An aromatic hydrocarbon refining agent, a preparation method and application thereof

Abstract

The application discloses an aromatic hydrocarbon refining agent and a preparation method and application thereof. The refining agent comprises a composite metal oxide and a solid super strong acid, the metal comprises divalent metal A and trivalent metal B, wherein the atomic molar ratio of A / (A+B) is 0.45-0.81; the preparation method of the refining agent comprises the following steps: a solution containing metal A and metal B is reacted with a mixed solution of sodium hydroxide and sodium carbonate, the obtained mixture is further reacted and calcined to obtain a composite metal layered oxide I, the composite metal layered oxide I is sequentially treated by a strong base and an acid to obtain a composite metal oxide II; then the solid super strong acid is loaded to obtain an aromatic hydrocarbon refining agent intermediate; finally, ammonium exchange and calcination are carried out to obtain the aromatic hydrocarbon refining agent. The prepared refining agent can solve the problem of poor dispersion of the super strong acid, improve the reaction activity of the super strong acid, and greatly prolong the service life of the refining agent.

Description

Technical Field

[0001] This invention relates to the field of aromatics production, and more specifically, to a refining agent and its preparation method for reducing the olefin content in C9 and above aromatics during the aromatics production process, especially during the production process of an aromatics complex. Background Technology

[0002] Among basic organic feedstocks, benzene, toluene, and p-xylene occupy a very important position. The aromatic feedstock obtained from hydrocracking has a high bromine index. In the aromatics complex production process, naphtha reforming, disproportionation and alkyl transfer, and isomerization are required to generate the target product, a mixture of C8 aromatics, which is then separated by adsorption to obtain the p-xylene product. The various reaction products or intermediates contain many impurities and have a high bromine index. After bromine index reduction treatment, they can enter the downstream xylene tower. C8 aromatics are separated at the top of the xylene tower, while the product at the bottom is converted into the target C8 aromatics through disproportionation and alkyl transfer units. The C8 aromatics separated at the top of the xylene tower require an extremely low bromine index; therefore, the efficiency of C8 aromatics de-olefinization is of great concern.

[0003] Industrially, two main technical routes are generally used to remove olefins from aromatic hydrocarbons: hydrogenation and liquid-solid phase alkylation catalytic reactions, thereby reducing their bromine index. Commonly used refining agents include clay and molecular sieves.

[0004] CN102008976A discloses a de-olefin refining agent, which uses 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. However, due to the limitations of the pore structure, it is difficult to achieve high efficiency for olefins in C9 and above aromatics. CN103041841B prepares a non-hydrogen-dependent de-olefin refining agent for aromatics using Y molecular sieve. It uses Y molecular sieve as the active center, and the reaction within its pores is more effective for olefins of C8 and below. However, due to the limitations of the molecular sieve pore structure, the removal efficiency for olefins in C9 and above aromatics is relatively low. CN102039160B discloses a reforming oil deolefin refining agent containing, by weight, 0.1 to 10 parts of at least one metal or oxide selected from Ni, Mo, Zr, Nb, or the element thereof; 0.01 to 2.00 parts of at least one element or oxide selected from Cl, Br, S; 0.05 to 5 parts of at least one element or oxide selected from F, P; 20 to 90 parts of molecular sieve; and 10 to 80 parts of at least one catalyst selected from SiO2, Al2O3, or a mixture thereof. This method has acidity in the macropores to a certain extent, but since the reaction mainly utilizes the acidity of the molecular sieve, the acidity outside the molecular sieve is restricted by the pores, which is more likely to cause coking and deactivation, resulting in low olefin removal efficiency in C9 and above aromatics. CN104907090A discloses a catalytic reforming oil refining agent for removing olefins and its preparation method, which includes 30% to 70% Al2O3 and 30% to 70% molecular sieves. It uses molecular sieves as active carriers and alumina modification method, but the effect of removing olefins from C9 and above aromatics is poor.

[0005] In summary, while existing catalysts or refining agents using different molecular sieves can reduce the bromine index, their efficiency in removing olefins from C9 and above aromatic hydrocarbons is relatively low. Summary of the Invention

[0006] To address the problem of low deolefin removal efficiency in C9 and above aromatics in existing technologies, this invention provides a novel aromatic refining agent, its preparation method, and its application. Using the refining agent of this invention significantly improves the deolefin removal efficiency, especially for C9 and above aromatics, solving the current problem of low deolefin removal efficiency in high-boiling-point fractions, and resulting in stable quality aromatic products.

[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 to 0.81.

[0008] According to the present invention, the solid superacid includes 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 as oxide is 10% to 50%.

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

[0013] (1) A solution containing metal A and metal B reacts 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 composite metal layered oxide I;

[0015] (3) The composite metal layered oxide I obtained in step (2) is subjected to strong alkali treatment and acid treatment in sequence to obtain composite metal oxide II;

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

[0017] (5) Impregnate the aromatic refining intermediate obtained in step (4) with ammonium salt solution, and calcine to obtain the aromatic refining preparation.

[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 halide salts, 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 halide salts, 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 and metal B satisfies: A / (A+B) is 0.60 to 0.83.

[0020] According to the present invention, in step (1), the molar ratio of sodium hydroxide to sodium carbonate in the mixed solution of sodium hydroxide and 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 to carry out the reaction, and the reaction is carried out under stirring. The pH value at the end 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 and the reaction time is 2-120 h. The calcination temperature is 200-450°C and the calcination time is 0.5-48 h. The calcination atmosphere is an oxygen-containing gas or an inert gas.

[0023] According to the present invention, in step (2), after the reaction is completed, the mixture undergoes conventional filtration, washing, and drying. The washing can be performed with deionized water until neutral. The drying conditions are 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 inorganic strong bases or organic strong bases. 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 strong basic amines such as tetramethylamine, tetraethylamine, tetrapropylamine, tetrabutylamine, and trialkylamines. Further, the concentration of the strong base solution is not less than 0.1 mol / L, preferably 0.1–2.0 mol / L. Further, the liquid-to-solid mass ratio of the strong base solution to the composite metal layered oxide I is greater than 1, preferably 1.5–10. Further, the conditions for the strong base treatment are as follows: the treatment temperature is 10–100°C, and the treatment time is 1–12 h.

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

[0026] According to the present invention, in step (3), the atomic molar ratio of A / (A+B) in composite metal oxide II is 0.02 to 0.15 lower than that of A / (A+B) in composite metal layered oxide I. Preferably, the atomic molar ratio of A / (A+B) in 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 impregnation. In the impregnation solution, the tungsten source is one or more of ammonium tungstate, ammonium metatungstate, and tungstates (sodium salt, potassium salt, rubidium salt, cesium salt), preferably ammonium tungstate; the zirconium source is one or more of ZrOCl2 (zirconium oxychloride), zirconium nitrate, and 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 (calculated as tungsten oxide) to the zirconium source (calculated as 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 impregnation, the product undergoes routine filtration, washing, and drying. The drying temperature is 60–400℃, and the drying time is 0.2–24 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 0.1–5 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 impregnation, the intermediate undergoes conventional filtration, washing, and drying. 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 1-10h.

[0031] According to the present invention, in step (5), the material is subjected to a binder and molding before or after calcination, followed by drying and calcination to obtain a catalyst. The binder contains one or both of alumina and silicon dioxide.

[0032] A third aspect of the present invention provides the application of the above-mentioned aromatic refining agent in the refining reaction of reformed oil.

[0033] According to the present invention, the olefin content in the reaction raw materials is 200-5000 mgBr / 100g, calculated by the bromine index.

[0034] According to the present invention, the mass content of C8 aromatics in the reaction raw materials 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 and C9 and above aromatics in the reaction raw materials is 80% or more, preferably 85% to 99.9%.

[0035] According to the present invention, the reaction process conditions are as follows: liquid hourly space velocity (LISH) is 0.1 h⁻¹. -1 ~20h -1 The temperature ranges from 90 to 230°C, and the pressure ranges from 0.2 to 5.0 MPa.

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

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

[0038] This invention provides a novel aromatic hydrocarbon refining agent comprising a composite metal oxide and a solid superacid. The metal comprises divalent metal A and trivalent metal B, wherein the atomic molar ratio of A / (A+B) is 0.45–0.81. Using this refining agent, in downstream production of C8 aromatic hydrocarbons, the olefin removal efficiency from olefin impurities in C9 and higher aromatic hydrocarbons is improved, solving the current problems of low olefin removal efficiency for high-boiling-point fractions and short production cycles.

[0039] In existing technologies, superacids exhibit poor dispersibility and low reactivity. The inventors discovered that by sequentially treating a composite metal layered oxide I containing divalent metal A and trivalent metal B, where the atomic molar ratio of A / (A+B) is 0.60–0.83, with strong alkali and acid treatments, and by controlling the conditions of these treatments, the atomic molar ratio of A / (A+B) in the resulting composite metal oxide II can be controlled to be 0.02–0.15 lower than that in composite metal layered oxide I. Then, a solid superacid is loaded onto this oxide, allowing the superacid to be uniformly dispersed within the layered oxide. The resulting refined product effectively solves the problem of poor superacid dispersion and also improves the reactivity of the superacid, significantly extending the product's lifespan. Detailed Implementation

[0040] To facilitate understanding of the present invention, the following embodiments are provided, but these embodiments are merely for the purpose of helping to understand the present invention and should not be regarded as limitations on the present invention.

[0041] Example 1

[0042] (1) Dissolve magnesium nitrate and aluminum sulfate (Mg / Al molar ratio 3:1, magnesium nitrate 6 moles) in 500g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the pH of the system is 10, stir vigorously at 50℃ for 4h to carry out the reaction, and then obtain a mixture;

[0043] (2) The mixture obtained in step (1) was reacted at 120°C for 24 hours under stirring conditions, filtered and washed, then dried at 50°C for 12 hours, and finally calcined at 200°C for 4 hours to obtain composite metal layered oxide I.

[0044] (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℃ for 4 hours, then filter and wash, dry at 70℃ for 18 hours, then treat at room temperature for 3 hours in a mixture of 0.5mol / L sulfuric acid and 0.5mol / L oxalic acid (liquid-solid mass ratio of 4), filter and wash, dry at 80℃ for 12 hours to obtain composite metal oxide II;

[0045] (4) Prepare an impregnation solution containing ZrOCl2 (2.9 mol / L) and ammonium tungstate (0.29 mol / L), impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0046] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium carbonate solution (0.2mol / L, 40g), filter and wash, dry at 120℃ for 10h, and calcine at 550℃ for 3h to obtain the aromatic refining preparation A.

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

[0048] Example 2

[0049] (1) Dissolve zinc chloride and aluminum sulfate (Zn / Al molar ratio 2:1, zinc chloride 5 moles) in 500g water, mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the pH of the system is 9.5, stir vigorously at 70℃ for 8h to carry out the reaction, and then obtain a mixture;

[0050] (2) The mixture obtained in step (1) was reacted at 180°C for 20 hours under stirring conditions, filtered and washed, then dried at 100°C for 12 hours, and finally calcined at 280°C for 4 hours to obtain composite metal layered oxide I.

[0051] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of tetrapropylammonium hydroxide (concentration of 0.1mol / L), treat at 40℃ for 2 hours, then filter and wash, dry at 90℃ for 18 hours, then treat in a solution of 0.7mol / L oxalic acid (liquid-solid mass ratio of 6) at room temperature for 6 hours, filter and wash to obtain composite metal oxide II;

[0052] (4) Prepare an impregnation solution containing ZrOCl2 (4.81 mol / L) and ammonium tungstate (0.81 mol / L), impregnate the composite metal oxide II (45 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0053] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium carbonate solution (0.3mol / L, 40g), filter and wash, dry at 100℃ for 20h, and calcine at 500℃ for 4h to obtain the aromatic refining preparation B.

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

[0055] Example 3

[0056] (1) Dissolve ferric hypochlorite and aluminum sulfate (Fe / Al molar ratio 2:1, 5 moles of iron salt) in 500g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 1:1) until the pH of the system is 9.0, stir vigorously at 40℃ for 10h to carry out the reaction, and then obtain a mixture;

[0057] (2) The mixture obtained in step (1) was reacted at 150°C for 48 hours under stirring conditions, filtered and washed, then dried at 120°C for 10 hours, and then dried at 260°C for 10 hours to obtain 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℃ for 4 hours, then filter and wash, dry at 60℃ for 24 hours, then treat in a solution of 0.5mol / L acetic acid (liquid-solid mass ratio of 4) at room temperature for 6 hours, filter and wash, dry at 120℃ for 6 hours to obtain composite metal oxide II;

[0059] (4) Prepare an impregnation solution containing Zr(NO3)2 (4.63mol / L) and sodium tungstate (0.98mol / L), and impregnate the composite metal oxide II (30g) obtained in step (3) with the obtained impregnation solution (18g), filter, wash, and dry at 100℃ for 12h to obtain an aromatic refining intermediate;

[0060] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with potassium hydroxide solution (0.15mol / L, 40g), filter and wash it, dry it at 150℃ for 8h, and calcine it at 580℃ for 2h to obtain the aromatic refining preparation C.

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

[0062] Example 4

[0063] (1) Dissolve cobalt sulfate and chromium nitrate (Co / Cr molar ratio 4.5:1, chromium salt 5 moles) in 500g of water, mix thoroughly to obtain a mixed solution; add sodium carbonate solution to the system until pH=11, stir vigorously at 30℃ for 18h to carry out the reaction, and then obtain a mixture;

[0064] (2) The mixture obtained in step (1) was reacted at 110°C for 48 hours under stirring conditions, filtered and washed, and then dried at 120°C for 12 hours to obtain composite metal layered oxide I.

[0065] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of sodium carbonate (concentration of 0.3mol / L), treat at 99℃ for 6 hours, then filter and wash, dry at 160℃ for 10 hours, then treat in a solution of 0.5mol / L propionic acid (liquid-solid mass ratio of 8) at 60℃ for 12 hours, filter and wash, dry at 160℃ for 10 hours to obtain composite metal oxide II;

[0066] (4) Prepare an impregnation solution containing ZrOCl2 (8.2 mol / L) and ammonium tungstate (0.44 mol / L), and impregnate the composite metal oxide II (60 g) obtained in step (3) with the impregnation solution (20 g) obtained in step (4), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0067] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with potassium hydroxide solution (0.1mol / L, 40g), filter and wash it, dry it at 120℃ for 10h, and calcine it at 550℃ for 3h to obtain the aromatic refining agent D.

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

[0069] Example 5

[0070] (1) Dissolve copper sulfate and aluminum sulfate (Cu / Al molar ratio 2:1, copper salt 5 moles) in 500g water, mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 3:1) until the pH of the system is 10.5, stir vigorously at 20℃ for 9h to carry out the reaction, and then obtain a mixture;

[0071] (2) The mixture obtained in step (1) was reacted at 100°C for 42 hours under stirring, filtered and washed, and then dried at 150°C for 40 hours to obtain composite metal layered oxide I.

[0072] (3) Then take 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℃ for 4 hours, then filter and wash, and dry at 70℃ for 18 hours. Then treat in a mixture of 0.1mol / L nitric acid and 0.5mol / L oxalic acid (liquid-solid mass ratio of 8) at room temperature for 3 hours, then filter and wash, and dry at 80℃ for 12 hours to obtain composite metal oxide II;

[0073] (4) Prepare an impregnation solution containing ZrOCl2 (3.92 mol / L) and ammonium tungstate (0.66 mol / L), impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0074] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium acetate solution (0.2mol / L, 40g), filter and wash, dry at 120℃ for 10h, and calcine at 550℃ for 3h to obtain the aromatic refining agent E.

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

[0076] Example 6

[0077] (1) Dissolve zinc chloride and ferric sulfate (Zn / Fe molar ratio 1.5:1) in water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 5:1) until the pH of the system is 9.5, stir vigorously at 50°C for 5 hours to carry out the reaction, and then obtain a mixture;

[0078] (2) The mixture obtained in step (1) was reacted at 190°C for 20 hours under stirring conditions, filtered and washed, and then dried at 260°C for 12 hours to obtain composite metal layered oxide I.

[0079] (3) Then take 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℃ for 4 hours, then filter and wash, and dry at 70℃ for 18 hours. Then treat in a mixture of 0.1mol / L nitric acid and 0.5mol / L oxalic acid (liquid-solid mass ratio of 8) at room temperature for 3 hours, then filter and wash, and dry at 80℃ for 12 hours to obtain composite metal oxide II;

[0080] (4) Prepare 100g of impregnation solution containing ZrOCl2 (12.4mol / L) and ammonium tungstate (0.54mol / L), impregnate the composite metal oxide II (60g) obtained in step (3) with the obtained impregnation solution (20g), filter, wash, and dry at 100℃ for 12h to obtain an aromatic refining intermediate;

[0081] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium acetate solution (0.2mol / L, 40g), filter and wash, dry at 120℃ for 10h, and calcine at 550℃ for 3h to obtain the aromatic refining agent F.

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

[0083] Example 7

[0084] (1) Dissolve magnesium sulfate and aluminum sulfate (Mg / Al molar ratio 2:1, copper salt 5 moles) in 500g water, mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 1:2) until the pH of the system is 10.0, stir vigorously at 80℃ for 5h to carry out the reaction, and then obtain a mixture;

[0085] (2) The mixture obtained in step (1) was reacted at 190°C for 15 hours under stirring conditions, filtered and washed, and then dried at 120°C for 40 hours to obtain composite metal layered oxide I.

[0086] (3) Then take 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℃ for 4 hours, then filter and wash, and dry at 90℃ for 15 hours. Then treat in a mixture of 0.2mol / L sulfuric acid and 0.5mol / L propionic acid (liquid-solid mass ratio of 5) at room temperature for 3 hours, then filter and wash, and dry at 90℃ for 12 hours to obtain composite metal oxide II;

[0087] (4) Prepare an impregnation solution containing ZrOCl2 (5.13 mol / L) and ammonium tungstate (0.86 mol / L), impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 120 °C for 6 h to obtain an aromatic refining intermediate;

[0088] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium oxalate solution (0.2mol / L, 50g), filter and wash, dry at 120℃ for 10h, and calcine at 480℃ for 12h to obtain the aromatic refining agent G.

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

[0090] Example 8

[0091] (1) Dissolve magnesium chloride and aluminum nitrate (Mg / Al molar ratio 1.5:1, 7 moles of magnesium salt) in 600g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 1:1) until the pH of the system is 10.5, stir vigorously at 30℃ for 5h to carry out the reaction, and then obtain a mixture;

[0092] (2) The mixture obtained in step (1) was reacted at 120°C for 48 hours under stirring conditions, filtered and washed, and then dried at 120°C for 8 hours to obtain composite metal layered oxide I.

[0093] (3) Then take 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℃ for 4 hours, then filter and wash, and dry at 120℃ for 3 hours. Then treat in a solution of 0.2mol / L sulfuric acid (liquid-solid mass ratio of 3) at room temperature for 3 hours, then filter and wash, and dry at 190℃ for 6 hours to obtain composite metal oxide II;

[0094] (4) Prepare an impregnation solution containing ZrOCl2 (9.08 mol / L) and ammonium tungstate (0.89 mol / L), impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 70 °C for 48 h to obtain an aromatic refining intermediate;

[0095] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium formate solution (0.2mol / L, 50g), filter and wash it, dry it at 150℃ for 6h, and calcine it at 590℃ for 2h to obtain the aromatic refining agent H.

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

[0097] Example 9

[0098] (1) Dissolve magnesium nitrate and aluminum sulfate (Mg / Al molar ratio 4.5:1, magnesium salt 5 moles) in 600g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 1:2) until the pH of the system is 9.5, stir vigorously at 90℃ for 5h to carry out the reaction, and then obtain a mixture;

[0099] (2) The mixture obtained in step (1) was reacted at 210°C for 12 hours under stirring conditions, filtered and washed, and then dried at 180°C for 2 hours to obtain composite metal layered oxide I;

[0100] (3) Then take 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℃ for 4 hours, then filter and wash, and dry at 120℃ for 3 hours. Then treat in a solution of 0.2mol / L sulfuric acid (liquid-solid mass ratio of 3) at room temperature for 3 hours, then filter and wash, and dry at 190℃ for 6 hours to obtain composite metal oxide II;

[0101] (4) Prepare an impregnation solution containing ZrOCl2 (8.46 mol / L) and ammonium tungstate (2.21 mol / L), and impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 50 °C for 20 h to obtain an aromatic refining intermediate;

[0102] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium carbonate solution (0.3mol / L, 50g). Filter and wash, dry at 120℃ for 16h, then knead with 20g alumina monohydrate, 3g 60% nitric acid and 3g guar gum powder, extrude into strips, dry at 120℃ for 20h, and calcine at 550℃ for 3h to obtain the aromatic refining preparation I.

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

[0104] Example 10

[0105] (1) Dissolve zinc nitrate and chromium sulfate (Zn / Cr molar ratio 3:1, zinc salt 5 moles) in 500g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the pH of the system is 10.5, stir vigorously at 40℃ for 8h to carry out the reaction, and then obtain a mixture;

[0106] (2) The mixture obtained in step (1) was reacted at 160°C for 26 hours under stirring conditions, filtered and washed, and then dried at 120°C for 7 hours to obtain composite metal layered oxide I.

[0107] (3) Then take 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℃ for 3 hours, then filter and wash, and dry at 100℃ for 6 hours. Then treat in a solution of 0.2mol / L sulfuric acid (liquid-solid mass ratio of 5) at room temperature for 2 hours, then filter and wash, and dry at 120℃ for 6 hours to obtain composite metal oxide II;

[0108] (4) Prepare an impregnation solution containing ZrOCl2 (5.67 mol / L) and ammonium tungstate (0.95 mol / L), impregnate the composite metal oxide II (45 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 70 °C for 20 h to obtain an aromatic hydrocarbon refining preparation intermediate;

[0109] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium carbonate solution (0.3mol / L, 40g). Filter and wash, dry at 120℃ for 16h, then knead with 10g alumina monohydrate, 10g silica sol with a mass concentration of 40%, 3g nitric acid and 3g guar gum powder, extrude into strips, dry at 120℃ for 20h, and calcine at 580℃ for 3h to obtain the aromatic refining preparation I.

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

[0111] Comparative Example 1

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

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

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

[0115] Comparative Example 2

[0116] (1) Dissolve magnesium nitrate and aluminum sulfate (Mg / Al molar ratio 3:1, magnesium nitrate 6 moles) in 500g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the pH of the system is 10, stir vigorously at 50℃ for 4h to carry out the reaction, and then obtain a mixture;

[0117] (2) The mixture obtained in step (1) was reacted at 120°C for 24 hours under stirring conditions, filtered and washed, then dried at 50°C for 12 hours, and then dried at 200°C for 4 hours to obtain 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℃ for 4 hours, then filter and wash, dry at 70℃ for 18 hours, then treat at room temperature for 3 hours in a mixture of 0.5mol / L sulfuric acid and 0.5mol / L oxalic acid (liquid-solid mass ratio of 4), filter and wash, dry at 80℃ for 12 hours, and then calcine at 550℃ for 3 hours to obtain the aromatic refining agent DA-2.

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

[0120] Comparative Example 3

[0121] (1) Dissolve magnesium nitrate and aluminum sulfate (Mg / Al molar ratio 3:1, magnesium nitrate 6 moles) in 500g of water and mix thoroughly to obtain a mixed solution; add a mixed solution of sodium hydroxide and sodium carbonate (sodium hydroxide / sodium carbonate molar ratio 2:1) until the pH of the system is 10, stir vigorously at 50℃ for 4h to carry out the reaction, and then obtain a mixture;

[0122] (2) The mixture obtained in step (1) was reacted at 120°C for 24 hours under stirring conditions, filtered and washed, then dried at 50°C for 12 hours, and finally calcined at 200°C for 4 hours to obtain composite metal layered oxide I.

[0123] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of sodium hydroxide (concentration of 0.07mol / L), treat at 30℃ for 4 hours, then filter and wash, dry at 70℃ for 18 hours, then treat in a mixture of 0.01mol / L sulfuric acid (liquid-solid mass ratio of 4) at room temperature for 3 hours, filter and wash, dry at 80℃ for 12 hours to obtain composite metal oxide II;

[0124] (4) Prepare an impregnation solution containing ZrOCl2 (2.9 mol / L) and ammonium tungstate (0.29 mol / L), impregnate the composite metal oxide II (60 g) obtained in step (3) with the obtained impregnation solution (20 g), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0125] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with ammonium carbonate solution (0.2mol / L, 40g), filter and wash, dry at 120℃ for 10h, and calcine at 550℃ for 3h to obtain the aromatic refining agent DA-3.

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

[0127] Comparative Example 4

[0128] (1) Dissolve cobalt sulfate and chromium nitrate (Co / Cr molar ratio 4.5:1, chromium salt 5 moles) in 500g of water, mix thoroughly to obtain a mixed solution; add sodium carbonate solution to the system until pH=11, stir vigorously at 30℃ for 18h to carry out the reaction, and then obtain a mixture;

[0129] (2) The mixture obtained in step (1) was reacted at 110°C for 48 hours under stirring conditions, filtered and washed, and then dried at 120°C for 12 hours to obtain composite metal layered oxide I.

[0130] (3) Then take out 80g of the composite metal layered oxide I obtained in step (2), add 160g of sodium carbonate (concentration of 0.3mol / L), treat at 99℃ for 6 hours, then filter and wash, dry at 160℃ for 10 hours, then treat in a solution of 3.0mol / L sulfuric acid (liquid-solid mass ratio of 6) at 60℃ for 12 hours, filter and wash, dry at 160℃ for 10 hours to obtain composite metal oxide II;

[0131] (4) Prepare an impregnation solution containing ZrOCl2 (8.2 mol / L) and ammonium tungstate (0.44 mol / L), and impregnate the composite metal oxide II (60 g) obtained in step (3) with the impregnation solution (20 g) obtained in step (4), filter, wash, and dry at 100 °C for 12 h to obtain an aromatic refining intermediate;

[0132] (5) Take 30g of the aromatic refining intermediate obtained in step (4) and impregnate it with potassium hydroxide solution (0.1mol / L, 40g), filter and wash it, dry it at 120℃ for 10h, and calcine it at 550℃ for 3h to obtain the aromatic refining agent DA-4.

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

[0134] Table 1 shows the composition of the composite metal oxides obtained in each example.

[0135]

[0136] Table 2. Composition of the aromatic hydrocarbon refining preparations obtained in each case.

[0137]

[0138]

[0139] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing an aromatic hydrocarbon refining agent, 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) reacting and calcining the mixture obtained in step (1) to obtain a composite metal layered oxide I; (3) sequentially treating the composite metal layered oxide I obtained in step (2) with a strong base and an acid to obtain a composite metal oxide II; (4) loading the composite metal oxide II obtained in step (3) 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; In step (1), the divalent metal A is at least one selected from Mg, Fe, Co, Cd, Zn, Ni and Cu; and the trivalent metal B is at least one selected from Al and Fe. In step (1), the atomic molar ratio of A / (A+B) in the composite metal layered oxide I is 0.60-0.

83. In step (3), the atomic molar ratio of A / (A+B) in the composite metal oxide II is 0.02-0.15 lower than that in the composite metal layered oxide I. In step (4), the solid superacid comprises at least one of tungsten-zirconium composite oxide or tungsten-titanium composite oxide.

2. The method of claim 1, wherein: In step (1), the divalent metal A is at least one selected from Mg, Fe and Zn; and the trivalent metal B is Al. In step (4), the solid superacid is tungsten-zirconium composite oxide, wherein the mass ratio of tungsten oxide to zirconium oxide is 10-40:90-60.

3. The method of claim 1, wherein: In step (1), the metal A source in the solution containing metal A and metal B is one or more selected from soluble nitrate, sulfate, halide and halide salt; and the metal B source is one or more selected from soluble nitrate, sulfate, halide and halide salt.

4. The method of claim 1, wherein: In step (1), the molar ratio of sodium hydroxide to sodium carbonate in the mixed solution of sodium hydroxide and sodium carbonate is 0.1-5.

0. In step (1), the pH value at the end of the reaction is 9-11. In step (1), the reaction conditions are as follows: the temperature is 10-120℃, and the time is 2-72h.

5. The method of claim 4, wherein: In step (1), the pH value at the end of the reaction is 9-10. In step (1), the reaction conditions are as follows: the temperature is 20-90℃, and the time is 2-24h.

6. The method of claim 1, wherein: In step (2), the reaction conditions are as follows: the temperature is 50-210℃, and the time is 2-120h. In step (2), the calcination conditions are as follows: the temperature is 200-450℃, the time is 0.5-48h, and the calcination atmosphere is an oxygen-containing gas or an inert gas.

7. The method of claim 1, wherein: In step (3), the atomic molar ratio of A / (A+B) in the composite metal oxide II is 0.45-0.

81.

8. The method of claim 1, wherein: In step (3), the strong base is at least one selected from inorganic strong base or organic strong base; the inorganic strong base contains at least one ion selected from Li, Na, Cs and K elements; and the organic strong base is an organic amine. In step (3), the concentration of the strong base solution is not less than 0.1 mol / L. And / or, the liquid-solid mass ratio of the strong base solution to the composite metal layered oxide I is 1 or more; And / or, the strong base treatment is under the following conditions: temperature 10-100℃, time 1-12h.

9. The method of claim 8, wherein: In step (3), the organic strong base is one or more of tetramethylamine, tetraethylamine, tetrapropylamine, tetrabutylamine, and strong basic amine of trialkylamine; And / or, the concentration of the strong base solution is 0.1-2.0mol / L; And / or, the liquid-solid mass ratio of the strong base solution to the composite metal layered oxide I is 1.5-10.

10. The method of claim 1, wherein: In step (3), the acid is selected from at least one of inorganic strong acid or 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 organic carboxylic acid or organic sulfonic acid; And / or, the concentration of the acid solution is 0.02-1.5mol / L; And / or, the liquid-solid mass ratio of the acid solution to the composite metal layered oxide I is 3-10; And / or, the acid treatment is under the following conditions: temperature 0-99℃, time 0.5-48h.

11. The method of claim 10, wherein: In step (3), the organic acid is one or more of formic acid, acetic acid, oxalic acid, propionic acid, and benzenesulfonic acid.

12. The method of claim 1, wherein: In step (4), the impregnation method is used to load the solid superacid, and in the impregnation solution, the tungsten source is one or more of ammonium tungstate and ammonium metatungstate; the zirconium source is one or more of zirconium oxychloride, zirconium nitrate, and zirconium sulfate; the titanium source is one or more of titanium chloride, titanium oxalate, and titanic acid ester; And / or, the solid-liquid mass ratio of the composite metal oxide II to the impregnation solution is 0.1-4.0; And / or, the impregnation conditions are as follows: temperature 10-100℃, time 1-12h.

13. The method of claim 12, wherein: In step (4), the tungsten source is ammonium tungstate; the zirconium source is zirconium oxychloride; and the titanium source is titanium oxalate and titanic acid ester.

14. The method of claim 1, wherein: 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 0.1-5mol / L; and the solid-liquid mass ratio of the intermediate to the ammonium salt solution is 0.1-0.75; And / or, in step (5), the impregnation conditions are as follows: temperature 10-120℃, time 1-12h; And / or, in step (5), the calcination conditions are as follows: temperature 450-600℃, time 1-10h.

15. The aromatic hydrocarbon refining agent prepared by the preparation method of any one of claims 1-14.

16. The aromatic hydrocarbon treating agent of claim 15, wherein: The aromatic hydrocarbon refining agent comprises a composite metal oxide and a solid superacid; the content of the composite metal oxide is 50%-90% based on the mass of the refining agent, and the content of the solid superacid calculated as an oxide is 10%-50%.

17. The aromatic hydrocarbon refining agent of claim 15 or 16 for use in a reformate refining reaction.

18. The use according to claim 17, characterized in that: The reaction conditions are as follows: liquid hourly space velocity is 0.1 h -1 ~20 h -1 , temperature is 90~230 ℃, and pressure is 0.2~5.0 MPa.

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