Barium-containing alkaline macroporous material, preparation method thereof and alkaline catalyst

Abstract

The invention provides a barium-containing alkaline macroporous material, a preparation method thereof and an alkaline catalyst. The preparation method comprises the following steps: mixing a barium source, an aluminum source and water to obtain an aluminum-barium mixed solution, then adding an alkali source into the aluminum-barium mixed solution until the pH value is 8-11, aging, drying and roasting to obtain an aluminum-barium spinel alkaline material; the preparation method comprises the following steps: adding a silane coupling agent into an organic solvent to form a modified solution, adding an aluminum-barium spinel alkaline material into the modified solution, and uniformly mixing to obtain a modified aluminum-barium spinel alkaline material; the aluminum-barium mixed solution meets the following molar ratio: Ba: Al = (1-1.5): 2; the alkali source comprises 1-adamantyl trimethyl ammonium hydroxide. The barium-containing alkaline macroporous material has the characteristics of large pore volume, high alkali strength, multiple alkaline centers and difficulty in loss, is difficult to coke, and can be used as an alkaline catalyst for processing vacuum residuum, heavy oil, superheavy oil and the like.

Description

Technical Field

[0001] This invention relates to the field of heavy oil alkaline catalytic cracking technology, and in particular to a barium-containing alkaline macroporous material, its preparation method, and an alkaline catalyst. Background Technology

[0002] Currently, the trend towards heavier crude oil makes refineries increasingly eager to convert heavy residue oil into lighter, higher-priced products.

[0003] Currently, the main processes for converting heavy feedstocks into lighter oils include coking, hydrocracking, and catalytic cracking. Coking can process 100% residue oil feedstock with low investment and operating costs, making it the most widely used residue oil processing technology. However, it suffers from low liquid yield, high coke production, and poor product quality, resulting in underutilization of resource value. Hydrocracking offers high liquid yield and excellent product quality, but its investment and operating costs are relatively high, and it has strict feedstock requirements, making it unsuitable for direct residue oil processing. Catalytic cracking, due to its flexible operation, high light oil yield, and low investment and operating costs, is the most important secondary petroleum processing method, capable of processing vacuum gas oil and some vacuum residue.

[0004] Currently, conventional catalytic cracking mostly uses acidic molecular sieve catalysts, with various modified Y-type molecular sieves or ZSM-5 molecular sieves being common. Acidic catalysts are prone to hydrogen transfer and carbon deposition reactions, resulting in high yields of low-value-added products such as dry gas and coke. The feedstock for conventional catalytic cracking is typically a mixture of vacuum gas oil and vacuum residue, generally with vacuum residue comprising only 10-30%. In terms of feedstock composition, saturated hydrocarbon content is ≥50%, while aromatic hydrocarbon content is ≤30%. Conventional catalytic cracking cannot directly process pure residue feedstock or even lower-quality unconventional petroleum resources such as heavy oil, oil sands, and bitumen.

[0005] Due to their high aromatic and gum content, existing catalytic cracking methods have significant limitations when processing residue or extra-heavy oil feedstocks. On one hand, residue contains large amounts of macromolecular compounds such as gums and asphaltenes, which are prone to coking, leading to high coking rates, reduced unit throughput, and increased regenerator load. On the other hand, residue contains high levels of heavy metals (such as nickel and vanadium), which easily deposit on the catalyst, causing irreversible catalyst deactivation, thus increasing catalyst consumption and significantly raising operating costs. Existing acidic catalytic cracking catalysts cannot directly process full-fraction residue with high residual carbon content or extra-heavy oils such as oil sands bitumen. Furthermore, when processing light heavy oils, the presence of acidic centers easily leads to hydrogen transfer and dehydrogenation reactions, resulting in high dry gas content, high coke content, and low selectivity for low-carbon olefins.

[0006] The core technology of solid base catalysts lies in the synthesis of basic macroporous materials, and modified spinel is an important member of this category. Spinel, a magnesium-aluminum oxide with the chemical formula (Mg,Fe,Zn,Mn)(Al,Cr,Fe)₂O₄, exhibits widespread isomorphic substitution in its chemical composition and often contains elements such as iron, zinc, chromium, and manganese. Common spinels include zinc-aluminum spinel and magnesium-aluminum spinel, which possess characteristics such as resistance to phase transformation and good high-temperature stability, making them excellent macroporous supports. Current techniques have been used to study the synthesis of nano-magnesium-aluminum spinel.

[0007] CN107115853A discloses a Mg-Al type hydrotalcite catalyst for processing residual oil and extra-heavy oil feedstocks and its preparation method. The shortcomings of this technology are: the aging time of 8-20 hours during the preparation of the Mg-Al hydrotalcite is too long; the hydrotalcite lacks stability and undergoes a phase transformation at high temperatures, changing from a layered structure to a spinel structure; a large amount of acidic binder and nitric acid are added during the entire alkaline catalyst molding process, resulting in insufficient alkalinity and alkalinity strength of the catalyst, making it prone to coking when processing high-carbon residual heavy oil.

[0008] Patent CN100497173C provides a hydrothermal synthesis method for preparing microporous / mesoporous magnesium aluminate (MgAl2O4) with a high specific surface area: First, appropriate amounts of magnesium chloride, aluminum chloride, and urea (magnesium chloride:aluminum chloride:urea = 1:2:20, molar ratio) are dissolved in an ethanol-water solution (ethanol:water = 1:1, volume ratio); then, the mixture is hydrothermally reacted at 180°C for 24 hours. After separation, washing with water and alcohol, and drying at 80°C for 12 hours, magnesium aluminum spinel with a specific surface area of ​​220 m² is obtained. 2 / g. The drawbacks of this technology are: it requires high temperature and long time synthesis in a crystallization kettle, the spinel product has a small specific surface area and pore volume; zinc or magnesium spinel has relatively weak alkali strength and a low number of alkali centers.

[0009] Patent CN103143398A discloses a method for preparing magnesium aluminum spinel, which involves dissolving soluble aluminum salt, soluble magnesium salt, urea and / or hexamethylenetetramine, and a surfactant in a mixed solution of alcohol and water, and carrying out a hydrothermal reaction at 90-250°C. The hydrothermal product is then washed, dried, and calcined at 500-700°C, resulting in a magnesium aluminum spinel with a specific surface area of ​​210-250 m². 2 / g. However, the preparation of magnesium aluminum spinel using this method requires a high crystallization temperature.

[0010] Patent CN1634802A uses ammonium bicarbonate as a precipitant to co-precipitate aluminum nitrate and magnesium nitrate, followed by high-temperature calcination at above 1000℃ to prepare magnesium aluminum spinel nanoparticle powder. This method releases a large amount of CO2 gas, consumes a large amount of precipitant, and is energy-intensive and polluting to the environment; moreover, the magnesium aluminum spinel nanoparticle powder exhibits severe agglomeration.

[0011] Patent CN 101565194A describes adding an alkaline solution to a mixed solution of soluble aluminum and magnesium salts, along with a surfactant; the aged mixture is then hydrothermally crystallized at 120-180℃ for 4-72 hours; after washing, filtering, and drying, it is calcined at 500-700℃ for 4-6 hours to obtain magnesium aluminum spinel powder with a specific surface area of ​​200-400 m². 2 / gram, pore volume 0.20-0.55cm 3 / gram, particle diameter 10-15 nm. The disadvantages of this method are that it requires high temperature and long time synthesis in a crystallization kettle; it requires the simultaneous addition of precipitant and surfactant to carry out precipitation and pore formation, and the spinel product has a small specific surface area and pore volume; zinc or magnesium spinel has relatively weak alkali strength and low number of alkali centers.

[0012] Existing spinel materials have the characteristics of being resistant to phase transformation and having good high-temperature stability, making them excellent catalyst carriers. However, as active materials for heavy oil macromolecular cracking, they still have some problems, such as (1) small pore volume, which is not suitable for the entry and exit of heavy oil macromolecules; (2) low alkali strength, a small number of alkali centers that are easy to lose, and easy coking when processing heavy oil with high residual carbon; (3) harsh preparation conditions, high calcination temperature, and high energy consumption.

[0013] Therefore, there is a need for an alkaline catalyst that is highly basic, has a large pore volume, is simple to prepare, and can be used to treat heavy oil. Summary of the Invention

[0014] To address the aforementioned problems, the present invention aims to provide a barium-containing basic macroporous material, its preparation method, and an alkaline catalyst. This barium-containing basic macroporous material features large pore volume, high alkalinity, numerous alkaline centers that are not easily lost, and is less prone to coking, making it suitable for processing vacuum residue, heavy oil, and extra-heavy oil.

[0015] To achieve the above objectives, the present invention provides a method for preparing a barium-containing basic macroporous material, the method comprising:

[0016] S1. A barium source, an aluminum source, and water are mixed to obtain an aluminum-barium mixed solution. Then, an alkaline source is added to the aluminum-barium mixed solution until the pH value is 8-11 to obtain a raw material solution. The solution is aged, dried, and calcined to obtain an aluminum-barium spinel alkaline material. The aluminum-barium mixed solution satisfies the following molar ratio: Ba:Al = 1-1.5:2. The alkaline source includes 1-adamantyltrimethylammonium hydroxide.

[0017] S2. Add a silane coupling agent to an organic solvent to form a modified solution, add the aluminum barium spinel basic material to the modified solution and mix evenly to obtain the modified aluminum barium spinel basic material.

[0018] In the above preparation method, the aluminum-barium spinel basic material obtained by S1 is characterized by barium richness and large pore volume. Compared with aluminum-magnesium spinel, aluminum-barium spinel has higher basicity, which can reduce coking caused by hydrogen transfer reaction at strong acid centers and has better alkaline catalytic performance; the large pore volume facilitates the diffusion of heavy oil macromolecules and enhances the accessibility of heavy oil macromolecules.

[0019] In the above preparation method, barium and aluminum sources are used to synthesize aluminum barium spinel basic materials in step S1. Barium is more basic than other common alkaline earth metals. In aluminum barium spinel basic materials, barium mainly exists in the form of aluminum barium spinel, with a small amount of barium existing in the form of barium oxide. It has strong basicity and the basic centers are not easily lost.

[0020] In the above preparation method, in S1, the barium source includes a soluble barium salt, specifically barium nitrate and / or barium chloride, for example, barium nitrate alone can be used as the barium source.

[0021] In the above preparation method, in S1, the aluminum source includes soluble aluminum salts, specifically including one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, and potassium aluminum sulfate (such as potassium aluminum sulfate dodecahydrate). For example, aluminum nitrate alone can be used as the aluminum source.

[0022] In the above preparation method, the molar ratio of Ba to Al in the aluminum-barium mixed solution S1 is generally 1-1.5:2, specifically 1:2, 1.1:2, 1.2:2, 1.3:2, 1.4:2, 1.5:2, etc., and a range with any two of the above specific values ​​as endpoints, further being 1.1-1.3:2. This invention, by controlling the excess of barium in the aluminum-barium spinel alkaline material, can form BaO / BaAl2O4 material. The excess barium makes the material extremely alkaline.

[0023] In the above preparation method, the aluminum-barium mixed solution of S1 can satisfy the following molar ratio: Ba:Al:water = 1-1.5:2:18-30. The molar ratio of Al to water is generally controlled at 2:18-30, for example, it can be controlled as: 2:18, 2:19, 2:20, 2:21, 2:22, 2:23, 2:24, 2:25, 2:26, ​​2:27, 2:28, 2:29, 2:30, etc., as well as a range with any two of the above specific values ​​as endpoints.

[0024] In the above preparation method, in step S1, the alkali source includes 1-adamantyltrimethylammonium hydroxide. 1-adamantyltrimethylammonium hydroxide is a strong organic base with a molecular structure similar to ammonium hydroxide, but with a larger volume and stronger alkalinity. In the process of synthesizing aluminum-barium spinel alkaline materials in step S1, 1-adamantyltrimethylammonium hydroxide is used for modification. On the one hand, as a strong base, it can precipitate aluminum-barium; on the other hand, due to its large molecular volume, it has a certain pore-forming effect, promoting macropore formation. Furthermore, using 1-adamantyltrimethylammonium hydroxide as the alkali source does not introduce inorganic impurities and avoids a complex water washing process.

[0025] In the above preparation method, in step S1, the amount of alkali source added can be determined according to the pH value of the raw material solution. The pH value of the raw material solution is generally controlled between 8 and 11, specifically 8, 8.5, 9, 9.5, 10, 10.5, 11, etc., or a range with any two of the above specific values ​​as endpoints; it can be further controlled between 9 and 10.

[0026] In the above preparation method, in S1, the aging temperature is 50℃-80℃, for example, specific values ​​such as 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, etc., and a range with any two of the above specific values ​​as endpoints.

[0027] In the above preparation method, in S1, the aging time is 30min-60min, for example, specific values ​​such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, and a range with any two of the above specific values ​​as endpoints.

[0028] In the above preparation method, the drying in S1 can be spray drying.

[0029] In the above preparation method, in S1, the calcination process can cause the organic components in the raw materials to burn, releasing a large amount of heat, which is then discharged in gaseous form. This not only lowers the spinel formation temperature but also increases the specific surface area and pore volume of the material. In some specific embodiments, the surface area of ​​the aluminum barium spinel alkaline material obtained in S1 is greater than or equal to 300 m². 2 / g, pore volume greater than or equal to 0.6cm 3 / g. The calcination temperature is generally 400℃-600℃, specifically 400℃, 450℃, 500℃, 550℃, 600℃, etc., and any two of the above specific values ​​as endpoints, and further can be 450℃-550℃. The calcination time is 2h-4h, specifically 2h, 2.5h, 3h, 3.5h, 4h, etc., and any two of the above specific values ​​as endpoints.

[0030] In the above preparation method, in step S2, the alkaline material of aluminum barium spinel is modified by using a silane coupling agent to prevent the loss of alkalinity. Specifically, the silane coupling agent has hydrolyzable groups (taking γ-aminopropyltriethoxysilane as an example, which has three hydrolyzable ethoxy groups). In the reaction, the hydrolyzable groups first hydrolyze to generate silanol. Silanol is unstable and readily combines with the hydroxyl groups on the surface of the alkaline material of aluminum barium spinel for dehydration. On the one hand, this shields some acidic hydroxyl groups, reducing the acidity of the material; on the other hand, it forms a silica film, which can prevent the loss of the alkaline barium oxide center in subsequent reactions.

[0031] In the above preparation method, in step S2, the mass of the silane coupling agent is 0.1%-5% of the mass of the organic solvent, and can be further controlled to be 0.2%-1%. In some specific embodiments, the mass of the silane coupling agent can be a specific value of 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of the mass of the organic solvent, or a range with any two of the above specific values ​​as endpoints.

[0032] In the above preparation method, the silane coupling agent may include γ-aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane.

[0033] In the above preparation method, the organic solvent may include petroleum ether and / or anhydrous ethanol.

[0034] In the above preparation method, the aluminum barium spinel basic material can be added to the modification solution in equal volumes and mixed evenly, that is, the volume ratio of the modification solution to the aluminum barium spinel basic material can be 1:1. After the organic solvent evaporates, the silane coupling agent in the modification solution can completely enter the aluminum barium spinel basic material.

[0035] According to a specific embodiment of the present invention, the preparation method of the above-mentioned barium-containing basic macroporous material may include:

[0036] S1. A barium source, an aluminum source, and water are mixed to obtain an aluminum-barium mixed solution. Then, an alkali source is added to the aluminum-barium mixed solution until the pH value is 8-11 to obtain a raw material solution. The solution is aged at 50℃-80℃ for 30-60 minutes, dried, and calcined at 400℃-600℃ for 2-4 hours to obtain an aluminum-barium spinel alkaline material. The aluminum-barium mixed solution satisfies the following molar ratio: Ba:Al:water = 1-1.5:2:18-30. The alkali source includes 1-adamantyltrimethylammonium hydroxide.

[0037] S2. Add a silane coupling agent to an organic solvent to form a modified solution. The mass of the silane coupling agent is 0.1%-5% of the mass of the organic solvent. Add an equal volume of aluminum barium spinel basic material to the modified solution and mix evenly to obtain the modified aluminum barium spinel basic material.

[0038] The present invention also provides a barium-containing basic macroporous material, which is obtained by the above preparation method.

[0039] In a specific implementation scheme, the specific surface area of ​​the barium-containing alkaline macroporous material can be 310 m². 2 / g-380m 2 / g.

[0040] In a specific implementation scheme, the pore volume of the barium-containing alkaline macroporous material can be 0.60 cm³. 3 / g-0.90cm 3 / g.

[0041] In a specific implementation scheme, the number of alkali centers in the barium-containing basic macroporous material can be 5 mmol / g to 10 mmol / g.

[0042] In a specific implementation, the pore size of the barium-containing basic macroporous material can be 8nm-17nm.

[0043] The present invention also provides an alkaline catalyst made from the above-mentioned barium-containing alkaline macroporous material.

[0044] In a specific implementation scheme, the alkaline catalyst can be used to catalyze the catalytic cracking reaction of at least one of extra-heavy oil, residue oil (vacuum residue, atmospheric residue), and heavy oil.

[0045] The beneficial effects of this invention include:

[0046] 1. The alkaline macroporous material provided by this invention is rich in barium, has strong alkalinity, and the alkaline centers are not easily lost.

[0047] 2. The alkali source used in this invention includes 1-adamantyltrimethylammonium hydroxide, which is highly alkaline and has a pore-forming effect, thereby improving the alkalinity and pore volume of barium-containing alkaline macroporous materials.

[0048] 3. The present invention uses a silane coupling agent to modify the material, which can shield some of the hydroxyl groups on the material surface and form a silicon film on the material surface to prevent the loss of basic centers.

[0049] 4. The barium-containing alkaline macroporous material provided by the present invention has the characteristics of low calcination temperature, large pore volume, strong alkalinity, and easy loss of alkaline centers, and is suitable for catalytic cracking treatment of 100% residue oil or extra-heavy oil feedstock. Attached Figure Description

[0050] Figure 1 The image shows the XRD pattern of the aluminum barium spinel synthesized in Example 2. Detailed Implementation

[0051] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0052] The testing methods used in the following experiments are as follows:

[0053] The specific surface area and pore volume of the samples were analyzed using the Omnisorb-360 fully automated specific surface area and porosity adsorption instrument from Coulter Corporation, USA, and the classic nitrogen adsorption-desorption isotherm method.

[0054] The basicity and total base number of the catalyst were determined using the Hammett indicators method, including bromothymol (H_ = 7.2), phenolphthalein (H_ = 9.8), 2,4-dinitroaniline (H_ = 15.0), and 4-nitroaniline (H_ = 18.4). Here, "H_" represents the surface basicity. The basicity of the catalyst used (approximately 0.3 g) was determined using an indicator ethanol solution. The total base number of the catalyst was determined by the amount of benzoic acid consumed by the catalyst.

[0055] The reaction performance evaluation was conducted on an FFB fixed fluidized bed reactor manufactured by Beijing Huier Company. Macroporous basic materials were first tableted, then pulverized, and the 20-80 mesh fraction was collected for reaction evaluation. The catalyst was aged before evaluation (at 800℃ and 100% steam for 17 hours). Evaluation reaction: Mixed vacuum residue was used as the reactant; catalyst dosage was 200g; reaction temperature was 530℃; regeneration temperature was 640℃; reaction time was 60s; stripping time was 30min; catalyst-to-oil ratio was 4; and reaction space velocity was 15h⁻¹. -1 After the reaction is complete, the gas volume and temperature in the gas collecting bottle, as well as the amount of coke generated, are recorded. Gas and liquid samples are collected, and then the product distribution is calculated. The composition of the mixed vacuum residue is shown in Table 1.

[0056] Table 1 Composition of Mixed Vacuum Residue

[0057] <![CDATA[Density, g / cm 3 > 1.01 N, wt% 0.57 H / C ratio 1.51 Ni,wt 51.34 Residual carbon, wt% 16.17 V, wt 36.21 Acid value, mgKOH% 3.86 Saturated hydrocarbons, wt% 22.03 C, wt% 86.24 Aromatic hydrocarbons, wt% 52.51 H, wt% 11.01 Gel, wt% 20.18 S, wt% 2.73 Asphalt, wt% 5.25

[0058] Example 1

[0059] This embodiment provides a barium-containing basic macroporous material, the preparation method of which includes:

[0060] (1) Aluminum barium spinel alkaline material: Barium nitrate and aluminum nitrate were added to water and stirred for 10 minutes to form an aluminum barium mixed solution. 1-adamantyltrimethylammonium hydroxide was added to the aluminum barium mixed solution under vigorous stirring until the pH was 11. The solution was aged at 80°C for 60 minutes, spray dried, and calcined at 600°C for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio was Ba:Al:water = 1.5:2:30.

[0061] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane was added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane was 4.9% of the mass of petroleum ether; an equal volume of aluminum barium spinel basic material was added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-A.

[0062] Example 2

[0063] This embodiment provides a barium-containing basic macroporous material, the preparation method of which includes:

[0064] (1) Aluminum barium spinel alkaline material: Barium chloride and aluminum chloride are added to water to form an aluminum barium mixed solution. Stir for 5 minutes, and 1-adamantyltrimethylammonium hydroxide is added to the aluminum barium mixed solution under vigorous stirring until the pH is 8. Aging is carried out at 50℃ for 30 minutes, spray drying is performed, and calcination is carried out at 400℃ for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio is Ba:Al:water = 1.05:2:18.

[0065] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 0.3% of the mass of petroleum ether; an equal volume of aluminum barium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-B.

[0066] Figure 1 The image shows the XRD pattern of spinel-B, the modified aluminum barium spinel basic material synthesized in Example 2. Figure 1 As can be seen, the sample in this embodiment has a series of characteristic diffraction peaks of 2θ = 19.6°, 28.3°, 34.3°, 40.1°, 45.0°, and 57.8°, which are consistent with the BaAl2O4 spinel standard spectrum card (PDF#00-017-0306), indicating that the sample has a typical spinel structure.

[0067] Example 3

[0068] This embodiment provides a barium-containing basic macroporous material, the preparation method of which includes:

[0069] (1) Aluminum barium spinel alkaline material: Barium nitrate and aluminum sulfate were added to water and stirred for 8 minutes to form an aluminum barium mixed solution. 1-adamantyltrimethylammonium hydroxide was added to the aluminum barium mixed solution under vigorous stirring until the pH was 9.5. The solution was aged at 68°C for 45 minutes, spray dried, and calcined at 550°C for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio was Ba:Al:water = 1.3:2:25.

[0070] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 2.5% of the mass of petroleum ether; an equal volume of barium-rich macroporous aluminum barium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-C.

[0071] Example 4

[0072] This embodiment provides a barium-containing basic macroporous material, the preparation method of which includes:

[0073] (1) Aluminum barium spinel alkaline material: Barium chloride and potassium aluminum sulfate dodecahydrate were added to water and stirred for 7 minutes to form an aluminum barium mixed solution. 1-adamantyltrimethylammonium hydroxide was added to the aluminum barium mixed solution under vigorous stirring until the pH was 9.8. The solution was aged at 60°C for 35 minutes, spray dried, and calcined at 580°C for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio was Ba:Al:water = 1.4:2:25.

[0074] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 1.2% of the mass of petroleum ether; an equal volume of aluminum barium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-D.

[0075] Example 5

[0076] This embodiment provides a barium-containing basic macroporous material, the preparation method of which includes:

[0077] (1) Aluminum barium spinel alkaline material: Barium nitrate and aluminum nitrate were added to water and stirred for 10 minutes to form an aluminum barium mixed solution. 1-adamantyltrimethylammonium hydroxide was added to the aluminum barium mixed solution under vigorous stirring until the pH was 10.5. The solution was aged at 75°C for 55 minutes, spray dried, and calcined at 550°C for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio was Ba:Al:water = 1.1:2:20.

[0078] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 3.7% of the mass of petroleum ether; an equal volume of aluminum barium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-E.

[0079] Comparative Example 1

[0080] This comparative example provides an aluminum-magnesium spinel material, which is synthesized according to the method disclosed in patent CN106518045B (application number 201510582294.8, invention title: magnesium-aluminum spinel and high-temperature methanation catalyst and preparation method thereof). The specific preparation method is as follows:

[0081] 37.51 g of Al(NO3)3·9H2O, 12.82 g of Mg(NO3)2·6H2O, 27 g of urea, and 0.22 g of sodium dodecyl sulfate were dissolved in 100 mL of an aqueous ethanol solution (30 mL of ethanol and 70 mL of deionized water). The mixture was stirred for 30 min, and then transferred to a 200 mL polytetrafluoroethylene-lined stainless steel autoclave. The autoclave was hydrothermally reacted at 130 °C for 10 h, and then allowed to cool naturally to room temperature. The solution was filtered, and the resulting solid was washed three times with deionized water and anhydrous ethanol. The washed solid was dried at 110 °C and then calcined at 600 °C for 4 h to obtain magnesium aluminum spinel-F.

[0082] Comparative Example 2

[0083] This comparative example provides an aluminum barium spinel basic material, the preparation method of which includes:

[0084] Barium nitrate and aluminum nitrate were added to water and stirred for 10 minutes to form an aluminum-barium mixed solution. 1-adamantyltrimethylammonium hydroxide was added to the aluminum-barium mixed solution under vigorous stirring until the pH reached 10.5. The solution was aged at 75°C for 55 minutes, spray-dried, and calcined at 550°C for 2 hours to obtain the aluminum-barium spinel basic material spinel-G. The raw material molar ratio was Ba:Al:water = 1.1:2:20.

[0085] Comparative Example 3

[0086] This comparative example provides an aluminum barium spinel basic material, the preparation method of which includes:

[0087] (1) Aluminum barium spinel alkaline material: Barium nitrate and aluminum nitrate were added to water and stirred for 10 minutes to form an aluminum barium mixed solution. Sodium hydroxide was added to the aluminum barium mixed solution under vigorous stirring until the pH was 10.5. The solution was aged at 75°C for 55 minutes, spray dried, and calcined at 550°C for 2 hours to obtain aluminum barium spinel alkaline material. The raw material molar ratio was Ba:Al:water = 1.1:2:20.

[0088] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 3.7% of the mass of petroleum ether; an equal volume of aluminum barium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum barium spinel basic material spinel-H.

[0089] Comparative Example 4

[0090] This comparative example provides a magnesium-containing basic macroporous material, the preparation method of which includes:

[0091] (1) Alkaline material of aluminum-magnesium spinel: Add magnesium nitrate and aluminum nitrate to water and stir for 10 minutes to form an aluminum-magnesium mixed solution. Add 1-adamantyltrimethylammonium hydroxide to the aluminum-magnesium mixed solution under vigorous stirring until the pH is 10.5. Aging at 75℃ for 55 minutes, spray drying, and calcination at 550℃ for 2 hours to obtain alkaline material of aluminum-magnesium spinel; The molar ratio of raw materials is Mg:Al:water = 1.1:2:20.

[0092] (2) Organosilicon post-modification: γ-aminopropyltriethoxysilane is added to petroleum ether to form a modification solution, wherein the mass of γ-aminopropyltriethoxysilane is 3.7% of the mass of petroleum ether; an equal volume of aluminum magnesium spinel basic material is added to the modification solution, stirred and dried to obtain modified aluminum magnesium spinel basic material spinel-I.

[0093] The physicochemical properties of the materials prepared in the above embodiments and comparative examples are summarized in Table 2.

[0094] Table 2 Comparison of Physicochemical Properties of Macroporous Materials

[0095]

[0096] Stability*: Retention rate of alkaline centers before and after hydrothermal aging at 800℃ for 17 hours.

[0097] Comparative analysis of Examples 1-5 and Comparative Examples 1-4 shows that the barium-containing basic macroporous material synthesized in this invention has the characteristics of low calcination temperature, large pore volume, strong alkalinity, many alkaline centers that are not easily lost, and is suitable for processing 100% residue oil or extra-heavy oil feedstock, with good coke selectivity.

[0098] Comparative analysis of Comparative Example 1, Comparative Example 4 and Example 5 shows that barium has more basic centers than magnesium, which is more conducive to the catalytic reaction of heavy oil by barium-containing basic macroporous materials and can reduce coking.

[0099] Comparative analysis of Comparative Example 3 and Example 5 shows that, compared with conventional alkaline sources such as sodium hydroxide, the use of 1-adamantyltrimethylammonium hydroxide as an alkaline source in this invention is beneficial for increasing the pore volume and specific surface area of ​​barium-containing alkaline macroporous materials and reducing the calcination temperature.

[0100] Comparative analysis of Comparative Example 2 and Example 5 shows that the present invention, by using silane coupling agents such as γ-aminopropyltriethoxysilane for modification, is beneficial to improving the stability of the alkaline centers of barium-containing basic macroporous materials and reducing alkaline loss.

[0101] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a barium-containing basic macroporous material, the method comprising: A barium source, an aluminum source, and water are mixed to obtain an aluminum-barium mixed solution. Then, an alkali source is added to the aluminum-barium mixed solution until the pH value is 8-11 to obtain a raw material solution. The solution is aged, dried, and calcined to obtain an aluminum-barium spinel alkaline material. A silane coupling agent is added to an organic solvent to form a modified solution. The aluminum barium spinel basic material is then added to the modified solution and mixed evenly to obtain the modified aluminum barium spinel basic material. The aluminum-barium mixed solution satisfies the following molar ratio: Ba:Al = 1-1.5:2; the alkali source includes 1-adamantyltrimethylammonium hydroxide.

2. The preparation method according to claim 1, wherein, The barium source includes barium nitrate and / or barium chloride.

3. The preparation method according to claim 1, wherein, The aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, and potassium aluminum sulfate.

4. The preparation method according to claim 1, wherein, The aluminum-barium mixed solution satisfies the following molar ratio: Ba:Al:water = 1-1.5:2:18-30.

5. The preparation method according to claim 1, wherein, The aging temperature is 50℃-80℃, and the aging time is 30min-60min.

6. The preparation method according to claim 1, wherein, The roasting temperature is 400℃-600℃, and the roasting time is 2h-4h.

7. The preparation method according to claim 1, wherein, The mass of the silane coupling agent is 0.1%-5% of the mass of the organic solvent.

8. The preparation method according to claim 1 or 7, wherein, The silane coupling agent includes γ-aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane.

9. A barium-containing basic macroporous material, obtained by the preparation method according to any one of claims 1-8.

10. The barium-containing alkaline macroporous material according to claim 9, wherein, The specific surface area of ​​the barium-containing basic macroporous material is 310 m². 2 / g-380m 2 / g; The pore volume of the barium-containing alkaline macroporous material is 0.60 cm³. 3 / g-0.90cm 3 / g; The number of alkali centers in the barium-containing basic macroporous material is 5 mmol / g-10 mmol / g.

11. An alkaline catalyst made from the barium-containing alkaline macroporous material as described in claim 9 or 10.

12. The alkaline catalyst according to claim 11, wherein, The alkaline catalyst is used to catalyze the catalytic cracking reaction of at least one of vacuum residue, heavy oil, and extra-heavy oil.

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