A nickel-based adsorbent and its preparation method and application

Abstract

The present invention relates to a nickel-based adsorbent, a preparation method and application thereof, wherein the nickel-based adsorbent comprises a porous skeleton material and a loaded adsorbent material filled inside the porous skeleton material; the loaded adsorbent material comprises a composite carrier, an active component and an auxiliary agent, and the active component and the auxiliary agent are both loaded on the composite carrier; the active component comprises nickel, cobalt and copper; the composite carrier comprises any one of silicon oxide, zirconium oxide or niobium oxide, or a combination of at least two thereof. The preparation method provided by the present invention first mixes a mixture solution containing nickel salt, cobalt salt and copper salt, ammonia water and a composite carrier to prepare an ammonia complex solution, and sequentially evaporates ammonia and dries the ammonia complex solution to obtain a nickel-based adsorbent precursor; then, the nickel-based adsorbent is prepared from the nickel-based adsorbent precursor, the skeleton material, a pore-forming agent, water and auxiliary salt. The nickel-based adsorbent provided by the present invention has an excellent effect on removing thiophene from benzene and has good adsorption stability.

Description

Technical Field

[0001] The present invention relates to the field of chemical industry, and in particular to a nickel-based adsorbent and a preparation method and application thereof. Background Art

[0002] Benzene is an important basic organic chemical raw material, and many of its downstream derivatives are widely used in industries such as polymers, pharmaceuticals, and military. However, benzene raw materials often contain certain impurities, particularly sulfur compounds. Sulfur compounds can be divided into two categories: active and inactive. Elemental sulfur, hydrogen sulfide, and mercaptans are active sulfur compounds. Their active chemical properties make them easily bound to adsorbents and removed from benzene. Thiophenes, on the other hand, are inactive sulfur compounds. Their complex molecular structure and similar physical and chemical properties to benzene make their removal particularly difficult. Therefore, the presence of thiophene sulfur compounds significantly limits the scope of benzene's use.

[0003] The process for producing cyclohexene using partial hydrogenation of benzene as a raw material is a green, environmentally friendly, and pollution-free technology currently being refined. This process uses benzene as the raw material and proceeds through steps such as partial hydrogenation of benzene to produce cyclohexene, hydration of cyclohexanol to produce cyclohexanol, and oxidation of cyclohexanol with nitric acid, ultimately producing adipic acid. However, when partially hydrogenating benzene to produce cyclohexene over a ruthenium adsorbent, trace amounts of thiophene can severely reduce the activity, selectivity, and lifespan of the ruthenium adsorbent, leading to permanent deactivation of the precious metal ruthenium catalyst. Consequently, stricter requirements are placed on the thiophene content in benzene, generally requiring it to be controlled at no more than 10 ppb.

[0004] CN106732323A discloses a nickel-based adsorbent for deep dethiophening of benzene, and its preparation method and application. The nickel-based adsorbent comprises nickel, aluminum, and an optional auxiliary agent; wherein, based on the weight percentage of the nickel-based adsorbent, the nickel content is 40-80% by weight, the aluminum content is 20-60% by weight, and the content of the auxiliary agent is 0-10% by weight; the auxiliary agent is selected from one or more elements selected from Pd, Ru, Ag, Cu, Zn, Fe, Mn, and Mo. However, the catalyst disclosed therein is a Raney nickel-type catalyst with nickel as the active site. It is not only expensive, but also has high energy consumption in the preparation process, generates a large amount of wastewater during the activation process, and is easily oxidized and ignited when exposed to air, which is dangerous.

[0005] Therefore, how to efficiently and stably remove sulfur-containing compounds such as thiophene from raw benzene while reducing the cost of industrial adsorbents is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0006] In response to the above problems, the purpose of the present invention is to provide a nickel-based adsorbent, a preparation method and application thereof. Compared with the prior art, the nickel-based adsorbent and the preparation method thereof provided by the present invention can significantly improve the effective sulfur capacity of the adsorbent, have a strong thiophene adsorption capacity, can purify raw material benzene with a high thiophene content, can carry out a dethiophene reaction at room temperature, and have low cost, simple process, and can be industrially applied.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a nickel-based adsorbent, which includes a porous skeleton material and a loaded adsorbent material filled inside the porous skeleton material; the loaded adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent; the nickel-based adsorbent precursor includes a composite carrier and an active component loaded on the composite carrier; the auxiliary agent is loaded on the composite carrier; the active component includes nickel, cobalt and copper; the composite carrier includes any one of silicon dioxide, zirconium dioxide or niobium pentoxide, or a combination of at least two of them.

[0009] In the present invention, the porous framework material can increase the contact area with the reactants; at the same time, the composite support, active composition, and auxiliary agent in the nickel-based adsorbent precursor cooperate with each other and work synergistically to achieve a good adsorption effect. Specifically, the use of three non-precious metal active components, nickel, cobalt, and copper, enhances the physical and chemical adsorption capacity for thiophene, enabling the purification of raw benzene with a high thiophene concentration. At the same time, the effective sulfur capacity of the adsorbent is also greatly improved, and the dethiophene reaction can be carried out at lower temperatures, even at room temperature, which helps to reduce the process difficulty and achieve industrial application. The use of a composite support of silicon oxide, zirconium oxide, and niobium oxide can increase acid sites, further promote the adsorption of thiophene by the adsorbent, and enhance the diffusion of thiophene in the benzene raw material on the adsorbent, thereby further increasing the adsorption activity.

[0010] In the present invention, the "normal temperature" generally refers to 10-40°C.

[0011] Preferably, the raw materials for preparing the active component include a mixture of nickel salt, cobalt salt and copper salt.

[0012] Preferably, the nickel salt comprises any one or a combination of at least two of nickel nitrate, nickel sulfate, nickel chloride, nickel oxalate or nickel acetate, wherein typical but non-limiting combinations include a combination of nickel nitrate and nickel sulfate or a combination of nickel sulfate and nickel chloride.

[0013] Preferably, the cobalt salt comprises any one or a combination of at least two of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt oxalate or cobalt acetate, wherein typical but non-limiting combinations include a combination of cobalt nitrate and cobalt sulfate or a combination of cobalt chloride and cobalt oxalate.

[0014] Preferably, the copper salt comprises any one or a combination of at least two of copper nitrate, copper sulfate, copper chloride, copper oxalate or copper acetate, wherein typical but non-limiting combinations include a combination of copper nitrate and copper sulfate or a combination of copper chloride and copper oxalate.

[0015] Preferably, the porous framework material comprises an alumina framework.

[0016] Preferably, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent.

[0017] Preferably, the skeleton material comprises any one or a combination of at least two of silicon-free boehmite, low-silicon boehmite, high-silicon boehmite, pseudo-boehmite, hydrotalcite, montmorillonite or kaolin, wherein typical but non-limiting combinations include a combination of silicon-free boehmite and low-silicon boehmite or a combination of high-silicon boehmite and pseudo-boehmite.

[0018] Preferably, the pore-forming agent comprises any one of starch, dextrin or sesbania powder or a combination of at least two of them, wherein typical but non-limiting combinations include a combination of starch and dextrin or a combination of dextrin and sesbania powder.

[0019] Preferably, the mass of the skeleton material is 5-40% of the mass of the nickel-based adsorbent precursor, for example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] Preferably, the mass of the pore-forming agent is 1-10% of the mass of the nickel-based adsorbent precursor, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] Preferably, the auxiliary agent includes gallium trioxide and bismuth trioxide; the raw materials for preparing the auxiliary agent include gallium salt and bismuth salt; the active components and auxiliary agents are loaded on a composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5.

[0022] In the present invention, gallium trioxide and bismuth trioxide are used as composite additives, which can make the adsorbed active sites more stable and the active nickel microcrystal particles are not easy to aggregate and grow, thereby increasing the desulfurization activity of the adsorbent and ensuring the stability of the adsorbent activity.

[0023] Preferably, the gallium salt is gallium nitrate, and the bismuth salt is bismuth nitrate.

[0024] Preferably, the supported adsorption material comprises, by mass percentage:

[0025] The mass percentage of nickel is 30-70%, for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 40-60%.

[0026] The mass percentage of cobalt is 0.5-10%, for example, it can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 1-6%.

[0027] The mass percentage of copper is 0.5-10%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 1-6%.

[0028] The mass percentage of gallium trioxide is 0.1-2%, for example, it can be 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 0.2-1%.

[0029] The mass percentage of bismuth trioxide is 0.1-2%, for example, it can be 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 0.2-1%.

[0030] The mass percentage of silicon dioxide is 20-55%, for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52% or 55%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 25-45%.

[0031] The mass percentage of zirconium dioxide is 1-10%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 2-8%.

[0032] The mass percentage of niobium pentoxide is 1-10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. Preferably, it is 2-8%.

[0033] The present invention preferably controls the mass percentage of nickel, cobalt, copper, gallium trioxide, bismuth trioxide, silicon dioxide, zirconium dioxide, and niobium pentoxide in the supported adsorption material within a specific range. By adjusting the proportion of each component, the adsorption activity and stability of the nickel-based adsorbent can be further improved.

[0034] Preferably, the specific surface area of ​​silicon dioxide in the nickel-based adsorbent is 200-450 m 2 / g, for example, it can be 200m 2 / g, 240m 2 / g, 280m 2 / g、320m 2 / g、360m 2 / g, 400m 2 / g, 440m 2 / g or 450m 2 / g, but not limited to the listed values, other values ​​not listed in the numerical range are also applicable; the specific surface area of ​​zirconium dioxide is 30-180m 2 / g, the specific surface area of ​​niobium pentoxide is 20-180m 2 / g, for example, it can be 30m 2 / g, 50m 2 / g、70m 2 / g、90m 2 / g、110m 2 / g, 140m 2 / g, 160m 2 / g or 180m 2 / g, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] Preferably, the pore volume of silica in the nickel-based adsorbent is 0.5-2 cm 3 / g, for example, it can be 0.5cm 3 / g, 1cm 3 / g, 1.5cm 3 / g or 2cm 3 / g, but not limited to the listed values, other values ​​not listed in the numerical range are also applicable; the pore volume of the zirconium dioxide carrier is 0.1-0.8cm 3 / g, for example, it can be 0.1cm 3 / g, 0.2cm 3 / g, 0.4cm 3 / g, 0.6cm 3 / g or 0.8cm 3 / g, but not limited to the listed values, other values ​​not listed in the numerical range are also applicable; the pore volume of niobium pentoxide is 0.1-0.8cm 3 / g, for example, it can be 0.1cm 3 / g, 0.2cm 3 / g, 0.4cm 3 / g, 0.6cm 3 / g or 0.8cm 3 / g, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] In a second aspect, the present invention provides a method for preparing the nickel-based adsorbent according to the first aspect of the present invention, the preparation method comprising the following steps:

[0037] (1) mixing a mixture solution containing nickel salt, cobalt salt and copper salt, ammonia water and a composite carrier, adjusting the pH of the mixed solution to 10-13 to obtain an ammonia complex solution; and sequentially performing ammonia evaporation and drying on the ammonia complex solution to obtain a nickel-based adsorbent precursor;

[0038] (2) The nickel-based adsorbent precursor, skeleton material, pore-forming agent, water and auxiliary salt obtained in step (1) are mixed, and then molded, calcined, reduced and passivated in sequence to obtain a nickel-based adsorbent.

[0039] In the preparation method provided by the present invention, a nickel-based adsorbent precursor is prepared by sequentially evaporating ammonia and drying an ammonia complex solution. The solvent and ammonia are removed during the ammonia evaporation process, and the nickel, copper, and cobalt crystals obtained in this process are smaller in size and more easily anchored on the irregular surface of the carrier, thereby enhancing the chemical and mechanical stability of the active metal sites of the adsorbent, thereby greatly improving the ability to remove thiophene. At the same time, the loss of active metal sites of the adsorbent can be avoided, thereby avoiding affecting the activity of the subsequent benzene partial hydrogenation reaction.

[0040] In the present invention, the auxiliary agent salt refers to the raw material for preparing the auxiliary agent, preferably gallium salt and bismuth salt.

[0041] Preferably, the total molar concentration of nickel salt, cobalt salt and copper salt in the mixture solution of step (1) is 0.1-2 mol / L, for example, it can be 0.1 mol / L, 0.4 mol / L, 0.8 mol / L, 1.2 mol / L, 1.6 mol / L or 2 mol / L, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 0.5-2 mol / L.

[0042] Preferably, the molar concentration of the ammonia water is 1.2-2 times the total molar concentration of the nickel salt, cobalt salt and copper salt, for example, it can be 1.2 times, 1.4 times, 1.6 times, 1.8 times or 2 times, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] Preferably, the ammonia water is dripped into the mixture solution containing nickel salt, cobalt salt and copper salt, and then stirred for 3-8 hours.

[0044] Preferably, the pressure in the ammonia evaporation process is 500-3000 Pa, for example, 500 Pa, 600 Pa, 1000 Pa, 1500 Pa, 2000 Pa, 2500 Pa or 3000 Pa, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0045] Preferably, the temperature of the ammonia evaporation is 40-120°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0046] Preferably, the drying temperature is 80-120°C, for example, it can be 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] Preferably, the calcination temperature in step (2) is 200-550°C, for example, it can be 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, 420°C, 440°C, 460°C, 480°C, 500°C or 550°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0048] Preferably, the reduction temperature in step (2) is 300-600°C, for example, it can be 300°C, 320°C, 340°C, 360°C, 380°C, 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, 520°C, 540°C, 560°C, 580°C or 600°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0050] (1) mixing a mixture solution containing nickel salt, cobalt salt and copper salt, ammonia water and a composite carrier, adjusting the pH of the solution to 10-13 to obtain an ammonia complex solution; distilling ammonia from the ammonia complex solution at 500-3000 Pa and 40-120° C., and then drying at 80-120° C. to obtain a nickel-based adsorbent precursor;

[0051] The total molar concentration of the nickel salt, cobalt salt and copper salt in the mixture solution is 0.1-2 mol / L, and the molar concentration of the ammonia water is 1.2-2 times the total molar concentration of the nickel salt, cobalt salt and copper salt;

[0052] (2) The nickel-based adsorbent precursor, skeleton material, pore-forming agent, water and auxiliary salt obtained in step (1) are mixed, and then molded, calcined, reduced and passivated in sequence to obtain a nickel-based adsorbent.

[0053] In a third aspect, the present invention provides a use of the nickel-based adsorbent as described in the first aspect of the present invention, wherein the nickel-based adsorbent is used to remove thiophene from benzene.

[0054] The nickel-based adsorbent provided by the present invention has a high effective sulfur capacity, especially an excellent adsorption effect on thiophene. It can refine the raw material benzene at a relatively low temperature or even room temperature or at a relatively high thiophene concentration. The thiophene content in the refined benzene is less than 0.01 μg / g, and can be applied industrially.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The nickel-based adsorbent provided by the present invention deeply adsorbs thiophene in benzene through the synergistic effect of the nickel-based adsorbent precursor, porous skeleton material and auxiliary agent. Among them, the porous skeleton material increases the adsorption stability and the contact area with the reactant; the three non-precious metal active components cooperate with each other to enhance the physical adsorption capacity and chemical adsorption capacity of thiophene; further, the composite carrier and auxiliary agent are used to make the active site more stable, and the active nickel microcrystal particles are not easy to aggregate and grow, thereby increasing the desulfurization activity and stability of the nickel-based adsorbent. At the same time, the composite carrier has more acidic sites, which promotes the adsorption of thiophene by the adsorbent, enhances the diffusion of thiophene in the raw material on the adsorbent, and increases the activity of the adsorbent; the nickel-based adsorbent provided by the present invention can also effectively replace precious metal adsorbents, greatly reducing production costs.

[0057] (2) In the preparation method provided by the present invention, the crystal size of the active component is reduced by distilling ammonia, so that it is anchored on the irregular surface of the carrier, thereby enhancing the stability of the active metal site and improving the dethiophene ability. It can also prevent the loss of active metal sites and avoid affecting the activity of the subsequent benzene partial hydrogenation reaction. At the same time, the present invention does not use high-energy-consuming equipment, the preparation method is simple, and it is easy to scale up production, meeting the needs of industrial application.

[0058] (3) The nickel-based adsorbent provided by the present invention is used in the process of benzene dethiophening, which can reduce the operating temperature of the reaction and greatly improve the effective sulfur capacity. Under optimal conditions, the effective sulfur capacity for deep adsorption of thiophene in benzene reaches 9.8 g S / kg adsorbent. Under more optimal conditions, it reaches more than 12.7 g S / kg adsorbent. Raw benzene with a higher thiophene concentration can be refined, and the thiophene content in the refined benzene is less than 0.01 μg / g. DETAILED DESCRIPTION

[0059] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0060] Example 1

[0061] This embodiment provides a nickel-based adsorbent, which includes a porous skeleton material and a supported adsorbent material filled inside the porous skeleton material; the supported adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent;

[0062] The nickel-based adsorbent precursor includes a composite carrier and active components loaded on the composite carrier, the active components are nickel, cobalt and copper, the composite carrier is silicon dioxide, zirconium dioxide and niobium pentoxide, the porous skeleton material is an alumina skeleton, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent, the skeleton material is low-silicon boehmite, the pore-forming agent is sesbania powder, the mass of the low-silicon boehmite is 30% of the mass of the nickel-based adsorbent precursor, the mass of the sesbania powder is 5% of the mass of the nickel-based adsorbent precursor, the auxiliary agents are gallium trioxide and bismuth trioxide, the raw materials for preparing the auxiliary agents are gallium nitrate and bismuth nitrate, the active components and auxiliary agents are loaded on the composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5;

[0063] The supported adsorption material comprises, by weight percentage, 60% nickel, 1% cobalt, 1% copper, 0.5% gallium trioxide, 0.5% bismuth trioxide, 25% silicon dioxide, 6% zirconium dioxide, and 6% niobium pentoxide; the specific surface area of ​​the silicon dioxide is 400 m 2 / g, pore volume is 0.5cm 3 / g, the specific surface area of ​​zirconium dioxide is 50m 2 / g, pore volume is 0.8cm 3 / g, the specific surface area of ​​niobium pentoxide is 40m2 / g, pore volume is 0.8cm 3 / g.

[0064] This embodiment provides a method for preparing the nickel-based adsorbent, which comprises the following steps:

[0065] (1) 297.14 g of nickel nitrate hexahydrate, 3.80 g of copper nitrate trihydrate, and 4.94 g of cobalt nitrate hexahydrate were added to 1050 g of deionized water and stirred and dissolved uniformly until the solution was clear to obtain a mixture solution, wherein the total molar concentration of nickel salt, cobalt salt, and copper salt in the mixture solution was 1.0 mol / L; 25 g of silicon dioxide, 6 g of zirconium dioxide, and 6 g of niobium pentoxide were added to the mixture solution, and then 208 mL of 25-28% ammonia water was slowly added dropwise thereto. After the addition was completed, stirring was continued for 8 h. The pH of the solution was 13, thereby obtaining an ammonia complex solution;

[0066] Then, the ammonia complex solution is subjected to ammonia evaporation at 500 Pa and 60° C., and then dried at 120° C. to obtain a nickel-based adsorbent precursor;

[0067] (2) 100 g of the nickel-based adsorbent precursor obtained in step (1), 30 g of low-silicon boehmite, 5 g of sesbania powder, 60 g of water, 1.36 g of hydrated gallium nitrate and 1.04 g of bismuth nitrate pentahydrate were mixed, and then formed on a turntable pelletizer. The formed material was calcined at 350° C., reduced at 350° C., and then passivated to obtain a nickel-based adsorbent.

[0068] Example 2

[0069] This embodiment provides a nickel-based adsorbent, which includes a porous skeleton material and a supported adsorbent material filled inside the porous skeleton material; the supported adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent;

[0070] The nickel-based adsorbent precursor includes a composite carrier and active components loaded on the composite carrier, the active components are nickel, cobalt and copper, the composite carrier is silicon dioxide, zirconium dioxide and niobium pentoxide, the porous skeleton material is an alumina skeleton, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent, the skeleton material is silicon-free boehmite, the pore-forming agent is sesbania powder and starch, the mass of the silicon-free boehmite is 10% of the mass of the nickel-based adsorbent precursor, the mass of the sesbania powder and starch is 5% of the mass of the nickel-based adsorbent precursor, the auxiliary agents are gallium trioxide and bismuth trioxide, the raw materials for preparing the auxiliary agents are gallium nitrate and bismuth nitrate, the active components and auxiliary agents are loaded on the composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5;

[0071] The supported adsorption material comprises, by weight percentage, 40% nickel, 1% cobalt, 1% copper, 1% gallium trioxide, 1% bismuth trioxide, 45% silicon dioxide, 8% zirconium dioxide, and 3% niobium pentoxide; the specific surface area of ​​the silicon dioxide is 250 m 2 / g, pore volume is 2cm 3 / g, the specific surface area of ​​zirconium dioxide is 160m 2 / g, pore volume is 0.1cm 3 / g, the specific surface area of ​​niobium pentoxide is 100m 2 / g, pore volume is 0.6cm 3 / g.

[0072] This embodiment provides a method for preparing the nickel-based adsorbent, which comprises the following steps:

[0073] (1) 161.98 g of nickel chloride hexahydrate, 3.93 g of copper sulfate pentahydrate, and 4.23 g of cobalt acetate tetrahydrate were added to 500 g of deionized water and stirred and dissolved uniformly until the solution was clear to obtain a mixture solution, wherein the total molar concentration of nickel salt, cobalt salt, and copper salt in the mixture solution was 1.43 mol / L; 45 g of silicon dioxide, 8 g of zirconium dioxide, and 3 g of niobium pentoxide were added to the mixture solution, and then 212 mL of 25-28% ammonia water was slowly added dropwise thereto. After the addition was completed, stirring was continued for 2 h. The pH of the solution was 10, thereby obtaining an ammonia complex solution;

[0074] Then, the ammonia complex solution is subjected to ammonia evaporation at 3000 Pa and 120° C., and then dried at 80° C. to obtain a nickel-based adsorbent precursor;

[0075] (2) 100 g of the nickel-based adsorbent precursor obtained in step (1), 10 g of silicon-free boehmite, 3 g of sesbania powder, 2 g of starch, 45 g of water, 2.72 g of hydrated gallium nitrate and 2.08 g of bismuth nitrate pentahydrate are mixed, and then formed on a turntable pelletizer. The formed material is calcined at 500° C., reduced at 400° C., and then passivated to obtain a nickel-based adsorbent.

[0076] Example 3

[0077] This embodiment provides a nickel-based adsorbent, which includes a porous skeleton material and a supported adsorbent material filled inside the porous skeleton material; the supported adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent;

[0078] The nickel-based adsorbent precursor includes a composite carrier and active components loaded on the composite carrier, the active components are nickel, cobalt and copper, the composite carrier is silicon dioxide, zirconium dioxide and niobium pentoxide, the porous skeleton material is an alumina skeleton, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent, the skeleton material is low-silicon boehmite, the pore-forming agent is sesbania powder, the mass of the low-silicon boehmite is 30% of the mass of the nickel-based adsorbent precursor, the mass of the sesbania powder is 5% of the mass of the nickel-based adsorbent precursor, the auxiliary agents are gallium trioxide and bismuth trioxide, the raw materials for preparing the auxiliary agents are gallium nitrate and bismuth nitrate, the active components and auxiliary agents are loaded on the composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5;

[0079] The supported adsorption material comprises, by weight percentage, 41% nickel, 6% cobalt, 6% copper, 0.2% gallium, 0.8% bismuth, 30% silicon dioxide, 8% zirconium dioxide, and 8% niobium pentoxide; the specific surface area of ​​the silicon dioxide is 350 m 2 / g, pore volume is 1.2cm 3 / g, the specific surface area of ​​zirconium dioxide is 80m 2 / g, pore volume is 0.4cm 3 / g, the specific surface area of ​​niobium pentoxide is 160m 2 / g, pore volume is 0.1cm 3 / g,.

[0080] This embodiment provides a method for preparing the nickel-based adsorbent, which comprises the following steps:

[0081] (1) 203.05 g of nickel nitrate hexahydrate, 23.58 g of copper sulfate pentahydrate, and 29.64 g of cobalt nitrate hexahydrate were added to 533.8 g of deionized water and stirred and dissolved uniformly until the solution was clear to obtain a mixture solution, wherein the total molar concentration of nickel salt, cobalt salt, and copper salt in the mixture solution was 2.0 mol / L; 30 g of silicon dioxide, 6 g of zirconium dioxide, and 6 g of niobium pentoxide were added to the mixture solution, and then 169.2 mL of 25-28% ammonia water was slowly added dropwise thereto. After the addition was completed, stirring was continued for 3 h. The pH of the solution was 13, thereby obtaining an ammonia complex solution;

[0082] Then, the ammonia complex solution is subjected to ammonia evaporation at 500 Pa and 40° C., and the obtained solid is dried at 120° C. to obtain a nickel-based adsorbent precursor;

[0083] (2) 100 g of the nickel-based adsorbent precursor obtained in step (1), 30 g of low-silicon boehmite, 5 g of sesbania powder, 60 g of water, 0.54 g of hydrated gallium nitrate and 1.66 g of bismuth nitrate pentahydrate are mixed, and then formed on a turntable pelletizer. The formed material is calcined at 300° C., reduced at 550° C., and then passivated to obtain a nickel-based adsorbent.

[0084] Example 4

[0085] This embodiment provides a nickel-based adsorbent, which includes a porous skeleton material and a supported adsorbent material filled inside the porous skeleton material; the supported adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent;

[0086] The nickel-based adsorbent precursor includes a composite carrier and active components loaded on the composite carrier, the active components are nickel, cobalt and copper, the composite carrier is silicon dioxide, zirconium dioxide and niobium pentoxide, the porous skeleton material is an alumina skeleton, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent, the skeleton materials are kaolin and hydrotalcite, the pore-forming agent is dextrin, the mass of the kaolin and hydrotalcite is 20% of the mass of the nickel-based adsorbent precursor, the mass of the dextrin is 2% of the mass of the nickel-based adsorbent precursor, the auxiliary agents are gallium trioxide and bismuth trioxide, the raw materials for preparing the auxiliary agents are gallium nitrate and bismuth nitrate, the active components and auxiliary agents are loaded on the composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5;

[0087] The supported adsorption material comprises, by weight percentage, 55% nickel, 2% cobalt, 4% copper, 0.8% gallium trioxide, 0.2% bismuth trioxide, 30% silicon dioxide, 2% zirconium dioxide, and 6% niobium pentoxide; the specific surface area of ​​the silicon dioxide is 450 m 2 / g, pore volume is 1.4cm 3 / g, the specific surface area of ​​zirconium dioxide is 60m 2 / g, pore volume is 0.4cm 3 / g, the specific surface area of ​​niobium pentoxide is 60m 2 / g, pore volume is 0.5cm 3 / g,.

[0088] This embodiment provides a method for preparing the nickel-based adsorbent, which comprises the following steps:

[0089] (1) 272.38 g of nickel nitrate hexahydrate, 15.75 g of copper sulfate pentahydrate, and 8.46 g of cobalt acetate tetrahydrate were added to 744 g of deionized water and stirred and dissolved uniformly until the solution was clear to obtain a mixture solution, wherein the total molar concentration of nickel salt, cobalt salt, and copper salt in the mixture solution was 1.5 mol / L; 30 g of silicon dioxide, 2 g of zirconium dioxide, and 6 g of niobium pentoxide were added to the mixture solution, and then 235.8 mL of 25-28% ammonia water was slowly added dropwise thereto. After the addition was completed, stirring was continued for 4 h. The pH of the solution was 12, thereby obtaining an ammonia complex solution;

[0090] Then, the ammonia complex solution is subjected to ammonia evaporation at 1000 Pa and 80° C., and then dried at 85° C. to obtain a nickel-based adsorbent precursor;

[0091] (2) 100 g of the nickel-based adsorbent precursor obtained in step (1), 5 g of white clay, 15 g of hydrotalcite, 2 g of dextrin, 30 g of water, 2.18 g of hydrated gallium nitrate and 0.42 g of bismuth nitrate pentahydrate were mixed, and then formed on a turntable pelletizer. The formed material was calcined at 400° C., reduced at 475° C., and then passivated to obtain a nickel-based adsorbent.

[0092] Example 5

[0093] This embodiment provides a nickel-based adsorbent, which includes a porous skeleton material and a supported adsorbent material filled inside the porous skeleton material, wherein the supported adsorbent material includes a nickel-based adsorbent precursor and an auxiliary agent;

[0094] The nickel-based adsorbent precursor includes a composite carrier and active components loaded on the composite carrier, the active components are nickel, cobalt and copper, the composite carrier is silicon dioxide, zirconium dioxide and niobium pentoxide, the porous skeleton material is an alumina skeleton, the raw materials for preparing the porous skeleton material include a skeleton material and a pore-forming agent, the skeleton material is silicon-free boehmite, the pore-forming agent is sesbania powder, the mass of the silicon-free boehmite is 16% of the mass of the nickel-based adsorbent precursor, the mass of the sesbania powder is 2% of the mass of the nickel-based adsorbent precursor, the auxiliary agents are gallium trioxide and bismuth trioxide, the raw materials for preparing the auxiliary agents are gallium nitrate and bismuth nitrate, the active components and auxiliary agents are loaded on the composite carrier to form a loaded adsorption material with a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5;

[0095] The supported adsorption material comprises, by weight percentage, 58% nickel, 2% cobalt, 2% copper, 0.5% gallium, 0.5% bismuth, 32% silicon dioxide, 2% zirconium dioxide, and 3% niobium pentoxide. The specific surface area of ​​the silicon dioxide is 400 m 2 / g, pore volume is 1.6cm 3 / g, the specific surface area of ​​zirconium dioxide is 80m 2 / g, pore volume is 0.5cm 3 / g, the specific surface area of ​​niobium pentoxide is 50m 2 / g, pore volume is 0.6cm 3 / g.

[0096] This embodiment provides a method for preparing the nickel-based adsorbent, which comprises the following steps:

[0097] (1) 287.23 g of nickel nitrate hexahydrate, 7.61 g of copper nitrate trihydrate, and 9.88 g of cobalt nitrate hexahydrate were added to 584.7 g of deionized water and stirred and dissolved uniformly until the solution was clear to obtain a mixture solution, wherein the total molar concentration of nickel salt, cobalt salt, and copper salt in the mixture solution was 1.8 mol / L; 32 g of silicon dioxide, 2 g of zirconium dioxide, and 3 g of niobium pentoxide were added to the mixture solution, and then 278 mL of 25-28% ammonia water was slowly added dropwise thereto. After the addition was completed, stirring was continued for 3 h. The pH of the solution was 12, thereby obtaining an ammonia complex solution;

[0098] Then, the ammonia complex solution is subjected to ammonia evaporation at 3000 Pa and 75° C., and the obtained solid is dried at 80° C. to obtain a nickel-based adsorbent precursor;

[0099] (2) 100 g of the nickel-based adsorbent precursor obtained in step (1), 16 g of silicon-free boehmite, 2 g of sesbania powder, 70 g of water, 1.36 g of hydrated gallium nitrate and 1.04 g of bismuth nitrate pentahydrate were mixed, and then formed on a turntable pelletizer. The formed material was calcined at 425° C., reduced at 425° C., and then passivated to obtain a nickel-based adsorbent.

[0100] Example 6

[0101] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that the total mass percentage of nickel, cobalt, and copper in the supported adsorption material remains unchanged, while the mass percentage of copper is adjusted to 0.3%, the mass percentage of cobalt is adjusted to 0.3%, and the mass percentage of nickel is adjusted to 61.4%.

[0102] Example 7

[0103] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that the total mass percentage of nickel, cobalt, and copper in the supported adsorption material remains unchanged, and the mass percentage of copper is adjusted to 15%, the mass percentage of cobalt is adjusted to 10%, and the mass percentage of nickel is adjusted to 37%.

[0104] Example 8

[0105] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that the raw material for preparing the auxiliary agent, gallium nitrate, is replaced by lanthanum nitrate, and the mass percentage of lanthanum in the supported adsorption material is ensured to be the same as that of gallium in Example 1.

[0106] Example 9

[0107] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that zirconium oxide and niobium oxide in the composite carrier are replaced by silicon oxide. After the replacement, the mass percentage of silicon oxide in the supported adsorption material is equal to the sum of silicon oxide, zirconium oxide and niobium oxide in Example 1.

[0108] Example 10

[0109] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that silicon oxide and zirconium oxide in the composite carrier are replaced by niobium oxide. After the replacement, the mass percentage of niobium oxide in the supported adsorption material is equal to the sum of silicon oxide, zirconium oxide and niobium oxide in Example 1.

[0110] Example 11

[0111] This embodiment provides a nickel-based adsorbent, which differs from Example 1 only in that silicon oxide and niobium oxide in the composite carrier are replaced by zirconium oxide. After the replacement, the mass percentage of zirconium oxide in the supported adsorption material is equal to the sum of silicon oxide, zirconium oxide and niobium oxide in Example 1.

[0112] Comparative Example 1

[0113] This comparative example provides a nickel-based adsorbent, which differs from Example 1 only in that it does not contain an auxiliary agent.

[0114] Comparative Example 2

[0115] This comparative example provides a nickel-based adsorbent, which differs from Example 1 only in that cobalt and copper in the active components are replaced by nickel. After the replacement, the mass percentage of nickel in the supported adsorption material is equal to the sum of nickel, cobalt and copper in Example 1.

[0116] Comparative Example 3

[0117] This comparative example provides a nickel-based adsorbent, which differs from Example 1 only in that nickel and copper in the active components are replaced by cobalt. After the replacement, the mass percentage of cobalt in the supported adsorption material is equal to the sum of nickel, cobalt and copper in Example 1.

[0118] Comparative Example 4

[0119] This comparative example provides a nickel-based adsorbent, which differs from Example 1 only in that nickel and cobalt in the active components are replaced by copper. After the replacement, the mass percentage of copper in the supported adsorption material is equal to the sum of nickel, cobalt and copper in Example 1.

[0120] Comparative Example 5

[0121] This comparative example provides a method for preparing a nickel-based adsorbent, which differs from Example 1 in that a direct tableting method is adopted. The specific operation is as follows: 76.35g of nickel oxide, 1.25g of copper oxide, 1.27g of cobalt oxide, 25g of silicon dioxide, 6g of zirconium dioxide, 6g of niobium pentoxide, 30g of low-silicon boehmite, 5g of sesbania powder, 0.5g of gallium trioxide, 0.5g of bismuth trioxide and 6g of water are mixed uniformly in a kneader, and the mixture is tableted with a tableting machine, calcined at 350°C, and reduced and passivated at 350°C to obtain an adsorbent. The contents of active components and auxiliary agents in the obtained adsorbent are the same as those in Example 1.

[0122] Comparative Example 6

[0123] This comparative example provides a method for preparing a nickel-based adsorbent, which differs from Example 1 in that a direct extrusion method is used. The specific operation is as follows: 202.47 g of basic nickel carbonate, 1.74 g of basic copper carbonate, 1.75 g of basic cobalt carbonate, 25 g of silicon oxide, 6 g of zirconium oxide, 6 g of niobium oxide, 5 g of sesbania powder and 30 g of low-silicon boehmite are mixed uniformly in a kneader to obtain a mixed powder, and then a prepared solution containing 1.36 g of hydrated gallium nitrate, 1.04 g of bismuth nitrate pentahydrate, 20 g of 40% nitric acid and 180 g of deionized water is poured into the mixed powder and kneaded for 30 minutes. The adsorbent is prepared by extrusion, calcination at 350°C and reduction and passivation at 350°C. The contents of active components and additives in the obtained adsorbent are the same as those in Example 1.

[0124] The nickel-based adsorbents in Examples 1-11 and Comparative Examples 1-6 were heated at a temperature of 120°C, a pressure of 0.8 MPa, and a raw benzene air velocity of 3 h -1 , under the condition that the thiophene concentration is 200 ppm, the dethiophene reaction is carried out until the thiophene content in the product is less than 0.01 μg / g, and the sulfur capacity is calculated, as shown in Table 1.

[0125] Table 1

[0126] Sulfur capacity / (g sulfur / kg adsorbent) Example 1 13.1 Example 2 9.8 Example 3 9.9 Example 4 12.7 Example 5 13.0 Example 6 6.4 Example 7 3.2 Example 8 7.6 Example 9 3.6 Example 10 0.9 Example 11 0.7 Comparative Example 1 6.2 Comparative Example 2 8.2 Comparative Example 3 0 Comparative Example 4 0 Comparative Example 5 0.4 Comparative Example 6 0.6

[0127] The following points can be seen from the data in Table 1:

[0128] (1) From the data of Examples 1-5, it can be seen that under optimal conditions, the sulfur capacity of the nickel-based adsorbent provided by the present invention for the dethiophene reaction can reach more than 9.8 g sulfur / kg adsorbent, and under more optimal conditions, it can reach more than 12.7 g sulfur / kg adsorbent.

[0129] (2) A comprehensive comparison of Example 1 and Examples 6-7 shows that the only difference between Example 6-7 and Example 1 is that the mass percentages of nickel, cobalt, and copper are not within the preferred range of the present invention. The sulfur capacity in Example 1 is much higher than that in Examples 6-7. This shows that the present invention preferably controls the mass percentages of nickel, cobalt, and copper within a specific range, which can further improve the sulfur capacity of the adsorbent.

[0130] (3) Comprehensively comparing Example 1, Example 8 and Comparative Example 1, the only difference between Example 8 and Example 1 is that the gallium nitrate in the auxiliary agent preparation raw material is replaced by lanthanum nitrate, and the only difference between Comparative Example 1 and Example 1 is that it does not contain an auxiliary agent. The sulfur capacity in Example 1 can reach 13.1 g sulfur / kg adsorbent, while that in Example 8 can only reach 7.6 g sulfur / kg adsorbent, and that in Comparative Example 1 can only reach 6.2 g sulfur / kg adsorbent. It can be seen that the present invention can further improve the sulfur capacity of the adsorbent by adding an auxiliary agent and controlling the auxiliary agent to be a combination of gallium trioxide and bismuth trioxide.

[0131] (4) A comprehensive comparison of Example 1 and Examples 9-11 shows that the only difference between Examples 9-11 and Example 1 is that only silicon oxide, niobium oxide, and zirconium oxide are used as supports, respectively. The sulfur capacity in Example 1 is significantly higher than that in Examples 9-11. This shows that the present invention can increase the acid sites by controlling the support to be a composite support of silicon oxide, zirconium oxide, and niobium oxide, thereby further promoting the adsorption of thiophene by the adsorbent.

[0132] (5) A comprehensive comparison of Example 1 and Comparative Examples 2-4 shows that the only difference between Comparative Examples 2-4 and Example 1 is that only one active component is added to each. The sulfur capacity in Example 1 is much better than that in Comparative Examples 1-2, while the adsorption effect cannot even be achieved in Comparative Examples 3-4. This shows that the present invention achieves excellent adsorption effect by using nickel, cobalt and copper as active components, significantly improving the sulfur capacity of the dethiophene reaction.

[0133] (6) A comprehensive comparison of Example 1 and Comparative Examples 5-6 shows that the only difference between Comparative Examples 5-6 and Example 1 is that the adsorbents are prepared by the sheeting method and the extrusion method, respectively. The sulfur capacity in Example 1 is much higher than that in Comparative Examples 5-6. It can be seen that the preparation method of the adsorbent provided by the present invention reduces the crystal size of the active component by evaporating ammonia, anchoring it on the irregular surface of the carrier, enhancing the stability of the active metal site, preventing the loss of the active metal site, improving the dethiophene ability, and significantly improving the sulfur capacity of the adsorbent.

[0134] In summary, the nickel-based adsorbent provided by the present invention is used in the process of benzene dethiophening, which can reduce the operating temperature of the reaction and greatly improve the effective sulfur capacity.

[0135] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A nickel-based adsorbent, characterized in that: The nickel-based adsorbent includes a porous skeleton material and a supported adsorption material filled inside the porous skeleton material; The supported adsorption material includes a nickel-based adsorbent precursor and an auxiliary agent; The nickel-based adsorbent precursor includes a composite carrier and an active component loaded on the composite carrier; The auxiliary agent is loaded on the composite carrier; The active components include nickel, cobalt and copper; The composite support comprises silicon dioxide, zirconium dioxide and niobium pentoxide; The auxiliary agent includes gallium trioxide and bismuth trioxide; The active components and auxiliary agents are loaded on a composite carrier to form a loaded adsorption material having a structure of Ni-Co-Cu-Ga2O3-Bi2O3 / SiO2-ZrO2-Nb2O5; The supported adsorption material comprises, by weight percentage, 30-70% nickel, 0.5-10% cobalt, 0.5-10% copper, 0.1-2% gallium trioxide, 0.1-2% bismuth trioxide, 20-55% silicon dioxide, 1-10% zirconium dioxide, and 1-10% niobium pentoxide. The nickel-based adsorbent is obtained by the following preparation method: (1) mixing a mixture solution containing nickel salt, cobalt salt and copper salt, ammonia water and a composite carrier, adjusting the pH of the mixed solution to 10-13 to obtain an ammonia complex solution; and sequentially performing ammonia evaporation and drying on the ammonia complex solution to obtain a nickel-based adsorbent precursor; (2) The nickel-based adsorbent precursor, skeleton material, pore-forming agent, water and auxiliary salt obtained in step (1) are then sequentially molded, calcined, reduced and passivated to obtain a nickel-based adsorbent.

2. The nickel-based adsorbent according to claim 1, characterized in that The raw materials for preparing the active component include a mixture of nickel salt, cobalt salt and copper salt; The nickel salt includes any one of nickel nitrate, nickel sulfate, nickel chloride, nickel oxalate or nickel acetate, or a combination of at least two thereof; The cobalt salt includes any one of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt oxalate or cobalt acetate, or a combination of at least two thereof; The copper salt includes any one of copper nitrate, copper sulfate, copper chloride, copper oxalate or copper acetate, or a combination of at least two of them.

3. The nickel-based adsorbent according to claim 1, characterized in that The porous skeleton material comprises an alumina skeleton; The raw materials for preparing the porous skeleton material include skeleton material and pore-forming agent; The skeleton material comprises any one or a combination of at least two of silicon-free boehmite, low-silicon boehmite, high-silicon boehmite, pseudo-boehmite, hydrotalcite, montmorillonite or clay; The pore-forming agent includes any one of starch, dextrin or sesbania powder or a combination of at least two of them.

4. The nickel-based adsorbent according to claim 3, characterized in that The mass of the skeleton material is 5-40% of the mass of the nickel-based adsorbent precursor; The mass of the pore-forming agent is 1-10% of the mass of the nickel-based adsorbent precursor.

5. The nickel-based adsorbent according to claim 1, characterized in that The raw materials for preparing the auxiliary agent include gallium salt and bismuth salt.

6. The nickel-based adsorbent according to claim 1, characterized in that The supported adsorption material comprises, by weight percentage: The mass percentage of nickel is 40-60%; The mass percentage of cobalt is 1-6%; The mass percentage of copper is 1-6%; The mass percentage of gallium trioxide is 0.2-1%; The mass percentage of bismuth trioxide is 0.2-1%; The mass percentage of silicon dioxide is 25-45%; The mass percentage of zirconium dioxide is 2-8%; The mass percentage of niobium pentoxide is 2-8%.

7. The nickel-based adsorbent according to claim 1, characterized in that The specific surface area of ​​silicon dioxide in the nickel-based adsorbent is 200-450 m 2 / g, pore volume of 0.5-2cm 3 / g; the specific surface area of ​​zirconium dioxide is 30-180m 2 / g, pore volume of 0.1-0.8cm 3 / g; the specific surface area of ​​niobium pentoxide is 20-180m 2 / g, pore volume of 0.1-0.8cm 3 / g.

8. A method for preparing the nickel-based adsorbent according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) mixing a mixture solution containing nickel salt, cobalt salt and copper salt, ammonia water and a composite carrier, adjusting the pH of the mixed solution to 10-13 to obtain an ammonia complex solution; and sequentially performing ammonia evaporation and drying on the ammonia complex solution to obtain a nickel-based adsorbent precursor; (2) The nickel-based adsorbent precursor, skeleton material, pore-forming agent, water and auxiliary salt obtained in step (1) are then sequentially molded, calcined, reduced and passivated to obtain a nickel-based adsorbent.

9. The preparation method according to claim 8, characterized in that The total molar concentration of nickel salt, cobalt salt and copper salt in the mixture solution of step (1) is 0.1-2 mol / L; The molar concentration of the ammonia solution is 1.2-2 times the total molar concentration of the nickel salt, cobalt salt and copper salt; The pressure during the ammonia distillation process is 500-3000 Pa; The temperature of the ammonia distillation is 40-120°C; The drying temperature is 80-120°C.

10. The preparation method according to claim 9, characterized in that The total molar concentration of nickel salt, cobalt salt and copper salt in the mixture solution of step (1) is 0.5-2 mol / L.

11. Use of the nickel-based adsorbent according to any one of claims 1 to 7, characterized in that: The nickel-based adsorbent is used to remove thiophene from benzene.