CN108067243B

CN108067243B - Hydrotreating catalyst and preparation method and application thereof

Info

Publication number: CN108067243B
Application number: CN201611011340.XA
Authority: CN
Inventors: 唐兆吉; 杨占林; 姜艳; 姜虹; 温德荣
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-11-17
Filing date: 2016-11-17
Publication date: 2020-03-17
Anticipated expiration: 2036-11-17
Also published as: CN108067243A

Abstract

The invention discloses a hydrotreating catalyst and a preparation method and application thereof, comprising the following steps: (1) preparing or selecting an alumina carrier; (2) dipping the alumina carrier prepared or selected in the step (1) in a nitrogen-containing organic acid solution or an aromatic carboxylic acid solution; (3) carrying out low-temperature drying treatment on the alumina carrier soaked in the pyridine dicarboxylic acid solution or the aromatic carboxylic acid solution in the step (2); (4) and (3) impregnating the alumina carrier subjected to low-temperature drying treatment with an active component solution or active metal and an auxiliary agent, and performing high-temperature thermal treatment after impregnation to prepare the hydrotreating catalyst. The catalyst prepared by the method not only has high metal component dispersion degree and vulcanization degree, is easy to fully vulcanize, generates more active sites and is beneficial to improving the intrinsic activity of the catalyst, but also has simple preparation method and low production cost.

Description

Hydrotreating catalyst and preparation method and application thereof

Technical Field

The invention relates to a hydrotreating catalyst, a preparation method and application thereof, in particular to a hydrotreating catalyst suitable for heavy distillate oil hydrodenitrogenation and desulfurization processes, and a preparation method and application thereof.

Background

In the hydrotreating process, the contents of impurities such as nitrogen, sulfur, oxygen, metal and the like in crude oil are continuously increased, the heavy degree of the crude oil is continuously deepened, and the fact that the impurities are put in front of people is made.

The hydrotreating process is to load metal oxide containing VIII and VIB groups in the periodic table into refractory inorganic porous material, and alumina, silica, titania, silicon carbide, boron oxide, zirconia and their combined composite carrier are used. The catalyst precursor is prepared through an impregnation process, and the finished catalyst is prepared through a plurality of drying and roasting processes. The finished catalyst is presulfided before use, i.e., the oxidized catalyst is converted to a sulfided catalyst in the presence of hydrogen sulfide, sulfur-containing organic compounds, or elemental sulfur.

The purpose of hydrogenation pretreatment is to remove impurities such as nitrogen, sulfur, oxygen and the like in the raw oil, so that the quality and the quantity of the middle distillate oil are increased. For example, hydrocracking and hydro-reforming reactions require a pretreatment of the feedstock oil to remove impurities from the feedstock oil and to prevent catalyst poisoning. Therefore, the hydrotreating process is one of the indispensable and very important steps in the refinery process. It is known in the art that the dispersibility of active components is high without calcining the catalyst, and weak van der waals force exists between the active metal and the carrier, thereby effectively improving the catalyst reactivity. The research of the catalyst with high activity, high stability, low cost and no pollution in the preparation process is always the bottleneck to be broken through in the field, the catalyst adopting the characteristics in the industry not only can produce more target products, but also can ensure that the reaction is carried out under a milder condition, the running period is prolonged, and the production cost is reduced.

In the field, a great deal of work is done on the aspect of improving the activity of the hydrogenation catalyst, and a lot of documents report and obtain great results, thereby laying the foundation for the future research and development. For example: US 5338717 describes a process for the preparation of a hydrogenation catalyst which is impregnated with a heteropolyacid-containing metal impregnation solution, the support being a refractory porous oxide material and the finished catalyst not requiring a calcination process. However, the method has a disadvantage that drying under vacuum condition before vulcanization is difficult to be carried out industrially.

CN 85103891 describes a method for preparing a hydroconversion catalyst. The method is that a phosphorus-containing substance and a soluble amine compound are respectively added into an impregnation solution, the two solutions are mixed together for impregnation, and the pH value of the impregnation solution and the temperature of the impregnation solution need to be adjusted in the impregnation process. The method for preparing the catalyst has complex process conditions, the ammonium hydroxide emits ammonia gas in the dissolving process, the ammonium hydroxide is harmful to the environment, the denitrification effect is not obvious, and the industrial production is not easy to realize.

Chinese patent CN 101590416A describes a method for preparing a molybdenum-nickel hydrogenation catalyst, which comprises the steps of kneading-impregnating to prepare the catalyst, firstly, kneading molybdenum oxide, a titanium-containing compound, a phosphorus-containing compound and alumina in the presence of nitric acid, extruding to form strips, drying and roasting to obtain an alumina forming product containing titanium, phosphorus and molybdenum, then impregnating in a nickel-containing phosphoric acid solution, drying and roasting to obtain the molybdenum-nickel hydrogenation catalyst. Chinese patent CN 1052501a discloses a preparation method of a hydrogenation catalyst. In order to improve the activity of the catalyst, the method comprises the steps of adding an auxiliary agent P, F, B into an impregnation liquid containing three metals of Co-W-Mo, impregnating by adopting a segmented impregnation method, drying and roasting to obtain the finished catalyst. The method is characterized in that after the impregnation and loading of the active metal, the active metal component is roasted at high temperature, the acting force between the active metal component and the carrier is strong, the vulcanization effect of the catalyst is influenced, and part of the active metal component is aggregated to influence the dispersion degree of the active metal, so that the activity of the catalyst is influenced.

Japanese patent JP 04-166231 describes a process for preparing a hydrogenation catalyst. The method comprises the steps of dipping step by step, dipping a carrier with a phosphorus-containing active metal component solution, drying at room temperature-200 ℃, contacting the dried dipped carrier with a polyhydroxy compound solution, and drying at the temperature lower than 200 ℃ to obtain the finished catalyst. US patent US 6281333 discloses a method for preparing a hydroprocessing catalyst. The carrier loads active metal impregnation liquid containing organic volatile components, and the catalyst is obtained without roasting. In the preparation process of the catalyst, the organic auxiliary agent is added into the impregnation liquid, so that the viscosity of the impregnation liquid is increased, the dispersion of the active metal on the surface of the carrier is not facilitated, the impregnated catalyst particles are easy to stick together and have a blocking phenomenon, and the metal precipitation phenomenon exists on the surface of the dried catalyst, so that the high dispersion of the active component on the surface of the carrier is influenced, and the activity of the catalyst is not influenced. Chinese patent CN99113281.5 discloses a distillate oil hydrorefining catalyst and a preparation method thereof. The catalyst takes alumina or silicon-containing alumina as a carrier, takes W, Mo and Ni as active components, and adds phosphoric acid as an auxiliary agent. By adopting the sectional impregnation method, the metal distribution on the catalyst is more uniform, and the hydrodenitrogenation activity of the catalyst is greatly improved. Chinese patent CN200910012488.9 provides a preparation method of a hydrotreating catalyst, which adopts the impregnation liquid prepared by the conventional method to prepare the hydrotreating catalyst. The impregnation liquid has strong acidity, which causes serious destructive influence on the specific surface area and pore volume of the catalyst, and after the catalyst is roasted at high temperature, active components are easy to aggregate on the surface of a carrier, which influences the reaction activity. Chinese patent CN1552794A discloses a dipping solution for hydrogenation catalyst and a preparation method thereof. According to the method, an active component is dissolved by deionized water, and then an organic carboxylic acid substance is added to form a stable complex with a main metal, wherein the impregnation liquid has the characteristics of good stability and low viscosity, but under the conventional roasting condition, the organic carboxylic acid is partially coked on the surface of the catalyst, so that the number of active metal centers is reduced. Chinese patent CN101089132A discloses a hydrodesulfurization catalyst with four active components of W-Mo-Ni-Co, which adopts W-Mo-Ni-Co-P active components with specific proportions and is impregnated on an alumina carrier by a saturated Co-impregnation technology, but the loading capacity of the active components is limited, and more total active metals cannot be provided; in the dipping process, the adsorption of active components on the carrier can be weakened by the action of phosphorus and carrier surface groups, so that metal components are easy to agglomerate, the dispersion degree of the active components in the catalyst is reduced, and the activity of the catalyst is weakened. US4,317,746 describes the impregnation of the support with the active component after the presoaking and partial steam presoaking, which suitably improves the distribution of the active component on the surface of the support and thus the catalyst activity. European patent EP0870003B2 describes a process for preparing a hydrogenation catalyst comprising: impregnating the carrier with a solution containing a group VIB and group VIII metal compound and an organic alcohol and/or sugar, and drying at a temperature of 200 ℃ or less to obtain the finished catalyst.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a hydrotreating catalyst and a preparation method and application thereof. The catalyst prepared by the method not only has high metal component dispersion degree and vulcanization degree, is easy to fully vulcanize, generates more active sites and is beneficial to improving the intrinsic activity of the catalyst, but also has simple preparation method and low production cost.

The preparation method of the hydrotreating catalyst of the invention comprises the following steps:

(1) preparing or selecting an alumina carrier;

(2) dipping the alumina carrier prepared or selected in the step (1) in a nitrogen-containing organic acid solution or an aromatic carboxylic acid solution;

(3) carrying out low-temperature drying treatment on the alumina carrier soaked in the pyridine dicarboxylic acid solution or the aromatic carboxylic acid solution in the step (2);

(4) and (3) impregnating the alumina carrier subjected to low-temperature drying treatment with an active component solution or active metal and an auxiliary agent, and performing high-temperature thermal treatment after impregnation to prepare the hydrotreating catalyst.

In the method of the present invention, the alumina carrier in step (1) can be prepared by a commercially available method or a conventional method. The preparation process of the conventional method is as follows: the aluminum hydroxide dry glue powder and SB powder are kneaded, molded, dried and roasted to prepare the catalyst carrier. In the kneading process, conventional forming aids such as extrusion aids, binders, peptizers and the like can be added according to the needs. The alumina carrier can contain an auxiliary agent component. The drying conditions were as follows: the drying temperature is 50-300 ℃, preferably 100-150 ℃, and the drying time is 0.5-22 h, preferably 8-15 h. The drying atmosphere may be an air atmosphere, a vacuum atmosphere, a water vapor atmosphere, an inert gas atmosphere, or the like, and drying under an air atmosphere is preferable. The roasting conditions are as follows: the roasting temperature is 350-650 ℃, preferably 450-550 ℃, and the roasting time is 0.5-22 h, preferably 8-15 h, and most preferably 6-10 h. The forming method mainly comprises the steps of tabletting, template, powder rolling ball, strip extrusion, oil column forming and the like, and the shape of the carrier can be spherical, flaky, strip (clover or clover special-shaped strip) and the like. The shape of the carrier can be selected according to specific needs, and is preferably a strip shape, and the size of the carrier can be selected to be different according to requirements.

In the method, the nitrogen-containing organic acid in the step (2) comprises one or more of pyridine-2, 3-dicarboxylic acid, pyridine-2, 4-dicarboxylic acid, pyridine-2, 5-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, pyridine-3, 4-dicarboxylic acid, pyridine-3, 5-dicarboxylic acid, furan-dicarboxylic acid and 2,2 '-bipyridine-5, 5' -dicarboxylic acid, and the aromatic carboxylic acid is biphenyltetracarboxylic acid or adamantane carboxylic acid.

In the method of the invention, the amount of the nitrogen-containing organic acid or aromatic carboxylic acid impregnated in the step (2) is 0.5-5%, preferably 1-3% of the weight of the alumina carrier.

In the method, the low-temperature drying temperature in the step (3) is 60-150 ℃, preferably 100-120 ℃, and the drying time is 0.5-10 hours, preferably 2-6 hours. The drying may be vacuum drying, conventional drying or microwave drying. Preferably, the dry basis of the dried carrier is controlled to be 70-90%, preferably 85-90%, and the proper dry basis content is maintained, so that the interaction between the nitrogen organic acid or the aromatic carboxylic acid and the active groups of the alumina carrier is favorably improved, and the aggregation of active metals is further reduced.

In the method, the active component in the step (4) comprises a VIII group metal and/or a VIB group metal, wherein the VIII group metal is Ni and/or Co, and the VIB group metal is W and/or Mo. The impregnation liquid is provided with active metal compounds, tungsten mainly comes from one or two of ammonium metatungstate and ammonium tetrathiotungstate, molybdenum mainly comes from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate and ammonium paramolybdate, nickel mainly comes from one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride and nickel acetate, and cobalt mainly comes from one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate and cobalt chlorate. The auxiliary agent is one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium,

the impregnation method adopted in the step (4) of the method can be saturated impregnation or supersaturated impregnation, and saturated impregnation is preferred. The impregnation liquid containing the active metal can be impregnated on the carrier in one step or in steps, and during the step impregnation, after each impregnation, the impregnation liquid needs to be dried, and then the next step of impregnation is carried out.

According to the method, the high-temperature heat treatment conditions after the dipping in the step (4) are as follows: the treatment temperature is 180-500 ℃, preferably 200-400 ℃, the heat treatment time is 1-10 hours, preferably 2-6 hours, and the carbon content in the carrier after high-temperature heat treatment is preferably 0.1-3%, preferably 0.3-2%. By controlling proper high-temperature treatment conditions and proper carbon content in the carrier after high-temperature treatment, the nitrogen-containing organic acid or aromatic carboxylic acid with weaker acting force with the carrier can be ensured to be burnt, and the nitrogen-containing organic acid or aromatic carboxylic acid with stronger acting force with the carrier is subjected to in-situ carbon deposition, so that the re-interaction of the migration effect in the heat treatment process of the active metal and the high-activity site of the carrier and the ineffective site occupation of redundant nitrogen-containing organic acid or aromatic carboxylic acid are effectively prevented.

In the method of the present invention, the heat treatment in step (4) is preferably carried out in a mixed atmosphere of oxygen and ammonia, and the volume concentration of oxygen in the mixed atmosphere is controlled to be 10ppm to 90ppm, preferably 50ppm to 80 ppm. The atmosphere is favorable for carbon deposition of the nitrogen-containing organic acid or the aromatic carboxylic acid which acts with the high active site of the carrier and removal of the nitrogen-containing organic acid or the aromatic carboxylic acid which acts with the low active site of the carrier.

The hydrotreating catalyst is prepared by adopting the method, wherein the hydrotreating catalyst takes alumina as a carrier, VIII family and VIB family metals as active metal components, the VIII family metals are Co and/or Ni, the VIB family metals are W and/or Mo, and the content of the VIII family metals is 1-15 wt%, preferably 4-10 wt% and 10-30 wt% in terms of oxides based on the weight of the catalyst. Preferably 15 to 25 weight percent, and the weight content of the auxiliary agent in the catalyst is 0.01 to 10 percent, preferably 0.01 to 2 percent.

The application of the hydrotreating catalyst prepared by the method has the following process conditions: the reaction temperature is 300-380 ℃, preferably 320-360 ℃, the reaction pressure is 4-8MPa, preferably 5-7 MPa, and the hydrogen-oil ratio is 600:1-1200:1, preferably 800:1-1000: 1.

Compared with the prior art, the hydrotreating catalyst and the preparation method and application thereof have the following advantages:

when the catalyst is dipped in a nitrogen-containing organic acid solution or an aromatic carboxylic acid solution, the nitrogen-containing organic acid or the aromatic carboxylic acid functional group can fully occupy the coordination unsaturated center on the surface of the carrier alumina, so that the strong interaction between the metal and the carrier is effectively prevented, and the generated number of the active center of the catalyst is increased. Meanwhile, after impregnation, the amount of the medium-strong acid on the surface of the catalyst is increased, so that the intrinsic activity of the catalyst is improved, a certain amount of carbon exists on the surface of the catalyst after heat treatment, the carbon on the catalyst is distributed among active components, the aggregation of the active components can be effectively prevented, the active components can be well dispersed on the surface of alumina, more active sites are formed, the matching of the degree of vulcanization and the dispersity of the catalyst to a certain degree is ensured by using the method disclosed by the patent, and the activity of the catalyst is improved.

Detailed Description

The following examples and comparative examples further illustrate the action and effect of the process of the present invention, but the following examples are not intended to limit the process of the present invention. In the present invention,% is mass% unless otherwise specified.

The embodiment of the invention adopts a 50ml small hydrogenation reaction device to carry out activity evaluation test, the used raw material is the common third-line diesel oil, and the properties are shown in table 1. The catalyst is pre-sulfurized before use, the sulfurized oil is straight-run kerosene, 5wt% of DMDS (dimethyl disulfide) is added, and after pre-sulfurization, raw oil is directly introduced for test reaction. The prevulcanisation and the test conditions are shown in table 2.

TABLE 1 Properties of the stock oils

TABLE 2 prevulcanization and test conditions

Example 1

Preparing a catalyst precursor by adopting pseudo-boehmite dry rubber powder, weighing 200 g of the dry rubber powder and 100 g of SB powder, adding 4 g of sesbania powder and 4 g of citric acid respectively, uniformly mixing, and adding an acid solution, wherein the concentration of nitric acid in the acid solution is 2wt%, and the balance is distilled water. Rolling for 15-25 minutes, extruding strips by using a clover orifice plate with the diameter of 1.7mm, drying for 12 hours at 120 ℃, and roasting for 3 hours at 550 ℃ to obtain a catalyst carrier, namely Z-1, which has the following properties: the pore volume is 0.72ml/g, the specific surface area is 342m²/g。

Example 2

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing dipicolinic acid, wherein the content of the dipicolinic acid in the impregnation liquid is 1 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing Mo, Ni and P, wherein the composition of the impregnation liquid is MoO₃The content of (2) was 88.5g/100ml, the NiO content was 15 g/100ml, and the P content was 2.3g/100ml, and the impregnated sample was aged at room temperature for 10 hours and heat-treated at 200 ℃ for 3 hours in an air atmosphere to obtain catalyst C-1 having a carbon content of 2.5%.

Example 3

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing furoic acid, wherein the content of pyridinedicarboxylic acid in the impregnation liquid is 2 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier by using impregnation liquid containing Mo, Ni and P, and the composition of the impregnation liquid is MoO₃The content of (A) is 89.5g/100ml, the NiO content is 15 g/100ml, the P content is 2.5g/100ml, the immersed sample is aged for 10 hours at room temperature and is left empty at 300 DEG CHeat treatment is carried out for 3 hours under the gas atmosphere to obtain the catalyst C-2, and the carbon content in the catalyst is 0.75 percent.

Example 4

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing biphenyltetracarboxylic acid, wherein the content of the biphenyltetracarboxylic acid in the impregnation liquid is 2 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing W, Ni and P, and the composition of the impregnation liquid is WO₃The content of (b) was 85.5g/100ml, the NiO content was 26.02 g/100ml, the P content was 2.8g/100ml, the impregnated sample was aged at room temperature for 6 hours, and heat-treated at 350 ℃ for 4 hours in an air atmosphere to obtain catalyst C-3 having a carbon content of 0.58%.

Example 5

Weighing a proper amount of catalyst carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing adamantane carboxylic acid, wherein the content of the adamantane carboxylic acid in the impregnation liquid is 3 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing Mo, Co and P, wherein the impregnation liquid consists of MoO₃The content of (A) was 89.5g/100ml, the CoO content was 13.5 g/100ml, the P content was 2.2g/100ml, the impregnated sample was aged at room temperature for 8 hours, and heat-treated at 400 ℃ for 3 hours in an air atmosphere to obtain catalyst C-4 having a carbon content of 0.15%.

Example 6

Weighing a proper amount of catalyst carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing pyridine-2, 6-dicarboxylic acid, wherein the content of the pyridine-2, 6-dicarboxylic acid in the impregnation liquid is 3 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing Mo, Co and P, wherein the impregnation liquid is MoO₃The content of (A) was 89.5g/100ml, the CoO content was 13.5 g/100ml, the P content was 2.2g/100ml, the impregnated sample was aged at room temperature for 8 hours, and heat-treated at 400 ℃ for 3 hours in a mixed atmosphere of oxygen and ammonia gas to obtain a catalyst C-5 having a carbon content of 0.18%.

Example 7

Weighing proper amount of carrier Z-1, pre-impregnating carrier Z-1 with soaking solution containing pyromellitic benzoic acidThe content of the carrier is 2.5 percent of the mass of the carrier, the impregnated carrier is dried for 3 hours at 120 ℃, and then is impregnated with impregnation liquid containing Mo, Ni and P, and the composition of the impregnation liquid is MoO₃The content of (A) is 89.5g/100ml, the content of NiO is 15 g/100ml, the content of P is 2.5g/100ml, the impregnated sample is aged for 10 hours at room temperature, and is subjected to heat treatment for 3 hours at 300 ℃ in an oxygen and ammonia mixed atmosphere to obtain a catalyst C-6, wherein the carbon content in the catalyst is 0.8%.

Example 8

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using an impregnation liquid containing 2,2 '-bipyridine-5, 5' -dicarboxylic acid, wherein the content of the 2,2 '-bipyridine-5, 5' -dicarboxylic acid in the impregnation liquid is 1.8 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with an impregnation liquid containing W, Ni and P, wherein the composition of the impregnation liquid is WO₃The content of (b) was 85.5g/100ml, the NiO content was 26.02 g/100ml, the P content was 2.8g/100ml, the impregnated sample was aged at room temperature for 6 hours, and heat-treated at 350 ℃ for 4 hours in an air atmosphere to obtain catalyst C-7 having a carbon content of 0.5%.

Example 9

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using an impregnation liquid containing 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and adamantanic acid, wherein the content of the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, the content of the adamantanic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with the impregnation liquid containing W, Ni and P, wherein the composition of the impregnation liquid is WO₃The content of (A) was 85.5g/100ml, the NiO content was 26.02 g/100ml, the P content was 2.8g/100ml, the impregnated sample was aged at room temperature for 6 hours, and heat-treated at 350 ℃ for 4 hours in a mixed atmosphere of oxygen and ammonia gas to obtain a catalyst C-8 having a carbon content of 0.65%.

Example 10

Weighing a proper amount of carrier Z-1, pre-impregnating the carrier Z-1 by using an impregnation liquid containing 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and adamantanic acid, wherein the content of the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, the content of the adamantanic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, and the impregnated carrier is dried for 3 hours at 120 DEG CThen, the substrate was dipped in a dipping solution containing W, Ni and P, the composition of the dipping solution being WO₃The content of (b) was 85.5g/100ml, the NiO content was 26.02 g/100ml, the P content was 2.8g/100ml, the impregnated sample was aged at room temperature for 6 hours, and heat-treated at 350 ℃ for 4 hours in an air atmosphere to obtain catalyst C-9 having a carbon content of 0.8% in the catalyst.

Example 11

Weighing a proper amount of catalyst carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing pyridine-2, 6-dicarboxylic acid and 2,2 '-bipyridine-5, 5' -dicarboxylic acid, wherein the content of the pyridine-2, 6-dicarboxylic acid in the impregnation liquid is 0.8 percent of the mass of the carrier, the content of the 2,2 '-bipyridine-5, 5' -dicarboxylic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing Mo, Co and P, wherein the composition of the impregnation liquid is MoO₃The content of (A) was 89.5g/100ml, the CoO content was 13.5 g/100ml, the P content was 2.2g/100ml, the impregnated sample was aged at room temperature for 8 hours, and heat-treated at 400 ℃ for 3 hours in a mixed atmosphere of oxygen and ammonia gas to obtain a catalyst C-10 having a carbon content of 0.18%.

Example 12

Weighing a proper amount of catalyst carrier Z-1, pre-impregnating the carrier Z-1 by using impregnation liquid containing pyridine-2, 6-dicarboxylic acid and 2,2 '-bipyridine-5, 5' -dicarboxylic acid, wherein the content of the pyridine-2, 6-dicarboxylic acid in the impregnation liquid is 0.8 percent of the mass of the carrier, the content of the 2,2 '-bipyridine-5, 5' -dicarboxylic acid in the impregnation liquid is 1.2 percent of the mass of the carrier, drying the impregnated carrier at 120 ℃ for 3 hours, and then impregnating the impregnated carrier with impregnation liquid containing Mo, Co and P, wherein the composition of the impregnation liquid is MoO₃The content of (A) was 89.5g/100ml, the CoO content was 13.5 g/100ml, the P content was 2.2g/100ml, the impregnated sample was aged at room temperature for 8 hours, and heat-treated at 400 ℃ for 3 hours in an air atmosphere to obtain catalyst C-11 having a carbon content of 0.18% in the catalyst.

Comparative example 1

Weighing a proper amount of carrier Z-1, and carrying out equal-volume impregnation on the carrier Z-1 by using impregnation liquid containing Mo, Ni and P, wherein the impregnation liquid consists of MoO₃The content of (B) is 89.5g/100ml, the NiO content is 15 g/100ml, the P content is 2.5g/100ml, the impregnation is followed by aging at room temperature for 10 hours, drying at 115 ℃ for 3 hours in an air atmosphere,after calcination at 480 ℃ for 3 hours, catalyst C-12 was obtained.

Comparative example 2

Weighing proper amount of carrier Z-1, and soaking in soaking solution containing W, Ni and diethanolamine, wherein the soaking solution comprises WO₃The content of (A) was 22g/100ml, the NiO content was 3g/100ml, the amount of diethanolamine was 2.1g/100ml, and the molar ratio of the amount of diethanolamine to the Ni content in the final catalyst was 0.5: 1. The catalyst C-13 is obtained after aging for 10 hours at room temperature and drying for 3 hours at 120 ℃ in air atmosphere by adopting an isometric immersion method.

Comparative example 3

Weighing proper amount of catalyst carrier Z-1, and soaking in Mo, Co and P solution of MoO₃Has a content of 89.5g/100ml, a CoO content of 13.5 g/100ml and a P content of 2.2g/100 ml. The impregnated sample was aged at room temperature for 10 hours, dried at 120 ℃ for 3 hours in an air atmosphere, and then calcined at 480 ℃ for 3 hours. Then dipping the roasted catalyst into an aqueous solution containing succinic acid, wherein the dosage of the succinic acid is 1 percent of the mass of the carrier, drying the dipped sample at 120 ℃ for 3 hours, and roasting at 400 ℃ for 3 hours to obtain the catalyst C-14

TABLE 3 initial Activity evaluation results of catalysts

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7
								Relative denitrification activity,%	148	145	142	153	151	160	155
Relative desulfurization activity of%	142	149	140	145	149	158	152

TABLE 4 initial Activity evaluation results of catalysts

Catalyst numbering	C-8	C-9	C-10	C-11	C-12	C-13	C-14
								Relative denitrification activity,%	150	161	151	157	100	110	125
Relative desulfurization activity of%	145	155	149	152	99	108	118

The results of evaluating the initial activity of the C-1 to C-14 catalysts are shown in tables 3 and 4. As can be seen from the data in tables 3 and 4, the activity of the catalyst prepared by the method of the present invention is significantly higher than that of the catalyst prepared by the comparative example.

TABLE 5 evaluation results of 1200h Activity of catalyst

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7
								Relative denitrification activity,%	147	143	142	153	150	158	155
Relative desulfurization activity of%	140	145	139	145	147	157	150

TABLE 6 evaluation results of 1200h Activity of catalyst

Catalyst numbering	C-8	C-9	C-10	C-11	C-12	C-13	C-14
								Relative denitrification activity,%	155	150	150	150	100	122	125
Relative desulfurization activity of%	148	147	145	141	98	97	116

The 1200h activity evaluation results of the C-1-C-14 catalysts are shown in tables 5 and 6, and the data in tables 5 and 6 show that the catalysts prepared by the method have good stability and are beneficial to long-period operation.

Claims

1. A preparation method of a hydrotreating catalyst is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing or selecting an alumina carrier;

(4) impregnating the alumina carrier subjected to low-temperature drying treatment with an active component solution or active metal and an auxiliary agent, and performing high-temperature thermal treatment after impregnation to prepare a hydrotreating catalyst;

wherein, the high-temperature heat treatment conditions after the dipping in the step (4) are as follows: the treatment temperature is 180-500 ℃, the heat treatment time is 1-10 hours, the carbon content in the carrier after the high-temperature heat treatment is 0.1-3%, and the high-temperature heat treatment is carried out in the mixed atmosphere of oxygen and ammonia.

2. The method of claim 1, wherein: the alumina carrier in the step (1) is prepared by adopting a commercial product or a conventional method.

3. The method of claim 2, wherein: the preparation process of the conventional method is as follows: the aluminum hydroxide dry glue powder and SB powder are kneaded, molded, dried and roasted to prepare the catalyst carrier.

4. The method of claim 3, wherein: one or more forming aids of extrusion aid, binder and peptizing agent are added in the kneading process.

5. The method of claim 3, wherein: the drying conditions were as follows: the drying temperature is 50-300 ℃, and the drying time is 0.5-22 h.

6. The method of claim 3, wherein: the roasting conditions are as follows: the roasting temperature is 350-650 ℃, and the roasting time is 0.5-22 h.

7. The method of claim 1, wherein: the nitrogen-containing organic acid in the step (2) comprises one or more of pyridine-2, 3-dicarboxylic acid, pyridine-2, 4-dicarboxylic acid, pyridine-2, 5-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, pyridine-3, 4-dicarboxylic acid, pyridine-3, 5-dicarboxylic acid, furandicarboxylic acid and 2,2 '-bipyridine-5, 5' -dicarboxylic acid.

8. The method of claim 1, wherein: the aromatic carboxylic acid in the step (2) is biphenyl tetracarboxylic acid or adamantane carboxylic acid.

9. The method of claim 1, wherein: the amount of the nitrogen-containing organic acid or aromatic carboxylic acid impregnated in the step (2) is 0.5-5% of the weight of the alumina carrier.

10. The method of claim 1, wherein: the amount of the nitrogen-containing organic acid or aromatic carboxylic acid impregnated in the step (2) is calculated by taking the nitrogen-containing organic acid or aromatic carboxylic acid as 1-3% of the weight of the alumina carrier.

11. The method of claim 1, wherein: the low-temperature drying temperature of the step (3) is 60-150 ℃, and the drying time is 0.5-10 hours.

12. The method of claim 11, wherein: the low-temperature drying temperature of the step (3) is 100-120 ℃, and the drying time is 2-6 hours.

13. The method of claim 1, wherein: and (4) controlling the dry basis of the carrier after low-temperature drying in the step (3) to be 70-90%.

14. The method of claim 1, wherein: the active component in the step (4) comprises VIII family metal and/or VIB family metal, wherein the VIII family metal is Ni and/or Co, and the VIB family metal is W and/or Mo.

15. The method of claim 1, wherein: and (4) providing a compound of an active metal in the impregnation liquid, wherein tungsten is one or two of ammonium metatungstate and ammonium tetrathiotungstate, molybdenum is one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate and ammonium paramolybdate, nickel is one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride and nickel acetate, and cobalt is one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate and cobalt chlorate.

16. The method of claim 1, wherein: the auxiliary agent in the step (4) is selected from one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium and vanadium, the adopted impregnation mode is saturated impregnation or supersaturated impregnation, and impregnation liquid containing active metals is impregnated on the carrier in one step or step by step.

17. The method of claim 1, wherein: the high-temperature heat treatment conditions after the dipping in the step (4) are as follows: the treatment temperature is 200-400 ℃, the heat treatment time is 2-6 hours, and the carbon content in the carrier after high-temperature heat treatment is 0.3-2%.

18. The method of claim 1, wherein: and (4) treating in the heat treatment process in the step (4) under the mixed atmosphere of oxygen and ammonia gas, wherein the volume concentration of the oxygen in the mixed gas is controlled to be 10ppm-90 ppm.

19. A hydroprocessing catalyst prepared by the process of any one of claims 1 to 18, characterized by: the hydrotreating catalyst takes alumina as a carrier, VIII family and VIB family metals as active metal components, the VIII family metal is Co and/or Ni, the VIB family metal is W and/or Mo, the content of the VIII family metal is 1-15 wt% by weight of oxides, the content of the VIB family metal is 10-30 wt% by weight of oxides, and the weight content of an auxiliary agent in the catalyst is 0.01-10% by weight based on the weight of the catalyst.

20. The catalyst of claim 19, wherein: based on the weight of the catalyst, the content of the VIII family metal in terms of oxide is 4-10 wt%, the content of the VIB family metal in terms of oxide is 15-25 wt%, and the weight content of the auxiliary agent in the catalyst is 0.01-2%.

21. Use of a catalyst according to claim 19, wherein: the process conditions are as follows: the reaction temperature is 300-380 ℃, the reaction pressure is 4-8MPa, and the hydrogen-oil ratio is 600:1-1200: 1.

22. Use of a catalyst according to claim 21, wherein: the process conditions are as follows: the reaction temperature is 320-360 ℃, the reaction pressure is 5-7 MPa, and the hydrogen-oil ratio is 800:1-1000: 1.