CN108421554B

CN108421554B - Hydrofining catalyst and preparation method and application thereof

Info

Publication number: CN108421554B
Application number: CN201710080679.3A
Authority: CN
Inventors: 张乐; 褚阳; 夏国富; 刘锋; 习远兵; 李会峰
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-02-15
Filing date: 2017-02-15
Publication date: 2020-06-16
Anticipated expiration: 2037-02-15
Also published as: CN108421554A

Abstract

The invention relates to a hydrofining catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst; (2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting; (3) loading magnesium element and phosphorus element as auxiliary agents on a carrier; wherein step (3) is performed any one or more of before, during and after step (1) and before step (2). The catalyst provided by the invention is particularly suitable for hydrofining of light distillate oil and middle distillate oil by taking hydrodesulfurization and hydrodenitrogenation as purposes.

Description

Hydrofining catalyst and preparation method and application thereof

Technical Field

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

Background

Increasing awareness of environmental concerns and stricter environmental regulations are forcing the oil refining community to focus more on the development of clean fuel production technologies. The future market of vehicle fuel tends to be ultra-low sulfur, and fuel which can not meet the emission standard can not enter the market. Hydrogenation technology is used as an effective desulfurization means and plays an increasingly important role in the production of clean vehicle fuels, wherein a high-efficiency hydrogenation catalyst is a core technology of hydrogenation technology, and therefore, the development of a novel hydrofining catalyst with higher activity and selectivity is one of the most urgent needs of the oil refining industry.

Hydrofinishing catalysts are typically prepared by impregnation, i.e., by impregnating a support with a solution containing the desired active component (e.g., Ni, Mo, Co, W, etc.), followed by drying, calcination or no calcination.

CN103551162A discloses a diesel oil hydrodesulfurization and denitrification catalyst, which comprises a carrier, an auxiliary agent and active metal; the carrier being Al₂O₃-ZrO₂-TiO₂-SiO₂A multi-oxide composite support; the auxiliary agent is phosphorus; nickel, cobalt, molybdenum and tungsten are taken as active components; the catalyst comprises the following components in percentage by weight based on the weight of the catalyst: 1-6 wt% of cobalt oxide in terms of oxide; 1-15 wt% of nickel oxide, 2-12 wt% of molybdenum oxide, 12-35 wt% of tungsten oxide and 1.5-5 wt% of auxiliary agent phosphorus pentoxide; the pore volume of the catalyst is not less than 0.2mL/g, and the specific surface area is not less than 140m²(ii)/g, mechanical strength is not less than 15N/mm; the proportion of each component in the composite carrier in the carrier is respectively as follows: 2-15 wt% of titanium oxide, 2-20 wt% of silicon oxide and 5-15 wt% of zirconium oxide; the balance being alumina. The catalyst is prepared by a step impregnation method: the co-immersion liquid was divided into two equal volumes, the carrier was impregnated in two steps, and calcination was performed after completion of each step of impregnation.

CN103657667A discloses a preparation method of a novel heavy oil hydrodemetallization catalyst with a macroporous structure, which is characterized by comprising the following steps: the method specifically comprises the following steps: 1) preparing aluminum sol; 2) mixing asphalt residue powder and alumina sol to prepare a macroporous structure catalyst carrier; 3) impregnating the molded catalyst carrier by adopting an isometric fractional two-step impregnation method; finally, the catalyst is prepared. The two-step impregnation method of the preparation method comprises the following specific steps: the first step is to impregnate Mo, the second step is to impregnate Ni, and the impregnating solution does not contain organic complexing agent.

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

CN100469440C, CN102909027A disclose that Ni-W-Mo ternary metal hydrorefining catalysts are prepared by introducing organic dispersing agents or complexing agents (such as ethylene glycol, oxalic acid, citric acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, etc.) into the carrier during the preparation process. Compared with the catalyst provided by the existing method, the obtained catalyst has better hydrofining performance. There is still a need to further improve the catalyst activity.

Disclosure of Invention

Aiming at the problem of lower activity of the hydrofining catalyst in the prior art, the invention provides a novel preparation method of the hydrofining catalyst and the hydrofining catalyst prepared by the method, and the hydrofining catalyst prepared by the method has obviously higher catalytic activity and activity stability.

The inventor of the invention finds that the complexing impregnation technology can weaken the interaction between the active component and the carrier, improve the metal dispersion degree, change the metal vulcanization sequence, form more active phases and improve the number of active centers by introducing the complexing agent in the impregnation process and drying at low temperature. However, because low-temperature drying is adopted in the complex impregnation technology, and a high-temperature roasting process is not carried out, the metal compound still exists on the surface of the carrier in the form of metal salt, and the acting force of the active component and the carrier is weaker, so that metal is continuously aggregated in the reaction process under the conditions of high temperature and high pressure and hydrogenation reaction of a severe raw material, the auxiliary effect is weakened, the number of active centers is reduced, the intrinsic activity is reduced, and the activity and the stability of the catalyst are reduced. The catalyst prepared by the high-temperature roasting method has good stability, but the acting force of the active component and the carrier is strong, the intrinsic activity of the active center is low, and the dispersion and the blocking action of the complexing agent are avoided, so that the active component has large lamella, the number of the active centers is small, and the activity is low.

The inventor of the invention further discovers through research that the catalyst is prepared through a two-step impregnation method, the first step impregnation and the second step impregnation are respectively used for introducing a hydrogenation metal active component and an organic complexing agent, the organic complexing agent is added in the first step impregnation process and is converted into carbon through roasting, the activity of the catalyst can be improved, the high activity of the catalyst can be effectively maintained for a long time, and the service life of the catalyst is greatly prolonged. Presumably, the reason for this is that the organic complexing agent added in the first impregnation step hinders the aggregation of the active metal during the calcination process and makes it more uniformly dispersed; meanwhile, the metal compound can be converted into metal oxide by roasting after the first step of impregnation, and the organic complexing agent is converted into carbon, so that the combination between the active metal and the carrier is firmer, and the activity and the stability of the catalyst are improved. The organic complexing agent added in the second step of dipping process covers the surface of the catalyst, so that the aggregation of active metal in the vulcanization process can be effectively prevented, the metal dispersity is improved, and the formation of a II-type active phase with higher activity and the formation of more active centers are facilitated, so that the activity of the catalyst is further enhanced. Therefore, the technology can effectively overcome the technical defects of the conventional impregnation method and the existing complex impregnation method.

Therefore, the invention also provides a preparation method of the hydrofining catalyst, which comprises the following steps:

(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;

(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;

(3) loading magnesium element and phosphorus element as auxiliary agents on a carrier;

wherein step (3) is performed any one or more of before, during and after step (1) and before step (2).

In addition, the invention also provides a hydrofining catalyst prepared by the method.

The hydrofining catalyst prepared by the method has high catalytic activity and activity stability. For example, the sulfur and nitrogen contents of gasoline treated by the hydrofining catalyst S3 prepared by the method of the invention are lower than 0.5 microgram/g, while the sulfur content of gasoline treated by the hydrofining catalyst D2 prepared by the conventional impregnation method is as high as 68 microgram/g and the nitrogen content is 2.6 microgram/g under the same other conditions. Therefore, the hydrofining catalyst prepared by the method has obviously higher desulfurization and denitrification activity. And the method provided by the invention is simple to operate, so that the method has a good industrial application prospect.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

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

According to the present invention, it is preferable that the calcination conditions in the step (1) are such that the content of char in the semi-finished catalyst is 0.04 to 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 calcination temperature in the calcination conditions and the amount of introduction of a combustible gas, which may be one or more of various gases having an oxygen content of not less than 20% by volume, such as air, oxygen, and a mixed gas thereof.

The rate of introduction of the combustible gas is preferably not less than 0.2 liter/hour per gram of the carrier. On one hand, the combustible gas is introduced to meet the combustion condition, so that the salt of the active metal component is converted into oxide, and the organic complexing agent is converted into carbon; on the other hand, carbon dioxide and water formed by combustion and other components can be discharged to avoid the deposition on the catalyst to cause vacancy obstruction of the active phase.

Preferably, the combustible gas is introduced at a rate of 0.2 to 20 liters/hour, preferably 0.3 to 10 liters/hour, per gram of the support.

According to the present invention, preferably, the temperature of the calcination in step (1) is 350-. Controlling the roasting temperature within the range can ensure that the organic complexing agent can form carbon on the carrier within the content range to obtain the 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 to 1.5:1, more preferably 0.1 to 1.4: 1, more preferably 0.2 to 1.3: 1.

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

In the present invention, the organic complexing agents in step (1) and step (2) may be the same or different, and preferably, the organic complexing agents are selected from one or more of oxygen-containing and/or nitrogen-containing organic substances.

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

The organic alcohol is preferably a dihydric or higher polyhydric alcohol, more preferably a polyhydric alcohol having 2 to 6 carbon atoms or an oligomer or polymer thereof, such as one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, and butanediol. The molecular weight of the polyethylene glycol is preferably 200-1500.

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

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

The organic amine is preferably a compound containing one or more NH groups and having a carbon number of from 2 to 7, and can be a primary amine, a secondary amine or a tertiary amine, and particularly preferably ethylenediamine.

The organic ammonium salt is preferably EDTA.

In particular, the organic complexing agent is particularly preferably one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is preferably 200-.

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 or more of fatty acids of C2-C7. By using an organic acid as the organic complexing agent in step (1), a hydrorefining catalyst having 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 the step (1) and the step (2) may be the same or different.

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

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

According to the invention, preferably, the hydrogenation metal active component is used in an amount such that the content of the hydrogenation metal active component is 10 to 60 wt%, preferably 15 to 50 wt%, calculated as an oxide, based on the total amount of the hydrofining catalyst, and the auxiliary agent is phosphorus and magnesium; the content of auxiliaries is preferably from 0.5 to 5.5% by weight, more preferably from 1 to 5% by weight, and the molar ratio of phosphorus to magnesium, calculated as oxide, is from 0.5 to 3, preferably from 1.0 to 2.5.

According to the present invention, it is preferable that the concentration of the water-soluble salt of the hydrogenation metal active component is 0.2 to 8mol/L, preferably 0.2 to 5mol/L, and more preferably 0.2 to 2mol/L, in terms of the metal element. The concentrations herein are the respective concentrations of the water-soluble salts of the various hydrogenation metal active components, not the total concentration.

The water-soluble salt of the hydrogenation metal active component can be various water-soluble compounds with the solubility meeting the loading requirement or capable of forming the hydrogenation metal active component with the solubility meeting the requirement in water in the presence of a cosolvent, and can be one or more of nitrate, chloride, sulfate and carbonate, and is preferably nitrate.

According to the invention, preferably, the hydrogenation metal active component comprises at least one element selected from the group VIB metals and at least one element selected from the group VIII metals.

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

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

According to the present invention, preferably, the group VIB metal element-containing compound may be selected from one or more of ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide.

The group VIII metal element-containing compound may be one or more selected from the group consisting of group VIII metal nitrates, group VIII metal chlorides, group VIII metal sulfates, group VIII metal formates, group VIII metal acetates, group VIII metal phosphates, group VIII metal citrates, group VIII metal oxalates, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal phosphides, group VIII metal sulfides, group VIII metal aluminates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.

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

The group VIII metal element-containing compound may be selected from, but is not limited to, one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt hydroxycarbonate, cobalt chloride, and nickel chloride.

According to the present invention, the supporting manner of the hydrogenation metal active component is not particularly limited.

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

According to the present invention, the order of loading the hydrogenation metal active components on the carrier is not particularly limited, and all the hydrogenation metal active components may be loaded on the carrier in common by impregnating the carrier with a solution containing a plurality of water-soluble salts, or the hydrogenation metal active components may be sequentially loaded on the carrier by preparing the water-soluble salt-containing solutions to impregnate the carrier stepwise, respectively. When stepwise impregnation is used, it is preferred to dry and preferably to calcine further after each impregnation. The manner and conditions of drying and firing may be selected with reference to the prior art.

According to the present invention, the supporting method of the organic complexing agent is not particularly limited. The organic complexing agent can be prepared into an impregnation liquid impregnation carrier together with one or more of water-soluble salts of the hydrogenation metal active component, or can be prepared into the impregnation liquid impregnation carrier separately, preferably the former.

According to the invention, the introduction method of the auxiliary agent can be carried out in various ways, for example, during the preparation of the carrier, after the preparation of the carrier, by various means such as impregnation, or both during and after the preparation of the carrier.

It should be noted that when the carrier is introduced by the method of impregnating the carrier, the step of roasting after the magnesium additive is introduced is needed, the roasting temperature is 250-600 ℃, preferably 350-500 ℃, and the roasting time is 2-8h, preferably 3-6 h.

According to the invention, the magnesium adjuvant is introduced before step (2) to ensure that the organic complexing agent introduced in step (2) does not undergo a calcination process.

According to a preferred embodiment of the invention, when using the impregnation method, the magnesium adjuvant is loaded onto the support before step (1), and the phosphorus adjuvant is introduced into the support together with the metal active component and the organic complexing agent in step (1). The auxiliaries can be various soluble compounds of the auxiliaries, such as water-soluble salts of magnesium, preferably magnesium nitrate, water-soluble compounds of phosphorus, for example phosphoric acid, metaphosphoric acid or salts thereof.

According to the present invention, the impregnation method may be an equal volume impregnation or a supersaturation impregnation, the temperature of the impregnation is not particularly limited, and may be various temperatures that can be attained by the impregnation solution, and the time of the impregnation is not particularly limited as long as the required amount of the desired components can be supported, for example: the impregnation temperature may be 15-60 deg.C and the impregnation time may be 0.5-5 hours.

The drying temperature in the magnesium loading process is preferably 100-150 ℃, the time is preferably 2-6 hours, the roasting temperature is preferably 350-450 ℃, and the time is preferably 2-6 hours.

According to the present invention, the support may be various inorganic refractory oxides. According to the present invention, the term "inorganic refractory oxide" means an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ under an oxygen or oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃).

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

According to a preferred embodiment of the present invention, the inorganic refractory oxide is alumina, and more preferably alumina obtained by calcining a hydrated alumina (aluminum hydroxide) colloidal composite.

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

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

A preferred method for preparing alumina is to mix and calcine alumina and/or its precursors. The carrier can be made into various molding matters which are easy to operate according to different requirements, such as microspheres, spheres, tablets or strips. The molding may be carried out by a conventional method, and for example, may be a method of extruding the alumina and/or its precursor into a strip and firing the same. Wherein, the precursor of the alumina can be selected from one or more of various hydrated alumina and alumina sol. During extrusion molding, a proper amount of extrusion aid and/or adhesive can be added, and then extrusion molding is carried out. The kinds and amounts of the extrusion aid and the peptizing agent are well known to those skilled in the art and are not described herein. The roasting adopts the method and conditions which are conventional in the field, for example, the roasting temperature can be 350-650 ℃, and preferably 400-600 ℃; the calcination time is 2 to 6 hours, preferably 3 to 5 hours.

Before use, the catalyst provided by the invention is pre-sulfurized by one or more of sulfur, hydrogen sulfide, carbon disulfide, DMDS, polysulfide or sulfur-containing raw material at the temperature of 140-370 ℃ and preferably in the presence of hydrogen, wherein the pre-sulfurization can be carried out outside the reactor or in situ inside the reactor, so as to convert the catalyst into a sulfide type.

Compared with the prior art, the catalyst provided by the invention can obtain higher hydrodesulfurization, denitrification and olefin saturation activity at high airspeed, low hydrogen-oil ratio, low pressure and lower temperature when being used for hydrotreating raw materials with high sulfur content and high nitrogen content, is particularly suitable for the hydrofining process of the feeding of a reforming device for light distillate oil and middle distillate oil such as blending and blending coking gasoline raw materials and raw materials from other process sources, can be realized in any distillate oil hydrofining reaction device, and is not particularly limited. One-stage hydrofining can be adopted, and the operating conditions can be adjusted within the following ranges according to the properties of raw oil and the requirements on the quality of oil products: the reaction temperature is 200 ℃ and 400 ℃, and the volume space velocity is 4-15h^-1Preferably 8-12h^-1The hydrogen partial pressure is 0.8-6.0MPa, preferably 1-2MPa, and the hydrogen-oil volume ratio is 50-800:1, preferably 50-150: 1. The sulfur and nitrogen of the product after hydrotreating are reduced to below 0.5 mu g/g, which meets the requirement of reforming feed.

The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.

In the following examples, the alumina support is RPB-90 grade alumina available from the midpetrochemical ChangLing catalyst division.

In the following examples, the contents of the respective elements in the catalyst were analyzed and measured by a 3271E type X-ray fluorescence spectrometer, manufactured by japan food and electronics industries co. The carbon content in the catalyst semi-finished product was analyzed and measured using an EMIA-320V carbon sulfur analyzer manufactured by HORIBA, Japan. The method for measuring the water absorption of the catalyst carrier is as follows: the support (in weight g) was immersed in water (in volume ml) for 2 hours, the ratio of support (by weight) to water (by volume) being 1: and 3, separating the carrier after water absorption from water, and calculating the water absorption volume of the carrier, wherein the water absorption rate of the carrier is the water absorption volume of the carrier/weight of the carrier.

Preparation example 1

Weighing 250 g of magnesium nitrate, adding deionized water, stirring and dissolving, adding the deionized water to 850 ml, saturating and dipping 1000 g of alumina carrier for 2 hours, then drying at 120 ℃ for 2 hours, and roasting at 400 ℃ for 4 hours to obtain the magnesium-containing alumina carrier Z1 with the water absorption of 0.85 ml/g.

Preparation example 2

Weighing 80 g of magnesium nitrate, adding deionized water, stirring and dissolving, adding the deionized water to 850 ml, saturating and dipping 1000 g of alumina carrier for 2 hours, then drying at 100 ℃ for 2.5 hours, and roasting at 350 ℃ for 6 hours to obtain the magnesium-containing alumina carrier Z2 with the water absorption rate of 0.85 ml/g.

Preparation example 3

Weighing 165 g of magnesium nitrate, adding deionized water, stirring and dissolving, adding the deionized water to 850 ml, saturating and dipping 1000 g of alumina carrier for 2 hours, then drying at 100 ℃ for 3 hours, and roasting at 450 ℃ for 2 hours to obtain the magnesium-containing alumina carrier Z3 with the water absorption of 0.85 ml/g.

Example 1

Weighing 40 g of molybdenum trioxide, 19 g of basic cobalt carbonate, 11 g of phosphoric acid and 20 g of citric acid respectively, putting into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of magnesium-containing alumina carrier Z1 by adopting a saturated impregnation method for 2 hours, then drying at 120 ℃ for 2 hours, roasting at 400 ℃ for 2 hours in the state of introducing air flow, wherein the introducing speed of air is 2 liters/hour relative to per gram of carrier to obtain a semi-finished catalyst Z2-S1, and the carbon content of Z2-S1 is shown in Table 1; adding 5 g of ethanol into 150 g of deionized water, stirring to obtain a clear solution, soaking the Z1-S1 in the solution for 2 hours by adopting a saturated soaking method, and then drying the solution for 3 hours at 110 ℃ to obtain the catalyst S1. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S1 is shown in Table 1.

Comparative example 1

A hydrorefining catalyst was prepared in the same manner as in example 1, except that the hydrorefining catalyst S1 obtained in example 1 was calcined at 400 ℃ for 3 hours to obtain catalyst D1, and the content of the hydrogenation metal active component in the catalyst D1, in terms of oxide based on the total amount of D1, is shown in Table 1.

Example 2

Weighing 40 g of molybdenum trioxide, 21 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid respectively, putting into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of magnesium-containing alumina carrier Z2 by adopting a saturated impregnation method for 2 hours, then drying at 150 ℃ for 2 hours, roasting at 360 ℃ for 3 hours in a state of introducing air flow, wherein the introduction rate of air is 10 liters/hour relative to each gram of carrier to obtain a semi-finished catalyst Z2-S2, and the carbon content of Z2-S2 is shown in Table 1; adding 30 g of citric acid into 150 g of deionized water, stirring to obtain a clear solution, soaking Z2-S2 in the solution for 2 hours by adopting a saturated soaking method, and then drying at 150 ℃ for 3 hours to obtain the hydrofining catalyst S2. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S2 is shown in Table 1.

Example 3

Respectively weighing 30 g of nickel nitrate, 55 g of ammonium metatungstate (hydrate, molecular weight of 3037, the same below), 10 g of phosphoric acid and 10 g of diethylene glycol into 140 g of deionized water, stirring and dissolving to obtain a clear solution, soaking 200 g of alumina carrier Z3 in a saturated soaking method for 2 hours, then drying at 120 ℃ for 2 hours, roasting in a state of introducing air flow, wherein the roasting temperature is 450 ℃, the time is 4 hours, and the introduction rate of air is 0.3 liter/hour relative to each gram of carrier to obtain a semi-finished catalyst Z3-S3, wherein the carbon content of Z3-S3 is shown in Table 1; 10 g of diethylene glycol is put into 150 g of deionized water, stirred to obtain a clear solution, and the solution is used for soaking Z3-S3 for 2 hours by adopting a saturated soaking method, and then dried for 6 hours at 120 ℃ to obtain a catalyst S3. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S3 is shown in Table 1.

Comparative example 2

30 g of nickel nitrate, 55 g of ammonium metatungstate, 10 g of phosphoric acid and 10 g of diethylene glycol are respectively weighed and put into 140 g of deionized water, stirred and dissolved to obtain a clear solution, 200 g of alumina carrier Z3 is soaked in the clear solution by adopting a saturated soaking method for 2 hours, and then dried for 2 hours at 120 ℃ to obtain the catalyst D2. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D2, is shown in table 1.

Comparative example 3

A hydrofinishing catalyst was prepared according to the method of example 3 except that the alumina support Z3 was replaced by the same weight of magnesium unsupported alumina support to give catalyst D3. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D3, is shown in table 1.

Example 4

A hydrorefining catalyst was prepared in the same manner as in example 3, except that the metal active component was impregnated into the carrier and then calcined at 480 ℃ for 6 hours. The content of carbon in the obtained catalyst semi-finished product is shown in table 1, and the content of the hydrogenation metal active component in the obtained catalyst S4 is shown in table 1 in terms of oxide based on the total amount of S4.

Example 5

A hydrorefining catalyst was prepared in the same manner as in example 3, except that the rate of introduction of air was 1.0 liter/hr per gram of the carrier upon calcination, and the content of the hydrogenation metal active component in the resultant catalyst S5 in terms of oxides based on the total amount of S5 was as shown in Table 1.

Example 6

A hydrorefining catalyst was prepared in the same manner as in example 3, except that the amount ratio of the organic complexing agent in step (1) to that in step (2) was changed from 10 g: 10 g is changed into 5 g: 15 g of the catalyst S6 was obtained, and the content of the hydrogenation metal active component in terms of oxide based on the total amount of S6 was as shown in Table 1.

TABLE 1

Test example 1

In the present test example, the desulfurization and denitrification activities of the hydrorefining catalyst prepared by the method of the present invention and the hydrorefining catalyst provided in the comparative example were evaluated in the following manner, and the evaluation results are shown in table 3 below.

The activity of the catalyst is evaluated by blending the Zhenhai Changding gasoline with the Anqing coking gasoline. The properties of the feed oil are shown in Table 2. The evaluation unit was a 50ml fixed bed hydrogenation reactor with one pass of hydrogen. Before the reaction, the catalyst is first presulfurized to obtain a sulfur oil containing 2 wt% CS₂The natural gasoline is the natural gasoline. The vulcanization conditions are as follows: pressure of 1.6MPa, hydrogen-oil volume ratio of 200:1 and volume airspeed of 2.0h^-1The temperature was 290 ℃ and the time was 3 hours. The method is characterized in that the feeding is switched to the Zhehai ordinary top gasoline, after the feeding is stabilized for 30 hours, the feeding is switched to raw oil for reaction, and the reaction conditions comprise: the reaction temperature is 280 ℃, and the Liquid Hourly Space Velocity (LHSV) is 10h^-1The reaction pressure is 1.6MPa, and the hydrogen-oil ratio is 100 v/v. Samples were taken after 24 hours of reaction and analyzed, and the results are shown in Table 3.

TABLE 2

Test number	Raw materials
		Density (20 ℃ C.), g/cm³	0.7226
Sulfur,. mu.g/g	1660
		Total nitrogen,. mu.g/g	16.8
Bromine number, gBr/100g	5.8
		Diene number, gI2/100g	<0.2
Gum, mg/100ml	4
		Group composition, v%
Saturated hydrocarbons	89.4
		Olefins	3.7
Aromatic hydrocarbons	6.9
		Distillation range, deg.C
Initial boiling point	35
		50％	115
Dried cake	164

TABLE 3

The results in Table 3 show that the catalyst prepared by the method provided by the invention can reduce the sulfur and nitrogen to below 0.5 mu g/g and meet the requirements of reforming and feeding by hydrotreating the raw oil with high sulfur and high nitrogen content at high airspeed, low hydrogen-oil ratio, low pressure and lower temperature.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. Use of a hydrofinishing catalyst in the hydrofinishing of light distillate and/or middle distillate, the hydrofinishing conditions comprising: the reaction temperature is 200 ℃ and 400 ℃, and the liquid hourly space velocity is 4-15h^-1Hydrogen partial pressure of 0.8-6.0MPa and hydrogen-oil volume ratio of50-800；

Wherein, the hydrofining catalyst is prepared by the following steps:

2. The use according to claim 1, wherein the calcination conditions in step (1) are such that the amount of char in the semi-finished catalyst is from 0.04 to 0.4% by weight, based on the total amount of the semi-finished catalyst.

3. The application as claimed in claim 1, wherein the calcination in step (1) is carried out under the condition of gas introduction, the calcination temperature is 350-500 ℃, and the calcination time is 0.5-8 h; the gas is introduced at a rate of 0.2 to 20 liters per hour per gram of the carrier.

4. The application as claimed in claim 3, wherein the roasting in step (1) is carried out under the condition of gas introduction, the roasting temperature is 360-450 ℃, and the roasting time is 1-6 h; the gas is introduced at a rate of 0.3 to 10 liters per hour per gram of the carrier.

5. Use according to any one of claims 1 to 4, wherein in step (1), the molar ratio of organic complexing agent to metal active component is from 0.03 to 2: 1.

6. the use according to claim 5, wherein in step (1), the molar ratio of the organic complexing agent to the metal active component is 0.08-1.5: 1.

7. the use according to any one of claims 1 to 4, wherein the molar ratio of the organic complexing agent in step (1) to the organic complexing agent in step (2) is 1: 0.25-4.

8. The use according to any one of claims 1 to 4, wherein the organic complexing agent in step (1) is the same as or different from the organic complexing agent in step (2), and the organic complexing agents in step (1) and step (2) are selected from one or more of oxygen-containing organic substances and/or nitrogen-containing organic substances.

9. The use of claim 8, wherein the oxygen-containing organic substance is selected from one or more of organic alcohol and organic acid, and the nitrogen-containing organic substance is selected from one or more of organic amine and organic ammonium salt.

10. The use according to claim 8, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms.

11. The use according to claim 9, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms.

12. The use according to any one of claims 1 to 4, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is present in an amount of from 10 to 60% by weight, calculated as oxide, based on the total amount of the hydrofinishing catalyst; the content of the auxiliary agent is 0.5-5.5 wt%.

13. The use according to claim 12, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is present in an amount of 15 to 50 wt.% in terms of oxide, based on the total amount of the hydrofinishing catalyst; the content of the auxiliary agent is 1-5 wt%.

14. Use according to any one of claims 1 to 4, wherein the molar ratio of magnesium to phosphorus, expressed as oxides, in the adjuvant is from 1: 0.5-3.

15. The use according to any one of claims 1 to 4, wherein the hydrogenation metal active component is at least one element selected from group VIB metals and at least one element selected from group VIII metals; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.

16. The use according to claim 15, wherein the group VIB metal elements are molybdenum and/or tungsten and the group VIII metal elements are cobalt and/or nickel; the carrier is alumina.