Aromatic refining agent as well as preparation method and application thereof

Abstract

The invention discloses an aromatic hydrocarbon refining agent as well as a preparation method and application thereof. The refining agent comprises a composite metal oxide and a solid superacid, the metal comprises a divalent metal A and a trivalent metal B, and the atom molar ratio of A / (A + B) is 0.45-0.81; the preparation method of the refining agent comprises the following steps: reacting a solution containing metal A and metal B with a mixed solution of sodium hydroxide and sodium carbonate, further reacting and roasting the obtained mixture to obtain a composite metal layered oxide I, and sequentially carrying out strong alkali treatment and acid treatment to obtain a composite metal oxide II; then loading solid superacid to obtain an aromatic hydrocarbon refining agent intermediate; and finally, carrying out ammonium exchange and roasting to obtain the aromatic refining agent. The refining agent prepared by the invention can effectively solve the problem of poor dispersion of superacid, the reaction activity of superacid is improved, and the service life of the refining agent is greatly prolonged.

Description

Technical Field

[0001] The present invention relates to the field of aromatics production, and more specifically, to a refining agent for reducing the olefin content in aromatics with carbon number nine or above in an aromatics production process, especially in an aromatics combined unit production process, and a preparation method thereof. Background Art

[0002] Among the basic organic raw materials, benzene, toluene and para-xylene occupy a very important position. The aromatic raw materials obtained by hydrocracking have a high bromine index. In the production process of the aromatics complex, naphtha reforming, disproportionation and transalkylation, isomerization and other reaction processes are required to generate the target product C8 aromatics mixture, and then adsorption separation is obtained to obtain the para-xylene product. Among them, each reaction product or intermediate product has a large number of impurities and a high bromine index. It can only enter the downstream xylene tower after the bromine index is reduced. The top of the xylene tower separates C8 aromatics, and the product at the bottom of the tower is converted into the target product of C8 aromatics through disproportionation and transalkylation units. Among them, the C8 aromatics separated from the top of the xylene tower require an extremely low bromine index, so the effect of deolefination of C8 aromatics has attracted much attention.

[0003] In industry, two technical routes are generally used to remove olefins from aromatics, namely hydrogenation reaction and liquid-solid phase alkylation catalytic reaction, so as to reduce the bromine index. Commonly used refining agents are white clay and molecular sieves.

[0004] The deolefination refining agent disclosed in CN102008976A is based on ReUSY molecular sieve as the main active component, mordenite molecular sieve as the second active component, and alumina as a binder. Its main purpose is to remove olefins from C8 aromatics. Due to the influence of the pores, it is difficult to achieve a higher efficiency for olefins in aromatics with C9 and above. CN103041841B uses Y molecular sieve to prepare aromatic non-hydrogenation deolefination refining agent. It uses Y molecular sieve as the active center. The reaction in its pores is more effective for olefins with C8 and below. However, due to the influence of the molecular sieve pore structure, the removal efficiency of olefins in aromatics with C9 and above is relatively low. The reformed oil deolefination refining agent disclosed in CN102039160B contains, by weight, 0.1 to 10 parts of at least one metal selected from Ni, Mo, Zr, Nb or its oxide, 0.01 to 2.00 parts of at least one element selected from Cl, Br, S or its oxide, 0.05 to 5 parts of at least one element selected from F, P or its oxide, 20 to 90 parts of molecular sieves and 10 to 80 parts of at least one catalyst selected from SiO2, Al2O3 or a mixture thereof. The method has acidity in large pores to a certain extent, but because the acidity of the molecular sieve is mainly used in the reaction, the acidity outside the molecular sieve is limited by the pores, and is prone to coking and deactivation, resulting in a low efficiency in removing olefins from aromatic hydrocarbons of carbon nine and above. CN104907090A discloses a catalytic reforming oil refining deolefination refining agent and a preparation method thereof, comprising 30% to 70% Al2O3 and 30% to 70% molecular sieve, and adopts a molecular sieve as an active carrier and an alumina modification method, but has a poor effect on deolefination in aromatic hydrocarbons of carbon nine and above.

[0005] In summary, existing catalysts or refining agents use different molecular sieves to remove olefins. Although the bromine index can be reduced, the efficiency of removing olefins from aromatic hydrocarbons of carbon nine and above is low. Summary of the invention

[0006] In view of the problem of low deolefination efficiency in aromatic hydrocarbons with carbon content of 9 or more existing in the prior art, the present invention provides a new aromatic hydrocarbon refining agent and its preparation method and application. The use of the refining agent of the present invention greatly improves the efficiency of deolefination, especially the efficiency of deolefination of aromatic hydrocarbons with carbon content of 9 or more, solves the problem of low deolefination efficiency of high boiling point fractions existing in current production, and produces aromatic hydrocarbon products with stable quality.

[0007] The first aspect of the present invention provides an aromatic hydrocarbon refining agent, comprising a composite metal oxide and a solid superacid, wherein the metal comprises a divalent metal A and a trivalent metal B, wherein the atomic molar ratio of A / (A+B) is 0.45-0.81.

[0008] According to the present invention, the solid superacid comprises at least one of tungsten-zirconium composite oxide or tungsten-titanium composite oxide, preferably tungsten-zirconium composite oxide, wherein the mass ratio of tungsten oxide to zirconium oxide is preferably 10-40:90-60.

[0009] According to the present invention, the composite metal oxide is preferably a composite metal layered oxide.

[0010] According to the present invention, in the composite metal oxide, the divalent metal A is selected from at least one of Mg, Fe, Co, Cd, Zn, Ni, and Cu, preferably one of Mg, Fe, and Zn; the trivalent metal B is selected from at least one of Al, Cr, and Fe, preferably Al.

[0011] According to the present invention, based on the mass of the catalyst, the content of the composite metal oxide is 50% to 90%, and the content of the solid superacid in terms of oxide is 10% to 50%.

[0012] The second aspect of the present invention provides a method for preparing the above aromatic hydrocarbon refining agent, comprising the following steps:

[0013] (1) reacting a solution containing metal A and metal B with a mixed solution of sodium hydroxide and sodium carbonate to obtain a mixture;

[0014] (2) The mixture obtained in step (1) is reacted and calcined to obtain a composite metal layered oxide I;

[0015] (3) The composite metal layered oxide I obtained in step (2) is treated with a strong base and an acid in sequence to obtain a composite metal oxide II;

[0016] (4) The composite metal oxide II obtained in step (3) is loaded with a solid superacid to obtain an aromatic hydrocarbon refining agent intermediate;

[0017] (5) impregnating the aromatic hydrocarbon refining agent intermediate obtained in step (4) with an ammonium salt solution and calcining to obtain the aromatic hydrocarbon refining agent.

[0018] According to the present invention, in step (1), in the solution containing metal A and metal B, the source of metal A is selected from one or more of soluble nitrates, sulfates, halides, and halides, and the metal A is selected from at least one of Mg, Fe, Co, Cd, Zn, Ni, and Cu, preferably one of Mg, Fe, and Zn. The source of metal B is selected from one or more of soluble nitrates, sulfates, halides, and halides, and the metal B is selected from at least one of Al, Cr, and Fe, preferably Al.

[0019] According to the present invention, in step (1), the atomic molar ratio of metal A to metal B satisfies: A / (A+B) is 0.60 to 0.83.

[0020] According to the present invention, in step (1), in the mixed solution of sodium hydroxide and sodium carbonate, the molar ratio of sodium hydroxide to sodium carbonate is 0.1 to 5.0.

[0021] According to the present invention, in step (1), preferably, a mixed solution of sodium hydroxide and sodium carbonate is added to a solution containing metal A and metal B for reaction, and the reaction is carried out under stirring. The pH value at the end point of the reaction is 9 to 11, preferably 9 to 10. The reaction temperature is 10 to 120° C., preferably 20 to 90° C.

[0022] According to the present invention, in step (2), the reaction temperature is 50-210°C, the reaction time is 2-120h, the calcination temperature is 200-450°C, the calcination time is 0.5-48h, and the calcination atmosphere is oxygen-containing gas or inert gas.

[0023] According to the present invention, in step (2), after the reaction is completed, conventional filtration, washing and drying are performed. The washing can be performed with deionized water until neutral. The drying condition is 60-280° C. for 0.5-48 hours.

[0024] According to the present invention, in step (3), the strong base is selected from at least one of an inorganic strong base or an organic strong base. The inorganic strong base contains at least one ion selected from the elements Li, Na, Cs, and K. The organic strong base is an organic amine, preferably one or more of the strong alkaline amines of tetramethylamine, tetraethylamine, tetrapropylamine, tetrabutylamine, and trialkylamine. Further, the concentration of the strong base solution is not less than 0.1 mol / L, preferably 0.1 to 2.0 mol / L. Further, the liquid-to-solid mass ratio of the strong base solution to the composite metal layered oxide I is above 1, preferably 1.5 to 10. Further, the conditions for the strong base treatment are as follows: the treatment temperature is 10 to 100°C, and the treatment time is 1 to 12 hours.

[0025] According to the present invention, in step (3), the acid is selected from at least one of an inorganic strong acid or an organic acid. The inorganic strong acid is selected from at least one of sulfuric acid, nitric acid, and hydrochloric acid. The organic acid is at least one of an organic carboxylic acid or an organic sulfonic acid, preferably one or more of formic acid, acetic acid, oxalic acid, propionic acid, and benzenesulfonic acid. Further, the concentration of the acid solution is 0.02 to 1.5 mol / L. Further, the liquid-solid mass ratio of the acid solution to the composite metal layered oxide I is 3 to 10. Further, the conditions for the acid treatment are as follows: the treatment temperature is 0 to 99°C, and the treatment time is 0.5 to 48h. Further, after the strong base and acid treatment is completed, conventional filtration, washing, and drying are performed. The drying temperature is 60 to 400°C, and the drying time is 0.2 to 24h.

[0026] According to the present invention, in step (3), the atomic mole ratio of A / (A+B) in the composite metal oxide II is 0.02 to 0.15 lower than the atomic mole ratio of A / (A+B) in the composite metal layered oxide I. Preferably, the atomic mole ratio of A / (A+B) in the composite metal oxide II is 0.45 to 0.81.

[0027] According to the present invention, in step (4), the solid superacid is loaded by an impregnation method. In the impregnation solution, the tungsten source is one or more of ammonium tungstate, ammonium meta(secondary)tungstate, tungstate (sodium salt, potassium salt, rubidium salt, cesium salt), preferably ammonium tungstate; the zirconium source is one or more of ZrOCl2 (zirconium oxychloride), zirconium nitrate, zirconium sulfate, preferably ZrOCl2 (zirconium oxychloride); the titanium source is one or more of titanium chloride, titanium oxalate, titanium oxysulfate, and titanate, preferably titanium oxalate and titanate. Further, the mass ratio of the tungsten source in terms of tungsten oxide to the zirconium source in terms of zirconium oxide is 10-40:90-60. The concentration of the impregnation solution is 0.5-12.0 mol / L. Further, the solid-liquid mass ratio of the composite metal oxide II to the impregnation solution is 0.1-4.0. The impregnation conditions are as follows: the impregnation temperature is 10-100°C, and the impregnation time is 1-12 hours. After the impregnation, the mixture is filtered, washed and dried in a conventional manner. The drying temperature is 60 to 400° C. and the drying time is 0.2 to 24 hours.

[0028] According to the present invention, in step (5), the ammonium salt is one or more of ammonium carbonate, ammonium formate, and ammonium acetate. The concentration of the ammonium salt solution is 0.1 to 5 mol / L.

[0029] According to the present invention, in step (5), the solid-liquid mass ratio of the intermediate to the ammonium salt solution is 0.1 to 0.75. The impregnation conditions are as follows: the impregnation temperature is 10 to 120° C., and the impregnation time is 1 to 12 hours. After the impregnation is completed, conventional filtration, washing and drying are performed. The drying temperature is 60 to 400° C., and the drying time is 0.2 to 24 hours.

[0030] According to the present invention, in step (5), the calcination temperature is 450-600° C. and the calcination time is 1-10 hours.

[0031] According to the present invention, in step (5), before or after calcination, the material may be formed by a binder, dried and calcined to obtain a catalyst. The binder may contain one or both of aluminum oxide and silicon oxide.

[0032] The third aspect of the present invention provides an application of the above aromatics refining agent in the refining reaction of reforming oil.

[0033] According to the present invention, the olefin content in the reaction raw material is 200 to 5000 mgBr / 100g in terms of bromine index.

[0034] According to the present invention, the mass content of C8 aromatics in the reaction raw material is 8% to 85%, and the mass content of C9 and above aromatics is 5% to 91%. According to the present invention, the total mass content of C8 aromatics and C9 and above aromatics in the reaction raw material is more than 80%, preferably 85% to 99.9%.

[0035] According to the present invention, the reaction process conditions are as follows: the liquid hourly volume space velocity is 0.1h -1 ~20h -1 , temperature is 90~230℃, pressure is 0.2~5.0MPa.

[0036] According to the present invention, the bromine index of the refined reformate is less than 100 mgBr / 100 g, preferably 1 to 80 mgBr / 100 g. Preferably, the bromine index of the refined reformate is reduced by at least 90%, more preferably by 94.0% to 99.9%.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The novel aromatic hydrocarbon refining agent provided by the present invention comprises a composite metal oxide and a solid superacid, wherein the metal comprises a divalent metal A and a trivalent metal B, wherein the atomic molar ratio of A / (A+B) is 0.45 to 0.81. By adopting the refining agent of the present invention, in addition to producing C8 aromatic hydrocarbon products in the downstream, the olefin removal efficiency of olefin impurities in C9 and above aromatic hydrocarbons is improved, thereby solving the problem of low efficiency of high boiling point fraction olefin removal in current production and the problem of short life cycle in current production.

[0039] In the prior art, superacids have poor dispersibility and low reaction activity. The inventors have found through research that a composite metal layered oxide I containing a divalent metal A and a trivalent metal B, wherein the atomic molar ratio of A / (A+B) is 0.60-0.83, is sequentially subjected to a strong base treatment and an acid treatment. By adjusting the conditions of the base treatment and the acid treatment, the atomic molar ratio of A / (A+B) in the obtained composite metal oxide II is controlled to be 0.02-0.15 lower than the atomic molar ratio of A / (A+B) in the composite metal layered oxide I. Then, a solid superacid is loaded, so that the superacid is uniformly dispersed in the layered oxide. The refined preparation prepared in this way can effectively solve the problem of poor superacid dispersion, and can also improve the reaction activity of the superacid, thereby greatly extending the life of the refined preparation. DETAILED DESCRIPTION

[0040] In order to facilitate the understanding of the present invention, the present invention lists the following embodiments, but the embodiments are only used to help understand the present invention and should not be regarded as limiting the present invention.

[0041] Example 1

[0042] (1) dissolving magnesium nitrate and aluminum sulfate (Mg / Al molar ratio of 3:1, magnesium nitrate 6 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 2:1) until the system pH = 10, and vigorously stirring at 50° C. for 4 h to react, and then obtaining a mixture;

[0043] (2) reacting the mixture obtained in step (1) at 120° C. for 24 hours under stirring, filtering and washing, then drying at 50° C. for 12 hours, and finally calcining at 200° C. for 4 hours to obtain a composite metal layered oxide I;

[0044] (3) Then, 80 g of the composite metal layered oxide I obtained in step (2) was taken out, 160 g of sodium hydroxide (concentration of 0.1 mol / L) was added, and the mixture was treated at 30° C. for 4 hours, filtered and washed, and dried at 70° C. for 18 hours, and then treated with a mixed solution of 0.5 mol / L sulfuric acid and 0.5 mol / L oxalic acid (liquid-to-solid mass ratio of 4) at room temperature for 3 hours, filtered and washed, and dried at 80° C. for 12 hours to obtain a composite metal oxide II;

[0045] (4) preparing an impregnation solution containing ZrOCl2 (2.9 mol / L) and ammonium tungstate (0.29 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatics refining agent intermediate;

[0046] (5) 30 g of the aromatic hydrocarbon refining agent intermediate obtained in step (4) was impregnated with an ammonium carbonate solution (0.2 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic hydrocarbon refining agent A.

[0047] 5 g of catalyst A obtained in Example 1 was taken, and the reforming product oil (C8 aromatics mass content 45.0%, C9 and above aromatics mass content 54.2%, non-aromatics mass content 0.3%, toluene mass content 0.4%, benzene mass content 0.1%) with an olefin content of 1201 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 3 h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 30 mgBr / 100 g, and the bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 35 mgBr / 100 g.

[0048] Example 2

[0049] (1) dissolving zinc chloride and aluminum sulfate (Zn / Al molar ratio of 2:1, zinc chloride 5 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 2:1) until the system pH = 9.5, vigorously stirring at 70° C. for 8 h to react, and then obtaining a mixture;

[0050] (2) reacting the mixture obtained in step (1) at 180° C. for 20 hours under stirring conditions, filtering and washing, then drying at 100° C. for 12 hours, and finally calcining at 280° C. for 4 hours to obtain a composite metal layered oxide I;

[0051] (3) Then, 80 g of the composite metal layered oxide I obtained in step (2) was taken out, 160 g of tetrapropylammonium hydroxide (concentration of 0.1 mol / L) was added, and the mixture was treated at 40° C. for 2 hours, then filtered and washed, dried at 90° C. for 18 hours, and then treated at room temperature with a 0.7 mol / L oxalic acid solution (liquid-to-solid mass ratio of 6) for 6 hours, filtered and washed, to obtain a composite metal oxide II;

[0052] (4) preparing an impregnation solution containing ZrOCl2 (4.81 mol / L) and ammonium tungstate (0.81 mol / L), impregnating the composite metal oxide II (45 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatics refining agent intermediate;

[0053] (5) 30 g of the aromatic hydrocarbon refining agent intermediate obtained in step (4) was impregnated with an ammonium carbonate solution (0.3 mol / L, 40 g), filtered and washed, dried at 100° C. for 20 h, and calcined at 500° C. for 4 h to obtain the aromatic hydrocarbon refining agent B.

[0054] 5 g of catalyst B obtained in Example 2 was taken, and the reforming product oil (C8 aromatics mass content 48.0%, C9 and above aromatics content 51.2%, non-aromatics content 0.2%, toluene content 0.5%, benzene content 0.1%) with an olefin content of 2610 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 4 h -1 The reaction was evaluated at a pressure of 2.6 MPa and a temperature of 190°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 15 mgBr / 100 g, and the bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 20 mgBr / 100 g.

[0055] Example 3

[0056] (1) dissolving ferric hypochlorite and aluminum sulfate (Fe / Al molar ratio of 2:1, 5 moles of iron salt) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 1:1) until the system pH = 9.0, and vigorously stirring at 40° C. for 10 h to react, and then obtaining a mixture;

[0057] (2) reacting the mixture obtained in step (1) at 150° C. for 48 hours under stirring, filtering and washing, and then drying at 120° C. for 10 hours and finally drying at 260° C. for 10 hours to obtain a composite metal layered oxide I;

[0058] (3) Then take out 70g of the composite metal layered oxide I obtained in step (2), add 120g of tetramethylammonium hydroxide (concentration of 0.2mol / L), treat at 50°C for 4 hours, then filter and wash, dry at 60°C for 24 hours, and then treat at room temperature with a 0.5mol / L acetic acid solution (liquid-to-solid mass ratio of 4) for 6 hours, filter and wash, and dry at 120°C for 6 hours to obtain a composite metal oxide II;

[0059] (4) preparing an impregnation solution containing Zr(NO3)2 (4.63 mol / L) and sodium tungstate (0.98 mol / L), impregnating the composite metal oxide II (30 g) obtained in step (3) with the obtained impregnation solution (18 g), filtering, washing, and drying at 100°C for 12 h to obtain an aromatics refining agent intermediate;

[0060] (5) 30 g of the aromatic hydrocarbon refining agent intermediate obtained in step (4) was immersed in a potassium hydroxide solution (0.15 mol / L, 40 g), filtered and washed, dried at 150° C. for 8 h, and calcined at 580° C. for 2 h to obtain the aromatic hydrocarbon refining agent C.

[0061] 5 g of catalyst C obtained in Example 3 was taken, and the reforming product oil (C8 aromatics mass content 70.1%, C9 and above aromatics mass content 28.7%, non-aromatics mass content 0.9%, other aromatics mass content 0.3%) with olefin content calculated by bromine index of 408 mgBr / 100 g was used, and the liquid hourly volume space velocity was 8 h -1 The reaction was evaluated at a pressure of 2.0 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 3 mgBr / 100 g. The bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 5 mgBr / 100 g.

[0062] Example 4

[0063] (1) dissolving cobalt sulfate and chromium nitrate (Co / Cr molar ratio 4.5:1, chromium salt 5 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding the mixed solution of sodium carbonate until the system pH = 11, and vigorously stirring at 30° C. for 18 h to react, and then obtaining a mixture;

[0064] (2) reacting the mixture obtained in step (1) at 110° C. for 48 hours under stirring, filtering and washing, and then drying at 120° C. for 12 hours to obtain a composite metal layered oxide I;

[0065] (3) then taking out 80 g of the composite metal layered oxide I obtained in step (2), adding 160 g of sodium carbonate (concentration of 0.3 mol / L), treating at 99° C. for 6 hours, filtering and washing, drying at 160° C. for 10 hours, and then treating with a 0.5 mol / L propionic acid solution (liquid-to-solid mass ratio of 8) at 60° C. for 12 hours, filtering and washing, and drying at 160° C. for 10 hours to obtain a composite metal oxide II;

[0066] (4) preparing an impregnation solution containing ZrOCl2 (8.2 mol / L) and ammonium tungstate (0.44 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the impregnation solution (20 g) obtained in step (4), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0067] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was immersed in a potassium hydroxide solution (0.1 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic refining agent D.

[0068] 5 g of catalyst D obtained in Example 4 was taken, and the reforming product oil (C8 aromatics mass content 65.0%, C9 and above aromatics mass content 33.2%, non-aromatics mass content 0.4%, toluene mass content 1.2%, benzene mass content 0.2%) with an olefin content of 610 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 5 h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 190°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 2.0 mgBr / 100 g. The bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 3.0 mgBr / 100 g.

[0069] Example 5

[0070] (1) dissolving copper sulfate and aluminum sulfate (Cu / Al molar ratio 2:1, copper salt 5 mol) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 3:1) until the system pH = 10.5, and vigorously stirring at 20° C. for 9 h to react, and then obtaining a mixture;

[0071] (2) reacting the mixture obtained in step (1) at 100° C. for 42 hours under stirring conditions, filtering and washing, and then drying at 150° C. for 40 hours to obtain a composite metal layered oxide I;

[0072] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of potassium hydroxide (concentration of 0.1mol / L), treat at 30°C for 4 hours, then filter and wash, and dry at 70°C for 18 hours. Then treat with a mixed solution of 0.1mol / L nitric acid and 0.5mol / L oxalic acid (liquid-to-solid mass ratio 8) at room temperature for 3 hours, then filter and wash, and dry at 80°C for 12 hours to obtain composite metal oxide II;

[0073] (4) preparing an impregnation solution containing ZrOCl2 (3.92 mol / L) and ammonium tungstate (0.66 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatics refining agent intermediate;

[0074] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was impregnated with an ammonium acetate solution (0.2 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic refining agent E.

[0075] 5 g of catalyst E obtained in Example 5 was taken, and the reforming product oil (C8 aromatics mass content 45.0%, C9 and above aromatics content 54.2%, non-aromatics content 0.3%, toluene content 0.4%, benzene content 0.1%) with an olefin content of 1201 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 3 h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 30 mgBr / 100 g.

[0076] Example 6

[0077] (1) dissolving zinc chloride and ferric sulfate (Zn / Fe molar ratio of 1.5:1) in water, fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 5:1) until the system pH = 9.5, vigorously stirring at 50° C. for 5 h to react, and then obtaining a mixture;

[0078] (2) reacting the mixture obtained in step (1) at 190° C. for 20 hours under stirring, filtering and washing, and then drying at 260° C. for 12 hours to obtain a composite metal layered oxide I;

[0079] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of potassium hydroxide (concentration of 0.1mol / L), treat at 30°C for 4 hours, then filter and wash, and dry at 70°C for 18 hours. Then treat with a mixed solution of 0.1mol / L nitric acid and 0.5mol / L oxalic acid (liquid-to-solid mass ratio 8) at room temperature for 3 hours, then filter and wash, and dry at 80°C for 12 hours to obtain composite metal oxide II;

[0080] (4) preparing 100 g of an impregnation solution containing ZrOCl2 (12.4 mol / L) and ammonium tungstate (0.54 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0081] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was impregnated with an ammonium acetate solution (0.2 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic refining agent F.

[0082] 5 g of the catalyst F obtained in Example 6 was taken, and the reforming product oil (C8 aromatics mass content 40.6%, C9 and above aromatics mass content 58.2%, non-aromatics mass content 0.2%, toluene mass content 0.7%, benzene mass content 0.5%) with an olefin content of 960 mgBr / 100 g according to the bromine index was used, and the liquid hourly volume space velocity was 3 h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 50 mgBr / 100 g.

[0083] Example 7

[0084] (1) dissolving magnesium sulfate and aluminum sulfate (Mg / Al molar ratio of 2:1, copper salt 5 mol) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 1:2) until the system pH = 10.0, vigorously stirring at 80° C. for 5 h to react, and then obtaining a mixture;

[0085] (2) reacting the mixture obtained in step (1) at 190° C. for 15 hours under stirring, filtering and washing, and then drying at 120° C. for 40 hours to obtain a composite metal layered oxide I;

[0086] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of lithium hydroxide (concentration of 0.5mol / L), treat at 95°C for 4 hours, then filter and wash, and dry at 90°C for 15 hours. Then treat with a mixed solution of 0.2mol / L sulfuric acid and 0.5mol / L propionic acid (liquid-to-solid mass ratio of 5) at room temperature for 3 hours, then filter and wash, and dry at 90°C for 12 hours to obtain composite metal oxide II;

[0087] (4) preparing an impregnation solution containing ZrOCl2 (5.13 mol / L) and ammonium tungstate (0.86 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 120° C. for 6 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0088] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was impregnated with an ammonium oxalate solution (0.2 mol / L, 50 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 480° C. for 12 h to obtain the aromatic refining agent G.

[0089] 5 g of catalyst G obtained in Example 7 was taken, and the reforming product oil (C8 aromatics mass content 10.1%, C9 and above aromatics content 89.5%, non-aromatics content 0.2%, toluene content 0.1%, benzene content 0.1%) with an olefin content of 510 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 6 h -1 The reaction was evaluated at a pressure of 0.5 MPa and a temperature of 140°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 3 mgBr / 100 g.

[0090] Example 8

[0091] (1) dissolving magnesium chloride and aluminum nitrate (Mg / Al molar ratio of 1.5:1, magnesium salt 7 moles) in 600 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 1:1) until the system pH = 10.5, vigorously stirring at 30° C. for 5 h to react, and then obtaining a mixture;

[0092] (2) reacting the mixture obtained in step (1) at 120° C. for 48 hours under stirring, filtering and washing, and then drying at 120° C. for 8 hours to obtain a composite metal layered oxide I;

[0093] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of cesium hydroxide (concentration of 0.1mol / L), treat at 30°C for 4 hours, then filter and wash, and dry at 120°C for 3 hours. Then treat at room temperature for 3 hours with a 0.2mol / L sulfuric acid solution (liquid-to-solid mass ratio of 3), then filter and wash, and dry at 190°C for 6 hours to obtain composite metal oxide II;

[0094] (4) preparing an impregnation solution containing ZrOCl2 (9.08 mol / L) and ammonium tungstate (0.89 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 70° C. for 48 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0095] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was impregnated with an ammonium formate solution (0.2 mol / L, 50 g), filtered and washed, dried at 150° C. for 6 h, and calcined at 590° C. for 2 h to obtain the aromatic refining agent H.

[0096] 5 g of catalyst H obtained in Example 8 was used, and the reforming product oil (C8 aromatics mass content 61.3%, C9 and above aromatics content 9.5%, non-aromatics content 0.4%, toluene content 20.6%, benzene content 8.2%) with an olefin content of 406 mgBr / 100 g according to the bromine index) was used. The liquid hourly volume space velocity was 8 h -1 The reaction was evaluated at a pressure of 3.5 MPa and a temperature of 130°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 1.5 mgBr / 100 g.

[0097] Example 9

[0098] (1) dissolving magnesium nitrate and aluminum sulfate (Mg / Al molar ratio 4.5:1, magnesium salt 5 moles) in 600 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 1:2) until the system pH = 9.5, and vigorously stirring at 90° C. for 5 h to react, and then obtaining a mixture;

[0099] (2) reacting the mixture obtained in step (1) at 210° C. for 12 hours under stirring conditions, filtering and washing, and then drying at 180° C. for 2 hours to obtain a composite metal layered oxide I;

[0100] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of sodium hydroxide (concentration of 0.1mol / L), treat at 30°C for 4 hours, then filter and wash, and dry at 120°C for 3 hours. Then treat at room temperature for 3 hours with a 0.2mol / L sulfuric acid solution (liquid-to-solid mass ratio of 3), then filter and wash, and dry at 190°C for 6 hours to obtain composite metal oxide II;

[0101] (4) preparing an impregnation solution containing ZrOCl2 (8.46 mol / L) and ammonium tungstate (2.21 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 50° C. for 20 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0102] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was soaked in an ammonium carbonate solution (0.3 mol / L, 50 g), filtered and washed, and dried at 120° C. for 16 h. Then, 20 g of alumina monohydrate, 3 g of 60% nitric acid, and 3 g of sesbania powder were kneaded, extruded, dried at 120° C. for 20 hours, and calcined at 550° C. for 3 h to obtain the aromatic refining agent I.

[0103] 5 g of catalyst I obtained in Example 9 was taken, and the reforming product oil (C8 aromatics mass content 51.1%, C9 and above aromatics mass content 48.3%, non-aromatics mass content 0.2%, toluene mass content 0.3%, benzene mass content 0.1%) with an olefin content of 1201 mgBr / 100 g (bromine index) was used, and the liquid volume space velocity was 10 h -1 The reaction was evaluated at a pressure of 2.0 MPa and a temperature of 220°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 38 mgBr / 100 g.

[0104] Example 10

[0105] (1) dissolving zinc nitrate and chromium sulfate (Zn / Cr molar ratio 3:1, zinc salt 5 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the system pH = 10.5, vigorously stirring at 40° C. for 8 h to react, and then obtaining a mixture;

[0106] (2) reacting the mixture obtained in step (1) at 160° C. for 26 hours under stirring conditions, filtering and washing, and then drying at 120° C. for 7 hours to obtain a composite metal layered oxide I;

[0107] (3) Then take out 60g of the composite metal layered oxide I obtained in step (2), add 120g of sodium hydroxide (concentration of 0.2mol / L), treat at 60°C for 3 hours, then filter and wash, and dry at 100°C for 6 hours. Then treat at room temperature with a 0.2mol / L sulfuric acid solution (liquid-to-solid mass ratio of 5) for 2 hours, then filter and wash, and dry at 120°C for 6 hours to obtain composite metal oxide II;

[0108] (4) preparing an impregnation solution containing ZrOCl2 (5.67 mol / L) and ammonium tungstate (0.95 mol / L), impregnating the composite metal oxide II (45 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 70° C. for 20 h to obtain an aromatic hydrocarbon refined preparation intermediate;

[0109] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was soaked in an ammonium carbonate solution (0.3 mol / L, 40 g), filtered and washed, and dried at 120° C. for 16 h. Then, 10 g of alumina monohydrate, 10 g of 40% silica sol, 3 g of 60% nitric acid, and 3 g of sesbania powder were kneaded, extruded, dried at 120° C. for 20 hours, and calcined at 580° C. for 3 h to obtain the aromatic refining agent I.

[0110] 5 g of catalyst I obtained in Example 10 was used, and the reforming product oil (C8 aromatics mass content 51.1%, C9 and above aromatics mass content 48.3%, non-aromatics mass content 0.2%, toluene mass content 0.3%, benzene mass content 0.1%) with an olefin content of 1201 mgBr / 100 g according to the bromine index) was used, and the liquid volume space velocity was 6 h -1 The reaction was evaluated at a pressure of 2.0 MPa and a temperature of 180°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 62 mgBr / 100 g.

[0111] Comparative Example 1

[0112] (1) preparing a mixed solution containing ZrOCl2 (2.9 mol / L) and ammonium tungstate (0.29 mol / L);

[0113] (2) Take 20 g of the mixed solution obtained in step (1), add ammonium carbonate solution (0.2 mol / L, 40 g), filter, wash, dry at 120° C. for 10 h, and calcine at 550° C. for 3 h to obtain the aromatic refining agent DA-1.

[0114] Take 5g of the catalyst DA-1 obtained in Comparative Example 1, use the reforming product oil with an olefin content of 1201mgBr / 100g (C8 aromatics mass content 45.0%, C9 and above aromatics content 54.2%, non-aromatics content 0.3%, toluene content 0.4%, benzene content 0.1%), and the liquid volume space velocity is 3h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 712 mgBr / 100 g.

[0115] Comparative Example 2

[0116] (1) dissolving magnesium nitrate and aluminum sulfate (Mg / Al molar ratio of 3:1, magnesium nitrate 6 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 2:1) until the system pH = 10, and vigorously stirring at 50° C. for 4 h to react, and then obtaining a mixture;

[0117] (2) reacting the mixture obtained in step (1) at 120° C. for 24 hours under stirring, filtering and washing, and then drying at 50° C. for 12 hours and finally drying at 200° C. for 4 hours to obtain a composite metal layered oxide I;

[0118] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of sodium hydroxide (concentration of 0.1mol / L), treat at 30°C for 4 hours, then filter and wash, dry at 70°C for 18 hours, and then treat with a mixed solution of 0.5mol / L sulfuric acid and 0.5mol / L oxalic acid (liquid-to-solid mass ratio of 4) at room temperature for 3 hours, filter and wash, dry at 80°C for 12 hours, and then calcine at 550°C for 3h to obtain the aromatic refining agent DA-2.

[0119] Take 5g of the catalyst DA-2 obtained in Comparative Example 2, use the reforming product oil with an olefin content of 1201mgBr / 100g (C8 aromatics mass content 45.0%, C9 and above aromatics content 54.2%, non-aromatics content 0.3%, toluene content 0.4%, benzene content 0.1%), and the liquid volume space velocity is 3h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 1096 mgBr / 100 g.

[0120] Comparative Example 3

[0121] (1) dissolving magnesium nitrate and aluminum sulfate (Mg / Al molar ratio of 3:1, magnesium nitrate 6 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio of 2:1) until the system pH = 10, and vigorously stirring at 50° C. for 4 h to react, and then obtaining a mixture;

[0122] (2) reacting the mixture obtained in step (1) at 120° C. for 24 hours under stirring, filtering and washing, then drying at 50° C. for 12 hours, and finally calcining at 200° C. for 4 hours to obtain a composite metal layered oxide I;

[0123] (3) then taking out 80 g of the composite metal layered oxide I obtained in step (2), adding 160 g of sodium hydroxide (concentration of 0.07 mol / L), treating at 30° C. for 4 hours, then filtering and washing, drying at 70° C. for 18 hours, and then treating at room temperature with a mixed solution of 0.01 mol / L sulfuric acid (liquid-to-solid mass ratio of 4) for 3 hours, filtering and washing, and drying at 80° C. for 12 hours to obtain a composite metal oxide II;

[0124] (4) preparing an impregnation solution containing ZrOCl2 (2.9 mol / L) and ammonium tungstate (0.29 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatics refining agent intermediate;

[0125] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was impregnated with an ammonium carbonate solution (0.2 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic refining agent DA-3.

[0126] Take 5g of the catalyst DA-3 obtained in Comparative Example 1, use the reforming product oil with an olefin content of 1201mgBr / 100g (C8 aromatics mass content 45.0%, C9 and above aromatics content 54.2%, non-aromatics content 0.3%, toluene content 0.4%, benzene content 0.1%), and the liquid volume space velocity is 3h -1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 150°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 750 mgBr / 100 g. The bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 1103 mgBr / 100 g.

[0127] Comparative Example 4

[0128] (1) dissolving cobalt sulfate and chromium nitrate (Co / Cr molar ratio 4.5:1, chromium salt 5 moles) in 500 g of water, and fully dissolving and mixing to obtain a mixed solution; adding the mixed solution of sodium carbonate until the system pH = 11, and vigorously stirring at 30° C. for 18 h to react, and then obtaining a mixture;

[0129] (2) reacting the mixture obtained in step (1) at 110° C. for 48 hours under stirring, filtering and washing, and then drying at 120° C. for 12 hours to obtain a composite metal layered oxide I;

[0130] (3) then taking out 80 g of the composite metal layered oxide I obtained in step (2), adding 160 g of sodium carbonate (concentration of 0.3 mol / L), treating at 99° C. for 6 hours, filtering and washing, drying at 160° C. for 10 hours, and then treating with a 3.0 mol / L sulfuric acid solution (liquid-to-solid mass ratio of 6) at 60° C. for 12 hours, filtering and washing, and drying at 160° C. for 10 hours to obtain a composite metal oxide II;

[0131] (4) preparing an impregnation solution containing ZrOCl2 (8.2 mol / L) and ammonium tungstate (0.44 mol / L), impregnating the composite metal oxide II (60 g) obtained in step (3) with the impregnation solution (20 g) obtained in step (4), filtering, washing, and drying at 100° C. for 12 h to obtain an aromatic hydrocarbon refining agent intermediate;

[0132] (5) 30 g of the aromatic refining agent intermediate obtained in step (4) was immersed in a potassium hydroxide solution (0.1 mol / L, 40 g), filtered and washed, dried at 120° C. for 10 h, and calcined at 550° C. for 3 h to obtain the aromatic refining agent DA-4.

[0133] 5 g of the catalyst DA-4 obtained in Example 4 was taken, and the reforming product oil (C8 aromatics mass content 65.0%, C9 and above aromatics mass content 33.2%, non-aromatics mass content 0.4%, toluene mass content 1.2%, benzene mass content 0.2%) with an olefin content of 610 mgBr / 100 g according to the bromine index was used, and the liquid volume space velocity was 5 h- 1 The reaction was evaluated at a pressure of 1.9 MPa and a temperature of 190°C. The bromine index of the refined reformed oil obtained at the outlet after 10 hours of reaction was 310 mgBr / 100 g, and the bromine index of the refined reformed oil obtained at the outlet after 300 hours of reaction was 510 mgBr / 100 g.

[0134] Table 1 Composition of the composite metal oxides obtained in each example

[0135]

[0136] Table 2 Composition of aromatics refining agent obtained in each case

[0137]

[0138]

[0139] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An aromatic hydrocarbon refining agent, comprising a composite metal oxide and a solid superacid, wherein the metal comprises a divalent metal A and a trivalent metal B, wherein: The atomic molar ratio of A / (A+B) is 0.45 to 0.

81.

2. The refined preparation according to claim 1, characterized in that: The solid superacid comprises at least one of a tungsten-zirconium composite oxide or a tungsten-titanium composite oxide, preferably a tungsten-zirconium composite oxide, wherein the mass ratio of tungsten oxide to zirconium oxide is preferably 10-40:90-60.

3. The refined preparation according to claim 1, characterized in that: In the composite metal oxide, the divalent metal A is selected from at least one of Mg, Fe, Co, Cd, Zn, Ni, and Cu, preferably one of Mg, Fe, and Zn; the trivalent metal B is selected from at least one of Al, Cr, and Fe, preferably Al.

4. The refined preparation according to claim 1, characterized in that: Based on the mass of the catalyst, the content of the composite metal oxide is 50% to 90%, and the content of the solid super acid in terms of oxide is 10% to 50%.

5. A method for preparing the refined preparation according to any one of claims 1 to 4, comprising the following steps: (1) reacting a solution containing metal A and metal B with a mixed solution of sodium hydroxide and sodium carbonate to obtain a mixture; (2) The mixture obtained in step (1) is reacted and calcined to obtain a composite metal layered oxide I; (3) The composite metal layered oxide I obtained in step (2) is treated with a strong base and an acid in sequence to obtain a composite metal oxide II; (4) The composite metal oxide II obtained in step (3) is loaded with a solid superacid to obtain an aromatic hydrocarbon refining agent intermediate; (5) impregnating the aromatic hydrocarbon refining agent intermediate obtained in step (4) with an ammonium salt solution and calcining to obtain the aromatic hydrocarbon refining agent.

6. The preparation method according to claim 5, characterized in that: In step (1), in the solution containing metal A and metal B, the source of metal A is selected from one or more of soluble nitrates, sulfates, halides, and halides; the source of metal B is selected from one or more of soluble nitrates, sulfates, halides, and halides; And / or, in step (1), in the composite metal layered oxide I, the atomic molar ratio of A / (A+B) is 0.60 to 0.

83.

7. The preparation method according to claim 5, characterized in that: In step (1), in the mixed solution of sodium hydroxide and sodium carbonate, the molar ratio of sodium hydroxide to sodium carbonate is 0.1 to 5.0; And / or, in step (1), the pH value at the reaction end point is 9 to 11, preferably 9 to 10; And / or, in step (1), the reaction conditions are as follows: temperature is 10-120° C., preferably 20-90° C., and time is 2-72 h, preferably 2-24 h.

8. The preparation method according to claim 5, characterized in that: In step (2), the reaction conditions are as follows: temperature is 50 to 210° C., and time is 2 to 120 h; And / or, the calcination conditions are as follows: temperature is 200-450° C., time is 0.5-48 h, and the calcination atmosphere is oxygen-containing gas or inert gas.

9. The preparation method according to claim 5, characterized in that: In step (3), the atomic mole ratio of A / (A+B) in the composite metal oxide II is 0.02 to 0.15 lower than the atomic mole ratio of A / (A+B) in the composite metal layered oxide I; And / or, the atomic molar ratio of A / (A+B) in the composite metal oxide II is 0.45 to 0.

81.

10. The preparation method according to claim 5, characterized in that: In step (3), the strong base is selected from at least one of an inorganic strong base or an organic strong base; the inorganic strong base contains at least one ion selected from the elements Li, Na, Cs, and K; the organic strong base is an organic amine, preferably one or more of the strong alkaline amines of tetramethylamine, tetraethylamine, tetrapropylamine, tetrabutylamine, and trialkylamine; and / or, the concentration of the strong alkaline solution is not less than 0.1 mol / L, preferably 0.1 to 2.0 mol / L; and / or, the liquid-to-solid mass ratio of the strong alkaline solution to the composite metal layered oxide I is greater than 1, preferably 1.5 to 10; And / or, the conditions of strong alkali treatment are as follows: temperature is 10-100° C., and time is 1-12 h.

11. The preparation method according to claim 5, characterized in that: In step (3), the acid is selected from at least one of an inorganic strong acid or an organic acid; the inorganic strong acid is selected from at least one of sulfuric acid, nitric acid, and hydrochloric acid; the organic acid is at least one of an organic carboxylic acid or an organic sulfonic acid, preferably one or more of formic acid, acetic acid, oxalic acid, propionic acid, and benzenesulfonic acid; and / or, the concentration of the acid solution is 0.02 to 1.5 mol / L; and / or, the liquid-to-solid mass ratio of the acid solution to the composite metal layered oxide I is 3 to 10; And / or, the conditions of acid treatment are as follows: temperature is 0 to 99° C., and time is 0.5 to 48 h.

12. The preparation method according to claim 5, characterized in that: In step (4), the solid superacid is loaded by an impregnation method. In the impregnation solution, the tungsten source is one or more of ammonium tungstate, ammonium metatungstate, and tungstate, preferably ammonium tungstate; the zirconium source is one or more of zirconium oxychloride, zirconium nitrate, and zirconium sulfate, preferably zirconium oxychloride; the titanium source is one or more of titanium chloride, titanium oxalate, titanium oxysulfate, and titanate, preferably titanium oxalate and titanate; and / or, the solid-liquid mass ratio of the composite metal oxide II to the impregnation solution is 0.1 to 4.0; And / or, the immersion conditions are as follows: temperature is 10 to 100° C., and time is 1 to 12 hours.

13. The preparation method according to claim 5, characterized in that: In step (5), the ammonium salt is one or more of ammonium carbonate, ammonium formate, and ammonium acetate; the concentration of the ammonium salt solution is 0.1 to 5 mol / L; the solid-liquid mass ratio of the intermediate to the ammonium salt solution is 0.1 to 0.75; And / or, in step (5), the immersion conditions are as follows: temperature is 10 to 120° C., time is 1 to 12 hours; And / or, in step (5), the calcination conditions are as follows: temperature is 450-600° C., and time is 1-10 h.

14. Use of the aromatics refining agent according to any one of claims 1 to 4 in the refining reaction of reforming oil.

15. The use according to claim 14, characterized in that: The reaction conditions are as follows: liquid hourly volumetric space velocity is 0.1h -1 ~20h -1 , temperature is 90~230℃, pressure is 0.2~5.0MPa.

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