A sulfided type catalyst for pre-hydrogenation of catalytic cracking gasoline and its preparation method and application

Abstract

This invention provides a catalytic cracking gasoline pre-hydrogenation sulfidation catalyst, its preparation method, and its application. The catalyst comprises an alumina-acidic molecular sieve composite support and a primary active metal sulfide and a co-active metal sulfide supported on the composite support. In the composite support, the acidic molecular sieve is supported in the packing channels of the alumina, and the dry basis mass ratio of the acidic molecular sieve to the alumina is 1.0-5.0:1. The total acidity of the composite support is 1.0-2.0 mmol / g. Based on the total weight of the catalyst, the contents of the primary active metal and the co-active metal, calculated as their respective oxides, are 1.0-17.0 wt% and 2.0-20.0 wt%, respectively. The concentration of the primary active metal-co-active metal-sulfur active sites in the catalyst is 0.20-0.40 mmol / g, and the total acidity is 1.30-1.80 mmol / g. The catalyst of this invention exhibits high desulfurization, high diene removal, and high double bond isomerization activity.

Description

TECHNICAL FIELD

[0001] The present application relates to a catalytic cracking gasoline pre-hydrogen sulfide type catalyst and its preparation method and application, belongs to catalytic cracking gasoline hydrogenation technical field. BACKGROUND

[0002] FCC gasoline is a mixture of C4-C 12 hydrocarbons and trace amounts of sulfides, oxides and metal arsenides, according to the differences in the nature of crude oil and processing route of each refinery, FCC gasoline is a mixture of 18-55v% olefins, 12-20v% aromatic hydrocarbons and alkanes, the octane value characteristics of each component is aromatic hydrocarbon>olefin≈isomerized alkane>alkane. Generally, high sulfur, high olefin content and low octane value FCC gasoline accounts for a high proportion, while low sulfur content, low olefin content, high octane value alkylate oil, isomerate oil and reformate oil is low, which makes the cleaning of FCC gasoline needs to carry the three tasks of desulfurization, olefin reduction and octane value maintenance at the same time.

[0003] The most commonly used carrier of gasoline hydrodesulfurization catalyst is alumina, such as CN104275191A discloses a preparation method of a catalyst for FCC gasoline pre-hydrogenation, which is with alumina as carrier, using stepwise impregnation method to load active components Ni and Mo, to prepare eggshell type pre-sulfided selective hydrogenation catalyst Ni-Mo / Al2O3. The pre-sulfided selective hydrogenation catalyst Ni-Mo / Al2O3 provided by the prior art has simple preparation method, mild conditions, and good activity, selectivity and stability, and when applied to FCC pre-hydrogenation process, it does not need pre-sulfurization for start-up, is easy to operate and can greatly shorten the start-up time, is practical and economical, the diene conversion rate is more than 80%, and the light sulfur conversion rate is more than 90%. But the eggshell type pre-sulfided selective hydrogenation catalyst Ni-Mo / Al2O3 does not have the function of double bond isomerization.

[0004] CN109201072A discloses a catalytic cracking gasoline pre-hydrogenation catalyst and a preparation method thereof. The catalytic cracking gasoline pre-hydrogenation catalyst comprises a carrier and an active component, wherein the carrier comprises an alumina composite carrier containing 0.1-12wt% tungsten-doped lanthanum ferrite and one or more selected from ZSM-5, ZSM-11, ZSM-12, ZSM-35, mordenite, amorphous silica-alumina, SAPO-11, MCM-22, Y molecular sieve or beta molecular sieve, and the active component is one or more of cobalt, molybdenum, nickel and tungsten. The catalytic cracking gasoline pre-hydrogenation catalyst can be used for removing dienes and mercaptans in FCC gasoline, and converting terminal olefins into internal olefins through double bond isomerization, thereby making up for the octane loss caused by the saturation of olefins by the hydrogenation refining main catalyst. However, the preparation process of the carrier used in the catalytic cracking gasoline pre-hydrogenation catalyst is complex, and the simple acid component (such as amorphous silica-alumina, ZSM-5 molecular sieve, etc.) is kneaded with alumina, sesbania powder and deionized water to form a shape, which causes the acid component to be embedded by other carrier components; the active metal precursor-containing (such as ammonium heptamolybdate and nickel nitrate) aqueous solution is directly impregnated into the carrier, which causes the metal component to be embedded by the carrier Al 3+ There is a strong interaction between the species, and the metal component is not easy to form a high-activity type II Co(Ni)-Mo(W)-S active phase, and the acid sites (Al 3+ species) covering the surface of the composite carrier, that is, the density of the active sites of the metal component and the acid component is low.

[0005] Therefore, it has become a technical problem to be solved in the field to provide a new catalytic cracking gasoline pre-hydrogenation sulfided catalyst, a preparation method and application thereof. SUMMARY

[0006] In order to solve the above-mentioned defects and deficiencies, one object of the present application is to provide a catalytic cracking gasoline pre-hydrogenation sulfided catalyst.

[0007] Another object of the present application is also to provide a preparation method of the above-mentioned catalytic cracking gasoline pre-hydrogenation sulfided catalyst.

[0008] Still another object of the present application is also to provide the application of the above-mentioned catalytic cracking gasoline pre-hydrogenation sulfided catalyst in catalytic cracking gasoline hydrodesulfurization.

[0009] In order to achieve the above-mentioned objects, in one aspect, the present application provides a catalytic cracking gasoline pre-hydrogenation sulfided catalyst, wherein the catalytic cracking gasoline pre-hydrogenation sulfided catalyst comprises an alumina-acid molecular sieve composite carrier and a main active metal sulfide and an auxiliary active metal sulfide supported on the composite carrier.

[0010] In the alumina-acid molecular sieve composite carrier, the acid molecular sieve is loaded in the stacking channel of the alumina, the dry base mass ratio of the acid molecular sieve to the alumina is 1.0-5.0:1, preferably 2.0-4.0; the total acid amount of the composite carrier is 1.0-2.0 mmol / g, preferably 1.1-2.0 mmol / g;

[0011] The content of the main active metal in terms of oxide is 1.0-17.0 wt%, preferably 6.0-12.0 wt%, and the content of the auxiliary active metal in terms of oxide is 2.0-20.0 wt%, preferably 7.0-15.0 wt%, based on the total weight of the catalyst being 100%;

[0012] In the catalytic cracking gasoline pre-hydrogenation sulfided catalyst, the concentration of the main active metal-auxiliary active metal-sulfur active site is 0.20-0.40 mmol / g, preferably 0.22-0.40 mmol / g, and the total acid amount is 1.30-1.80 mmol / g.

[0013] As a specific embodiment of the above-mentioned catalyst of the present application, the acid molecular sieve comprises one or a combination of several of H-ZSM-5, SAPO-11, BEA, MWW and EUO; preferably, the acid molecular sieve comprises H-ZSM-5 or SAPO-11.

[0014] As a specific embodiment of the above-mentioned catalyst of the present application, the main active metal comprises Mo, etc., and the auxiliary active metal comprises Ni, etc.

[0015] In another aspect, the present application provides a preparation method of the above-mentioned catalytic cracking gasoline pre-hydrogenation sulfided catalyst, wherein the preparation method comprises the following steps:

[0016] Step (1): dissolving a water-soluble organic polymer in deionized water, then adding acid molecular sieve powder, stirring and drying to obtain acid molecular sieve powder coated with an organic polymer;

[0017] Step (2): kneading, extruding, drying and calcining the acid molecular sieve powder coated with an organic polymer, alumina powder, auxiliary extrusion agent and peptizing agent to obtain an alumina-acid molecular sieve composite carrier;

[0018] Step (3): preparing a co-impregnation solution containing a complexing agent, an auxiliary active metal salt and a main active metal salt;

[0019] Step (4): impregnating the co-impregnation solution into the alumina-acid molecular sieve composite carrier in an equal volume, then aging, drying and temperature sulfidation to obtain the catalytic cracking gasoline pre-hydrogenation sulfided catalyst.

[0020] As a specific embodiment of the preparation method of the above-mentioned application, in step (1), the mass ratio of the water-soluble organic polymer to deionized water is 0.001-0.10:1, preferably 0.005-0.05:1; the mass ratio of the acidic molecular sieve powder to deionized water is 0.1-1.0:1, preferably 0.25-0.95:1; and the mass ratio of the water-soluble organic polymer to the acidic molecular sieve powder is 0.01-0.1:1, preferably 0.02-0.09:1.

[0021] As a specific embodiment of the preparation method of the above-mentioned application, in step (1), the water-soluble organic polymer includes one or a combination of several of polyacrylammonium, polyquaternary ammonium salt, polyethylene glycol, alginic acid, and hydroxypropyl methyl cellulose; preferably, the water-soluble organic polymer includes one or a combination of several of polyethylene glycol, alginic acid, and hydroxypropyl methyl cellulose; and more preferably, the water-soluble organic polymer is one of polyethylene glycol, alginic acid, and hydroxypropyl methyl cellulose.

[0022] In step (1) of the preparation method of the above-mentioned application, a water-soluble organic polymer is used to obtain an organic polymer-coated acidic molecular sieve powder, and at this time, the acidic sites of the organic polymer-coated acidic molecular sieve powder are protected from being covered by the alumina powder during the molding process. After the calcination in step (2), the organic polymer is burned and decomposed, and thus the acidic sites of the organic polymer-coated acidic molecular sieve powder are exposed.

[0023] As a specific embodiment of the preparation method of the above-mentioned application, in step (2), the alumina powder, the extrusion aid, and the peptizing agent are all conventional substances, and their specific substances and amounts can be reasonably selected and adjusted according to the actual operation needs. For example, the alumina powder includes boehmite powder; the extrusion aid includes one or a combination of several of sesbania powder, polyacrylamide, graphite, and lubricating oil, and preferably one of sesbania powder, polyacrylamide, and graphite; and the peptizing agent includes one or a combination of several of nitric acid, hydrochloric acid, acetic acid, and citric acid, and preferably one of nitric acid, hydrochloric acid, and acetic acid.

[0024] As a specific embodiment of the preparation method of the above-mentioned application, in step (2), the purpose of the calcination is to burn the water-soluble organic polymer, and the calcination is performed at 550-600°C for 4-6h.

[0025] As a specific embodiment of the above-mentioned preparation method of the present application, in step (3), the molar ratio of the complexing agent to the promoter metal salt is 1.2-2.2:1, preferably 1.5-1.7:1.

[0026] As a specific embodiment of the above-mentioned preparation method of the present application, in step (3), the pH value of the co-impregnation solution is greater than 8.1, preferably greater than 8.2.

[0027] As a specific embodiment of the above-mentioned preparation method of the present application, in step (3), the complexing agent comprises one or a combination of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, ethylenediamine, cyclohexanediaminetetraacetic acid, citric acid, and ethylene glycol; preferably, the complexing agent comprises one or a combination of ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and the like.

[0028] As a specific embodiment of the above-mentioned preparation method of the present application, in step (3), the promoter metal salt comprises one or a combination of nitrate, acetate, and carbonate of the promoter metal, and the main active metal salt comprises one or a combination of ammonium salt and thioammonium salt of the main active metal. For example, when the promoter metal is nickel, its salt can be one or a combination of nickel nitrate, nickel acetate, and nickel carbonate, preferably nickel nitrate or nickel acetate; when the main active metal is molybdenum, its salt can be one or a combination of ammonium heptamolybdate, ammonium tetramolybdate, and ammonium tetrathiomolybdate, preferably ammonium heptamolybdate or ammonium tetrathiomolybdate.

[0029] As a specific embodiment of the above-mentioned preparation method of the present application, in step (4), the temperature for sulfuration is 230-360℃, preferably 300-360℃, the cumulative time for temperature rising and sulfuration is 20-100h, preferably 25-50h, the pressure for sulfuration is 1.0-3.0MPa, preferably 1.5-2.5MPa, the volume space velocity of the oil for sulfuration is 1.0-3.0h -1 , preferably 1.0-2.0h -1 , the hydrogen / oil volume ratio is 200:1-500:1, preferably 250:1-350:1.

[0030] As a specific embodiment of the above-mentioned preparation method of the present application, in step (4), the sulfuration reagent used for sulfuration comprises one or a combination of dimethyl disulfide, carbon disulfide, methyl mercaptan, ethyl mercaptan, and sulfide (such as dimethyl sulfide, etc.), preferably dimethyl disulfide or carbon disulfide.

[0031] In another aspect, the present application also provides the use of the above-mentioned catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst in catalytic cracking gasoline hydrodesulfurization.

[0032] Compared with the prior art, the present application has the following beneficial technical effects:

[0033] (1) In the preparation of the catalytic cracking gasoline pre-hydrogenation sulfided catalyst, the water-soluble organic polymer and the acidic molecular sieve powder are used to obtain the water-soluble organic polymer-coated acidic molecular sieve powder, and then the water-soluble organic polymer-coated acidic molecular sieve powder, alumina powder, extrusion aid and peptizing agent are kneaded, extruded, dried and calcined to obtain the alumina-acidic molecular sieve composite carrier with more exposed acidic sites. In this way, the alumina-acidic molecular sieve composite carrier with higher total acid amount can be obtained.

[0034] (2) In the preparation of the catalytic cracking gasoline pre-hydrogenation sulfided catalyst, a complexing agent is added to the co-impregnation solution. The complexing agent preferentially complexes with the main and auxiliary active metal cation species (mainly the auxiliary active metal cation species) and other active species (such as Al 3+ ) in the composite carrier, and by adjusting the molar ratio of the complexing agent to the auxiliary active metal salt and the pH value of the co-impregnation solution, the selective loading of the main and auxiliary active metal species on the inert surface of the composite carrier can be achieved. During the sulfidation process, more high-activity metal active sites are formed, and at the same time, due to the decomposition of the complexing agent, the protected acidic sites are exposed. Therefore, the catalytic cracking gasoline pre-hydrogenation sulfided catalyst provided by the present application has a higher concentration of main active metal-auxiliary active metal-sulfur active sites (such as NiMoS active sites) and a higher total acid amount.

[0035] (3) Since the catalytic cracking gasoline pre-hydrogenation sulfided catalyst provided by the present application has a higher concentration of main active metal-auxiliary active metal-sulfur active sites (such as NiMoS active sites) and a higher total acid amount, when it is used to catalyze the hydrodesulfurization of catalytic cracking gasoline, the removal rate of mercaptans, the removal rate of dienes, the increase of internal olefins and the increase of RON of the obtained hydrogenated gasoline product are all higher. DETAILED DESCRIPTION

[0036] It should be noted that the term "comprising" and any variation thereof in the specification and claims of the present application is intended to cover non-exclusive inclusion, for example, a process, method, system, product or apparatus including a series of steps or units does not have to be limited to only those steps or units clearly listed, but can include other steps or units that are not clearly listed or inherent to these processes, methods, products or apparatuses.

[0037] The ranges disclosed herein are meant to include any and all sub-ranges of the named ranges, including the range endpoints. For instance, a range from 60-120 should be interpreted to include not only 60-120 and 80- 110, but also 60-80, 60-81, 60-82, 60-83, 60-84, 60-85, 60-86, 60-87, 60-88, 60-89, 60-90, 60-91, 60-92, 60-93, 60-94, 60-95, 60-96, 60-97, 60-98, 60-99, 60-100, 60-101, 60-102, 60-103, 60-104, 60-105, 60-106, 60-107, 60-108, 60-109, 60-110, and so forth, as well as 80-81, 81-82, 82-83, 83-84, 84-85, 85-86, 86-87, 87-88, 88-89, 89-90, 90-91, 91-92, 92-93, 93-94, 94-95, 95-96, 96-97, 97-98, 98-99, 99-100, 100-101, 101-102, 102-103, 103-104, 104-105, 105-106, 106-107, 107-108, 108-109, 109-110, and so forth, as well as 110-111, 111-112, 112-113, 113-114, 114-115, 115-116, 116-117, 117-118, 118-119, 119-120, and so forth, as well as 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, and so forth. It will be further understood that the endpoints of the ranges are significant (i.e., the range is not intended to include the endpoint). It is specifically intended that the description set forth herein

[0038] In the present application, unless otherwise stated, the numerical range "a-b" means a shorthand notation for any real combination of the numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all the real numbers between "0-5" have been listed in the present application, and "0-5" is just a shorthand notation for these numerical combinations.

[0039] In the present application, all the embodiments mentioned in the present application and the preferred embodiments can be combined with each other to form new technical solutions, if there is no special statement.

[0040] In the present application, all the technical features mentioned in the present application and the preferred features can be combined with each other to form new technical solutions, if there is no special statement.

[0041] In the present application, all the steps mentioned in the present application can be performed in sequence or randomly, but preferably in sequence, if there is no special statement. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method also comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0042] In order to make the purposes, technical solutions and advantages of the present application clearer, the present application is further described in detail below in combination with the tables and examples. The examples described below are part of the examples of the present application, but not all the examples, which are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the examples in the present application, all the other examples obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments not mentioned by the manufacturers are all conventional products that can be purchased in the market.

[0043] Carrier examples and comparative examples

[0044] Example 1

[0045] The present example provides an alumina-acidic molecular sieve composite carrier, which is prepared by a preparation method comprising the following specific steps:

[0046] First, 7.5 g of polyethylene glycol is dissolved in 1500 g of deionized water, and then 375 g of H-ZSM-5 molecular sieve powder is added (the mass ratio of polyethylene glycol to deionized water is 0.005:1, the mass ratio of H-ZSM-5 molecular sieve powder to deionized water is 0.25:1, and the mass ratio of polyethylene glycol to acidic molecular sieve powder is 0.02:1), and after stirring and drying, polyethylene glycol-coated H-ZSM-5 molecular sieve powder is obtained. Then, it is mixed and kneaded with pseudo-boehmite powder, sesbania powder and nitric acid aqueous solution, extruded, dried, and calcined at 550℃ for 5h to obtain an alumina-H-ZSM-5 molecular sieve composite carrier with more exposed acidic sites, which is denoted as ZAT-1. In ZAT-1, the dry weight ratio of the molecular sieve to the alumina is 3.6:1.

[0047] Example 2

[0048] The present example provides an alumina-acidic molecular sieve composite carrier, which is different from that of Example 1 in that:

[0049] A water-soluble organic polymer alginate and an acidic molecular sieve SAPO-11 are used; the mass ratio of alginate to deionized water is 0.01:1; the mass ratio of SAPO-11 molecular sieve powder to deionized water is 0.38:1; and the mass ratio of alginate to SAPO-11 molecular sieve powder is 0.04:1.

[0050] The alumina-acidic molecular sieve composite carrier provided in the present example is denoted as ZAT-2, and in ZAT-2, the dry weight ratio of the molecular sieve to the alumina is 3.4:1.

[0051] Example 3

[0052] The embodiment provides an alumina-acidic molecular sieve composite carrier which is different from the embodiment 1 in that:

[0053] The mass ratio of the water-soluble organic polymer hydroxypropyl methyl cellulose to deionized water is 0.04:1; the mass ratio of the H-ZSM-5 molecular sieve powder to deionized water is 0.76:1; and the mass ratio of the hydroxypropyl methyl cellulose to the H-ZSM-5 molecular sieve powder is 0.08:1.

[0054] The alumina-acidic molecular sieve composite carrier provided in the embodiment is recorded as ZAT-3, and in the ZAT-3, the dry base weight ratio of the molecular sieve to the alumina is 3.2:1.

[0055] Embodiment 4

[0056] The embodiment provides an alumina-acidic molecular sieve composite carrier which is different from the embodiment 1 in that:

[0057] The mass ratio of the polyethylene glycol to deionized water is 0.05:1; the mass ratio of the SAPO-11 molecular sieve powder to deionized water is 0.95:1; and the mass ratio of the polyethylene glycol to the SAPO-11 molecular sieve powder is 0.06:1.

[0058] The alumina-acidic molecular sieve composite carrier provided in the embodiment is recorded as ZAT-4, and in the ZAT-4, the dry base weight ratio of the molecular sieve to the alumina is 3.0:1.

[0059] Comparative example 1

[0060] The embodiment provides an alumina-acidic molecular sieve composite carrier which is different from the embodiment 1 in that:

[0061] No water-soluble organic polymer material and acidic molecular sieve are used.

[0062] The alumina-acidic molecular sieve composite carrier obtained in the comparative example is recorded as ZAT-D2.

[0063] Comparative example 2

[0064] The embodiment provides an alumina-acidic molecular sieve composite carrier which is different from the embodiment 1 in that:

[0065] No water-soluble organic polymer material is used.

[0066] The alumina-acidic molecular sieve composite carrier obtained in the comparative example is recorded as ZAT-D2.

[0067] Test example 1

[0068] The total acid amount of ZAT-1 to ZAT-4 and ZAT-D1 to ZAT-D2 was measured by ammonia temperature programmed desorption method, and the experimental data are shown in Table 1.

[0069] Table 1

[0070]

[0071] As can be seen from Table 1, the alumina-acidic molecular sieve composite carrier provided by the application, i.e., ZAT-1 to ZAT-4, has a higher total acid amount compared with the comparative carrier, i.e., ZAT-D1 to ZAT-D2. This is due to the fact that, in the preparation of the catalytic cracking gasoline pre-hydrogenation sulfided catalyst, the water-soluble organic polymer coated acidic molecular sieve powder is obtained by mixing and kneading the water-soluble organic polymer and the acidic molecular sieve powder, the pseudo-boehmite powder and the sesbania powder, and the nitric acid aqueous solution, and then the water-soluble organic polymer coated acidic molecular sieve powder is extruded, dried and calcined, so that the alumina-acidic molecular sieve composite carrier with more exposed acid sites is obtained.

[0072] Catalyst examples and comparative examples

[0073] Example 5

[0074] The present example provides a catalytic cracking gasoline pre-hydrogenation sulfided catalyst prepared by a preparation method comprising the following specific steps:

[0075] A co-impregnation solution containing EDTA, nickel nitrate and ammonium heptamolybdate is prepared, wherein the molar ratio of the complexing agent (EDTA) to nickel nitrate is 1.5:1, and the pH of the co-impregnation solution is adjusted to 9.8 by adding concentrated ammonia water;

[0076] The co-impregnation solution is impregnated into the ZAT-1 carrier in an equal volume, and after the conventional aging and drying process, a semi-finished product is obtained.

[0077] The semi-finished product is loaded into a 200 mL fixed bed reactor for sulfidation; wherein the sulfidation oil is straight-run naphtha, and the sulfidation reagent is carbon disulfide, and the concentration is 1.5 wt.% based on the total weight of the sulfidation oil; the sulfidation pressure is 2.0 MPa, the hydrogen / oil volume ratio is 300:1, and the sulfidation oil volume space velocity is 1.5 h -1 ; the temperature rising process is: first, under a nitrogen atmosphere, the temperature is raised from room temperature to 180°C at a rate of 30°C / h, and then the nitrogen is switched to hydrogen, the sulfidation oil is injected, and the temperature is raised from 180°C to 230°C at a rate of 20°C / h, and then the temperature is kept constant for 4 h, and finally the temperature is raised from 230°C to 310°C at a rate of 20°C / h, and then the temperature is kept constant for 4 h, to obtain a catalytic cracking gasoline pre-hydrogenation sulfided catalyst, which is denoted as CAT-1.

[0078] Example 6

[0079] The present example provides a catalytically cracked gasoline pre-hydrogenation sulfided catalyst, which is prepared by a preparation method comprising the following specific steps:

[0080] A co-impregnation solution containing nitrilotriacetic acid, nickel acetate and ammonium tetrathiomolybdate is prepared, wherein the molar ratio of nitrilotriacetic acid / nickel acetate is 2.0:1, and the pH of the co-impregnation solution is adjusted to 8.8 by adding concentrated ammonia water;

[0081] The co-impregnation solution is impregnated into the ZAT-2 carrier in an equal volume, and after the conventional aging and drying procedures, a semi-finished product is obtained;

[0082] The semi-finished product is loaded into a 200 mL fixed bed reactor for sulfidation; wherein the sulfidation oil is straight-run naphtha, and the sulfidation reagent is methyl mercaptan, and the concentration is 1.5 wt.% based on the total weight of the sulfidation oil; the sulfidation pressure is 1.6 MPa, the hydrogen / oil volume ratio is 270:1; the sulfidation oil volume space velocity is 1.6 h -1 ; The temperature rising process is: first, under a nitrogen atmosphere, the temperature is raised from room temperature to 180°C at a rate of 30°C / h, and kept constant for 2 h, then the nitrogen is switched to hydrogen, the sulfidation oil is injected, and the temperature is raised from 180°C to 230°C at a rate of 20°C / h, and kept constant for 4 h, and finally the temperature is raised from 230°C to 330°C at a rate of 20°C / h, and kept constant for 5 h, to obtain a catalytically cracked gasoline pre-hydrogenation sulfided catalyst, denoted as CAT-2.

[0083] Example 7

[0084] The present example provides a catalytically cracked gasoline pre-hydrogenation sulfided catalyst, which is prepared by a preparation method comprising the following specific steps:

[0085] A co-impregnation solution containing nitrilotriacetic acid, nickel acetate and ammonium tetrathiomolybdate is prepared, wherein the molar ratio of nitrilotriacetic acid / nickel acetate is 2.0:1, and the pH of the co-impregnation solution is adjusted to 8.8 by adding concentrated ammonia water;

[0086] The co-impregnation solution is impregnated into the ZAT-3 carrier in an equal volume, and after the conventional aging and drying procedures, a semi-finished product is obtained;

[0087] The semi-finished product is loaded into a 200 mL fixed bed reactor for sulfidation; wherein the sulfidation oil is straight-run naphtha, and the sulfidation reagent is methyl mercaptan, and the concentration is 1.5 wt.% based on the total weight of the sulfidation oil; the sulfidation pressure is 1.6 MPa, the hydrogen / oil volume ratio is 270:1; the sulfidation oil volume space velocity is 1.6 h -1The temperature rising process is: first, under the atmosphere of nitrogen, the temperature is raised from room temperature to 180°C at a rate of 30°C / h, and then kept constant for 2h, then the nitrogen is switched to hydrogen, the sulfuration oil is injected, and the temperature is raised from 180°C to 230°C at a rate of 20°C / h, and then kept constant for 4h, finally, the temperature is raised from 230°C to 320°C at a rate of 20°C / h, and then kept constant for 2h, to obtain the pre-hydrogenation sulfuration type catalyst for catalytic cracking gasoline, which is denoted as CAT-3.

[0088] Example 8

[0089] The present embodiment provides a pre-hydrogenation sulfuration type catalyst for catalytic cracking gasoline, which is prepared by a preparation method comprising the following specific steps:

[0090] A co-impregnation solution containing ethylenediamine, nickel nitrate and ammonium heptamolybdate is prepared, wherein the molar ratio of ethylenediamine / nickel nitrate is 1.6:1, and the pH of the co-impregnation solution is adjusted to 9.8 by adding concentrated ammonia water;

[0091] The co-impregnation solution is impregnated into the ZAT-4 carrier in an equal volume, and after the conventional aging and drying procedures, a semi-finished product is obtained;

[0092] The semi-finished product is loaded into a 200mL fixed bed reactor for sulfuration; wherein the sulfuration oil is straight-run naphtha, and the sulfuration reagent is ethyl mercaptan, and the concentration is 1.5wt.% based on the total weight of the sulfuration oil; the sulfuration pressure is 1.9MPa, the hydrogen / oil volume ratio is 320:1, and the sulfuration oil volume space velocity is 1.8h -1 The temperature rising process is: first, under the atmosphere of nitrogen, the temperature is raised from room temperature to 180°C at a rate of 30°C / h, and then kept constant for 2h, then the nitrogen is switched to hydrogen, the sulfuration oil is injected, and the temperature is raised from 180°C to 230°C at a rate of 20°C / h, and then kept constant for 4h, finally, the temperature is raised from 230°C to 340°C at a rate of 20°C / h, and then kept constant for 4.5h, to obtain the pre-hydrogenation sulfuration type catalyst for catalytic cracking gasoline, which is denoted as CAT-4.

[0093] Example 9

[0094] The present embodiment provides a pre-hydrogenation sulfuration type catalyst for catalytic cracking gasoline, which is prepared by a preparation method comprising the following specific steps:

[0095] A co-impregnation solution containing EDTA, nickel nitrate and ammonium heptamolybdate is prepared, wherein the molar ratio of EDTA / nickel nitrate is 1.9:1, and the pH of the co-impregnation solution is adjusted to 9.8 by adding concentrated ammonia water;

[0096] The co-impregnation solution is impregnated into the ZAT-1 carrier in an equal volume, and after the conventional aging and drying procedures, a semi-finished product is obtained;

[0097] The semi-finished product was loaded into a 200 mL fixed bed reactor for sulfuration; wherein the sulfuration oil was straight-run naphtha, and the sulfuration reagent was ethyl mercaptan, and the concentration was 1.5 wt.% based on the total weight of the sulfuration oil; the sulfuration pressure was 1.9 MPa, the hydrogen / oil volume ratio was 320:1, and the sulfuration oil volume space velocity was 1.8 h-1. -1 The temperature rising process was as follows: first, under a nitrogen atmosphere, the temperature was raised from room temperature to 180℃ at a temperature rising rate of 30℃ / h, and then kept constant for 2 h; then the nitrogen was switched to hydrogen, the sulfuration oil was injected, and the temperature was raised from 180℃ to 230℃ at a temperature rising rate of 20℃ / h, and then kept constant for 4 h; finally, the temperature was raised from 230℃ to 340℃ at a temperature rising rate of 20℃ / h, and then kept constant for 4.5 h, to obtain a catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst, denoted as CAT-5.

[0098] Comparative Example 3

[0099] This comparative example provides a catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst, denoted as CAT-D1, which is only different from Example 5 in that:

[0100] ZAT-D1 is used as the carrier.

[0101] Comparative Example 4

[0102] This comparative example provides a catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst, denoted as CAT-D2, which is only different from Example 5 in that:

[0103] ZAT-D2 is used as the carrier.

[0104] Comparative Example 5

[0105] This comparative example provides a catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst, denoted as CAT-D3, which is only different from Example 5 in that:

[0106] ZAT-D2 is used as the carrier;

[0107] and no complexing agent is used.

[0108] Comparative Example 6

[0109] This comparative example provides a catalytic cracking gasoline pre-hydrogenation sulfuration type catalyst, denoted as CAT-D4, which is only different from Example 5 in that:

[0110] No complexing agent is used.

[0111] Comparative Example 7

[0112] The comparative example provides a catalytic cracking gasoline pre-hydrogenation sulfidation type catalyst, denoted as CAT-D5, which is only different from that of Example 5 in that the molar ratio of complexing agent (EDTA) to metal salt (nickel nitrate) is 1.0:1, and the pH of the co-impregnation solution is 7.8.

[0113] Test Example 2

[0114] The test example uses atomic absorption method to measure the MoO3 content and NiO content in CAT-1 to CAT-4 and CAT-D1 to CAT-D5, uses ammonia temperature programmed desorption method to measure the total acid content, and uses CO infrared spectroscopy method to measure the NiMoS active site concentration, and the obtained experimental data is shown in Table 2.

[0115] Table 2

[0116]

[0117] As can be seen from Table 2, compared with CAT-D1 to CAT-D5, the CAT-1 to CAT-4 provided by the present application not only has a higher NiMoS active site concentration, but also has a higher total acid content. This is due to the fact that the present application adds a complexing agent to the co-impregnation solution when preparing the catalytic cracking gasoline pre-hydrogenation sulfidation type catalyst, the complexing agent preferentially complexes with active metal cations and other active species (such as Al 3+ ) in the composite carrier, and by adjusting the molar ratio of the complexing agent to the active metal salt and the pH of the co-impregnation solution, the selective loading of the active metal species on the inert surface of the composite carrier can be achieved, so that more high-activity metal active sites are formed during the sulfidation process, and at the same time, due to the decomposition of the complexing agent, the protected acid sites are exposed.

[0118] Catalyst Performance Evaluation Example

[0119] The evaluation example uses a 200 mL fixed bed reactor, uses the same FCC gasoline as the raw material, and under the evaluation conditions of a fixed bed reactor inlet temperature of 110°C, a reaction pressure of 1.8 MPa, a volume space velocity of 5.0 h -1 , a hydrogen to oil volume ratio of 4:1, compares and evaluates CAT-1 to CAT-4 and CAT-D1 to CAT-D5, and according to SH / T0689-2000, the total sulfur content of the catalytic cracking gasoline and its hydrogenation modified product is measured, according to GB / T 5487-1995, the research method octane number (RON) of the catalytic cracking gasoline and its hydrogenation modified product is measured, and according to GB / T 11132, the olefin content of the catalytic cracking gasoline and its hydrogenation modified product is measured, and the obtained evaluation results are shown in Table 3.

[0120] Table 3 Hydrogenated gasoline product analysis data

[0121]

[0122]

[0123] As can be seen from Table 3, when the catalyst provided by the embodiment of the present application is used to catalyze catalytic cracking gasoline hydrodesulfurization, the mercaptan removal rate, diene removal rate, internal olefin increment, and RON of the obtained hydrogasoline product are all higher than those of the comparative agent. This is attributed to the fact that the catalytic cracking gasoline pre-hydrogenation sulfidation catalyst provided by the embodiment of the present application not only has a higher NiMoS active site concentration, but also has a higher total acid amount.

[0124] In summary, the catalytic cracking gasoline pre-hydrogenation sulfidation catalyst provided by the present application comprises an alumina-acid molecular sieve composite carrier with more acid sites and a metal component with more metal active sites, that is, the effective active site density of the active metal component and the acid component in the catalyst is higher, and when it is used to catalyze catalytic cracking gasoline hydrodesulfurization, it has high mercaptan removal, high diene removal, and high double bond isomerization activity.

[0125] The above is only a specific embodiment of the present application, and cannot limit the scope of the present application. Therefore, the replacement of equivalent components, or equivalent changes and modifications made within the scope of the present application, should still fall within the scope of the present patent. In addition, the technical features in the present application can be freely combined with each other, and the technical features can be freely combined with each other.

Claims

1. A pre-hydrogenated sulfurization catalyst for catalytic cracking of gasoline, characterized in that, The catalytic cracking gasoline pre-hydrogenated sulfidation catalyst includes an alumina-acidic molecular sieve composite support and a main active metal sulfide and a co-active metal sulfide supported on the composite support. In the alumina-acidic molecular sieve composite support, the acidic molecular sieve is loaded in the packing channels of alumina, the dry basis mass ratio of acidic molecular sieve to alumina is 1.0-5.0:1, and the total acidity of the composite support is 1.0-2.0 mmol / g. Based on the total weight of the catalyst (100%), the content of the main active metal (calculated as oxide) is 1.0-17.0 wt%, and the content of the co-active metal (calculated as oxide) is 2.0-20.0 wt%. In the pre-hydrogenated sulfurized catalyst for catalytic cracking of gasoline, the concentration of the main active metal-co-active metal-sulfur active sites is 0.20-0.40 mmol / g, and the total acid content is 1.30-1.80 mmol / g.

2. The catalyst according to claim 1, characterized in that, The acidic molecular sieve includes one or a combination of several of H-ZSM-5, SAPO-11, BEA, MWW, and EUO.

3. The catalyst according to claim 1 or 2, characterized in that, The primary active metal includes Mo, and the secondary active metal includes Ni.

4. The method for preparing the catalytic cracking gasoline pre-hydrogenation sulfidation catalyst according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: Step (1): Dissolve water-soluble organic polymers in deionized water, then add acidic molecular sieve powder, and obtain acidic molecular sieve powder coated with organic polymers after stirring and drying. Step (2): Mix, extrude, dry and calcine the organic polymer-coated acidic molecular sieve powder, alumina powder, extrusion aid and adhesive to obtain alumina-acidic molecular sieve composite carrier. Step (3): Prepare a co-impregnation solution containing a complexing agent, a co-active metal salt, and a main active metal salt; Step (4): The co-impregnation liquid is impregnated onto the alumina-acid molecular sieve composite support in equal volume, and then aged, dried and heated for sulfidation to obtain the catalytic cracking gasoline pre-hydrogenated sulfidation catalyst.

5. The preparation method according to claim 4, characterized in that, In step (1), the mass ratio of water-soluble organic polymer to deionized water is 0.001-0.10:1, the mass ratio of acidic molecular sieve powder to deionized water is 0.1-1.0:1, and the mass ratio of water-soluble organic polymer to acidic molecular sieve powder is 0.01-0.1:

1.

6. The preparation method according to claim 4 or 5, characterized in that, In step (1), the water-soluble organic polymer includes one or a combination of several of the following: ammonium polyacrylate, polyquaternary ammonium salt, polyethylene glycol, alginate and hydroxypropyl methylcellulose.

7. The preparation method according to claim 4, characterized in that, In step (2), the roasting is carried out at 550-600℃ for 4-6 hours.

8. The preparation method according to claim 4, characterized in that, In step (3), the molar ratio of the complexing agent to the co-active metal salt is 1.2-2.2:

1.

9. The preparation method according to claim 4 or 8, characterized in that, In step (3), the pH value of the co-impregnation solution is greater than 8.

1.

10. The preparation method according to claim 4 or 8, characterized in that, In step (3), the complexing agent includes one or a combination of several of ethylenediaminetetraacetic acid, nitric acid, ethylenediamine, cyclohexanediaminetetraacetic acid, citric acid and ethylene glycol.

11. The preparation method according to claim 4 or 8, characterized in that, In step (3), the auxiliary active metal salt includes one or a combination of several of the auxiliary active metal nitrates, acetates and carbonates, and the main active metal salt includes one or a combination of several of the main active metal ammonium salts.

12. The preparation method according to claim 11, characterized in that, The ammonium salt of the main active metal is one or a combination of several of the thioammonium salts of the main active metal.

13. The preparation method according to claim 4, characterized in that, In step (4), the sulfidation temperature is 230-360 ℃, the cumulative time for heating and sulfidation is 20-100 h, the sulfidation pressure is 1.0-3.0 MPa, and the volume hourly space velocity of the sulfidation oil is 1.0-3.0 h. -1 The hydrogen / oil volume ratio is 200:1-500:

1.

14. The preparation method according to claim 4 or 13, characterized in that, In step (4), the sulfiding reagent used in the sulfidation includes one or a combination of several of dimethyl disulfide, carbon disulfide, methanethiol, ethanethiol and thioether.

15. The application of the pre-hydrogenated sulfurized catalyst for catalytic cracking gasoline according to any one of claims 1-3 in the hydrodesulfurization of catalytic cracking gasoline.

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