron microscope (SEM) image of the microspheres prepared in Example 2;

[0036] Figure 3 is a scanning electron microscope (SEM) image of the microspheres prepared in Example 3;

[0037] Figure 4 is a scanning electron microscope (SEM) image of the microspheres prepared in Example 4. DETAILED DESCRIPTION

[0038] The present application will be further described below in combination with the drawings and examples, but the protection scope of the present application is not limited in this way.

[0039] In the present application, the specific surface area (S) is determined according to the GB / T 5816 standard, the pore volume (V) is determined according to the Q / SH 361 913 (petrochemical standard) standard, the average pore diameter (D) is calculated according to D=4V / S, and the bulk density is determined according to the Q / SH 361 928 (petrochemical standard). Example 1

[0040] (1) Spray drying: 26.0 g of ammonium tetramolybdate containing MoO3, 30.0 g of ammonium metatungstate containing WO3, 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 K2O were weighed and uniformly mixed, 20 mL of a nitric acid solution with a concentration of 20.0 g / 100 mL and deionized water were added, and a slurry was prepared. The liquid-solid mass ratio of the slurry is 5:1. The slurry is spray dried, the hot air inlet pressure of the spray drying equipment is 3.5 MPa, the inlet temperature is 350℃, and the outlet temperature is 150℃. The microspheres are prepared by a cyclone separator, and are recorded 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%.

[0041] (2) Extrusion molding: 80.0 g of the above microspheres and 20.0 g of pseudoboehmite containing Al2O3 are uniformly mixed, 79 mL of a dilute nitric acid solution with a concentration of 10 g / 100 mL and an appropriate amount of deionized water are added, and a wet cake is prepared. Then, extrusion molding is performed, and the catalyst is dried at 150℃ for 4 hours and calcined at 520℃ for 4 hours to prepare a strip-shaped catalyst, which is recorded as HMC-1. The catalyst composition is: MoO3(26.0 wt%)-WO3(30.0 wt%)-NiO(15.0 wt%)-CoO(5.0 wt%)-K2O(4.0 wt%) / Al2O3(20.0 wt%).

[0042] The properties of the catalyst are shown in Table 1. The hydrogenation desulfurization performance of the catalyst was investigated using raw gasoline-A and raw gasoline-B (properties shown in Table 2) respectively. Before testing, the catalyst was first presulfided. That is, the catalyst was loaded into a small fixed-bed hydrogenation reactor. The catalyst was presulfided, the sulfidation oil was straight-run gasoline (distillation range 40-175℃), the CS2 mass concentration was 2.0%, the sulfidation reaction pressure was 1.6 MPa, the hydrogen-oil volume ratio was 20:1, the liquid hourly space velocity was 3.0 h -1 , the temperature was 320℃, and the sulfidation time was 8 h.

[0043] Using raw gasoline-A as the raw oil, desulfurized product-A was obtained. The test conditions were: hydrogen-oil volume ratio was 20:1, liquid hourly space velocity was 5.0 h -1The reaction temperature was 265°C, the reaction pressure was 1.6 MPa, and after 10 hours of stable operation, sampling analysis was performed, and the properties of the obtained gasoline product are shown in Table 3.

[0044] The desulfurization product-B was obtained by using raw gasoline-B as the raw oil. The test conditions were as follows: the hydrogen / 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, and after 10 hours of stable operation, sampling analysis was performed, and the properties of the obtained gasoline product are shown in Table 3. Example 2

[0045] (1) Spray drying: 30.0 g of ammonium tetramolybdate containing MoO3, 26.0 g of ammonium metatungstate containing WO3, 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 K2O were weighed and uniformly mixed, 20 mL of a nitric acid solution with a concentration of 20.0 g / 100 mL and deionized water were added, and a slurry was prepared. 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 prepared through a cyclone separator, and the microspheres had a diameter of 20-50 µm, of which the microspheres with a diameter of 30-40 µm accounted for 85 wt%.

[0046] (2) Extrusion molding: 80.0 g of the above-mentioned microspheres and 20.0 g of pseudo-boehmite containing Al2O3 were uniformly mixed, 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, and a wet cake was prepared. Then, extrusion molding was performed, and the wet cake was dried at 150°C for 4 hours and calcined at 520°C for 4 hours to prepare a strip-shaped catalyst. The composition of the catalyst was: MoO3(30.0 wt%)-WO3(26.0 wt%)-NiO(15.0 wt%)-CoO(5.0 wt%)-K2O(4.0 wt%) / Al2O3(20.0 wt%).

[0047] The properties of the catalyst are shown in Table 1. The hydrogen desulfurization performance of the HMC-2 catalyst was investigated by using raw gasoline-A and raw gasoline-B (properties shown in Table 2) respectively. Before testing, the catalyst was first presulfided. That is, the catalyst was loaded into a small fixed-bed hydrogenation reactor. The catalyst was presulfided, and the sulfiding oil was straight-run gasoline (distillation range 40-175°C) with a CS2 mass concentration of 2.0%. The sulfiding reaction pressure was 1.8 MPa, the hydrogen / oil volume ratio was 20:1, the liquid hourly space velocity was 3.0 h -1 , and the reaction temperature was 320°C. Sulfidation was performed for 8 hours.

[0048] The raw material gasoline-A was used as raw oil to obtain the desulfurization product-A. The test conditions were as follows: the hydrogen / oil volume ratio was 20:1, the liquid hourly space velocity was 6.0h -1 -1, the reaction temperature was 270℃, the reaction pressure was 1.8MPa, after running stably for 10h, sampling and analysis, the properties of the obtained gasoline product were shown in Table 3.

[0049] The raw material gasoline-B was used as raw oil to obtain the desulfurization product-B. The test conditions were as follows: the hydrogen / oil volume ratio was 50:1, the liquid hourly space velocity was 6.0h -1 -1, the reaction temperature was 275℃, the reaction pressure was 1.8MPa, after running stably for 10h, sampling and analysis, the properties of the obtained gasoline product were shown in Table 3. Example 3

[0050] (1) Spray drying: 35.0g of ammonium tetramolybdate containing MoO3, 25.0g of ammonium metatungstate containing WO3, 15.0g of nickel nitrate containing NiO, 7.0g of basic cobalt carbonate containing CoO, and 3.0g of potassium dihydrogen phosphate containing K2O were weighed and uniformly mixed, 34mL of concentrated nitric acid with a concentration of 20.0g / 100mL and deionized water were added to prepare a slurry. The liquid-solid mass ratio of the slurry was 3:1. The slurry was spray dried, the hot air inlet pressure of the spray drying equipment was 3.5MPa, the inlet temperature was 350℃, and the outlet temperature was 150℃. The microspheres were prepared by a cyclone separator, and were recorded as HMS-3. The diameter of the microspheres was 20~50µm. Among them, the microspheres with a diameter of 30~40µm accounted for 85wt%.

[0051] (2) Extrusion molding: 85.0g of the above-mentioned microspheres and 15.0g of pseudoboehmite containing Al2O3 were uniformly mixed, 64mL of dilute nitric acid solution with a concentration of 10g / 100mL and an appropriate amount of deionized water were added to prepare a wet cake. Then, extrusion molding was performed, and the wet cake was dried at 150℃ for 4 hours and calcined at 520℃ for 4 hours to prepare a strip-shaped catalyst, which was recorded as HMC-3. The catalyst composition was: MoO3(35.0wt%)-WO3(25.0wt%)-NiO(15.0wt%)-CoO(7.0wt%)-K2O(3.0wt%) / Al2O3(15.0wt%).

[0052] The properties of the catalyst were shown in Table 1. The raw material gasoline-A and the raw material gasoline-B (properties shown in Table 2) were used to investigate the hydrodesulfurization performance of the catalyst. Before testing, the catalyst was first presulfided. The catalyst was loaded into a small fixed-bed hydrogenation reactor. The catalyst was presulfided, and the sulfiding oil was straight-run gasoline (distillation range 40~175℃) with a CS2 mass concentration of 2.0%. The sulfiding reaction pressure was 1.6MPa, the hydrogen / oil volume ratio was 20:1, and the liquid hourly space velocity was 3.0h -1The reaction temperature was 320℃ for 8 hours for sulfurization.

[0053] Using gasoline-A as the feedstock, desulfurization product-A was obtained. The test conditions were: hydrogen-to-oil volume ratio of 20:1 and liquid hourly space velocity of 5.0 h⁻¹. -1 The reaction temperature was 265℃, the reaction pressure was 1.6MPa, and samples were taken for analysis after 10 hours of stable operation. The properties of the obtained gasoline product are shown in Table 3.

[0054] Using gasoline-B as the feedstock, desulfurization product-B was obtained. The test conditions were: hydrogen-to-oil volume ratio of 50:1 and liquid hourly space velocity (LHSV) of 5.0 h⁻¹. -1 The reaction temperature was 270℃, the reaction pressure was 1.6MPa, and after 10 hours of stable operation, samples were taken for analysis. The properties of the obtained gasoline product are shown in Table 3. Example 4

[0055] (1) Spray drying: Weigh out 40.0g of ammonium tetramolybdate containing MoO3, 20.0g of ammonium metatungstate containing WO3, 15.0g of nickel nitrate containing NiO, 7.0g of basic cobalt carbonate containing CoO, and 3.0g of potassium dihydrogen phosphate containing K2O, grind and mix them evenly, add 34mL of nitric acid with a concentration of 20.0g / 100mL 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 3.5MPa, the inlet temperature is 350℃, and the outlet temperature is 150℃. The slurry is then processed into microspheres by a cyclone separator, designated as HMS-3. The diameter of the microspheres is 20~50µm. Among them, microspheres with a diameter of 30~40µm account for 85wt%.

[0056] (2) Extrusion molding: 85.0g of the above microspheres and 15.0g of pseudoboehmite of Al2O3 were ground and mixed evenly. 95mL of dilute nitric acid solution with a concentration of 10g / 100mL and an appropriate amount of deionized water were added to form a wet cake. Then, the cake was extruded and dried at 150℃ for 4 hours and calcined at 520℃ for 4 hours to prepare a strip-shaped catalyst, denoted as HMC-4. The catalyst composition is: MoO3 (40.0wt%)-WO3 (20.0wt%)-NiO (15.0wt%)-CoO (7.0wt%)-K2O (3.0wt%) / Al2O3 (15.0wt%).

[0057] The properties of the catalyst are shown in Table 1. The hydrogen desulfurization performance of the catalyst was investigated using raw gasoline-A and raw gasoline-B (properties shown in Table 2) respectively. Before testing, the catalyst was first presulfided. That is, the catalyst was loaded into a small fixed-bed hydrogenation reactor. The catalyst was first presulfided, and the sulfiding oil was straight-run gasoline (distillation range 40-175℃) with a CS2 mass concentration of 2.0%. The sulfiding reaction pressure was 1.6 MPa, the hydrogen / oil volume ratio was 20:1, the liquid hourly space velocity was 3.0h -1 , the reaction temperature was 320℃, and the sulfiding time was 8h.

[0058] Using raw gasoline-A as the raw oil, desulfurized product-A was obtained. The test conditions were as follows: hydrogen / oil volume ratio was 20:1, liquid hourly space velocity was 5.0h -1 , reaction temperature was 265℃, reaction pressure was 1.6 MPa, and after stable operation for 10h, sampling analysis was performed. The properties of the obtained gasoline product are shown in Table 3.

[0059] Using raw gasoline-B as the raw oil, desulfurized product-B was obtained. The test conditions were as follows: hydrogen / oil volume ratio was 50:1, liquid hourly space velocity was 5.0h -1 , reaction temperature was 270℃, reaction pressure was 1.6 MPa, and after stable operation for 10h, sampling analysis was performed. The properties of the obtained gasoline product are shown in Table 3.

[0060] Comparative Example 1

[0061] A MoO3-CoO-K2O / Al2O3 low-metal-content selective hydrogen desulfurization catalyst was prepared by a stepwise impregnation method according to CN103450935A.

[0062] 1000g of pseudo-boehmite (Al2O3 content of 78wt%) was weighed, 5wt% of Echinochloa crusgalli powder extrusion aid based on Al2O3 was added, and 5wt% of 10% mass concentration nitric acid aqueous solution based on Al2O3 was added, mixed and rolled into a plastic powder, and a cylindrical strip with a diameter of 1.5mm was prepared by an extruding machine. The catalyst carrier was dried at 120℃ for 8h and calcined at 500℃ for 5h.

[0063] According to the K2O content of 2.0wt% on the catalyst, a certain amount of potassium dihydrogen phosphate was taken, deionized water was added, and an impregnation solution of 120mL was prepared. Then, the solution was sprayed onto 160g of the above catalyst carrier. The K2O / Al2O3 catalyst intermediate was prepared by drying at 120℃ for 10h and calcining at 500℃ for 5h.

[0064] With a MoO3 content of 13.0 wt% and a CoO content of 4.0 wt% on the catalyst, a measured amount of molybdenum oxide and basic cobalt carbonate were added to deionized water to prepare a 60 mL impregnation solution, which was then sprayed onto 80 g of the above catalyst intermediate. The solution was dried at 120 °C for 8 hours and calcined at 490 °C for 6 hours to prepare a highly active MoO3 (13.0 wt%)-CoO (4.0 wt%)-K2O (2.0 wt%) / Al2O3 (81.0 wt%) catalyst.

[0065] The catalyst prepared in this example is an LM-R catalyst, and its properties 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 shown in Table 2), respectively. Before testing, the catalyst was pre-sulfurized. The pre-sulfurization method was the same as in Example 2.

[0066] Using gasoline-A as the feedstock, desulfurization product-A was obtained. The test conditions were: hydrogen-to-oil volume ratio of 20:1 and liquid hourly space velocity (LHSV) of 6.0 h⁻¹. -1 The reaction temperature was 270℃, the reaction pressure was 1.8MPa, and after 10 hours of stable operation, samples were taken for analysis. The properties of the obtained gasoline product are shown in Table 4.

[0067] Using gasoline-B as the feedstock, desulfurization product-B was obtained. The test conditions were: hydrogen-to-oil volume ratio of 50:1 and liquid hourly space velocity (LHSV) of 6.0 h⁻¹. -1 The reaction temperature was 275℃, the reaction pressure was 1.8MPa, and after 10 hours of stable operation, samples were taken for analysis. The properties of the obtained gasoline product are shown in Table 4.

[0068] The hydrodesulfurization performance of the catalyst in Comparative Example 1 under conventional process conditions was investigated using feedstock gasoline-A and feedstock gasoline-B (properties shown in Table 2).

[0069] Using gasoline-A as the feedstock, desulfurization product-A2 was obtained. The test conditions were: hydrogen-to-oil volume ratio of 200:1 and liquid hourly space velocity (LISH) of 4.0 h⁻¹. -1 The reaction temperature was 270℃, the reaction pressure was 1.8MPa, and samples were taken for analysis after 10 hours of stable operation. The properties of the obtained gasoline product are shown in Table 5.

[0070] Using gasoline-B as the feedstock, desulfurization product-B2 was obtained. The test conditions were: hydrogen-to-oil volume ratio of 200:1 and liquid hourly space velocity (LHSV) of 3.0 h⁻¹. -1 The reaction temperature was 275℃, the reaction pressure was 1.8MPa, and after 10 hours of stable operation, samples were taken for analysis. The properties of the obtained gasoline product are shown in Table 5.

[0071] Comparative Example 2

[0072] A high metal content hydrofining catalyst is prepared using a method of the prior art.

[0073] (1) Hydrothermal treatment: using a vertical hydrothermal treatment device, 33.3g Al2O3 pseudoboehmite is treated at 550℃, 1.0MPa steam pressure for 1 hour to produce modified alumina powder.

[0074] (2) Solution preparation: 30.0g of ammonium tetramolybdate, 26.0g of ammonium metatungstate, 15.0g of nickel nitrate, 5.0g of basic cobalt carbonate, and 4.0g of potassium phosphate are weighed out and mixed uniformly, and deionized water is added to prepare a 200mL metal solution under stirring and heating to 80℃ for 5 hours.

[0075] (3) Liquid-solid loading: the modified alumina powder obtained in step (1) is mixed with the metal solution obtained in step (2) to load the metal components onto the alumina, then filtered, dried at 120℃ for 4 hours, and then crushed and sieved to 100-200 mesh (74-150µm).

[0076] (4) Extrusion molding: the metal-loaded hydrogen metal powder obtained in step (3) is rolled for 30 minutes, then 5wt% of concentrated nitric acid solution with a concentration of 6g / 100mL is added based on the mass of the metal-loaded hydrogen metal powder, and the rolling is continued to form an extrusion paste, which is then extruded and molded, dried at 150℃ for 4 hours, and calcined at 530℃ for 4 hours to form a strip-shaped catalyst.

[0077] The comparative example catalyst is referred to as HM-R catalyst, and its composition is MoO3(30.0wt%)-WO3(26.0wt%)-NiO(15.0wt%)-CoO(5.0wt%)-K2O(4.0wt%) / Al2O3(20.0wt%).

[0078] The properties of the HM-R catalyst are shown in Table 1. The hydrogen desulfurization performance of the catalyst is investigated using raw gasoline-A and raw gasoline-B (properties shown in Table 2). Before testing, the catalyst is pre-sulfided. The pre-sulfiding method is the same as that of Example 2.

[0079] Using raw gasoline-A as raw oil, desulfurized product-A is obtained. The test conditions are: hydrogen / oil volume ratio of 20:1, liquid hourly space velocity of 6.0h -1 , reaction temperature of 270℃, reaction pressure of 1.8MPa, and sampling analysis after stable operation for 10h. The properties of the obtained gasoline product are shown in Table 4.

[0080] The raw material gasoline-B was used as the raw oil to obtain the desulfurized product-B. The test conditions were as follows: the hydrogen / oil volume ratio was 50:1, the liquid hourly space velocity was 6.0h-1, the reaction temperature was 275℃, and the reaction pressure was 1.8MPa. After stable operation for 10h, sampling analysis was performed, and the properties of the obtained gasoline product were shown in Table 4. -1 , the reaction temperature was 275℃, and the reaction pressure was 1.8MPa. After stable operation for 10h, sampling analysis was performed, and the properties of the obtained gasoline product were shown in Table 4.

[0081] Table 1 Composition and properties of the catalysts obtained in various examples

[0082]

[0083] Table 2 Properties of the raw gasoline

[0084]

[0085] Table 3 Properties of the gasoline products obtained in Examples 1-4

[0086]

[0087] Table 3 (continued)

[0088]

[0089] Table 4 Properties of the gasoline products obtained in Comparative Examples 1 and 2

[0090]

[0091] Table 5 Properties of the products obtained under conventional process conditions for the gasoline raw material in Comparative Example 1

[0092]

[0093] As can be seen from the data in the above tables, under the reaction conditions of low hydrogen / oil volume ratio and high volume space velocity, the high-metal-content hydrodesulfurization catalyst prepared by the method of the present application can produce a gasoline product meeting the national VI standard, wherein the sulfur content is ≯10µg / g, and the research octane number loss is ≯2.0. The low-metal-content hydrodesulfurization catalyst prepared by the prior art cannot meet the need for producing a product with a sulfur content of ≯10µg / g. The high-metal-content hydrodesulfurization catalyst prepared by the prior art can meet the need for producing a product with a sulfur content of ≯10µg / g, but the research octane number (RON) loss of the product is relatively large.

Claims

1. A gasoline selective hydrodesulfurization catalyst, comprising a hydrotreating metal component, an additive component, and a binder component; wherein the hydrotreating metal component comprises at least one group VIB metal and a group VIII metal; Based on the weight of the catalyst, The content of Group VIB metals, calculated as oxides, ranges from 50.0 wt% to 65.0 wt%. The content of Group VIII metals, calculated as oxides, ranges from 10.0 wt% to 25.0 wt%. The content of the auxiliary component, calculated as oxide, is 1.0 wt% to 8.0 wt%; The binder component, calculated as oxides, has a content of 10.0 wt% to 30.0 wt%. The catalyst has an average pore diameter of 6.0~8.0 nm; The Group VIB metal is W and / or Mo; The Group VIII metal is Ni and / or Co; The auxiliary component includes at least one of K, Ca, P, Si, F, B, Ti, and Zr; The binder component is aluminum oxide; The preparation method of the hydrodesulfurization catalyst includes: (1) The hydrogenated metal source, additives and acid solution are mixed to form a slurry, which is then spray-dried to obtain microspheres; (2) The microspheres and binder are mixed, shaped, and calcined to obtain the catalyst.

2. The catalyst according to claim 1, characterized in that, Based on the weight of the catalyst, The content of Group VIB metals, calculated as oxides, ranges from 55.0 wt% to 60.0 wt%. The content of Group VIII metals, calculated as oxides, ranges from 17.0 wt% to 22.0 wt%. The content of the auxiliary component, calculated as oxide, is 3.0 wt% to 5.0 wt%. The binder component, calculated as oxides, has a content of 15.0 wt% to 25.0 wt%.

3. The catalyst according to claim 1 or 2, characterized in that, The catalyst has a bulk density of 0.80~0.95 g / cm³. 3 .

4. A method for preparing the catalyst according to any one of claims 1 to 3, comprising: (1) The hydrogenated metal source, additives and acid solution are mixed to form a slurry, which is then spray-dried to obtain microspheres; (2) The microspheres and binder are mixed, shaped, and calcined to obtain the catalyst.

5. The method according to claim 4, characterized in that, The spray drying in step (1) is carried out in a spray drying equipment; the hot air inlet pressure of the spray drying equipment is 3.0~7.0MPa, the inlet temperature is 300~400℃, and the outlet temperature is 120~200℃.

6. The method according to claim 4, characterized in that, The microspheres mentioned in step (1) are particles with a diameter of 20~50µm; of which, by mass, microspheres with a diameter of 30~40µm account for 60wt%~95wt%.

7. The method according to claim 6, characterized in that, In step (1), the microspheres with a diameter of 30~40µm account for 80wt%~95wt% by mass.

8. The method according to claim 4, characterized in that, The calcination conditions described in step (2) are: calcination at 400~600℃ for 3.0~6.0 hours.

9. The use of a catalyst according to any one of claims 1 to 3 or a catalyst prepared by any one of claims 4 to 8 in the hydrodesulfurization reaction of gasoline.

10. The application according to claim 9, characterized in that, The gasoline is of inferior quality and is derived from the heavy fraction of catalytic cracking stabilized gasoline.

11. The application according to claim 10, characterized in that, The gasoline has a sulfur content of 20~300µg / g and an olefin content of 15.0~30.0wt%; the initial boiling point of the gasoline is 60~80℃ and the final boiling point is 190~205℃.

12. The application according to claim 9, characterized in that, The conditions for the hydrodesulfurization reaction are as follows: reaction pressure 1.0 MPa~4.5 MPa, reaction temperature 200℃~400℃, and liquid hourly space velocity 3.0 h⁻¹. -1 ~10.0h -1 The hydrogen-to-oil volume ratio is 10:1 to 100:

1.

13. The application according to claim 9, characterized in that, The conditions for the hydrodesulfurization reaction are as follows: reaction pressure 1.5 MPa~3.0 MPa, reaction temperature 250℃~300℃, and liquid hourly space velocity 5.0 h⁻¹. -1 ~7.0h -1 The hydrogen-to-oil volume ratio is 20:1 to 80:1.

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