CN108421554A - Hydrobon catalyst and its preparation method and application - Google Patents

Abstract

The invention relates to a hydrorefining catalyst and a preparation method thereof. The preparation method comprises: (1) loading a water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by an impregnation method, followed by drying, Roasting, obtain semi-finished catalyst, described roasting condition makes the total amount of semi-finished catalyst be a benchmark, and carbon content is 0.03-0.5% by weight in the semi-finished catalyst; 1) The resulting semi-finished catalyst is impregnated, then dried and not roasted; (3) loading magnesium and phosphorus as auxiliary agents on the carrier; wherein, step (3) is neutralized before and during step (1) After that and any one or more before step (2). The catalyst provided by the invention is particularly suitable for hydrofinishing of light distillate oil and middle distillate oil for the purpose of hydrodesulfurization and hydrodenitrogenation.

Description

Hydrofining catalyst and its preparation method and application

technical field

The invention relates to a preparation method of a hydrorefining catalyst, a hydrorefining catalyst prepared by the method and an application thereof.

Background technique

The increasing awareness of environmental protection and stricter environmental regulations force the refining industry to pay more attention to the development of clean fuel production technology. In the future, vehicle fuels in the market will tend to be "ultra-low sulfur", and fuels that cannot meet emission standards will not be able to enter the market. Hydrogenation technology, as an effective means of desulfurization, is playing an increasingly important role in the production of clean vehicle fuels. Among them, high-efficiency hydrogenation catalysts are the core technology of hydrogenation technology. Therefore, the development of catalysts with higher activity and Selective new hydrotreating catalysts have become one of the most urgent needs of the oil refining industry.

Hydrofining catalysts are usually prepared by impregnation, that is, impregnating a certain carrier with a solution containing the desired active components (such as Ni, Mo, Co, W, etc.), followed by drying, roasting or non-calcining.

CN103551162A discloses a diesel hydrodesulfurization and denitrification catalyst. The composition of the catalyst includes a carrier, an auxiliary agent and an active metal; the carrier is an Al ₂ O ₃ -ZrO ₂ -TiO ₂ -SiO ₂ multi-element oxide composite carrier; the auxiliary agent is phosphorus; Nickel, cobalt, molybdenum and tungsten are used as active components; the weight percentage content of each component based on the catalyst is: in terms of oxides, cobalt oxide 1-6wt%; nickel oxide 1-15wt%, molybdenum oxide 2-12wt% %, tungsten oxide 12-35wt%, additive phosphorus pentoxide 1.5-5wt%; catalyst pore volume ≮0.2mL/g, specific surface area ≮140m ² /g, mechanical strength ≮15N/mm; The proportions of the components in the carrier are as follows: titanium oxide accounts for 2-15 wt%, silicon oxide accounts for 2-20 wt%, zirconium oxide accounts for 5-15 wt%, and the balance is aluminum oxide. The catalyst is prepared by a step-by-step impregnation method: the co-impregnation solution is divided into two parts of equal volume, the carrier is impregnated in two steps, and the carrier is calcined after each step of impregnation.

CN103657667A discloses a preparation method of a novel macroporous structure heavy oil hydrogenation demetallization catalyst, which is characterized in that it specifically includes the following steps: 1) preparation of aluminum sol; 2) mixing pitch residue powder and aluminum sol to prepare a macroporous structure catalyst carrier; 3) impregnating the molded catalyst carrier by a two-step impregnation method with equal volumes; finally the catalyst is prepared. The two-step impregnation method of the preparation method is specifically: the first step is to impregnate Mo first, and the second step is to impregnate Ni, and the impregnation solution does not contain an organic complexing agent.

The two-step impregnation method provided by the prior art improves the activity of the hydrofining catalyst, but the degree of improvement is limited.

CN100469440C, CN102909027A disclose that Ni-W-Mo Ternary metal hydrorefining catalyst. Compared with the catalyst provided by the existing method, the obtained catalyst has better hydrofining performance. However, there is still a need to further improve the catalyst activity.

Contents of the invention

Aiming at the problem of low activity of hydrofinishing catalysts in the prior art, the present invention provides a new preparation method of hydrofinishing catalyst and the hydrofining catalyst prepared by the method, and the hydrofinishing catalyst prepared by the method It has significantly higher catalytic activity and activity stability.

The inventors of the present invention have found that the complex impregnation technique described above can weaken the interaction between the active component and the carrier, improve the dispersion of the metal, change the vulcanization order of the metal, and form More highly active active phases and increase the number of active centers. However, due to the low-temperature drying used in the complex impregnation technology and no high-temperature roasting process, the metal compound still exists on the surface of the carrier in the form of metal salts, and the active component and the carrier have a weak force, resulting in high temperature and high pressure. And under the hydrogenation reaction conditions of harsh raw materials, metals continue to accumulate during the reaction process, the additive effect is weakened, the number of active centers is reduced, and the intrinsic activity is reduced, so the activity and stability of the catalyst are reduced. However, although the catalyst prepared by the high-temperature calcination method has better stability, the active component has a stronger interaction with the carrier, and the intrinsic activity of the active center is lower. Larger, less number of active centers, very low activity.

The inventors of the present invention have further found through research that the catalyst is prepared by a two-step impregnation method, the first step impregnation and the second step impregnation are respectively used to introduce hydrogenation metal active components and organic complexing agents, and in the first step impregnation process Adding an organic complexing agent and turning it into carbon by roasting can not only improve the activity of the catalyst, but also effectively maintain the high activity of the catalyst for a long time, thereby greatly improving the service life of the catalyst. It is speculated that the reason may be due to the organic complexing agent added in the first step of impregnation. The presence of the organic complexing agent hinders the aggregation of active metals during the roasting process and makes them more uniformly dispersed; at the same time, the first step of impregnation after roasting It can convert metal compounds into metal oxides and organic complexing agents into carbon, so that the combination between the active metal and the support is stronger, and the activity and stability of the catalyst are improved. The organic complexing agent added in the second impregnation process covers the surface of the catalyst, which can effectively prevent the aggregation of active metals during the vulcanization process, improve the dispersion of metals, and be more conducive to the formation of type II active phases with higher activity and The formation of more active centers further increases the activity of the catalyst. Therefore, this technology can effectively solve the technical defects of the conventional impregnation method and the existing complex impregnation method.

Thereby, the present invention also provides a kind of preparation method of hydrorefining catalyst, and this preparation method comprises the following steps:

(1) The water-soluble salt of the hydrogenation metal active component and the organic complexing agent are loaded on the carrier by the impregnation method, then dried and roasted to obtain a semi-finished catalyst, and the roasting conditions are such that the total amount of the semi-finished catalyst is used as a benchmark , the carbon content in the semi-finished catalyst is 0.03-0.5% by weight;

(2) using the solution containing the organic complexing agent as the impregnating liquid, the semi-finished catalyst obtained in step (1) is impregnated, then dried without roasting;

(3) loading magnesium and phosphorus as additives on the carrier;

Wherein, step (3) is performed before, during and after step (1) and before step (2).

In addition, the present invention also provides the hydrorefining catalyst prepared by the above method.

The hydrorefining catalyst prepared by the method of the invention has high catalytic activity and activity stability. For example, the sulfur and nitrogen content of gasoline treated with the hydrorefining catalyst S3 prepared according to the method of the present invention are all lower than 0.5 micrograms per gram, while under the same conditions, the hydrorefining catalyst prepared by the conventional impregnation method After D2 treatment, the sulfur content of gasoline was as high as 68 μg/g and the nitrogen content was 2.6 μg/g. It can be seen that the hydrorefining catalyst prepared by the method of the present invention has significantly higher desulfurization and denitrogenation activities. And the method provided by the invention is simple to operate, therefore, the method of the invention has good industrial application prospect.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

According to the preparation method of the hydrotreating catalyst provided by the present invention, the preparation method comprises the following steps:

(1) The water-soluble salt of the hydrogenation metal active component and the organic complexing agent are loaded on the carrier by the impregnation method, then dried and roasted to obtain a semi-finished catalyst, and the roasting conditions are such that the total amount of the semi-finished catalyst is used as a benchmark , the carbon content in the semi-finished catalyst is 0.03-0.5% by weight;

(2) using the solution containing the organic complexing agent as the impregnating liquid, the semi-finished catalyst obtained in step (1) is impregnated, then dried without roasting;

(3) loading magnesium and phosphorus as additives on the carrier;

Wherein, step (3) is performed before, during and after step (1) and before step (2).

According to the present invention, preferably, the calcination condition in step (1) is such that the carbon content in the semi-finished catalyst is 0.04-0.4% by weight based on the total amount of the semi-finished catalyst.

In the present invention, the above-mentioned carbon content can be obtained by controlling the roasting temperature in the roasting conditions and the feeding amount of combustible gas, and the combustible gas can be various gases with an oxygen content of not less than 20% by volume, such as air , oxygen and one or more of their mixed gases.

The feeding rate of the combustible gas is preferably not lower than 0.2 liter/hour per gram of carrier. The introduction of the combustible gas, on the one hand, satisfies the conditions of combustion, so that the salt of the active metal component is converted into an oxide, and the organic complexing agent is converted into charcoal; on the other hand, the carbon dioxide, water and Other components are vented to avoid deposition on the catalyst causing vacancy hindrance to the active phase.

Preferably, the flammable gas is fed at a rate of 0.2-20 liters/hour, preferably 0.3-10 liters/hour, per gram of carrier.

According to the present invention, preferably, the calcination temperature in step (1) is 350-500°C, preferably 360-450°C, and the calcination time is 0.5-8h, preferably 1-6h. Controlling the calcination temperature within the above range can ensure that the organic complexing agent can form carbon on the carrier with the above content range, and obtain a semi-finished catalyst.

According to the present invention, preferably, the molar ratio of the organic complexing agent to the metal active component in step (1) is 0.03-2:1, preferably 0.08-1.5:1, more preferably 0.1-1.4:1, more preferably More preferably 0.2-1.3:1.

According to the present invention, preferably, the molar ratio of the organic complexing agent in step (1) and step (2) is 1:0.25-4, preferably 1:0.5-2.

In the present invention, the organic complexing agent described in step (1) and step (2) can be the same or different, preferably, the organic complexing agent is selected from one of oxygen-containing and/or nitrogen-containing organic compounds one or more species.

The oxygen-containing organic matter is preferably selected from one or more of organic alcohols and organic acids.

The organic alcohol is preferably a polyhydric alcohol with more than two valences, more preferably a polyhydric alcohol with 2-6 carbon atoms or its oligomer or polymer, such as ethylene glycol, glycerol, polyethylene glycol, One or more of diethylene glycol and butanediol. The molecular weight of the polyethylene glycol is preferably 200-1500.

The organic acid is preferably a C2-C7 compound containing one or more COOH groups, specifically acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, One or more of tartaric acid and malic acid.

The nitrogen-containing organic matter is preferably selected from one or more of organic amines and organic ammonium salts.

The organic amine is preferably a C2-C7 compound containing one or more NH groups, which may be a primary, secondary or tertiary amine, particularly preferably ethylenediamine.

The organic ammonium salt is preferably EDTA.

Specifically, the present invention particularly preferably described organic complexing agent is ethylene glycol, glycerol, polyethylene glycol (molecular weight is preferably 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, One or more of oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, ethylenediamine and EDTA.

Preferably, the organic complexing agent in step (1) is selected from one or more of organic acids, more preferably, the organic complexing agent in step (1) is selected from one of the fatty acids of C2-C7 one or more species. Using an organic acid as the organic complexing agent in step (1), a hydrorefining catalyst with higher activity can be obtained.

In the present invention, the drying conditions are not particularly limited, and may be various drying conditions commonly used in the art, and the drying conditions in step (1) and step (2) may be the same or different.

Preferably, the drying temperature in step (1) is 100-250°C, and the drying time is 1-12h.

Preferably, the drying temperature in step (2) is 100-200°C, and the drying time is 1-12h.

According to the present invention, preferably, the amount of the hydrogenation metal active component is such that, based on the total amount of the hydrofinishing catalyst, the content of the hydrogenation metal active component is 10-60% by weight in terms of oxides, It is preferably 15-50% by weight, and the auxiliary agent is phosphorus and magnesium; the content of the auxiliary agent is preferably 0.5-5.5% by weight, more preferably 1-5% by weight, and the molar ratio of phosphorus and magnesium in terms of oxide is 0.5-3, preferably 1.0-2.5.

According to the present invention, preferably, in terms of metal elements, the concentration of the water-soluble salt of the hydrogenation metal active component is 0.2-8 mol/L, preferably 0.2-5 mol/L, more preferably 0.2-2 mol/L. The concentrations here are the individual concentrations of the water-soluble salts of various hydrogenation metal active components, not the total concentration.

The water-soluble salt of the hydrogenation metal active component can be a water-soluble compound whose solubility meets the loading requirements or can form a hydrogenation metal active component with a solubility in water that meets the requirements in the presence of a cosolvent, for example, it can be nitric acid One or more of salt, chloride, sulfate, carbonate, preferably nitrate.

According to the present invention, preferably, the hydrogenation metal active component is at least one selected from Group VIB metal elements, at least one selected from Group VIII metal elements.

According to the present invention, the Group VIB metal element is preferably molybdenum and/or tungsten.

According to the present invention, the Group VIII metal element is preferably cobalt and/or nickel.

According to the present invention, preferably, the compound containing Group VIB metal elements can be selected from one or more of ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.

The compound containing a Group VIII metal element may be selected from the group consisting of nitrates of Group VIII metals, chlorides of Group VIII metals, sulfates of Group VIII metals, formates of Group VIII metals, acetylenes of Group VIII metals salts, phosphates of Group VIII metals, citrates of Group VIII metals, oxalates of Group VIII metals, carbonates of Group VIII metals, hydroxycarbonates of Group VIII metals, Hydroxides of Group VIII metals, Phosphates of Group VIII metals, Phosphides of Group VIII metals, Sulfides of Group VIII metals, Aluminates of Group VIII metals, Molybdates of Group VIII metals, One or more of tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.

Preferably, the compound containing a Group VIII metal element is selected from the group consisting of Group VIII metal oxalates, Group VIII metal nitrates, Group VIII metal sulfates, Group VIII metal acetates, Group VIII metal Metal chlorides, Group VIII metal carbonates, Group VIII metal hydroxycarbonates, Group VIII metal hydroxides, Group VIII metal phosphates, Group VIII metal molybdates , one or more of Group VIII metal tungstates and Group VIII metal water-soluble oxides.

Compounds containing Group VIII metal elements may be selected from, but not limited to, nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, cobalt chloride and nickel chloride one or more of .

According to the present invention, there is no particular limitation on the loading method of the hydrogenation metal active component.

According to the present invention, preferably, the loading of the hydrogenation metal active component is to load the hydrogenation metal active component on the support by an impregnation method.

According to the present invention, there is no particular limitation on the order in which the hydrogenation metal active components are loaded on the carrier. The carrier can be impregnated with a solution containing various water-soluble salts to load all the hydrogenation metal active components on the carrier together, or Solutions containing water-soluble salts can be separately prepared to impregnate the carrier step by step, and the hydrogenation metal active components are sequentially loaded on the carrier. When stepwise impregnations are used, each impregnation is preferably followed by drying and preferably further firing. The way and condition of drying and roasting can be selected with reference to the prior art.

According to the present invention, there is no particular limitation on the loading method of the organic complexing agent. The organic complexing agent can be formulated together with one or more of the water-soluble salts of hydrogenation metal active components to form an impregnating solution impregnated carrier, or can be formulated separately to form an impregnating solution impregnated carrier, preferably the former.

According to the present invention, the introduction method of the auxiliary agent can be through a variety of ways, for example, it can be introduced during the preparation of the carrier, it can also be introduced after the preparation of the carrier in various ways such as impregnation, or it can be introduced after the preparation of the carrier Introduced during the process, and then introduced after the preparation of the carrier.

It should be noted that when introduced by impregnating the carrier, a step of calcination is required after introducing the magnesium additive, the calcination temperature is 250-600°C, preferably 350-500°C, and the calcination time is 2-8h. Preferably 3-6h.

According to the present invention, the introduction of the magnesium additive needs to be carried out before step (2), so as to ensure that the organic complexing agent introduced in step (2) does not undergo a roasting process.

According to a preferred embodiment of the present invention, when using the impregnation method, the auxiliary agent magnesium is loaded on the carrier before step (1), and the auxiliary agent phosphorus is introduced together with the metal active component and the organic complexing agent in step (1) in the carrier. Various soluble compounds of auxiliary agents can be used, such as water-soluble salts of magnesium, preferably magnesium nitrate, water-soluble compounds of phosphorus such as phosphoric acid, metaphosphoric acid or salts thereof.

According to the present invention, the impregnation method can be equal-volume impregnation or supersaturated impregnation, the temperature of the impregnation is not particularly limited, it can be various temperatures that the impregnation solution can reach, and the impregnation time is not particularly limited , as long as the required amount of required components can be loaded, for example: the temperature of immersion can be 15-60°C, and the immersion time can be 0.5-5 hours.

The drying temperature of the magnesium loading process is preferably 100-150° C., and the time is preferably 2-6 hours. The calcination temperature is preferably 350-450° C., and the time is preferably 2-6 hours.

According to the present invention, the carrier can be various inorganic refractory oxides. According to the present invention, the term "inorganic heat-resistant oxide" refers to an inorganic oxygen-containing compound whose decomposition temperature is not lower than 300° C. (for example, the decomposition temperature is 300-1000° C.) under oxygen or an oxygen-containing atmosphere.

According to the present invention, the inorganic heat-resistant oxide may be various inorganic heat-resistant oxides commonly used in the field. The inorganic refractory oxide can be selected from alumina, silica, alumina-silica, titania, magnesia, silica-magnesia, silica-zirconia, silica-thoria, silica- Beryllium oxide, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica - one or more of alumina-zirconia.

According to a preferred embodiment of the present invention, the inorganic heat-resistant oxide is alumina, more preferably alumina obtained after firing a hydrated alumina (aluminum hydroxide) colloidal composite.

The invention also provides a hydrorefining catalyst prepared by the preparation method of the invention.

Compared with catalysts prepared by conventional methods, the hydrorefining catalyst prepared by the method provided by the invention has higher catalytic activity.

A preferred method for preparing alumina is obtained by mixing and calcining alumina and/or alumina precursors. The carrier can be made into various easy-to-handle moldings according to different requirements, such as microspheres, spheres, tablets or strips, and the like. Forming can be carried out by conventional methods, for example, it can be prepared by extruding and roasting the alumina and/or its precursor. Wherein, the precursor of alumina may be selected from one or more of various hydrated aluminas and aluminum sols. An appropriate amount of extrusion aid and/or adhesive can be added during extrusion molding, and then extruded. The type and amount of the extrusion aid and peptizer are well known to those skilled in the art, and will not be repeated here. The calcination adopts the methods and conditions commonly used in the art, for example, the calcination temperature can be 350-650°C, preferably 400-600°C; the calcination time is 2-6 hours, preferably 3-5 hours.

The invention also provides a hydrorefining catalyst prepared by the preparation method of the invention.

The catalyst provided by the present invention is pre-prepared with one or more of sulfur, hydrogen sulfide, carbon disulfide, DMDS, polysulfide or sulfur-containing raw materials at a temperature of 140-370 ° C, preferably in the presence of hydrogen, before use. Vulcanization, this pre-vulcanization can be carried out outside the device or in situ in the device to convert it into a sulfide type.

Compared with the prior art, when the catalyst provided by the present invention is used for hydrotreating raw materials with high sulfur content and high nitrogen content, it can achieve higher hydrogenation at high space velocity, low hydrogen-to-oil ratio, low pressure and lower temperature Desulfurization, denitrogenation and olefin saturation activity, especially suitable for the hydrofinishing process of reformer feeds for light distillates and middle distillates such as blending coker gasoline feedstocks and feedstocks from other process sources. Realized in the distillate oil hydrotreating reaction unit, the present invention is not particularly limited to this. One-stage hydrofining can be used, and its operating conditions can be adjusted within the following ranges according to the properties of the raw material oil and the requirements for oil quality: reaction temperature 200-400°C, volume space velocity 4-15h ^-1 preferably 8-12h ^-1 , The hydrogen partial pressure is 0.8-6.0MPa, preferably 1-2MPa, and the hydrogen-to-oil volume ratio is 50-800:1, preferably 50-150:1. The sulfur and nitrogen of the products after hydrotreatment are reduced to below 0.5 μg/g, meeting the requirements of reforming feed.

The implementation process and beneficial effects of the present invention are described in detail below through specific examples, which are intended to help readers understand the essence of the present invention more clearly, but cannot constitute any limitation to the implementation scope of the present invention.

In the following examples, the alumina carrier is RPB-90 alumina purchased from Sinopec Changling Catalyst Company.

In the following examples, a 3271E X-ray fluorescence spectrometer from Rigaku Electric Industries, Ltd. was used to analyze and measure the content of each element in the catalyst. The carbon content in the catalyst semi-finished product was analyzed and determined by EMIA-320V carbon and sulfur analyzer produced by Japan HORIBA Company. The water absorption rate of the catalyst carrier is measured by immersing the carrier (in g by weight) in water (in ml by volume) for 2 hours, and the ratio of carrier (by weight) to water (by volume) is 1:3 , and then the water-absorbed carrier is separated from the water, and the water-absorbed volume of the carrier is calculated, and the water-absorbed rate of the carrier=the water-absorbed volume of the carrier/weight of the carrier.

Preparation Example 1

Weigh 250 grams of magnesium nitrate, add deionized water and stir to dissolve, add deionized water to 850 ml, saturated impregnate 1000 grams of alumina carrier for 2 hours, then dry at 120 ° C for 2 hours, and roast at 400 ° C for 4 hours to obtain a water absorption rate of 0.85ml/g of magnesium-containing alumina carrier Z1.

Preparation example 2

Weigh 80 grams of magnesium nitrate, add deionized water and stir to dissolve, add deionized water to 850 ml, saturate and impregnate 1000 grams of alumina carrier for 2 hours, then dry at 100 ° C for 2.5 hours, and roast at 350 ° C for 6 hours to obtain a water absorption rate of 0.85ml/g of magnesium-containing alumina carrier Z2.

Preparation example 3

Weigh 165 grams of magnesium nitrate, add deionized water and stir to dissolve, add deionized water to 850 milliliters, saturated impregnate 1000 grams of alumina carrier for 2 hours, then dry at 100°C for 3 hours, and roast at 450°C for 2 hours to obtain a water absorption rate of 0.85ml/g of magnesium-containing alumina carrier Z3.

Example 1

Weigh 40 grams of molybdenum trioxide, 19 grams of basic cobalt carbonate, 11 grams of phosphoric acid, and 20 grams of citric acid into 140 grams of deionized water, heat and stir to dissolve to obtain a clarified impregnation solution, and use the saturated impregnation method to impregnate 200 grams of the above solution with For magnesium-containing alumina carrier Z1, the impregnation time is 2 hours, and then it is dried at 120°C for 2 hours, and then it is calcined under the state of flowing air, the calcining temperature is 400°C, and the time is 2 hours. gram of carrier, the feed rate of air is 2 liters/hour, obtain semi-finished catalyst Z2-S1, the carbon content of Z2-S1 is shown in Table 1; Impregnate Z1-S1 with the above solution for 2 hours, and then dry at 110°C for 3 hours to obtain catalyst S1. Based on the total amount of S1 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.

Comparative example 1

The hydrofinishing catalyst was prepared in the same manner as in Example 1, except that the hydrofinishing catalyst S1 obtained in Example 1 was roasted at 400° C. for 3 hours to obtain catalyst D1. In catalyst D1, the total amount of D1 As a benchmark, in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.

Example 2

Weigh 40 grams of molybdenum trioxide, 21 grams of basic nickel carbonate, 13 grams of phosphoric acid, and 30 grams of citric acid into 140 grams of deionized water, heat and stir to dissolve to obtain a clarified impregnation solution, and impregnate 200 grams of the above solution with the saturated impregnation method. The magnesia-containing alumina carrier Z2 is impregnated for 2 hours, then dried at 150°C for 2 hours, and then calcined under the condition of flowing air, the calcined temperature is 360°C, and the time is 3 hours. gram carrier, the feed rate of air is 10 liters/hour, obtains semi-finished catalyst Z2-S2, the carbon content of Z2-S2 is shown in Table 1; Impregnation method Impregnate Z2-S2 with the above solution for 2 hours, and then dry at 150° C. for 3 hours to obtain hydrorefining catalyst S2. Based on the total amount of S2 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.

Example 3

Take by weighing 30 grams of nickel nitrate, 55 grams of ammonium metatungstate (hydrate, molecular weight is 3037, the same below), 10 grams of phosphoric acid and 10 grams of diethylene glycol are put into 140 grams of deionized water, stir and dissolve to obtain a clear solution, and use Saturated impregnation method Use the above solution to impregnate 200 grams of alumina carrier Z3 for 2 hours, then dry it at 120°C for 2 hours, and then roast it under the state of air flow, the roasting temperature is 450°C, the time For 4 hours, with respect to every gram of carrier, the feed rate of air is 0.3 liters/hour, obtains semi-finished catalyst Z3-S3, and the carbon content of Z3-S3 is shown in Table 1; Put 10 grams of diethylene glycol into 150 grams of deionized Stir in water to obtain a clear solution, impregnate Z3-S3 with the above solution by saturated impregnation method for 2 hours, and then dry at 120°C for 6 hours to obtain catalyst S3. Based on the total amount of S3 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.

Comparative example 2

Weigh 30 grams of nickel nitrate, 55 grams of ammonium metatungstate, 10 grams of phosphoric acid and 10 grams of diethylene glycol into 140 grams of deionized water, stir and dissolve to obtain a clear solution, and use the saturated impregnation method to impregnate 200 grams of alumina with the above solution Carrier Z3 was impregnated for 2 hours, and then dried at 120° C. for 2 hours to obtain catalyst D2. Based on the total amount of D2, the content of hydrogenation metal active components is shown in Table 1 in terms of oxides.

Comparative example 3

The hydrorefining catalyst was prepared according to the method of Example 3, except that the alumina carrier Z3 was replaced by the same weight of alumina carrier not loaded with magnesium to obtain catalyst D3. Based on the total amount of D3 and in terms of oxides, the content of hydrogenation metal active components is shown in Table 1.

Example 4

The hydrorefining catalyst was prepared by the same method as in Example 3, except that after the metal active component was impregnated into the carrier, it was calcined at 480° C. for 6 hours. The carbon content in the obtained catalyst semi-finished product is shown in Table 1. In the obtained catalyst S4, based on the total amount of S4, the content of the hydrogenation metal active component is shown in Table 1.

Example 5

Adopt the method identical with embodiment 3 to prepare hydrorefining catalyst, difference is, during roasting, with respect to every gram carrier, the feed rate of air is 1.0 liters/hour, in the catalyst S5 that obtains, with the total amount of S5 being The benchmark, in terms of oxides, is shown in Table 1 for the content of hydrogenation metal active components.

Example 6

Adopt the method identical with embodiment 3 to prepare hydrorefining catalyst, difference is, the consumption ratio of step (1) and step (2) organic complexing agent is changed into 5 grams: 15 grams by 10 grams: 10 grams, obtains In the catalyst S6, based on the total amount of S6, the content of hydrogenation metal active components is shown in Table 1 in terms of oxides.

Table 1

Test example 1

In this test example, the desulfurization and denitrification activities of the hydrofinishing catalyst prepared by the method provided by the present invention and the hydrofinishing catalyst provided in the comparative example were evaluated according to the following method, and the evaluation results are shown in Table 3 below.

The activity of the catalyst was evaluated by using Zhenhai Changding gasoline mixed with Anqing coking gasoline. The properties of raw oil are shown in Table 2. The evaluation device is a 50ml fixed-bed hydrogenation reactor, and the hydrogen gas is passed through once. Before the reaction, the catalyst was firstly presulfurized, and the sulfurized oil was Zhenhai constant top gasoline containing 2% by weight of CS ₂ . The vulcanization conditions are: pressure 1.6MPa, hydrogen-oil volume ratio 200:1, volume space velocity 2.0h ^-1 , temperature 290°C, time 3 hours. Switch the feed to Zhenhai Changding gasoline. After 30 hours of stabilization, switch the feed to raw oil for reaction. The reaction conditions include: reaction temperature 280°C, liquid hourly space velocity (LHSV) 10h ^-1 , reaction pressure 1.6MPa, hydrogen oil than 100v/v. After 24 hours of reaction, samples were taken for analysis, and the results are listed in Table 3.

Table 2

Test No. raw material Density (20℃), g/ ^cm3 0.7226 Sulfur, μg/g 1660 Total nitrogen, μg/g 16.8 Bromine value, gBr/100g 5.8 Diene value, gI2/100g <0.2 Colloid, mg/100ml 4 Family composition, v% saturated hydrocarbon 89.4 Olefin 3.7 Aromatics 6.9 Distillation range, ℃ initial boiling point 35 50% 115 do it 164

table 3

The results in Table 3 show that the catalyst prepared according to the method provided by the present invention can convert sulfur and Nitrogen is reduced to below 0.5μg/g, which meets the requirements of reforming feed.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (12)

1. A preparation method for hydrorefining catalyst, the preparation method comprising: (1) The water-soluble salt of the hydrogenation metal active component and the organic complexing agent are loaded on the carrier by the impregnation method, then dried and roasted to obtain a semi-finished catalyst, and the roasting conditions are such that the total amount of the semi-finished catalyst is used as a benchmark , the carbon content in the semi-finished catalyst is 0.03-0.5% by weight; (2) using the solution containing the organic complexing agent as the impregnating liquid, the semi-finished catalyst obtained in step (1) is impregnated, then dried without roasting; (3) loading magnesium and phosphorus as additives on the carrier; Wherein, step (3) is performed before, during and after step (1) and before step (2). 2. The preparation method according to claim 1, wherein the roasting condition in step (1) is such that the carbon content in the semi-finished catalyst is 0.04-0.4% by weight based on the total amount of the semi-finished catalyst. 3. The preparation method according to claim 1 or 2, wherein the roasting in step (1) is carried out under the condition of feeding gas, and the roasting temperature is 350-500°C, preferably 360-450°C; The calcination time is 0.5-8 hours, preferably 1-6 hours; relative to each gram of support, the gas feeding rate is 0.2-20 liters/hour, preferably 0.3-10 liters/hour. 4. according to the preparation method described in any one in claim 1-3, wherein, in step (1), the mol ratio of organic complexing agent and metal active component is 0.03-2: 1, is preferably 0.08-1.5 :1. 5. The preparation method according to any one of claims 1-4, wherein the molar ratio of step (1) and step (2) organic complexing agent is 1:0.25-4. 6. according to the preparation method described in any one in claim 1-5, wherein, the organic complexing agent described in step (1) is identical or different with the organic complexing agent described in step (2), and described organic complexing agent The mixture is selected from one or more of oxygen-containing organic matter and/or nitrogen-containing organic matter, and the oxygen-containing organic matter is preferably selected from one or more of organic alcohols and organic acids, and the nitrogen-containing organic matter is preferably One or more selected from organic amines and organic ammonium salts. 7. The preparation method according to claim 6, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms. 8. The preparation method according to any one of claims 1-7, wherein the amount of the hydrogenation metal active component is such that, based on the total amount of the hydrotreating catalyst, in terms of oxides, hydrogenation The content of metal active components is 10-60% by weight, preferably 15-50% by weight; the content of auxiliary agents is 0.5-5.5% by weight, preferably 1-5% by weight. 9. The preparation method according to any one of claims 1-8, wherein, in the additives, the molar ratio of magnesium to phosphorus in terms of oxides is 1:0.5-3. 10. The preparation method according to any one of claims 1-9, wherein the hydrogenation metal active component is at least one metal element selected from Group VIB and at least one metal element selected from Group VIII , the VIB group metal element is preferably molybdenum and/or tungsten, and the VIII group metal element is preferably cobalt and/or nickel; the carrier is selected from γ-alumina, silicon oxide, aluminum oxide-silicon oxide, Titania, Magnesia, Silica-Magnesia, Silica-Zirconia, Silica-Thoria, Silica-Beryllia, Silica-Titania, Silica-Zirconia, Titania-Zirconia, Silica - one or more of alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, preferably the support is alumina. 11. The hydrorefining catalyst prepared by the preparation method described in any one of claims 1-10. 12. The application of the hydrorefining catalyst according to claim 11 in the hydrorefining of light distillates and/or middle distillates.