CN110935460B - High-selectivity hydrodesulfurization catalyst and preparation method thereof - Google Patents
High-selectivity hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a high-selectivity hydrodesulfurization catalyst, which consists of a carrier and an active component, wherein the carrier is potassium-containing mesoporous TiO 2 Wherein the carrier is mesoporous TiO with controllable potassium content obtained after the titanic acid is firstly obtained by twice ion exchange of potassium dititanate 2 The potassium content is 1-10 wt%; the active components are molybdenum and nickel, and the molybdenum and the nickel are respectively MoO 3 And NiO accounts for 5-35 wt% and 1.56-7.8 wt% of the catalyst respectively. Compared with the prior art, the hydrodesulfurization catalyst has high reaction selectivity, mainly removes sulfur in sulfur-containing species in a direct desulfurization mode, and can reduce the hydrogen consumption in the desulfurization process. The invention also discloses a preparation method of the high-selectivity hydrodesulfurization catalyst.
Description
Technical Field
The invention relates to the field of hydrodesulfurization catalysts, in particular to a high-selectivity hydrodesulfurization catalyst for light distillate oil and a preparation method thereof.
Background
As is well known, air pollution is a troublesome problem in today's society, and the emission of automobile exhaust is one of the important causes of air pollution. In recent years, to improve air quality and protect natural environment, the requirements of China on the composition of oil products are increasingly strict, especially on the content of sulfur. Beijing and the like have implemented the standard of Beijing VI at present, namely the sulfur content is less than 10 mu g/g.
The performance of hydrodesulfurization catalysts plays a critical role in desulfurization processes. Conventional hydrodesulfurization catalysts, while effective in desulfurization, can result in substantial saturation of the olefin and a substantial loss of octane number. To solve this problem, the development of catalysts having low olefin saturation and high desulfurization has become a focus of attention.
Currently, the main research contents in the research field include three aspects of screening active components, auxiliary agents and carriers.
In terms of active components, the transition metal elements are common hydrodesulfurization catalyst active components in industrial production, such as Mo, W, ni, co and the like. Almost all catalysts have active components composed of combinations of the above-mentioned metal elements, and binary active components, such as Ni Mo, ni W, co Mo systems, are commonly used. Wherein, the Co Mo binary component not only has higher desulfurization activity, but also has lower olefin saturation activity.
In terms of catalyst support, suitable supports can increase the dispersion of the active components and the auxiliary agents, thereby increasing the catalytic efficiency. Patents US4203829A and US4132632A both use MgO as a carrier, and the introduction of MgO can reduce the amount of active components, which is beneficial to improving the selectivity of hydrodesulfurization reaction, but the carrier is MgO, which deteriorates the mechanical strength of the catalyst and makes it difficult to meet the industrial requirements of hydrodesulfurization reaction.
In addition to the selection of suitable active components and carriers, the addition of auxiliaries also has a considerable effect on the improvement of the selectivity of the catalysts. US5525211A and US5423976A use MgAl 2 O 4 Or active carbon as carrier, alkali metal, alkali earth metal,Lanthanide rare earth metals, group IIIB metals, or compounds thereof are added to the catalyst as promoters, which can improve hydrodesulfurization selectivity. However, the catalyst has a major problem in that the stability of the reaction is poor, the selectivity decreases rapidly with the increase of the reaction time, and the industrial application is greatly limited.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a high selectivity hydrodesulfurization catalyst and a preparation method thereof, wherein the catalyst has high hydrogenation selectivity, can achieve low olefin saturation rate and high desulfurization rate, and can reduce the octane number loss of light distillate oil, especially gasoline fraction, when the catalyst is used for hydrodesulfurization of light distillate oil, especially gasoline fraction.
Therefore, the invention provides a high-selectivity hydrodesulfurization catalyst, which consists of a carrier and an active component, wherein the carrier is potassium-containing mesoporous TiO 2 Wherein the carrier is mesoporous TiO with controllable potassium content obtained after the titanic acid is firstly obtained by twice ion exchange of potassium dititanate 2 The potassium content is 1-10 wt%; the active components are molybdenum and nickel, and the molybdenum and the nickel are respectively MoO 3 And NiO accounts for 5-35 wt% and 1.56-7.8 wt% of the catalyst respectively.
The high-selectivity hydrodesulfurization catalyst provided by the invention is prepared from potassium-containing mesoporous TiO 2 Preferably anatase, and the specific surface area is preferably 30-130 m 2 The pore volume is preferably 0.1-0.4 cm/g 3 The average pore diameter is preferably from 8 to 23 nm/g.
The high-selectivity hydrodesulfurization catalyst provided by the invention is characterized in that the two ion exchange steps are preferably as follows:
(1) Dropwise adding deionized water into the potassium dititanate, continuously stirring, sealing and storing, and standing for 7-10 days to obtain a sample;
(2) Dispersing the sample into excessive water, ensuring that the solid-to-liquid ratio is 1-1;
(3) Immersing the dried titanic acid into KOH solution for the second ion exchange reaction, standing for 2-24 h with the solution concentration of 5-30 wt%, filtering, drying and roasting to obtain the potassium-containing mesoporous TiO 2 。
The highly selective hydrodesulfurization catalyst provided by the invention is characterized in that the acid used in the first ion exchange is preferably one or more selected from hydrochloric acid, nitric acid and acetic acid.
In the highly selective hydrodesulfurization catalyst according to the present invention, in the step (2), the pH of the solution is preferably maintained between 1 and 7, and more preferably between 4 and 6.
In the highly selective hydrodesulfurization catalyst of the present invention, in the step (3), the calcination conditions are preferably: roasting at 350-700 deg.c for 1-8 hr.
The preparation method of the high-selectivity hydrodesulfurization catalyst provided by the invention is characterized in that the roasting temperature is preferably 350-500 ℃, and the roasting time is preferably 1-2 h.
The invention also provides a preparation method of the high-selectivity hydrodesulfurization catalyst, which is the preparation method of the catalyst and comprises the following steps:
s1, taking potassium dititanate as a raw material, and obtaining potassium-containing mesoporous TiO after twice ion exchange, washing, drying and roasting 2 ；
S2, preparing the potassium-containing mesoporous TiO 2 Adding the catalyst into the impregnation solution to load active components by an impregnation method, and drying and roasting at high temperature to obtain the final hydrodesulfurization catalyst.
In the preparation method of the high-selectivity hydrodesulfurization catalyst, in step S2, the solutes of the impregnation solution are preferably ammonium molybdate and nickel nitrate.
In the preparation method of the high-selectivity hydrodesulfurization catalyst, in step S2, the calcination temperature is preferably 450 to 600 ℃.
The preparation of the potassium dititanate of the invention can refer to Chinese patent application CN03158274.5
The second embodiment: mixing amorphous titanium dioxide, potassium nitrate and H 2 O is mixed homogeneously, wherein TiO 2 /K 2 O =3 (mol ratio); (2) the mixed reaction materials are evenly coated on an alumina backing plate, the reaction temperature is 810 ℃, the reaction time is 1 hour, and the sintered product is potassium dititanate.
The process of the invention can be described in particular as follows:
s1, taking potassium dititanate as a raw material, dropwise adding deionized water into the potassium dititanate, continuously stirring, sealing and storing, and standing for 7 days to obtain a sample;
dispersing the sample into excessive water, ensuring that the solid-to-liquid ratio is 1-1;
immersing the dried titanic acid into KOH solution for the second ion exchange reaction, the concentration of the solution is 5-30 wt%, standing for 2-24 h, filtering, drying, roasting at 350-500 ℃ for 2h to obtain the potassium-containing mesoporous TiO 2 。
S2, preparing the mesoporous TiO containing potassium 2 Adding the active component into an impregnation solution consisting of ammonium molybdate and nickel nitrate, loading the active component by an impregnation method, drying, and roasting at the high temperature of 450-600 ℃ to obtain the final hydrodesulfurization catalyst.
The catalyst prepared by the invention has the advantages that:
(1) The preparation method is simple to operate, does not need complex process flow and equipment, uses low-price raw materials and is beneficial to industrial production;
(2) The catalyst is prepared by adding exogenous potassium to carry out secondary ion exchange in the process of controlling the preparation of a carrier, namely, the carrier is prepared by carrying out first ion exchange on potassium dititanate to obtain dititanic acid, and then carrying out secondary ion exchange sintering on the dititanic acid and KOH solution to obtain mesoporous TiO with controllable potassium content 2 The method can quantitatively regulate the potassium content and the active component loading in the carrier, and has good desulfurization effect and obvious reaction selectivity under mild hydrogenation conditions.
(3) Can improve the selectivity of the hydrodesulfurization catalyst, and the preparation method gives full play to the mesoporous TiO of the active carrier 2 The method has the advantages that the content of K in the carrier is controlled in the preparation process, so that the selectivity of the hydrodesulfurization catalyst is improved, sulfur in sulfur-containing species is removed mainly in a direct desulfurization mode, and the hydrogen consumption in the desulfurization process can be reduced. The method has the advantages of low cost and simple process, and is suitable for large-scale industrial production.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The hydrodesulfurization catalyst comprises a carrier and an active component, wherein the carrier is potassium-containing mesoporous TiO 2 Wherein the carrier is mesoporous TiO with controllable potassium content obtained by firstly obtaining titanic acid through twice ion exchange by potassium dititanate 2 The potassium content is 1-10 wt%; the active components are molybdenum and nickel, and the molybdenum and the nickel are respectively MoO 3 And NiO accounts for 5-35 wt% and 1.56-7.8 wt% of the catalyst respectively.
Wherein the potassium-containing mesoporous TiO 2 The crystal form of (A) is anatase, and the specific surface area is 30-130 m 2 Per gram, pore volume of 0.1-0.4 cm 3 (ii)/g, the average pore diameter is 8-23 nm.
The preparation method of the high-selectivity hydrodesulfurization catalyst is the preparation method of the catalyst, and comprises the following steps:
s1, taking potassium dititanate as a raw material, and obtaining potassium-containing mesoporous TiO after twice ion exchange, washing, drying and roasting 2 ；
S2, preparing the potassium-containing mesoporous TiO 2 Adding the obtained product into an impregnation solution to load active components by an impregnation method, and drying and roasting at high temperature to obtain the final hydrodesulfurization catalyst.
Wherein the two ion exchanges comprise the following steps:
(1) Dripping deionized water into the potassium dititanate, continuously stirring, sealing, storing, and standing for 7-10 days to obtain a sample;
(2) Dispersing the sample into excessive water to enable the solid-liquid ratio to be 1-1;
(3) Immersing the dried titanic acid into KOH solution for the second ion exchange reaction, the concentration of the solution is 5-30 wt%, standing for 2-24 h, filtering, drying, and roasting to obtain the potassium-containing mesoporous TiO 2 。
Wherein, the acid used in the first ion exchange is selected from one or more of hydrochloric acid, nitric acid and acetic acid;
in the step S1, the roasting temperature is preferably 350-700 ℃, and the time is preferably 1-8 h; in the step S2, the solutes of the impregnation solution are preferably ammonium molybdate and nickel nitrate, and the roasting temperature is preferably 450-600 ℃; in the step (3), the roasting conditions are preferably as follows: roasting for 1-8 h at 350-700 ℃.
The preparation of the potassium dititanate of the invention can refer to Chinese patent application CN03158274.5
Example two: mixing amorphous titanium dioxide, potassium nitrate and H 2 O is mixed homogeneously, wherein TiO 2 /K 2 O =3 (mol ratio); (2) uniformly coating the mixed reaction materials on an alumina backing plate, wherein the reaction temperature is 810 ℃, the reaction time is 1 hour, and the sintered product is potassium dititanate.
Example 1
Mesoporous TiO containing potassium 2 Preparation of the supportThe method comprises the following three steps: k is 2 Ti 2 O 5 Preparation, ion exchange and high-temperature roasting.
K 2 Ti 2 O 5 Preparation of
Mixing amorphous titanium dioxide, potassium nitrate and H 2 O is mixed homogeneously, wherein TiO 2 /K 2 O =3 (molar ratio); (2) uniformly coating the mixed reaction materials on an alumina backing plate, wherein the reaction temperature is 810 ℃, the reaction time is 1 hour, and the sintered product is potassium dititanate (K) 2 Ti 2 O 5 ). To K 2 Ti 2 O 5 Deionized water is added into the powder to ensure that no excessive free water exists in the process, and the powder is placed into a sealing system for standing for 7 to 10 days after the powder is pasty.
Ion exchange
In the first ion exchange process, the sample is dispersed in water (solid-to-liquid ratio is 1 to 500), a dilute nitric acid solution is slowly added dropwise to the system to maintain the pH at 1, the mixture is vigorously stirred for 24 hours, then the mixture is settled, filtered, the solvent is replaced, and the process is repeated for 3 to 5 times while maintaining the solid-to-liquid ratio at 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 )。
The dried titanic acid obtained under these conditions was further immersed in an excess 5wt% KOH aqueous solution for the second ion exchange, allowed to stand for 8 hours, and then filtered off to remove the solution and dried again to obtain a calcined precursor.
High temperature roasting
Roasting the roasting precursor at 500 ℃ for 2h to obtain the potassium-containing mesoporous TiO with the potassium content of 1.1wt% 2 A material.
The support material prepared as described above is impregnated with MoO as oxide 3 Preparing MoNi/TiO in 50% ammonium molybdate and nickel nitrate mixed aqueous solution with the mass ratio of NiO being 3 2 Catalyst of which MoO 3 The loading of NiO is 5wt% and 1.56wt% of the catalyst respectively.
The structural parameters of the catalyst are shown in Table 2.
At temperatureAt 200 ℃, the hydrogen partial pressure is 2MPa, and the mass space velocity is 2h -1 The hydrodesulfurization performance was evaluated under the conditions of a hydrogen-oil ratio of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 2
K is carried out as described in example 1 2 Ti 2 O 5 The preparation of (1) was carried out by dispersing the obtained sample in water (solid-to-liquid ratio: 1: 300), slowly adding a dilute hydrochloric acid solution dropwise to the system to maintain the pH at 2, vigorously stirring for 24 hours, then precipitating, suction-filtering and replacing the solvent, maintaining the solid-to-liquid ratio at 1:300, and repeating the procedure 3 to 5 times. After the first ion exchange process, the precipitate is collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess of 30% KOH aqueous solution for a second ion exchange, allowed to stand for 2 hours, and then filtered off to remove the solution and dried again to obtain a calcined precursor. Roasting the roasting precursor at 350 ℃ for 2h to obtain mesoporous TiO with the potassium content of 6.2wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 Preparing MoNi/TiO in 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO being 7 2 Catalyst of which MoO 3 The loading amounts of NiO are respectively 11wt% and 1.56wt% of the mass of the catalyst.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the hydrodesulfurization performance was evaluated under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 3
K is carried out as described in example 1 2 Ti 2 O 5 The preparation of (1) was carried out by dispersing the obtained sample in an aqueous solution at a solid-to-liquid ratio of 1The process is carried out for 3-5 times. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess of a 10wt% KOH aqueous solution to perform a second ion exchange, allowed to stand for 5 hours, and then filtered off to obtain a solution, which was dried again to obtain a calcined precursor. Roasting the roasting precursor at 700 ℃ for 2h to obtain mesoporous TiO with the potassium content of 2.6wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 Preparing MoNi/TiO from 50% ammonium molybdate and nickel nitrate mixed solution with mass ratio of NiO being 13 2 Catalyst of which MoO 3 The loading of NiO is respectively 20wt% and 1.56wt% of the mass of the catalyst.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the hydrodesulfurization performance was evaluated under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 4
K was carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). Immersing the dried titanic acid obtained under the conditions in an excessive amount of aqueous solution of 20% KOH for a second ion exchange, standing for 24 hours, and then filtering off the solution to obtain a calcined precursor, followed by drying again. Roasting the roasting precursor at 500 ℃ for 2h to obtain mesoporous TiO with the potassium content of 6.6% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 Preparing MoNi/TiO from 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 4.5 2 Catalyst of which MoO 3 The supported amount of NiO was 35wt% and 7.8wt% based on the weight of the catalyst, respectively.
The various structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 And hydrogen-oil ratio: the hydrodesulfurization performance was evaluated under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 5
K was carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess of 10% KOH aqueous solution for the second ion exchange, allowed to stand for 2 hours, and then filtered off to remove the solution and dried again to obtain a calcined precursor. Roasting the roasting precursor at 550 ℃ for 2h to obtain mesoporous TiO with the potassium content of 3.0wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 The MoNi/TiO is prepared from 50 percent ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 4.5 2 Catalyst of which MoO 3 The supported amount of NiO was 25wt% and 5.5wt% based on the weight of the catalyst, respectively.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the above was subjected to evaluation of hydrodesulfurization performance under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 6
K was carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess of a 10wt% KOH aqueous solution to perform a second ion exchange, allowed to stand for 2 hours, and then filtered off to obtain a solution, which was dried again to obtain a calcined precursor. Roasting the roasted precursor at 450 ℃ for 2h to obtain mesoporous TiO with the potassium content of 3.1% 2 A material.
The support material prepared as described above is impregnated with MoO as oxide 3 Preparing MoNi/TiO from 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 3 2 Catalyst of which MoO 3 The supported amount of NiO was 5wt% and 1.56wt% based on the weight of the catalyst, respectively.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the above was subjected to evaluation of hydrodesulfurization performance under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 7
K is carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate is collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions is re-immersed in excess25wt% of KOH aqueous solution, performing a second ion exchange, standing for 6h, filtering off the solution, and drying again to obtain a calcined precursor. Roasting the roasting precursor at 500 ℃ for 2h to obtain mesoporous TiO with the potassium content of 6.8wt% 2 A material.
The support material prepared as described above is impregnated with MoO as oxide 3 Preparing MoNi/TiO from 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 3 2 Catalyst of which MoO 3 The supported amount of NiO was 11wt% and 3.5wt% based on the weight of the catalyst, respectively.
The various structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the above was subjected to evaluation of hydrodesulfurization performance under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 8
K was carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess 5wt% KOH aqueous solution for the second ion exchange, allowed to stand for 24 hours, and then filtered off from the solution to obtain a dried product, which was dried again to obtain a calcined precursor. Roasting the roasting precursor at 500 ℃ for 2h to obtain mesoporous TiO with the potassium content of 3.5wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 The MoNi/TiO is prepared from 50 percent ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 7 2 Catalyst of which MoO 3 The loading amounts of NiO are respectively 11wt% and 1.56wt% of the mass of the catalyst.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the hydrodesulfurization performance was evaluated under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 9
K was carried out as described in example 1 2 Ti 2 O 5 Dispersing the obtained sample into an aqueous solution, wherein the solid-to-liquid ratio is 1. After the first ion exchange process, the precipitate was collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). The dried titanic acid obtained under these conditions was further immersed in an excess 5wt% KOH aqueous solution for the second ion exchange, allowed to stand for 10 hours, and then filtered off to remove the solution and dried again to obtain a calcined precursor. Roasting the roasting precursor at 500 ℃ for 2h to obtain mesoporous TiO with the potassium content of 2.4wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 Preparing MoNi/TiO from 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO of 3 2 Catalyst of which MoO 3 The supported amount of NiO was 5wt% and 1.56wt% based on the weight of the catalyst, respectively.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the hydrodesulfurization performance was evaluated under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
Example 10
K was carried out as described in example 1 2 Ti 2 O 5 The obtained sample was dispersed in an aqueous solution at a solid-to-liquid ratio of 1:400, and an acetic acid solution was slowly added dropwise to the system to maintain the pH at a value of 110, after stirring vigorously for 24 hours, settling, filtering, replacing the solvent, keeping the solid-liquid ratio at 1. After the first ion exchange process, the precipitate is collected by filtration, washed with a large amount of water, and dried at 70 ℃ to obtain titanic acid (H) 2 Ti 2 O 5 ). Immersing the dried titanic acid obtained under the conditions in an excessive amount of 30wt% KOH aqueous solution again for a second ion exchange, standing for 20 hours, and then filtering off the solution to obtain a dried product again, to obtain a calcined precursor. Roasting the roasting precursor at 450 ℃ for 2h to obtain mesoporous TiO with the potassium content of 10.0wt% 2 A material.
The support material prepared as described above is impregnated with MoO as an oxide 3 Carrying out second ion exchange in a 50% ammonium molybdate and nickel nitrate mixed solution with the mass ratio of NiO being 4.5 2 Catalyst of which MoO 3 The loading amounts of NiO are respectively 20wt% and 4.5wt% of the catalyst mass.
The structural parameters of the catalyst are shown in Table 2.
At a temperature of 200 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: the above was subjected to evaluation of hydrodesulfurization performance under the conditions of 200. The desulfurization rate and hydrodesulfurization selectivity of the catalyst are shown in Table 3.
TABLE 2 structural parameters of the catalyst
TABLE 3 catalyst hydrodesulfurization Performance parameters
Comparative example 1
The existing selective hydrodesulfurization catalyst for light distillate oil (see CN201010252648. X) adopts a complex precipitation method to prepare a composite carrier. Adding potassium salt, sesbania powder and deionized water into the composite carrier, uniformly stirring, extruding and forming at 100-150 DEG CDrying and roasting at 450-550 ℃ to obtain ZrO 2 -Al 2 O 3 Composite catalyst support of which ZrO 2 Is 0.1-20% of the composite carrier. Preparing stable Co-Mo Co-immersion liquid containing phosphorus and magnesium, and preparing the catalyst by adopting an isometric spraying immersion method.
Evaluation of catalyst
At a temperature of 250 ℃, a hydrogen partial pressure of 2MPa, a mass space velocity: 2h -1 The hydrogen-oil ratio: 300, the desulfurization selectivity was 67% when the desulfurization rate of the catalyst was 85%.
As can be seen from the comparison of examples 1-10 with comparative example 1 above, the advantages of the catalyst prepared according to the present invention are:
(1) The preparation method is simple to operate, does not need complex process flow and equipment, uses low-price raw materials and is beneficial to industrial production;
(2) The catalyst is added with exogenous potassium to carry out secondary ion exchange by controlling the preparation process of the carrier, namely the carrier is prepared by carrying out first ion exchange on potassium dititanate to obtain titanic acid, and then carrying out second ion exchange sintering on the titanic acid and KOH solution to obtain mesoporous TiO with controllable potassium content 2 The content of potassium in the carrier and the loading of active components can be quantitatively regulated, and the catalyst has a good desulfurization effect and can show obvious reaction selectivity under mild hydrogenation conditions.
(3) Can improve the selectivity of the hydrodesulfurization catalyst, and the preparation method gives full play to the mesoporous TiO of the active carrier 2 The method has the advantages that the content of K in the carrier is controlled in the preparation process, so that the selectivity of the hydrodesulfurization catalyst is improved. The method has the advantages of low cost and simple process, and is suitable for large-scale industrial production.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. High selectionThe hydrodesulfurization catalyst is characterized by comprising a carrier and an active component, wherein the carrier is potassium-containing mesoporous TiO 2 Wherein the carrier is mesoporous TiO with controllable potassium content obtained after the titanic acid is firstly obtained by twice ion exchange of potassium dititanate 2 The potassium content is 1-10 wt%; the active components are molybdenum and nickel, and the molybdenum and the nickel are respectively MoO 3 And NiO accounts for 5-35 wt% and 1.56-7.8 wt% of the catalyst respectively.
2. The highly selective hydrodesulfurization catalyst of claim 1 wherein the mesoporous TiO containing potassium is 2 The crystal form of (A) is anatase, and the specific surface area is 30-130 m 2 Per g, pore volume of 0.1-0.4 cm 3 (ii)/g, the average pore diameter is 8-23 nm.
3. The highly selective hydrodesulfurization catalyst of claim 1 wherein the two ion exchange steps are:
(1) Dripping deionized water into the potassium dititanate, continuously stirring, sealing, storing, and standing for 7-10 days to obtain a sample;
(2) Dispersing the sample into excessive water to enable the solid-liquid ratio to be 1-1;
(3) Immersing the dried titanic acid into KOH solution for the second ion exchange reaction, standing for 2-24 h with the solution concentration of 5-30 wt%, filtering, drying and roasting to obtain the potassium-containing mesoporous TiO 2 。
4. The high-selectivity hydrodesulfurization catalyst according to claim 3, wherein the acid used in the first ion exchange is one or more selected from hydrochloric acid, nitric acid and acetic acid.
5. The highly selective hydrodesulfurization catalyst of claim 3 wherein in step (2) the solution pH is maintained between 1 and 7.
6. The highly selective hydrodesulfurization catalyst of claim 3, wherein in step (3), the calcination conditions are: roasting at 350-700 deg.c for 1-8 hr.
7. The highly selective hydrodesulfurization catalyst of claim 6 wherein the calcination is carried out at a temperature of 350-500 ℃ for a period of 1-2 hours.
8. A method for preparing a highly selective hydrodesulfurization catalyst, which is the method for preparing the catalyst according to any one of claims 1 to 7, comprising the steps of:
s1, taking potassium dititanate as a raw material, and obtaining potassium-containing mesoporous TiO after twice ion exchange, washing, drying and roasting 2 ；
S2, preparing the potassium-containing mesoporous TiO 2 Adding the catalyst into the impregnation solution to load active components by an impregnation method, and drying and roasting at high temperature to obtain the final hydrodesulfurization catalyst.
9. The method for preparing a highly selective hydrodesulfurization catalyst according to claim 8, wherein the solutes of the impregnation solution in step S2 are ammonium molybdate and nickel nitrate.
10. The method for preparing a highly selective hydrodesulfurization catalyst according to claim 8, wherein the calcination temperature in step S2 is 450 to 600 ℃.
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