CN112237908A

CN112237908A - Catalyst carrier, hydrotreating catalyst, preparation method and application

Info

Publication number: CN112237908A
Application number: CN202011066209.XA
Authority: CN
Inventors: 王耀岽; 曹春香; 陈子莲; 张伯梁; 姚安邦
Original assignee: SHANDONG GONGQUAN CHEMICAL CO Ltd
Current assignee: SHANDONG GONGQUAN CHEMICAL CO Ltd
Priority date: 2020-09-30
Filing date: 2020-09-30
Publication date: 2021-01-19

Abstract

The invention discloses a catalyst carrier, a hydrotreating catalyst, a preparation method and application. Wherein, the preparation method comprises the following steps: s1, adding the alumina dry glue powder into deionized water to prepare first slurry; s2, adding an organic auxiliary agent into the first slurry to prepare second slurry; s3, filtering, washing and drying the second slurry to obtain a catalyst precursor; and S4, adding an acidic solution into the catalyst precursor, mixing, drying and roasting to obtain the catalyst carrier. In the catalyst carrier prepared by the method, the alumina dry glue powder exists in the slurry in the form of suspended matters, the organic auxiliary agent can be uniformly dispersed on the alumina dry glue to occupy unsaturated coordination centers on the surface of alumina, a high-activity reaction center can be formed after active components are subsequently impregnated, and simultaneously the surface acidity of the catalyst is improved, so that the content of strong acid of the catalyst prepared by the catalyst carrier is reduced, and the content of medium strong acid is increased.

Description

Catalyst carrier, hydrotreating catalyst, preparation method and application

Technical Field

The invention relates to the technical field of catalysts, and particularly relates to a catalyst carrier, a hydrotreating catalyst, a preparation method and an application.

Background

The hydrotreating catalyst is obtained by loading metal oxides containing VIII family and VIB family in a periodic table into a refractory inorganic porous material, wherein a carrier generally adopts alumina, silica, titanium dioxide, silicon carbide, boron oxide, zirconia and a composite carrier formed by combining the alumina, the silica, the titanium dioxide, the silicon carbide, the boron oxide and the zirconia, a catalyst precursor is prepared by an impregnation process, and a finished product catalyst is prepared by drying and roasting steps. 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 the 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 pretreatment of the feedstock to prevent impurities in the feedstock from poisoning the catalyst, which, once poisoned, results in an immeasurable loss. 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 of a catalyst is high without roasting, and weak van der waals acting force exists between active metal and a carrier, so that the reaction activity of the catalyst can be effectively improved, but the stability of the catalyst is poor, so that the development of a catalyst with high activity and high stability is a bottleneck to be broken through in the field.

Much work has been done in the art to improve the activity of hydrogenation catalysts, and many documents report and have made certain results, but some technical problems still remain, such as: CN00110018.1 discloses a hydrogenation catalyst and a preparation method thereof, the catalyst takes VIB group and VIII group metals as hydrogenation active components, inorganic auxiliary agent fluorine is added, meanwhile, one or a mixture of boron, silicon, phosphorus, magnesium, titanium, zirconium and gallium is loaded as an auxiliary agent, the catalyst is prepared by adopting a coprecipitation method, the active metals can enter a bulk phase or are covered by alumina particles in the coprecipitation and extrusion processes, and the utilization rate of the active metals is reduced; in japanese patent JP11033412, a method of preparing a supported metal catalyst is disclosed. Adding a surfactant and a metal salt solution into a porous medium material, placing for more than 1 hour, then treating the impregnation liquid with ultrasonic waves for 2 hours, drying the impregnated porous medium material at 120 ℃ for 12 hours after ultrasonic treatment, and roasting for 2 hours at 500 ℃ in an air atmosphere to obtain the finished catalyst. The method for preparing the catalyst has the advantages of complex process engineering and low activity, and is not suitable for industrial mass production.

Therefore, there is still a need to develop a new preparation method for preparing a highly active hydrotreating catalyst.

Disclosure of Invention

The invention aims to provide a catalyst carrier, a hydrotreating catalyst, a preparation method and application, so as to improve the reaction activity of the hydrotreating catalyst.

In order to achieve the above object, according to one aspect of the present invention, there is provided a method of preparing a catalyst carrier. The preparation method comprises the following steps: s1, adding the alumina dry glue powder into deionized water to prepare first slurry; s2, adding an organic auxiliary agent into the first slurry to prepare second slurry; s3, filtering, washing and drying the second slurry to obtain a catalyst precursor; and S4, adding an acidic solution into the catalyst precursor, mixing, drying and roasting to obtain the catalyst carrier.

Further, in S2, the organic auxiliary is in the form of an organic auxiliary solution, and is added to the first slurry under high-speed stirring, where high-speed stirring means a stirring speed of more than 1000 r/min.

Further, the organic auxiliary is one or more selected from the group consisting of isobutyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, methyltributanonoximosilane, methyltriacetoxysilane and vinyltributonoximosilane.

Further, the solvent in the organic auxiliary agent solution is one or more selected from the group consisting of dimethyl sulfoxide, triethanolamine, ammonium citrate and citric acid.

Further, in S3, the drying temperature is 20-150 ℃ and the drying time is 0.5-22 h; preferably, in S3, the drying temperature is 60-80 ℃ and the drying time is 1-8 h; preferably, in S4, the drying temperature is 60-120 ℃, and the drying time is 0.5-24 h; the roasting temperature is 300-500 ℃, and the roasting time is 1-6 h.

According to another aspect of the present invention, a method of preparing a hydroprocessing catalyst is provided. The preparation method comprises the following steps: 1) preparing a catalyst carrier; and 2) dipping the active components of the catalyst carrier, drying and roasting to obtain a hydrotreating catalyst; wherein, the catalyst carrier is prepared by any preparation method.

Further, the active component includes a group VIII metal and a group VIB metal; wherein the metal of the VIII family is nickel and/or cobalt, and the metal of the VIB family is tungsten and/or molybdenum; preferably, the group VIII metal is present in an amount of from 1 wt% to 12 wt%, preferably from 4 wt% to 10 wt%, calculated as oxide, and the group VIB metal is present in an amount of from 10 wt% to 30 wt%, more preferably from 18 wt% to 23 wt%, calculated as oxide, based on the weight of the final catalyst.

Further, the active component includes tungsten, molybdenum, nickel or cobalt; preferably, 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; preferably, the concentration of the active ingredient solution used when the active ingredient impregnation in 2) is performed is 10 wt% to 60 wt%.

Further, in 2), the drying temperature is 60-120 ℃, and the time is 0.5-24 hours; roasting at the temperature of 300-500 ℃ for 1-6 h; preferably, the molar ratio of the organic auxiliary agent used in the preparation of the catalyst support in 1) to Mo and/or W in the final catalyst is 1: 2-1: 30, more preferably 1: 10-1: 20.

according to yet another aspect of the present invention, a catalyst support is provided. The catalyst carrier is prepared by any one of the preparation methods.

According to yet another aspect of the present invention, a hydroprocessing catalyst is provided. The hydrotreating catalyst is prepared by any of the above-mentioned preparation methods.

According to a further aspect of the present invention, there is provided a use of the above hydrotreating catalyst in hydrodenitrogenation and desulfurization processes of heavy distillate oil.

In the catalyst carrier prepared by the method, the alumina dry glue powder exists in the slurry in the form of suspended matters, the organic auxiliary agent can be uniformly dispersed on the alumina dry glue to occupy unsaturated coordination centers on the surface of alumina, a high-activity reaction center can be formed after active components are subsequently impregnated, and simultaneously the surface acidity of the catalyst is improved, so that the content of strong acid of the catalyst prepared by the catalyst carrier is reduced, and the content of medium strong acid is increased. Moreover, the organic auxiliary agent can be used as a barrier molecule on the surface of the carrier, and after the active component is impregnated, the acting force between the active component and the carrier can be weakened, so that the active component is easy to reduce, and more active centers are generated.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

In the present invention, wt% is a mass fraction.

According to an exemplary embodiment of the present invention, a method of preparing a catalyst support is provided. The preparation method comprises the following steps: s1, adding the alumina dry glue powder into deionized water to prepare first slurry; s2, adding an organic auxiliary agent into the first slurry to prepare second slurry; s3, filtering, washing and drying the second slurry to obtain a catalyst precursor; and S4, adding an acidic solution into the catalyst precursor, mixing, drying and roasting to obtain the catalyst carrier.

In one embodiment of the present invention, preferably, in S1, the mass ratio of the alumina dry glue powder to the deionized water is 5: (1-1.5); in S2, the adding amount of the organic auxiliary agent is 10-50% of the proportion of the alumina dry glue powder; in S3, the acidic solution may be one or more of nitric acid, acetic acid, citric acid, and hydrochloric acid.

Preferably, in S2, the organic assistant is in the form of an organic assistant solution, and is added to the first slurry under high-speed stirring, where high-speed stirring means a stirring speed of more than 1000 r/min. This helps the alumina dry glue powder to be present in the slurry as a suspension and the organic auxiliary agent to be uniformly dispersed on the alumina dry glue. In an embodiment of the invention, the content of the organic additive in the organic additive solution is 0.08-0.12% by Si content.

According to a typical embodiment of the present invention, the organic adjuvant is one or more selected from the group consisting of isobutyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, methyltributanoxime silane, methyltriacetoxysilane and vinyltributoxime silane. The organic compound can be uniformly dispersed on the alumina dry gel, occupies unsaturated coordination centers on the surface of the alumina, forms high-activity reaction centers after dipping active components, improves the surface acidity of the catalyst, reduces the content of strong acid in the catalyst, and increases the content of medium strong acid. Moreover, the organic auxiliary agent can be used as a barrier molecule on the surface of the carrier, and after the active component is impregnated, the acting force between the active component and the carrier can be weakened, so that the active component is easy to reduce, and more active centers are generated.

Preferably, the solvent in the organic auxiliary solution is one or more selected from the group consisting of dimethyl sulfoxide, triethanolamine, ammonium citrate and citric acid. Preferably, in S3, the drying temperature is 20-150 ℃ and the drying time is 0.5-22 h; more preferably, in S3, the drying temperature is 60-80 ℃ and the drying time is 1-8 h; the catalyst has good appearance and strength at the drying temperature, can decompose part of organic auxiliary agents, has a dry basis of about 65-75%, is beneficial to long-term use of subsequent roasting equipment, and is beneficial to complete subsequent roasting. ,

preferably, in S4, the drying temperature is 60-120 ℃, and the drying time is 0.5-24 h; the roasting temperature is 300-500 ℃, and the roasting time is 1-6 h. Drying and roasting under the condition can obtain proper pore volume, specific surface area and accessible pore diameter, can roast and decompose other substances in the catalyst completely, and can adjust the surface acidity of the catalyst at the roasting temperature.

In accordance with an exemplary embodiment of the present invention, a method for preparing a hydroprocessing catalyst is provided. The preparation method comprises the following steps: 1) preparing a catalyst carrier; and 2) dipping the active components of the catalyst carrier, drying and roasting to obtain a hydrotreating catalyst; wherein, the catalyst carrier is prepared by the preparation method of the catalyst carrier. The catalyst prepared by the method has high degree of vulcanization, and the active components are uniformly dispersed on the surface of the carrier, so that the degree of vulcanization and the degree of dispersion are well matched, and the reaction activity of the catalyst is greatly improved.

In a typical embodiment of the invention, the active components include a group VIII metal and a group VIB metal; wherein the metal of the VIII family is nickel and/or cobalt, and the metal of the VIB family is tungsten and/or molybdenum; preferably, the group VIII metal is present in an amount of from 1 wt% to 12 wt%, preferably from 4 wt% to 10 wt%, calculated as oxide, and the group VIB metal is present in an amount of from 10 wt% to 30 wt%, more preferably from 18 wt% to 23 wt%, calculated as oxide, based on the weight of the final catalyst.

Preferably, the active component comprises tungsten, molybdenum, nickel or cobalt; more preferably, tungsten is one or two of ammonium metatungstate and ammonium tetrathiomungstate, 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; 2) the concentration of the active component solution adopted when the active component is impregnated is 10 wt% -60 wt%.

In a typical embodiment of the invention, the drying temperature is 60-120 ℃ and the drying time is 0.5-24 h; roasting at the temperature of 300-500 ℃ for 1-6 h; preferably, the molar ratio of the organic auxiliary agent used in the preparation of the catalyst support in 1) to Mo and/or W in the final catalyst is 1: 2-1: 30, more preferably 1: 10-1: 20.

according to an exemplary embodiment of the present invention, a catalyst support is provided. The catalyst carrier is prepared by the preparation method of the catalyst carrier.

According to an exemplary embodiment of the present invention, a hydroprocessing catalyst is provided. The hydrotreating catalyst is prepared by the preparation method of the hydrotreating catalyst. The catalyst prepared by the method has high degree of vulcanization, and the active components are uniformly dispersed on the surface of the carrier, so that the degree of vulcanization and the degree of dispersion are well matched, and the reaction activity of the catalyst is greatly improved.

According to an exemplary embodiment of the present invention, there is provided a use of the above hydrotreating catalyst in hydrodenitrogenation and desulfurization processes of heavy distillate oil.

The following examples are provided to further illustrate the advantageous effects of the present invention.

Example 1

Weighing 125g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 5L of water to prepare a solution A1, weighing 30g of isobutyltriethoxysilane and dissolving the isobutyltriethoxysilane in 120ml of water solution containing 4% dimethyl sulfoxide to obtain a solution B1, adding the solution B into the solution A under the condition of high-speed stirring, and washing and filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at 100 ℃ for 4 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2g of hydroxymethyl cellulose; dissolving 9.8mL of nitric acid (65 wt%) in 120mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 100 ℃ for 6 hours, roasting at 400 ℃ for 6 hours to obtain a supported catalyst Z1,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃Weighing 25.3 g of impregnation liquid, adding deionized water to dilute to a certain volume, impregnating a carrier Z1, drying an impregnated sample at 80 ℃, and roasting at 420 ℃ to obtain the finished catalyst C1, wherein the content of the impregnation liquid is 88.5g/100ml, the content of NiO is 15g/100ml, and the content of P is 2.2g/100 ml.

Example 2

Weighing 125g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 6L of water to prepare a solution A2, weighing 28g of isobutyl trimethoxy silane and dissolving the isobutyl trimethoxy silane into 100ml of aqueous solution containing 2% of dimethyl sulfoxide to obtain a solution B2, adding the solution B2 into the solution A2 under the condition of high-speed stirring, and washing and filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at the temperature of 90 ℃ for 2 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2.5g of hydroxymethyl cellulose; dissolving 11mL of nitric acid (65 wt%) in 110mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 100 ℃ for 6 hours, roasting at 400 ℃ for 6 hours to obtain a supported catalyst Z2,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃The content of (3) is 88.5g/100ml, the NiO content is 15g/100ml, the P content is 2.2g/100ml, 25.3 g of impregnation liquid is weighed, deionized water is added to dilute the impregnation liquid to a certain volume, and a carrier is impregnatedAnd Z2, drying the impregnated sample at 90 ℃, and roasting at 400 ℃ to obtain the finished catalyst C2.

Example 3

Weighing 125g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 6L of water to prepare a solution A3, weighing 25g of methyl tributyrinoxime silane and dissolving the methyl tributyrinoxime silane into 100ml of aqueous solution containing 2% of ammonium citrate to obtain a solution B3, adding the solution B3 into the solution A3 under the condition of high-speed stirring, and washing and suction-filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at the temperature of 90 ℃ for 2 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2.5g of hydroxymethyl cellulose; dissolving 10.5mL of nitric acid (65 wt%) in 120mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 95 ℃ for 4 hours, roasting at 400 ℃ for 6 hours to obtain a supported catalyst Z3,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃Weighing 26.3 g of impregnation liquid, adding deionized water to dilute to a certain volume, impregnating a carrier Z3, drying an impregnated sample at 90 ℃ and roasting at 400 ℃ to obtain the finished catalyst C3, wherein the content of the impregnation liquid is 86.5g/100ml, the content of NiO is 15g/100ml and the content of P is 2.5g/100 ml.

Example 4

Weighing 130g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 5L of water to prepare a solution A4, weighing 7g of vinyl tributyrinoxime silane and dissolving the vinyl tributyrinoxime silane into 50ml of aqueous solution containing 2% of citric acid to obtain a solution B4, adding the solution B4 into the solution A4 under the condition of high-speed stirring, and washing and filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at 100 ℃ for 2 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2.5g of hydroxymethyl cellulose; dissolving 10.5mL of nitric acid (65 wt%) in 120mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 95 ℃ for 4 hours, roasting at 400 ℃ for 6 hours to obtain a supported catalyst Z4,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃In an amount of88.5g/100ml, 14.2g/100ml of NiO and 2.3g/100ml of P, weighing 27.3 g of impregnation liquid, adding deionized water to dilute to a certain volume, impregnating the carrier Z4, drying the impregnated sample at 90 ℃, and roasting at 400 ℃ to obtain the finished catalyst C4.

Example 5

Weighing 130g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 5L of water to prepare a solution A5, weighing 6g of methyl triacetoxysilane and dissolving the methyl triacetoxysilane into 80ml of water solution containing 3% of triethanolamine to obtain a solution B5, adding the solution B5 into the solution A5 under the condition of high-speed stirring, and washing and filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at 100 ℃ for 2 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2.5g of hydroxymethyl cellulose; dissolving 10.5mL of nitric acid (65 wt%) in 120mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 95 ℃ for 4 hours, roasting at 400 ℃ for 6 hours to obtain a supported catalyst Z5,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃Weighing 27.3 g of impregnation liquid, adding deionized water to dilute to a certain volume, impregnating a carrier Z5, drying an impregnated sample at 90 ℃, and roasting at 400 ℃ to obtain the finished catalyst C5, wherein the content of the impregnation liquid is 88.5g/100ml, the content of NiO is 14.2g/100ml, and the content of P is 2.3g/100 ml.

Example 6

Weighing 130g of alumina dry glue powder (dry basis is 75 wt%) and putting the alumina dry glue powder into 5L of water to prepare a solution A6, weighing 8g of dimethyl dimethoxy silane and dissolving the dimethyl dimethoxy silane into 90ml of water solution containing 3% of triethanolamine to obtain a solution B6, adding the solution B6 into the solution A6 under the condition of high-speed stirring, and washing and filtering to obtain a silicon-containing catalyst precursor. Carrying out heat treatment at 100 ℃ for 2 hours, controlling the dry basis of the precursor to be not more than 40%, crushing the precursor, and adding 4g of sesbania powder, 4g of citric acid and 2.5g of hydroxymethyl cellulose; dissolving 10.5mL of nitric acid (65 wt%) in 100mL of deionized water to prepare an acid solution, rolling for 25min, extruding into 1.7mm clover strips on a strip extruding machine, drying at 95 ℃ for 4 hours, roasting at 430 ℃ for 4 hours to obtain a supported catalyst Z6,

preparing molybdenum nickel phosphorus impregnation liquid by adopting a conventional method, wherein the impregnation liquid consists of MoO₃Weighing 28.5 g of impregnation liquid, adding deionized water to dilute to a certain volume, impregnating a carrier Z6, drying an impregnated sample at 90 ℃, and roasting at 430 ℃ to obtain the finished catalyst C6, wherein the content of the impregnation liquid is 88.5g/100ml, the content of NiO is 14.2g/100ml, and the content of P is 2.3g/100 ml.

Reference ratio 1

And (3) preparing a reference catalyst. Weighing 135g of dry alumina gel powder and 4g of hydroxymethyl cellulose, putting the dry alumina gel powder and the hydroxymethyl cellulose into a rolling machine, dry-mixing for 10 minutes, adding 121ml of acid solution prepared from 9.8g of nitric acid and 6g of citric acid, kneading, rolling, preparing paste capable of extruding strips, and extruding and forming the strips. Drying at 110 deg.C for 8 hr, placing in a muffle furnace, and calcining in air at 550 deg.C for 4 hr to obtain reference carrier. The Mo-Ni-P solution is soaked in the reference agent carrier, the soaked sample is dried at 120 deg.c for 4 hr and roasted at 480 deg.c for 2 hr to obtain the reference agent C10 with the composition of 23% MoO3, 3.6% NiO and 1.6% p, and the main physical properties are shown in Table 1.

The catalyst vulcanization adopts kerosene with the content of 5 wt% of dimethyl disulfide as vulcanized oil. The prevulcanization conditions were as follows: the hydrogen partial pressure is 14.7MPa, the vulcanization temperature is 340 ℃, the volume space velocity is 1.0h < -1 >, and the volume ratio of hydrogen to oil is 1000. The reaction process conditions of the catalysts of the examples and the catalysts of the comparative examples were: the pressure is 14.7MPa, the space velocity is 1.0, the temperature is 370 ℃, and the volume ratio of hydrogen to oil is 1000.

The catalysts of the above examples and comparative examples were subjected to activity evaluation tests in a 100ml small-sized hydrogenation reaction apparatus, and the used starting material was catalytic diesel oil, and the properties thereof are shown in Table 2. The catalyst is pre-sulfurized before use, the sulfurized oil is straight-run kerosene, 5 wt% of DMDS (dimethyl disulfide) is added, and after pre-sulfurization, raw oil is directly introduced for test reaction. The prevulcanization and the test conditions are shown in Table 3, and the evaluation results are shown in Table 4.

TABLE 1

TABLE 2

Raw oil name	Catalytic diesel fuel
		Sulfur content, μ g/g	980
Nitrogen content,. mu.g/g	1000

TABLE 3

TABLE 4

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7	C-8	C-9	C-10
											Relative denitrification activity,%	141	158	143	145	128	121	132	138	110	100
Relative desulfurization activity of%	138	146	129	128	110	101	121	126	106	100

As can be seen from the data in Table 4, the activity of the catalyst prepared by the process of the present invention is significantly higher than that of the catalyst prepared by the comparative example.

TABLE 5

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7	C-8	C-9	C-10
											Relative denitrification activity,%	139	155	140	142	132	118	121	123	115	100
Relative desulfurization activity of%	132	145	128	121	102	102	110	103	102	100

The results of 1200h activity evaluation of the C-1-C-10 catalyst are shown in Table 5, and the data in Table 5 show that the catalyst prepared by the method has good stability and is beneficial to long-period operation.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a catalyst carrier, comprising the steps of:

s1, adding the alumina dry glue powder into deionized water to prepare first slurry;

s2, adding an organic auxiliary agent into the first slurry to prepare second slurry;

s3, filtering, washing and drying the second slurry to obtain a catalyst precursor; and

and S4, adding an acidic solution into the catalyst precursor, mixing, drying and roasting to obtain the catalyst carrier.

2. The method according to claim 1, wherein in the step S2, the organic auxiliary is in the form of an organic auxiliary solution, and is added to the first slurry under high-speed stirring, wherein the high-speed stirring is performed at a stirring speed of more than 1000 r/min.

3. The method according to claim 1, wherein the organic auxiliary is one or more selected from the group consisting of isobutyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, methyltributanoxime silane, methyltriacetoxysilane and vinyltributoxime silane.

4. The method according to claim 2, wherein the solvent in the organic auxiliary solution is one or more selected from the group consisting of dimethyl sulfoxide, triethanolamine, ammonium citrate, and citric acid.

5. The preparation method according to claim 1, wherein in the step S3, the drying temperature is 20-150 ℃ and the drying time is 0.5-22 h;

preferably, in the S3, the drying temperature is 60-80 ℃ and the drying time is 1-8 h;

preferably, in the S4, the drying temperature is 60-120 ℃, and the drying time is 0.5-24 hours; the roasting temperature is 300-500 ℃, and the roasting time is 1-6 h.

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

1) preparing a catalyst carrier; and

2) impregnating the catalyst carrier with active components, drying and roasting to obtain the hydrotreating catalyst;

wherein the catalyst carrier is prepared by the preparation method of any one of claims 1 to 5.

7. The method of claim 6, wherein the active components comprise a group VIII metal and a group VIB metal; wherein the group VIII metal is nickel and/or cobalt, and the group VIB metal is tungsten and/or molybdenum;

preferably, the group VIII metal is present in an amount of from 1 wt% to 12 wt%, preferably from 4 wt% to 10 wt%, calculated as oxide, and the group VIB metal is present in an amount of from 10 wt% to 30 wt%, more preferably from 18 wt% to 23 wt%, calculated as oxide, based on the weight of the final catalyst.

8. The method of claim 7, wherein the active component comprises tungsten, molybdenum, nickel, or cobalt;

preferably, 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;

preferably, the concentration of the active ingredient solution used in the impregnation of the active ingredient in 2) is 10 wt% to 60 wt%.

9. The preparation method according to claim 6, wherein in the step 2), the drying temperature is 60-120 ℃ and the drying time is 0.5-24 h; the roasting temperature is 300-500 ℃, and the roasting time is 1-6 h;

preferably, the molar ratio of the organic auxiliary agent used in preparing the catalyst carrier in 1) to Mo and/or W in the final catalyst is 1: 2-1: 30, more preferably 1: 10-1: 20.

10. a catalyst carrier produced by the production method according to any one of claims 1 to 5.

11. A hydroprocessing catalyst, characterized by being produced by the production method according to any one of claims 6 to 9.

12. Use of the hydrotreating catalyst of claim 11 in the hydrodenitrogenation and desulfurization of heavy distillate oils.