CN114433120A

CN114433120A - Desulfurization catalyst and preparation method and application thereof

Info

Publication number: CN114433120A
Application number: CN202210187860.5A
Authority: CN
Inventors: 陈燕蝶; 魏春生
Original assignee: China Criminal Police University
Current assignee: China Criminal Police University
Priority date: 2022-02-28
Filing date: 2022-02-28
Publication date: 2022-05-06
Anticipated expiration: 2042-02-28
Also published as: CN114433120B

Abstract

Embodiments of the present disclosure relate to a desulfurization catalyst, and a preparation method and application thereof, wherein the catalyst comprises at least one group VIII metal, at least two group VIB metals, and a group IVA nonmetal. The invention also discloses a preparation method and application of the catalyst. The invention is used for hydrodesulfurization of diesel oil fractions containing 4, 6-dimethyldibenzothiophene, shows extremely high hydrodesulfurization activity, realizes ultra-deep desulfurization, and reduces the cost of a catalyst by introducing non-metals of IVA group.

Description

Desulfurization catalyst and preparation method and application thereof

Technical Field

The disclosure relates to a desulfurization catalyst and a preparation method and application thereof, and belongs to the technical field of energy treatment.

Background

Because the petroleum reserves are reduced, the problems of petroleum heaviness and deterioration are more and more prominent, high-sulfur crude oil is increased year by year in the world, and the requirements of environmental legislation of various countries on the limitation of the sulfur content in fuel oil are increasingly strict, the development of the ultra-deep hydrodesulfurization catalyst with excellent performance not only becomes the core of the hydrodesulfurization field, but also makes the hydrotreating technology increasingly paid attention to in the petroleum processing industry. Sulfides in oil products are a main source of air pollution, SOx generated after organic sulfur-containing compounds in fuel oil are combusted can not only cause acid rain, but also can cause irreversible poisoning of a three-way catalyst of an automobile engine tail gas purification system, and can also participate in forming dust particles PM2.5 to cause gradually increased haze weather, so that the environment and human health are seriously harmed, and people are attracted to pay attention to the environment widely. Therefore, strict fuel oil sulfur content standards are promulgated by various countries, Europe has realized that the sulfur content of diesel oil is less than 10ppmw standard in 2005, China has executed the JingV clean diesel oil index with the sulfur content of less than 10ppmw in 6 and 1 days in 2012 first in Beijing, and has completely executed the diesel oil sulfur index equivalent to the Europe IV (<50ppmw) emission standard in 2015 nationwide, and has completely executed the clean diesel oil sulfur index equivalent to the Europe V (<10ppmw) emission standard in 2017 and 1 days.

With the increasing standards for sulfur content, the adjustment of process operating conditions and the use of new reactors require a significant investment cost, compared to the development of a new catalyst capable of ultra-deep hydrodesulfurization at existing plant operating conditions, which is a more economical and feasible process.

U.S. Pat. Nos. 09/518741, 08/900389, 09/869988 all report a NiMoW bulk catalyst. The synthesis method of said catalyst uses ammonia water as complexing agent and reacts with reaction raw material Ni²⁺Complexing, through slow heating process, the Ni-ammonia complex slowly decomposes to obtain Ni²⁺Reacting with molybdenum and tungsten in the solution to generate a NiMoW catalyst precursor, and then roasting and vulcanizing to form the NiMoWS sulfide catalyst. Chinese patent CN1339985A also discloses a method for synthesizing a NiMoW catalyst, which is mainly to react molybdenum and tungsten salts with basic nickel carbonate in an aqueous solution, at least ensure that part of the metal components exist in a solid state during the reaction, and finally obtain the catalyst by sulfurization.

From the reported work, it is not difficult to find that the existing synthesis method of the bulk catalyst has the following defects:

(1) the used raw materials are not friendly to the environment;

(2) the preparation cost of the catalyst is high;

(3) the specific surface area, pore volume and activity of the catalyst are yet to be further improved.

Disclosure of Invention

The purpose of the present disclosure is to provide a desulfurization catalyst, a preparation method and an application thereof.

To achieve the above objects, in one aspect of the present disclosure there is provided a desulfurization catalyst comprising a mixed metal oxide of at least one group VIII metal, at least two group VIB metals, and a group IVA nonmetal;

wherein, calculated by oxide, the catalyst contains 1-50 wt% of VIII group metal, 1-50 wt% of VIB group metal and 1-50 wt% of IVA group nonmetal.

Further, the catalyst comprises at least one group VIII metal, two group VIB metals and one group IVA nonmetal, and the molar ratio of the group VIII metal to the group VIB metal is 20:1-1: 20; the molar ratio of the group VIII metal to the group IVA nonmetal is 20:1 to 1: 1; the molar ratio of the two group VIB metals is 5:1-1: 5.

Further, the group VIII metal includes Ni or Co; the group VIB metal comprises Mo and W; the group IVA nonmetal comprises Si.

Further, the catalyst has a layered porous structure, and the specific surface area of the layered porous structure is 80-300m²The pore volume is 0.1-0.5 ml/g.

Another aspect of the present disclosure also provides a method of preparing a desulfurization catalyst, the method comprising:

adding at least one soluble salt of VIII group metal into a solvent to prepare a solution A, adding at least one soluble salt of IVA group nonmetal into water to prepare a solution B, and mixing and reacting the solution A and the solution B to obtain a catalyst precursor solution;

adding soluble salts of at least two VIB group metals into a polar solvent to prepare a solution C, and mixing and reacting the solution C with the catalyst precursor solution to obtain the catalyst.

Further, the concentration of the VIII group metal ions in the solution A is 0.01-0.3 mol/L, the concentration of the IVA group non-metal ions in the solution B is 0.01-0.3 mol/L, the concentration of the catalyst precursor solution is 0.01-0.9 mol/L, and the concentration of the VIB group metal ions in the solution C is 0.01-0.2 mol/L.

Further, the solution A and the solution B react for 4 to 50 hours at the temperature of 20 to 200 ℃, and the solution C and the catalyst precursor solution react for 4 to 50 hours at the temperature of 20 to 200 ℃.

Further, the soluble salt of the group IVA nonmetal comprises one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, the soluble salt of the group VIII metal comprises one or more of nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate, and the soluble salt of the group VIB metal anion comprises one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid or sodium tungstate.

In another aspect, the present disclosure also provides a use of the desulfurization catalyst in hydrodesulfurization reaction of sulfur-containing organic compound fuel oil.

Further, the hydrodesulfurization reaction conditions are as follows: the temperature is 250 ℃ and 450 ℃, the hydrogen pressure is 1-20MPa, and the volume ratio of the hydrogen to the sulfur-containing organic compound fuel oil is 50-1500Nm³/m³(ii) a The volume space velocity of the sulfur-containing organic compound fuel oil is 0.1-10h^-1。

Compared with the prior art, the method has the advantages that:

1) in the method, the compound with the layered structure is used as a precursor of the synthetic catalyst, the multi-metal bulk catalyst with the layered structure is designed and synthesized, the synthetic process is easy to operate and environment-friendly, and the catalyst can be industrially produced.

2) The VIB group active metal is successfully introduced between the layers of the precursor, so that the distribution and dispersion of the active metal are more uniform, more active centers are formed, the catalyst is determined to have ultrahigh hydrodesulfurization activity, and under mild operation conditions, the sulfur in the 4, 6-dimethyldibenzothiophene in the diesel fraction can be removed from 521ppm to below 10ppm, so that ultra-deep desulfurization is realized.

3) By introducing the IVA group non-metal, the cost of the catalyst is reduced.

Drawings

FIG. 1 is a NiSiO solid prepared in example 1 of the present disclosure₃XRD patterns of nanotubes and their catalyst precursors.

FIG. 2 shows a layered NiSiO crystal prepared according to the embodiments of the disclosure₃TEM images of nanotubes.

Fig. 3 is an SEM image of a NiSiMoW catalyst prepared according to an example of the disclosure.

Fig. 4 is a graph showing the variation of hydrodesulfurization activity of the NiSiMoW catalysts prepared in examples 1 to 7 according to the present disclosure.

Detailed Description

The catalyst, the preparation method and the application thereof are disclosed and provided in detail in the following with reference to the accompanying drawings.

An embodiment of the present disclosure provides a desulfurization catalyst comprising a mixed metal oxide of at least one group VIII metal, at least two group VIB metals, and a group IVA nonmetal; wherein, calculated by oxide, the catalyst contains 1-50 wt% of VIII group metal, 1-50 wt% of VIB group metal and 1-50 wt% of IVA group nonmetal.

In other embodiments of the disclosure, the group VIII metal content may be 5 wt%, 10 wt%, 15 wt%, or 25 wt%, 30 wt%, calculated as oxide; the group VIB metal content may be 10 wt%, 15 wt%, 20 wt% or 30 wt%, 45 wt%; the content of the group IVA nonmetal may be 15 wt%, 20 wt%, 30 wt%, or 35 wt%, 45 wt%.

In one disclosed embodiment, the catalyst comprises at least one group VIII metal, two group VIB metals, and one group IVA nonmetal, wherein the group VIII metal and group VIB metal are in a molar ratio of 20:1 to 1: 20; the molar ratio of the VIII group metal to the IVA group nonmetal is 20:1 to 1: 1; the molar ratio of the two group VIB metals is 5:1-1: 5.

In other embodiments of the disclosure, the molar ratio of the group VIII metal and the VIB metal may be 10: 5. 10: 15. 15: 5 or 18: 15; the molar ratio of group VIII metal to group IVA nonmetal may be 5: 10. 10: 12. 15: 5. 15: 10 or 20: 5; the molar ratio of the two group VIB metals may be 1: 2. 2: 5 or 5: 2.

in one embodiment of the disclosure, the catalyst is NiSiMoW, i.e., the group VIII metal in the catalyst comprises Ni, the group VIB metal comprises Mo and W, and the group IVA nonmetal comprises Si.

In one embodiment of the disclosure, the group VIII metal comprises Co, the group VIB metal comprises Mo and W, and the group IVA nonmetal comprises Si.

In one embodiment of the present disclosure, the catalyst has a layered porous structure having a specific surface area of 80 to 300m²The pore volume is 0.1-0.5 ml/g. In other embodiments of the disclosure, the specific surface area of the catalyst may be 100-150m²/g、120-180m²/g、150-200m²(g or 200-)²The pore volume may be 0.1-0.3ml/g, 0.25-0.3ml/g or 0.3-0.35 ml/g.

In other embodiments of the present disclosure, a method of preparing a catalyst is provided, the method comprising:

s01: adding at least one soluble salt of VIII group metal into a solvent to prepare a solution A, adding at least one soluble salt of IVA group nonmetal into water to prepare a solution B, and mixing the solution A and the solution B for reaction to obtain a catalyst precursor solution;

s02: adding soluble salts of at least two VIB group metals into a polar solvent to prepare a solution C, and mixing the solution C and the catalyst precursor solution for reaction to obtain the catalyst.

In an embodiment of the present disclosure, S01 specifically includes: adding at least one soluble salt of VIII group metal into a mixed solution of water, an organic solvent and a surfactant to prepare a solution A of soluble salt, dissolving a soluble salt of IVA group nonmetal in water to prepare a solution B, and finally adding the solution B into the solution A containing the at least one soluble salt of VIII group metal to carry out coprecipitation reaction to obtain a catalyst precursor with a layered structure; s02 specifically includes: mixing the slurry of the catalyst precursor with a layered structure with a polar solvent containing soluble salts of at least two VIB group metal anions to carry out an ion exchange reaction, and after the reaction is finished, separating, washing, drying and roasting at 400-500 ℃ for 2-10 hours to obtain the multi-metal bulk catalyst with the layered structure, which contains at least one VIII group metal, one IVA group nonmetal and two VIB group metals.

In one embodiment of the present disclosure, the surfactant in S01 is one or more of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyltrimethylammonium bromide or octadecyltrimethylammonium chloride, PEG-400, PEG-600, PEG-800, PEG-4000, PVA, SA 20.

In one embodiment of the disclosure, the concentration of the group VIII metal ions in the solution A is 0.01-0.3 mol/L, the concentration of the group IVA non-metal ions in the solution B is 0.01-0.3 mol/L, the concentration of the catalyst precursor solution is 0.01-0.9 mol/L, and the concentration of the group VIB metal ions in the solution C is 0.01-0.2 mol/L.

In one embodiment of the disclosure, solution a is reacted with solution B at 20 ℃ to 200 ℃ for 4 to 50 hours, and solution C is reacted with the catalyst precursor solution at 20 ℃ to 200 ℃ for 4 to 50 hours.

In one embodiment of the disclosure, the soluble salt of a group IVA nonmetal comprises one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, the soluble salt of a group VIII metal comprises one or more of nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate, and the soluble salt of a group VIB metal anion comprises one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid or sodium tungstate.

In one embodiment of the present disclosure, the pH of the ion exchange reaction system is 1 to 11, which can be adjusted by an acid, such as nitric acid, or a base, such as aqueous ammonia.

To further illustrate the preparation of the catalysts of the present disclosure, the following examples are given.

Example 1

This example illustrates the preparation of a NiSiMoW catalyst in this disclosure:

a) separately weigh out nickel nitrate (29.08g, Ni therein)²⁺0.1mol), sodium silicate (28.42g, of which SiO is present₃ ^2-0.1mol) were added, and they were dissolved in 200mlAdjusting the pH value to 12 in a mixed solution containing water, an organic solvent and a surfactant, heating to a reaction temperature to form a light green mixed reaction solution, and carrying out reflux reaction on the light green mixed reaction solution at a reaction temperature of 80 ℃ for 25 hours to obtain a light green product; the pale green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiSiO having a layered structure)₃A catalyst precursor); adding the catalyst precursor into 200ml of water to prepare a slurry precursor A;

b) ammonium molybdate (5.4g, wherein Mo) was weighed out separately⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol), dissolving the raw materials in a polar solvent (300ml) to form a solution, heating the solution to the reaction temperature, and continuously stirring to form a colorless transparent solution B; subsequently heating the slurry precursor a prepared in step a) to a reaction temperature; slowly adding the slurry into the colorless transparent solution B to form a light green reaction solution, and carrying out reflux reaction at the reaction temperature of 80 ℃ for 5 hours to obtain light green powder; the pale green powder obtained from the reaction was filtered, washed, and dried at 120 ℃ to obtain a NiSiMoW catalyst (16.0 g). The specific surface area of the catalyst, as determined by low temperature nitrogen adsorption, was 241.7m²The pore volume is 0.19 ml/g.

The catalyst is light green powder, and the molecular expression of the catalyst is NiO SiO measured by XRF₂·MoO₃·WO₃. The catalyst synthesized in this example is represented by NiSiMoW-1. Its precursor NiSiO₃And XRD characterization of the catalyst as shown in FIG. 1, it can be found in NiSiO₃In the spectrum of (a), characteristic peaks of the layered structure were present at 10 °,20 °,26 °,36 ° and 62 °. The characteristic peaks of the catalyst, which are lamellar, remain after further reaction with the Mo and W salts, and some peaks shift from 20 ℃ to 17 ℃, which all well demonstrate the success of the synthesis of NiSiO with a lamellar structure₃Mo and W active metals were also successfully introduced between the layers to form a bulk catalyst with highly dispersed active species. Precursor NiSiO₃The TEM representation result is shown in FIG. 2, and NiSiO3 is seen to have a more obvious layered structure and a plurality of fragmented nanotube structures. SEM characterization of NiSiMoW-1 is shown in FIG. 3, where it can be seen that catalysis was after the introduction of Mo and WThe agent still retains the layered structure well.

Example 2

This example illustrates the preparation of a NiSiMoW bulk catalyst in the present disclosure:

a) separately weigh out nickel nitrate (29.08g, Ni therein)²⁺0.1mol), sodium silicate (28.42g, of which SiO is present₃ ^2-0.1mol), dissolving the raw materials in 200ml of mixed solution containing water, organic solvent and surfactant, adjusting the pH value to 12, heating to the reaction temperature to form light green mixed reaction liquid, and carrying out reflux reaction on the light green mixed reaction liquid at the reaction temperature of 80 ℃ for 25 hours to obtain a light green product; the pale green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiSiO having a layered structure)₃A catalyst precursor); adding the catalyst precursor into 200ml of water to prepare a slurry precursor;

b) ammonium molybdate (10.8g, Mo therein) was weighed out separately⁶⁺0.06mol) and ammonium metatungstate (14.4g, wherein W⁶⁺0.06mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (27.4g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-2, the material morphology of this catalyst being similar to that of the NiSiMoW-1 catalyst. Its ultrahigh hydrodesulfurization activity is shown in FIG. 4. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 206.8m²The pore volume was 0.19 ml/g.

Example 3

b) ammonium molybdate (16.2g, Mo therein) was weighed out separately⁶⁺0.09mol) and ammonium metatungstate (21.6g, wherein W⁶⁺0.09mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (37.2g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-3, the material morphology of this catalyst being similar to that of the NiSiMoW-1 catalyst. Its ultrahigh hydrodesulfurization activity is shown in FIG. 4. The specific surface area of the catalyst was 183.5m as determined by low temperature nitrogen adsorption²The pore volume is 0.19 ml/g.

Example 4

a) separately weighing nickel nitrate (29.08g, Ni therein)²⁺0.1mol), sodium silicate (28.42g, of which SiO is present₃ ^2-0.1mol), dissolving the raw materials in 200ml of mixed solution containing water, organic solvent and surfactant, adjusting the pH value to 12, heating to the reaction temperature to form light green mixed reaction liquid, and carrying out reflux reaction on the light green mixed reaction liquid at the reaction temperature of 80 ℃ for 25 hours to obtain a light green product; the pale green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiSiO having a layered structure)₃A catalyst precursor); adding the catalyst precursor into 200ml of water to prepare a slurry precursor;

b) ammonium molybdate (16.2g, Mo therein)⁶⁺0.09mol) and ammonium metatungstate (14.4g, wherein W⁶⁺0.06mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (29.1g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-4, the material morphology of this catalyst being similar to that of the NiSiMoW-1 catalyst. The hydrodesulfurization activity is shown in FIG. 4. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 174.3m²The pore volume is 0.19 ml/g.

Example 5

b) ammonium molybdate (21.6g, Mo therein) was weighed separately⁶⁺0.12mol) and ammonium metatungstate (14.4g, wherein W⁶⁺0.06mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (37.8g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-5, the material morphology of this catalyst being similar to that of the NiSiMoW-1 catalyst. Its ultrahigh hydrodesulfurization activity is shown in FIG. 4. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 176.6m²The pore volume is 0.19 ml/g.

Example 6

a) separately weigh out nickel nitrate (29.08g, Ni therein)²⁺0.1mol), sodium silicate (28.42g, of which SiO is present₃ ^2-0.1mol), dissolving the raw materials in 200ml of mixed solution containing water, organic solvent and surfactant, adjusting the pH value to 12, heating to the reaction temperature to form light green mixed reaction liquid, and carrying out reflux reaction on the light green mixed reaction liquid at the reaction temperature of 80 ℃ for 25 hours to obtain a light green product; the pale green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiSiO having a layered structure)₃A catalyst precursor); catalyzing thisAdding the agent precursor into 200ml of water to prepare a slurry precursor;

b) ammonium molybdate (7.2g, wherein Mo) was weighed out separately⁶⁺0.045mol) and ammonium metatungstate (10.8g, wherein W is⁶⁺0.045mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶ ⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (20.1g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-2, the material morphology of this catalyst being similar to that of the NiSiMoW-2 catalyst. Its ultrahigh hydrodesulfurization activity is shown in fig. 4. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 210.4m²The pore volume is 0.19 ml/g.

Example 7

This example illustrates the preparation of a NiSiMoW bulk catalyst according to the invention:

b) ammonium molybdate (13.5g, wherein Mo) was weighed out separately⁶⁺0.075mol) and ammonium metatungstate (18.0g, where W is⁶⁺0.075mol) instead of ammonium molybdate (5.4g, in which Mo is present) as used in example 1⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶ ⁺0.03mol) in the same manner as in example 1 a multimetallic bulk catalyst (24.6g) was prepared, the synthesized multimetallic bulk catalyst being denoted by NiSiMoW-7, the material morphology of this catalyst being similar to that of the NiSiMoW-1 catalyst. Its ultrahigh hydrodesulfurization activity is shown in FIG. 4. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 182.1m²The pore volume is 0.19 ml/g.

Example 8

A multimetallic bulk catalyst (15.2g) was prepared in the same manner as described in example 1, except that in step a, a reaction at 100 ℃ for 10 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-a, which is a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 202.1m²The pore volume is 0.17 ml/g.

Example 9

A multimetallic bulk catalyst (15.8g) was prepared in the same manner as described in example 1, except that in step a reaction at 100 ℃ for 25 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-B, which is a pale green powder. The specific surface area of the catalyst, as determined by low temperature nitrogen adsorption, was 213.2m²The pore volume is 0.19 ml/g.

Example 10

A multimetallic bulk catalyst (15.5g) was prepared in the same manner as described in example 1, except that in step a, a reaction at 100 ℃ for 45 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-C, which is a pale green powder. The specific surface area of the catalyst, as determined by low temperature nitrogen adsorption, was 209.2m²The pore volume is 0.18 ml/g.

Example 11

A multimetallic bulk catalyst (16.1g) was prepared in the same manner as described in example 1, except that in step a, a reaction at 150 ℃ for 15 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-D, this Cat-D catalyst being a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 204.2m²The pore volume is 0.19 ml/g.

Example 12

Prepared in the same manner as described in example 1 except that the reaction at 150 ℃ for 25 hours was used in step a instead of the reaction at 80 ℃ for 25 hours used in example 1A multimetallic bulk catalyst (15.9g) was prepared and the synthesized multimetallic bulk catalyst was denoted Cat-E, which was a pale green powder. The specific surface area of the catalyst was 203.0m as measured by low temperature nitrogen adsorption²The pore volume is 0.19 ml/g.

Example 13

A multimetallic bulk catalyst (15.3g) was prepared in the same manner as described in example 1, except that in step a, a reaction at 150 ℃ for 45 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-F, which is a pale green powder. The specific surface area of the catalyst, as determined by low temperature nitrogen adsorption, was 205.7m²The pore volume is 0.19 ml/g.

Example 14

A multimetallic bulk catalyst (15.4G) was prepared in the same manner as described in example 1, except that in step b a reaction at 50 ℃ for 4 hours was used instead of the reaction at 80 ℃ for 5 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-G, which is a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 204.1m²The pore volume is 0.19 ml/g.

Example 15

A multimetallic bulk catalyst (15.2g) was prepared in the same manner as described in example 1, except that in step b, a reaction at 50 ℃ for 10 hours was used instead of the reaction at 80 ℃ for 5 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-H, this Cat-H catalyst being a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 204.5m²The pore volume is 0.18 ml/g.

Example 16

A multimetallic bulk catalyst (15.2g) was prepared in the same manner as described in example 1, except that in step b a reaction at 50 ℃ for 25 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-I, which is a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 202.3m²Per g, pore volume of 0.19ml/g。

Example 17

A multimetallic bulk catalyst (17.1g) was prepared in the same manner as described in example 1, except that in step b a reaction at 50 ℃ for 45 hours was used instead of the reaction at 80 ℃ for 25 hours used in example 1, the synthesized multimetallic bulk catalyst being denoted by Cat-J, which is a pale green powder. The specific surface area of the catalyst, determined by low-temperature nitrogen adsorption, was 210.7m²The pore volume is 0.19 ml/g.

Example 18

This example illustrates the preparation of a NiCoSiMoW bulk catalyst of the invention:

a) separately weighing nickel nitrate (23.264g, wherein Ni is present)²⁺0.08mol), cobalt chloride (4.758g, wherein Co²⁺0.02mol), sodium silicate (28.42g, SiO therein₃ ^2-0.1mol), dissolving the raw materials in 200ml of mixed solution containing water, organic solvent and surfactant, adjusting the pH value to 12, heating to the reaction temperature to form a gray-green mixed reaction solution, and carrying out reflux reaction on the gray-green mixed reaction solution at the reaction temperature of 80 ℃ for 25 hours to obtain a gray-green product; the gray-green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiCoSiO having a layered structure)₃A catalyst precursor); adding the catalyst precursor into 200ml of water to prepare a slurry precursor A;

b) ammonium molybdate (5.4g, wherein Mo) was weighed out separately⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol), dissolving the raw materials in a polar solvent (300ml) to form a solution, heating the solution to the reaction temperature, and continuously stirring to form a colorless transparent solution B; subsequently heating the slurry precursor a prepared in step a) to a reaction temperature; slowly adding the slurry into the colorless transparent solution B to form a gray-green reaction solution, and carrying out reflux reaction on the gray-green reaction solution at the reaction temperature of 80 ℃ for 5 hours to obtain gray-green powder; the grayish green powder obtained by the reaction was filtered, washed, and dried at 120 ℃ to obtain a NiCoSiMoW catalyst (15.8 g). The NiCoSiMoW catalyst synthesized in this example is represented by Cat-K. The specific surface area of the catalyst was 231.7m as determined by low temperature nitrogen adsorption²The pore volume is 0.18 ml/g.

Example 19

This example illustrates the preparation of a NiCoSiMoW bulk catalyst in this disclosure:

a) separately weighing nickel nitrate (17.448g, wherein Ni is present)²⁺0.06mol), cobalt chloride (9.516g, of which Co is present²⁺0.04mol), sodium silicate (28.42g, SiO therein₃ ^2-0.1mol), dissolving the raw materials in 200ml of mixed solution containing water, organic solvent and surfactant, adjusting the pH value to 12, heating to the reaction temperature to form a gray-green mixed reaction solution, and carrying out reflux reaction on the gray-green mixed reaction solution at the reaction temperature of 80 ℃ for 25 hours to obtain a gray-green product; the gray-green product obtained by the reaction was filtered and washed to obtain a catalyst precursor (i.e., NiCoSiO having a layered structure)₃A catalyst precursor); adding the catalyst precursor into 200ml of water to prepare a slurry precursor A;

b) ammonium molybdate (5.4g, wherein Mo) was weighed out separately⁶⁺0.03mol) and ammonium metatungstate (7.2g, wherein W⁶⁺0.03mol), dissolving the raw materials in a polar solvent (300ml) to form a solution, heating the solution to the reaction temperature, and continuously stirring to form a colorless transparent solution B; subsequently heating the slurry precursor a prepared in step a) to a reaction temperature; slowly adding the slurry into the colorless transparent solution B to form a gray-green reaction solution, and carrying out reflux reaction on the gray-green reaction solution at the reaction temperature of 80 ℃ for 5 hours to obtain gray-green powder; the grayish green powder obtained by the reaction was filtered, washed, and dried at 120 ℃ to obtain a NiCoSiMoW catalyst (15.8 g). The NiCoSiMoW catalyst synthesized in this example is represented by Cat-L. The specific surface area of the catalyst was 238.3m as determined by low temperature nitrogen adsorption²The pore volume is 0.18 ml/g.

In another embodiment of the present disclosure, there is provided the use of a catalyst as described above in the hydrodesulfurization of sulfur containing organic compound fuel oil.

In one embodiment of the present disclosure, the hydrodesulfurization reaction conditions of the catalyst prepared in the above embodiment are: the temperature is 250 ℃ and 450 ℃, the hydrogen pressure is 1-20MPa, and the volume ratio of the hydrogen to the sulfur-containing organic compound fuel oil is 50-1500Nm³/m³And sulfur-containing organic compoundsThe volume space velocity of the oil is 0.1-10h^-1。

The catalyst is pretreated before the hydrodesulfurization reaction as follows: a) grinding, kneading and molding; and b) carrying out in-situ presulfurization on the mixed gas of the sulfur-containing compound and hydrogen at the temperature of 250-450 ℃ in a hydrodesulfurization fixed bed reactor; the prevulcanization time is 2-10 hours.

In one embodiment of the present disclosure, the sulfur-containing compound may be hydrogen sulfide, carbon disulfide, or dimethyl disulfide. Evaluation of catalyst Performance in hydrodesulfurization reactions

The performance of the catalyst in hydrodesulfurization reactions, carried out in a fixed bed reactor, was examined with a diesel fraction (4, 6-DMDBT dissolved in decalin solvent) having a sulphur content of 521 ppm. The reaction conditions are as follows: the catalyst mass was 0.5g, the reaction temperature was 300 deg.C, the hydrogen pressure was 3.0MPa, and the ratio of hydrogen to diesel oil fraction was 800Nm³Hydrogen/m³Diesel oil fraction, volume space velocity 9h^-1. For the measurement of the sulfur content in the sample, an ANTEK sulfur determinator was used.

The hydrodesulfurization activity of the catalysts prepared in examples 1 to 7 is shown in fig. 4, and it can be seen that the desulfurization rate of these catalysts can be as high as 97% or more, and the sulfur in the diesel fraction, i.e., 4, 6-dimethyldibenzothiophene, can be removed from 521ppm to 10ppm or less, thereby achieving ultra-deep desulfurization.

The sulfur content of the diesel fractions after hydrodesulfurization over the catalysts prepared in examples 8-19 is given in Table 1.

In the hydrodesulfurization reaction of diesel oil fractions, the desulfurization result of the catalyst prepared by the embodiment of the disclosure shows that the desulfurization effect of all the catalysts is optimal, and the sulfur content in the raw material can be reduced from 521ppm to below 10 ppm.

TABLE 1 comparison of catalyst Performance in hydrodesulfurization reactions

Commercial reference reagent of Table 1The national petrochemical company provides the composition of Co₃O₄·2.2NiO·5.9MoO₃·2WO₃。

The activity of the catalysts prepared in the examples of the present disclosure is expressed as relative activity, i.e., the activity of the reference agent at 200 hours of operation is 100, and the activity obtained by comparing the catalysts of the present invention with the reference agent represents the relative activity of the catalysts of the present invention. The relative desulfurization activity was calculated by the following formula:

relative desulfurization activity of 100 × [ (1/S)_p)^0.65-(1/S_f)^0.65]/[(1/S_pr)^0.65-(1/S_fr)^0.65]

In the formula S_fr、S_prRespectively representing the sulfur concentration, S, of the diesel fraction used as a reference agent and the product obtained after hydrotreating the reference agent_f、S_pRespectively showing the sulfur concentration of the diesel oil fraction used by the catalyst and the product after the hydrogenation treatment by the catalyst.

In summary, the disclosed embodiments synthesize a multi-metal bulk catalyst with a layered structure, which has a higher specific surface area, a higher pore volume and an ultrahigh hydrodesulfurization activity than those of patents and literatures, the catalyst has a layered structure, and active metals are exchanged between layers, the dispersion degree of the active metals is higher, more active centers are displayed, and the catalyst can remove sulfur in a diesel oil fraction containing 4,6-DMDBT from 521ppmw to below 10ppmw through hydrodesulfurization reaction under mild operation conditions, so that the ultra-deep desulfurization is realized, and the catalyst shows a great industrial application potential.

Claims

1. A desulfurization catalyst characterized by: mixed metal oxides comprising at least one group VIII metal, at least two group VIB metals, and a group IVA nonmetal;

2. The catalyst of claim 1, wherein the catalyst comprises at least one group VIII metal, two group VIB metals, and one group IVA nonmetal, and the molar ratio of the group VIII metal to the group VIB metal is from 20:1 to 1: 20; the molar ratio of the group VIII metal to the group IVA nonmetal is 20:1 to 1: 1; the molar ratio of the two group VIB metals is 5:1-1: 5.

3. The catalyst of claim 1 wherein the group VIII metal comprises Ni or Co; the group VIB metal comprises Mo and W; the group IVA nonmetal comprises Si.

4. The catalyst according to claim 1, wherein the catalyst has a layered porous structure having a specific surface area of 80 to 300m²The pore volume is 0.1-0.5 ml/g.

5. A method for preparing a desulfurization catalyst, comprising:

6. The method according to claim 5, wherein the concentration of the group VIII metal ions in the solution A is 0.01-0.3 mol/L, the concentration of the group IVA non-metal ions in the solution B is 0.01-0.3 mol/L, the concentration of the catalyst precursor solution is 0.01-0.9 mol/L, and the concentration of the group VIB metal ions in the solution C is 0.01-0.2 mol/L.

7. The method of claim 5, wherein said solution A is reacted with said solution B at 20-200 ℃ for 4-50 hours, and said solution C is reacted with said catalyst precursor solution at 20-200 ℃ for 4-50 hours.

8. The method of claim 5, wherein the soluble salt of the group IVA nonmetal comprises one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, the soluble salt of the group VIII metal comprises one or more of nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate or cobalt acetate, and the soluble salt of the group VIB metal anion comprises one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid or sodium tungstate.

9. Use of a catalyst according to any one of claims 1 to 4 in the hydrodesulphurisation of sulphur containing organic compound fuels.

10. The use according to claim 9, characterized in that the hydrodesulfurization reaction conditions are: the temperature is 250 ℃ and 450 ℃, the hydrogen pressure is 1-20MPa, and the volume ratio of the hydrogen to the sulfur-containing organic compound fuel oil is 50-1500Nm³/m³(ii) a The volume space velocity of the sulfur-containing organic compound fuel oil is 0.1-10h^-1。