An acidic mesoporous material, its preparation method and application

Abstract

The application provides an acidic mesoporous material and a preparation method and application thereof. The preparation method comprises the following steps: mixing a NaY molecular sieve crystallization mother liquor, an aluminum source solution and a pore expanding agent, then adjusting the pH value to 7-10 by using an acidic solution to obtain a mixed solution, and reacting the mixed solution at 60-100 DEG C to obtain a gel; mixing the gel with water with a mass ratio of 3-6 times of the gel, and adjusting the pH value to 3-4 by using an acidic solution, and then filtering, washing and drying to obtain the acidic mesoporous material; wherein the aluminum source comprises at least one of aluminum sulfate, aluminum nitrate and aluminum chloride. The acidic mesoporous material prepared by the technical scheme provided by the application has the characteristics of meeting the pore size requirement of heavy oil cracking / cracking, strong acidity, large pore volume and high specific surface area, is suitable for being used as a matrix material component of a heavy oil catalytic cracking / cracking catalyst, and can obviously improve the heavy oil conversion rate.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of oil refining catalysts, and relates to an acidic mesoporous material which can be used as a matrix component of a catalytic cracking / catalytic cracking catalyst and a preparation method of the acidic mesoporous material and application of the acidic mesoporous material. BACKGROUND

[0002] Cracking / cracking process is the most important secondary processing process in a refinery and is the main means of heavy oil lightening and refining integration. The cracking / cracking process takes heavy oil such as wax oil and residual oil as raw material, and under the action of a solid acid catalyst, is converted into dry gas, liquefied gas, gasoline, diesel, oil slurry and coke and other products. The fundamental task of the cracking / cracking process is heavy oil conversion, that is, the efficient conversion of heavy oil such as wax oil and residual oil into liquefied gas, gasoline and other light products with high added value.

[0003] The catalytic cracking / cracking catalyst, as one of the core technologies of the cracking / cracking process, has the ability to catalyze the conversion of heavy oil into light products with high added value, which is the key to determining the overall economic benefit of the cracking / cracking process. The catalytic cracking / cracking catalyst has the characteristics of strong regulation ability, large regulation range, fast effect, high return and small risk, and is the key to adjusting and optimizing the production of the cracking / cracking process. For the cracking / cracking of heavy oil, the accessibility of heavy oil macromolecules to active centers becomes a great challenge. In the preparation process of the heavy oil catalytic cracking / cracking catalyst, the addition of a mesoporous or macroporous matrix material with pre-cracking activity can effectively improve the heavy oil conversion rate. At present, the mesopore of the heavy oil catalytic cracking / cracking catalyst matrix is mainly provided by pseudo-boehmite. The N2 adsorption characterization of pseudo-boehmite shows that the pore volume is 0.35 mL / g, the BET specific surface area is 316 m 2 / g, and the N2 adsorption isotherm of pseudo-boehmite is a typical type IV curve, and a hysteresis loop appears at about P / P0=0.4, and from the BJH pore distribution, the most probable pore diameter is about 3.4 nm. The micro-reaction activity of pseudo-boehmite itself is only 4-6 wt%, which is difficult to meet the requirements of rapid diffusion and effective conversion of heavy oil molecules.

[0004] The catalytic cracking / cracking catalyst is a solid acid catalyst, and the catalytic cracking / cracking reaction is an acid center catalytic reaction. There are mainly two kinds of acids in the catalyst: one is The acid is referred to as B acid, and the other is Lewis acid, referred to as L acid. The catalytic mechanism of B acid and L acid is different, and the role in the catalytic reaction is also different. The active center molecular sieve is rich in B acid center, and its reaction follows the carbonium ion mechanism, and the selectivity of gasoline and coke is good, while the substrate is basically L acid center, which follows the free radical reaction mechanism and is easy to produce coke and gas. At present, the catalytic cracking / cracking catalyst substrate is basically L acid center without B acid center. It is of great significance to introduce B acid into the catalytic cracking / cracking catalyst substrate to reduce the coke yield and improve the heavy oil conversion capacity.

[0005] The design idea of heavy oil catalytic cracking / cracking catalyst generally focuses on improving the accessibility of catalyst activity. Mesoporous or macroporous active materials are used as catalyst additives. Heavy oil molecules are required to be cracked on the active substrate material first, and heavy oil molecules with a diameter of 2-15 nm are cut into smaller intermediate molecules to realize the accessibility of oil and gas molecules to the active center of the molecular sieve, and then gradient selective cracking reaction is carried out in turn. Catalytic cracking / cracking reaction belongs to parallel sequential reaction, and the active center is Y-type molecular sieve and ZSM-5 molecular sieve. Due to the limitation of space size, heavy oil macromolecules cannot enter the inside of the molecular sieve. Therefore, the cracking of heavy oil macromolecules is mainly carried out on the substrate. The heavy oil macromolecules are cracked into secondary molecules on the substrate, and the secondary molecules further enter the molecular sieve to be cracked into small molecules. Due to the diffusion limitation, the ideal pore size of heavy oil cracking / cracking is 6-10 times of the molecular diameter, and the corresponding pore size range is 6-60 nm. However, the pore size of the traditional catalytic cracking / cracking catalyst is less than 5 nm, and the pore volume is small, which cannot meet the needs of heavy oil cracking / cracking. For heavy oil cracking / cracking, the accessibility of heavy oil macromolecules to the active center has become an important challenge for heavy oil cracking / cracking. Medium macroporous catalytic cracking / cracking catalyst is one of the main directions of the development of catalytic cracking / cracking catalyst. At the same time, in order to adjust the cracking / cracking product distribution and reduce the coke yield, the catalytic cracking / cracking catalyst also needs to have a good pore structure. First, the introduction of macroporous structure into the catalytic cracking / cracking catalyst is beneficial to the rapid diffusion of reactant molecules and product molecules; second, compared with conventional crude oil, heavy crude oil has the characteristics of high density, high boiling point, low H / C atomic ratio, high content of metals (Ni, V, Fe, Cu, Na) and the like. In addition, the residue is rich in most of the sulfur, nitrogen and metal compounds in crude oil. These substances are not only difficult to crack and easy to coke, but also easy to poison the catalyst surface and lose activity. Therefore, the heavy oil FCC catalyst requires more mesoporous and macroporous to accelerate the diffusion and mass transfer of heavy oil molecules in the catalyst; in addition, improving the pore structure of the catalyst is beneficial to improving the stripping performance of the catalyst, reducing the oil gas carried into the regenerator between the pores and particles of the catalyst in the circulation process, that is, reducing the stripping coke.

[0006] In summary, it is necessary to study a method for preparing an acidic mesoporous silica-alumina material with a pore size meeting the requirements of heavy oil cracking / cracking, a large pore volume, a high specific surface area, a high B acid content, low cost and a simple process. SUMMARY

[0007] The present application aims to provide a technical solution capable of adjusting the pore size of a silica-alumina material to meet the requirements of heavy oil cracking / cracking and significantly improving the B acid content and pore volume of the silica-alumina material; the silica-alumina material prepared by the technical solution has a high specific surface area in addition to a suitable pore size, a high B acid content and a high pore volume.

[0008] To achieve the above-mentioned object, the present application provides the following three technical solutions.

[0009] In a first aspect, the present application provides a method for preparing an acidic mesoporous material, wherein the method comprises:

[0010] The NaY molecular sieve crystallization mother liquor (i.e. the liquid phase part in the product after crystallization in the process of preparing NaY molecular sieve), an aluminum source solution and a pore-expanding agent are mixed, and then an acidic solution is used to adjust the pH value to 7-10 to obtain a mixed solution; the mixed solution is reacted at 60-100 DEG C to obtain a gel;

[0011] The gel is mixed with water in an amount of 3-6 times the mass of the gel and an acidic solution is used to adjust the pH value to 3-4; after filtration, washing, drying and calcination, the acidic mesoporous material is obtained.

[0012] The aluminum source includes at least one of aluminum sulfate, aluminum nitrate and aluminum chloride.

[0013] The method for preparing the acidic mesoporous material provided by the present application is to prepare the acidic mesoporous material through a silica-alumina self-assembly reaction of a silica source and an aluminum source under specific conditions; specifically, a mixed solution including a NaY molecular sieve crystallization mother liquor, a specific aluminum source solution and a pore-expanding agent with a pH value of 7-10 is used to react to obtain a gel, and then the gel is diluted with water and adjusted to an acidic pH value to obtain the acidic mesoporous material. The prepared acidic mesoporous material has a B acid content of 100-200 μmol / g, an average pore diameter of 6-12 nm, a pore volume of 0.7-1.1 cm 3 / g and a specific surface area of 460-560 m 2 / g. The method for preparing the acidic mesoporous material provided by the present application provides a Si-O-Al structure for the acidic mesoporous material through a self-assembly reaction of the secondary structure of the molecular sieve that is not completely crystallized in the NaY molecular sieve crystallization mother liquor and the silica source and the aluminum source, thereby providing the formation of the pore wall of the mesoporous material and providing acidity. The method for preparing the acidic mesoporous material provided by the present application forms a large number of mesopores through a self-assembly reaction of the silica source and the aluminum source and calcination after the occupation of the pore-expanding agent.

[0014] In the preparation method of the acid mesoporous material, the adding amount of the aluminum source solution is determined by the pH value of the mixed solution, and the adding amount of the aluminum source solution can satisfy that the pH value of the obtained mixed solution is 7-10. When the pH value of the obtained mixed solution is too low, the acid strength of the finally prepared acid mesoporous material is weak; and when the pH value of the obtained mixed solution is too high, the pore size of the finally prepared acid mesoporous material is small.

[0015] According to a preferred embodiment of the first aspect, the NaY molecular sieve crystallization mother liquor is selected from a NaY molecular sieve crystallization mother liquor produced in the industrial production of NaY molecular sieve.

[0016] According to a preferred embodiment of the first aspect, the NaY molecular sieve crystallization mother liquor mainly contains SiO2 and Na2O;

[0017] In the NaY molecular sieve crystallization mother liquor, the content of SiO2 is 40-240 g / L, based on the volume of the NaY molecular sieve crystallization mother liquor; further, the content of SiO2 in the NaY molecular sieve crystallization mother liquor is 100-200 g / L; and the NaY molecular sieve crystallization mother liquor provides a silicon source for the acid mesoporous material.

[0018] In the NaY molecular sieve crystallization mother liquor, the content of Na2O is 20-80 g / L, based on the volume of the NaY molecular sieve crystallization mother liquor; further, the content of Na2O in the NaY molecular sieve crystallization mother liquor is 40-70 g / L.

[0019] According to a preferred embodiment of the first aspect, the NaY molecular sieve crystallization mother liquor can be, but is not limited to, a NaY molecular sieve crystallization mother liquor produced by the following method:

[0020] The silica source, the aluminum source, the alkali source and water are used to prepare a colloid, and then the colloid is crystallized to prepare the NaY molecular sieve. The product obtained by the crystallization is subjected to solid-liquid separation, and the filtrate is the NaY mother liquor.

[0021] Further, the silica source (for example, water glass), the aluminum source (for example, aluminum sulfate), the alkali source (for example, sodium hydroxide) and water are used to prepare a colloid in a ratio of (2-6) Na2O:1 Al2O3:(6-12) SiO2:(150-350) H2O, and then the colloid is crystallized (for example, at normal pressure and 100°C for 18-36 h) to prepare the NaY molecular sieve. The product obtained by the crystallization is subjected to solid-liquid separation, and the filtrate is the NaY mother liquor.

[0022] According to a preferred embodiment of the first aspect, the molar ratio of SiO2 in the NaY molecular sieve crystallization mother liquor to Al2O3 in the aluminum source solution is 4-34:1.

[0023] According to the preferred embodiment of the first aspect, the content of the aluminum source in the aluminum source solution mixed with the NaY molecular sieve crystallization mother liquor is 60-120 g / L, based on the volume of the aluminum source solution; further, the content of the aluminum source in the aluminum source solution is 60-100 g / L.

[0024] According to the preferred embodiment of the first aspect, the reaction time of the mixed solution is 0.5-3 h.

[0025] According to the preferred embodiment of the first aspect, the pH value of the mixed solution is 8-9.5.

[0026] According to the preferred embodiment of the first aspect, the acid solution used for adjusting the pH value to 7-10 and the acid solution used for adjusting the pH value to 3-4 can be the same or different.

[0027] According to the preferred embodiment of the first aspect, the mass concentration of the acidic substance in the acid solution is 1-4 wt.%, based on 100% of the mass of the acid solution.

[0028] According to the preferred embodiment of the first aspect, the acid solution includes but is not limited to at least one of hydrochloric acid, sulfuric acid, nitric acid and ammonium salt solution with obvious acidity.

[0029] According to the preferred embodiment of the first aspect, the pore-expanding agent includes but is not limited to at least one of cetyltrimethylammonium bromide (CTAB), block copolymer P123, polyquaternary ammonium salt-6 and urea.

[0030] According to the preferred embodiment of the first aspect, the molar ratio of the pore-expanding agent to Al2O3 in the aluminum source solution ranges from 0.01-0.1:1.

[0031] In the second aspect, the present application provides an acidic mesoporous material prepared by the method for preparing the acidic mesoporous material according to the first aspect.

[0032] The B acid content of the acidic mesoporous material is 100-200 μmol / g, the average pore diameter of the acidic mesoporous material is 6-12 nm, the pore volume is 0.7-1.1 cm 3 / g, and the specific surface area is 460-560 m 2 / g.

[0033] The average pore diameter of the acidic mesoporous material provided by the present application is 6-12 nm, which belongs to the category of mesoporous materials. According to the regulation of the International Union of Pure and Applied Chemistry (IUPAC), the mesoporous material refers to a kind of porous material with a pore diameter of 2-50 nm.

[0034] The acid mesoporous material provided by the application has at least two sources of acidity: one part is from the secondary structure of the uncompletely crystallized molecular sieve in the crystallization mother liquor of the raw material NaY molecular sieve, and the uncompletely crystallized molecular sieve secondary structure has multiple Si-O-Al structures with potential acidity, which are transferred to the pore wall of the mesoporous material in the subsequent reaction and exhibit acidity; the other part is from the new Si-O-Al structure formed by the self-assembly reaction of the silicon source and the aluminum source, and the Si-O-Al structure forms the pore wall of the mesoporous material and exhibits acidity.

[0035] The acid mesoporous material provided by the application has at least two ways to form the mesoporous structure: one is to form the mesoporous structure through the self-assembly reaction of the silicon source and the aluminum source, and the other is to form the mesoporous structure through the occupation of the template agent / pore expander and calcination.

[0036] In a third aspect, the application provides an application of the acid mesoporous material provided in the second aspect as a matrix material component in a heavy oil catalytic cracking / cracking catalyst.

[0037] The acid mesoporous material prepared by the technical scheme provided by the application has the characteristics of meeting the pore size requirement of heavy oil cracking / cracking, strong acidity, large pore volume, and high specific surface area, and is suitable for being used as a matrix material component of a heavy oil catalytic cracking / cracking catalyst, and can significantly improve the heavy oil conversion rate. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The physical adsorption isotherm graph of the acid mesoporous material provided for Example 1.

[0039] Figure 2 The pore size distribution curve graph of the acid mesoporous material provided for Example 1. DETAILED DESCRIPTION

[0040] In order to have a clearer understanding of the technical features, objects and beneficial effects of the application, the technical scheme of the application will be described in detail below, but it cannot be understood as limiting the implementable scope of the application.

[0041] The type and quantity of the acidity of the material in the application are based on the acid property data measured by a pyridine-infrared instrument, and the average pore size, pore volume and specific surface area of the material are based on the pore structure data measured by a nitrogen physical adsorption instrument.

[0042] The sources of the raw materials involved in the examples and comparative examples of the application are as follows:

[0043] NaY zeolite crystallization mother liquor: The NaY zeolite crystallization mother liquor was provided by Lanzhou Petrochemical Company. It was prepared by the following method: using water glass, aluminum sulfate, sodium hydroxide, and water in a ratio of 3Na2O:1Al2O3:10SiO2:250H2O to prepare a colloid, and then crystallizing at normal pressure and 100℃ for 24h in a crystallization tank. After cooling, the material in the crystallization tank was separated by solid-liquid separation through a belt filter. The solid was NaY zeolite, and the filtrate was the NaY zeolite crystallization mother liquor. The SiO2 content in the filtrate was 40-240g / L, and the Na2O content was 20-80g / L.

[0044] Aluminum sulfate, aluminum nitrate, and aluminum chloride: analytical pure, commercially available.

[0045] CTAB, P123, polyquaternary ammonium salt-6, and urea: analytical pure, commercially available.

[0046] The analysis method involved in the present application:

[0047] (1) Acid test:

[0048] The acid strength and acid amount of the catalyst were determined by a TENSOR27 infrared spectrometer of Bruker Company, Germany. The specific operation was as follows: first, about 10mg of the powder sample to be tested was pressed into a sheet to obtain a 13mm×13mm×1mm (length×width×height) thin sheet, which was fixed in an infrared cell, and then vacuum purified at 350℃ and 1×10 -3 Pa for 2h, and then cooled to 200℃ and subjected to pyridine adsorption at this temperature. Subsequently, the temperature was programmed to the determination temperature (200℃ and 350℃), and vacuum desorption was carried out for half an hour at each temperature, and the infrared spectrum in the 1700-1400cm -1 region was recorded. When the desorption temperature was 200℃, the acid amount of L acid and B acid was the total acid amount of different acid strengths of each acid type. When the desorption temperature was 350℃, the acid amount of L acid and B acid was the total acid amount of medium-strong acid and strong acid of each acid type.

[0049] (2) Pore structure test:

[0050] The pore structure properties such as the specific surface area, pore volume, and pore size distribution of the sample to be tested were measured by an ASAP 2020 physical adsorption instrument of Micromeritics Company, USA, at liquid nitrogen temperature (77K). The sample to be tested was vacuum degassed at 100℃ for 4h before testing. The specific surface area of the sample to be tested was calculated by the BET method, and the total pore volume was the adsorption amount of the sample at a relative pressure p / p0=0.95.

[0051] (3) Micro-reaction activity test (MAT):

[0052] The micro-activity of the sample was tested by a micro-activity evaluation device produced by Beijing Hui Er San Ji Green Chemical Technology Co., Ltd. The reaction raw material was Dagang light diesel oil, the reaction temperature was 460°C, the reaction time was 70s, the diesel oil amount was 1.56mL, and the sample amount was 5g. The liquid product was analyzed by a gas chromatograph (GC-2014C) produced by Japan SHIMADZU Co., Ltd.

[0053] The micro-activity of the fresh sample was obtained by testing the micro-activity of the fresh sample, and the micro-activity of the hydrothermally aged sample was obtained by testing the micro-activity of the sample after hydrothermal aging treatment. The aging conditions of the sample after hydrothermal aging treatment were 800°C, 100% water vapor, and 17h.

[0054] (4) Reaction performance evaluation (ACE)

[0055] The reaction performance of the FCC catalyst was evaluated by an advanced catalytic cracking evaluation device (ACE) developed by KTI Co., Ltd. of the United States. The catalyst needs to be hydrothermally aged before evaluation. The aging conditions were 800°C, 100% water vapor, and 17h for the fresh catalyst. The reaction conditions during the catalyst evaluation process were as follows: the reaction raw material was Lanzhou Petrochemical catalytic cracking material (75wt% waxy oil + 25wt% residue oil, wherein the C content was about 87.3% and the H content was about 12.5%), the catalyst dosage was 9g (a mixture of LDC-200 catalytic cracking catalyst provided by Lanzhou Petrochemical Co., Ltd. of China Petroleum and an acidic mesoporous material), the reaction temperature was 530°C, the regeneration temperature was 700°C, and the agent / oil ratio was 5. The reaction conditions of the blank agent experiment were as follows: the reaction raw material was Lanzhou Petrochemical catalytic cracking material (75wt% waxy oil + 25wt% residue oil, wherein the C content was about 87.3% and the H content was about 12.5%), the catalyst dosage was 9g (LDC-200 catalytic cracking catalyst provided by Lanzhou Petrochemical Co., Ltd. of China Petroleum), the reaction temperature was 530°C, the regeneration temperature was 700°C, and the agent / oil ratio was 5. The gas composition and liquid composition produced in the reaction were analyzed online by a gas chromatograph, and the amount of coke was analyzed by an online CO2 analyzer.

[0056] Example 1

[0057] The present embodiment provides an acidic mesoporous material prepared by the following preparation method:

[0058] Take 100g of NaY molecular sieve crystallization mother liquor (SiO2 content 180g / L, Na2O content 60g / L), and slowly add 40g of aluminum sulfate solution (Al2O3 concentration of aluminum sulfate solution is 70g / L) and 5g of urea under stirring. Then, adjust the pH value with hydrochloric acid solution with a mass concentration of 2.5wt% to obtain a mixed solution with a pH value of 9. The mixed solution is reacted at 90℃ for 2h to obtain a gel. Add 5 times the mass of the gel to water, and adjust the pH value to 3.5 with hydrochloric acid solution with a mass concentration of 2.5wt%. After filtration, washing, drying, and calcination at 550℃ for 2h, acidic mesoporous material is obtained.

[0059] The acidic mesoporous material provided in this embodiment was subjected to acid testing and pore structure testing (results are shown below). Figure 1 , Figure 2 (as shown), microreactive assay, and reaction performance evaluation (ACE).

[0060] The Brønsted acid content of the acidic mesoporous material was measured to be 150 μmol / g using a pyridine-infrared instrument.

[0061] Nitrogen physisorption analysis revealed that the average pore size of this acidic mesoporous material was 10 nm, and the pore volume was 0.9 cm³. 3 / g, specific surface area of ​​550m² 2 / g.

[0062] The microreactivity index of the fresh sample was 52%; the microreactivity index of the sample after hydrothermal aging was 38%.

[0063] The results of the reaction performance evaluation are shown in Table 1.

[0064] Table 1

[0065]

[0066]

[0067] * Ycoke represents coke yield, and X represents conversion rate.

[0068] *Total liquefaction recovery = LPG production rate + Gasoline production rate + Diesel production rate

[0069] *Δ represents the difference between the data after introducing the acidic mesoporous material and the blank agent.

[0070] Example 2

[0071] This embodiment provides an acidic mesoporous material, which is prepared by the following method:

[0072] Take NaY molecular sieve crystallization mother liquor (SiO2 content 160 g / L, Na2O content 56 g / L) 100 g, slowly add aluminum nitrate solution (the concentration of Al2O3 in the aluminum nitrate solution is 80 g / L) 35 g, cetyltrimethylammonium bromide (CTAB) 8 g under stirring, and then use a nitric acid solution with a mass concentration of 3.5 wt% to adjust the pH value to obtain a mixed solution with a pH value of 8.5; the mixed solution is reacted at 80°C for 1 h to obtain a gel; the obtained gel is added into 5 times the mass of water, and the pH value is adjusted to 3.8 using a nitric acid solution with a mass concentration of 3.5 wt%, and after filtration, washing, drying, and calcination at 540°C for 3 h, an acidic mesoporous material is obtained.

[0073] The acidic mesoporous material provided in this example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0074] The B acid content of the acidic mesoporous material is 146 μmol / g, measured by a pyridine-infrared instrument.

[0075] The average pore diameter of the acidic mesoporous material is 8 nm, the pore volume is 1.0 cm 3 / g, and the specific surface area is 542 m 2 / g, measured by nitrogen physical adsorption.

[0076] The micro-reaction activity index of the fresh sample is 50%, and the micro-reaction activity index of the sample after hydrothermal aging is 37%.

[0077] Example 3

[0078] The acidic mesoporous material provided in this example is prepared by the following preparation method:

[0079] Take NaY molecular sieve crystallization mother liquor (SiO2 content 140 g / L, Na2O content 50 g / L) 100 g, slowly add aluminum chloride solution (the concentration of Al2O3 in the aluminum chloride solution is 90 g / L) 30 g, and 6 g of block copolymer P123 under stirring, and then use a sulfuric acid solution with a mass concentration of 1.5 wt% to adjust the pH value to obtain a mixed solution with a pH value of 8; the mixed solution is reacted at 85°C for 1.5 h to obtain a gel; the obtained gel is added into 5 times the mass of water, and the pH value is adjusted to 3.2 using a sulfuric acid solution with a mass concentration of 1.5 wt%, and after filtration, washing, drying, and calcination at 560°C for 4 h, an acidic mesoporous material is obtained.

[0080] The acidic mesoporous material provided in this example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0081] The B acid content of the acidic mesoporous material is 138 μmol / g, measured by a pyridine-infrared instrument.

[0082] The average pore size of the acid mesoporous material is 7 nm, the pore volume is 0.8 cm 3 / g, and the specific surface area is 528 m 2 / g.

[0083] The micro-reaction activity index of the fresh sample is 51%, and the micro-reaction activity index of the sample after hydrothermal aging is 35%.

[0084] Example 4

[0085] The acid mesoporous material provided in the example is prepared by the following preparation method:

[0086] 100 g of a NaY molecular sieve crystallization mother liquor (SiO2 content of 120 g / L, Na2O content of 45 g / L) is slowly added with 50 g of an aluminum chloride solution (Al2O3 concentration of the aluminum chloride solution is 60 g / L), 10 g of polyquaternary ammonium salt-6 under stirring, and then a mixed solution with a pH value of 9.5 is obtained by using a 2.5 wt% ammonium chloride solution to adjust the pH value; the mixed solution is reacted at 70°C for 3 h to obtain a gel; the obtained gel is added with 5 times the mass of water of the gel, and a 2.5 wt% ammonium chloride solution is used to adjust the pH value to 4.0, and after filtration, washing, drying, and calcination at 570°C for 5 h, an acid mesoporous material is obtained.

[0087] The acid mesoporous material provided in the example is subjected to acid testing, pore structure testing, and micro-reaction activity testing.

[0088] The pyridine-infrared instrument measures that the B acid content of the acid mesoporous material is 129 μmol / g.

[0089] The nitrogen physical adsorption measures that the average pore size of the acid mesoporous material is 9 nm, the pore volume is 0.7 cm 3 / g, and the specific surface area is 510 m 2 / g.

[0090] The micro-reaction activity index of the fresh sample is 48%, and the micro-reaction activity index of the sample after hydrothermal aging is 36%.

[0091] Comparative Example 1

[0092] The acid mesoporous material provided in the comparative example is prepared by the following preparation method:

[0093] Take sodium silicate solution (SiO2 content 180 g / L, Na2O content 60 g / L) 100 g, slowly add aluminum sulfate solution (Al2O3 concentration of aluminum sulfate solution is 70 g / L) 40 g, urea 5 g under stirring, and then use HCl solution with mass concentration of 2.5 wt% to adjust the pH value to obtain a mixed solution with pH value of 9; the mixed solution is reacted at 90 ℃ for 2 h to obtain a gel; the obtained gel is added into water with 5 times the mass of the gel, and the pH value is adjusted to 3.5 using HCl solution with mass concentration of 2.5 wt%, and then filtered, washed, dried, and calcined at 550 ℃ for 2 h to obtain an acidic mesoporous material.

[0094] The acidic mesoporous material provided by the present comparative example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0095] The B acid content of the acidic mesoporous material is 46 μmol / g measured by pyridine-infrared instrument.

[0096] The average pore diameter of the acidic mesoporous material is 7 nm, the pore volume is 0.6 cm 3 / g, and the specific surface area is 490 m 2 / g measured by nitrogen physical adsorption.

[0097] The micro-reaction activity index of the fresh sample is 20%, and the micro-reaction activity index of the sample after hydrothermal aging is 14%.

[0098] Comparative Example 2

[0099] The present comparative example provides an acidic mesoporous material prepared by the following preparation method:

[0100] Take NaY molecular sieve crystallization mother liquor (SiO2 content 160 g / L, Na2O content 56 g / L) 100 g, slowly add sodium metaaluminate solution (Al2O3 concentration of sodium metaaluminate solution is 80 g / L) 35 g, cetyltrimethylammonium bromide (CTAB) 8 g under stirring, and then use HNO3 solution with mass concentration of 3.5 wt% to adjust the pH value to obtain a mixed solution with pH value of 8.5; the mixed solution is reacted at 80 ℃ for 1 h to obtain a gel; the obtained gel is added into water with 5 times the mass of the gel, and the pH value is adjusted to 3.8 using HNO3 solution with mass concentration of 3.5 wt%, and then filtered, washed, dried, and calcined at 540 ℃ for 3 h to obtain an acidic mesoporous material.

[0101] The acidic mesoporous material provided by the present comparative example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0102] The B acid content of the acidic mesoporous material is 26 μmol / g measured by pyridine-infrared instrument.

[0103] The average pore size of the acid mesoporous material is 5 nm, the pore volume is 0.4 cm 3 / g, and the specific surface area is 142 m 2 / g.

[0104] The micro-reaction activity index of the fresh sample is 15%, and the micro-reaction activity index of the sample after hydrothermal aging is 7%.

[0105] Comparative Example 3

[0106] The present comparative example provides an acid mesoporous material prepared by the following preparation method:

[0107] 100 g of NaY molecular sieve crystallization mother liquor (SiO2 content 180 g / L, Na2O content 60 g / L) is slowly added with 40 g of aluminum sulfate solution (Al2O3 concentration of aluminum sulfate solution is 70 g / L) under stirring, and then a mixed solution with pH value of 9 is obtained by adjusting the pH value using a hydrochloric acid solution with mass concentration of 2.5 wt%; the mixed solution is reacted at 90°C for 2 h to obtain a gel; the obtained gel is added with 5 times the mass of water of the gel, and the pH value is adjusted to 3.5 using a hydrochloric acid solution with mass concentration of 2.5 wt%; after filtration, washing, drying and calcination at 550°C for 2 h, an acid mesoporous material is obtained.

[0108] The acid mesoporous material provided in the present comparative example is subjected to acid test, pore structure test and micro-reaction activity test.

[0109] The pyridine-infrared instrument measures that the B acid content of the acid mesoporous material is 103 μmol / g.

[0110] The nitrogen physical adsorption measures that the average pore size of the acid mesoporous material is 7 nm, the pore volume is 0.6 m 3 / g, and the specific surface area is 450 m 2 / g.

[0111] The micro-reaction activity index of the fresh sample is 32%, and the micro-reaction activity index of the sample after hydrothermal aging is 19%.

[0112] Comparative Example 4

[0113] The present comparative example provides an acid mesoporous material prepared by the following preparation method:

[0114] Take NaY molecular sieve crystallization mother liquor (SiO2 content 160 g / L, Na2O content 56 g / L) 100 g, slowly add aluminum nitrate solution (the concentration of Al2O3 in the aluminum nitrate solution is 80 g / L) 35 g under stirring, and then use HNO3 solution with a mass concentration of 3.5 wt% to adjust the pH value to obtain a mixed solution with a pH value of 6.5; the mixed solution is reacted at 50°C for 1 h to obtain a gel; the obtained gel is added with 5 times the mass of water of the gel, and the pH value is adjusted to 3.8 using HNO3 solution with a mass concentration of 3.5 wt%, and after filtration, washing, drying, and calcination at 540°C for 3 h, an acidic mesoporous material is obtained.

[0115] The acidic mesoporous material provided by the present comparative example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0116] The B acid content of the acidic mesoporous material is 56 μmol / g, which is measured by a pyridine-infrared instrument.

[0117] The average pore diameter of the acidic mesoporous material is 8 nm, the pore volume is 0.9 cm 3 / g, and the specific surface area is 352 m 2 / g, which are measured by nitrogen physical adsorption.

[0118] The micro-reaction activity index of the fresh sample is 29%, and the micro-reaction activity index of the sample after hydrothermal aging is 16%.

[0119] Comparative Example 5

[0120] The present comparative example provides an acidic mesoporous material, which is prepared by the following preparation method:

[0121] Take NaY molecular sieve crystallization mother liquor (SiO2 content 180 g / L, Na2O content 60 g / L) 100 g, slowly add aluminum sulfate solution (the concentration of Al2O3 in the aluminum sulfate solution is 70 g / L) 40 g and urea 5 g under stirring, and then use HCl solution with a mass concentration of 2.5 wt% to adjust the pH value to obtain a mixed solution with a pH value of 11; the mixed solution is reacted at 120°C for 2 h to obtain a gel; the obtained gel is added with 5 times the mass of water of the gel, and the pH value is adjusted to 3.5 using HCl solution with a mass concentration of 2.5 wt%, and after filtration, washing, drying, and calcination at 550°C for 2 h, an acidic mesoporous material is obtained.

[0122] The acidic mesoporous material provided by the present comparative example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0123] The B acid content of the acidic mesoporous material is 68 μmol / g, which is measured by a pyridine-infrared instrument.

[0124] The average pore size of the acidic mesoporous material is 4.8 nm, the pore volume is 0.5 cm 3 / g, and the specific surface area is 265 m 2 / g.

[0125] The micro-reaction activity index of the fresh sample is 18%, and the micro-reaction activity index of the sample after hydrothermal aging is 7%.

[0126] Comparative Example 6

[0127] The present comparative example provides an acidic mesoporous material prepared by the following preparation method:

[0128] 100 g of NaY molecular sieve crystallization mother liquor (SiO2 content 160 g / L, Na2O content 56 g / L) is slowly added with stirring 35 g of aluminum nitrate solution (concentration of Al2O3 in the aluminum nitrate solution is 80 g / L), 8 g of cetyltrimethylammonium bromide (CTAB), and then a nitric acid solution with a mass concentration of 3.5 wt% is used to adjust the pH value to obtain a mixed solution with a pH value of 8.5; the mixed solution is reacted at 80°C for 1 h to obtain a gel; the obtained gel is directly filtered, washed, dried, and calcined at 540°C for 3 h to obtain the acidic mesoporous material.

[0129] The acidic mesoporous material provided in the present comparative example is subjected to acid test, pore structure test, and micro-reaction activity test.

[0130] The pyridine-infrared instrument measures that the B acid content of the acidic mesoporous material is 76 μmol / g.

[0131] The nitrogen physical adsorption measures that the average pore size of the acidic mesoporous material is 6 nm, the pore volume is 0.5 cm 3 / g, and the specific surface area is 302 m 2 / g.

[0132] The micro-reaction activity index of the fresh sample is 25%, and the micro-reaction activity index of the sample after hydrothermal aging is 9%.

Claims

1. A method for preparing an acidic mesoporous material, wherein, The method includes: The mother liquor of NaY molecular sieve crystallization was mixed with aluminum source solution and pore expander, and then the pH value was adjusted to 7-10 using acidic solution to obtain a mixed solution. The mixed solution was reacted at 60-100℃ to obtain a gel. The gel was mixed with 3-6 times its weight of water and the pH was adjusted to 3-4 using an acidic solution. After filtration, washing, and drying, the acidic mesoporous material was obtained. The aluminum source includes at least one of aluminum sulfate, aluminum nitrate, and aluminum chloride; The NaY molecular sieve crystallization mother liquor is selected from the NaY molecular sieve crystallization mother liquor produced by the following method: Using silicon source, aluminum source, alkali source and water, a colloid is prepared in the ratio of (2-6)Na2O:1Al2O3:(6-12)SiO2:(150-350)H2O. Then, NaY molecular sieve is prepared by crystallization. The crystallization product is subjected to solid-liquid separation, and the filtrate is NaY mother liquor. The acidic mesoporous material has a Brønsted acid content of 100-200 µmol / g, an average pore size of 6-12 nm, and a pore volume of 0.7-1.1 cm³. 3 / g, specific surface area of ​​460-560m² 2 / g.

2. The method according to claim 1, wherein, Based on the volume of the NaY molecular sieve crystallization mother liquor, the SiO2 content in the NaY molecular sieve crystallization mother liquor is 40-240 g / L.

3. The method according to claim 2, wherein, The SiO2 content in the mother liquor of NaY molecular sieve crystallization is 100-200 g / L.

4. The method according to claim 1, wherein, Based on the volume of the NaY molecular sieve crystallization mother liquor, the Na2O content in the NaY molecular sieve crystallization mother liquor is 20-80 g / L.

5. The method according to claim 4, wherein, The Na2O content in the mother liquor of NaY molecular sieve crystallization is 40-70 g / L.

6. The method according to claim 1, wherein, For the aluminum source solution mixed with the NaY molecular sieve crystallization mother liquor, the aluminum source content in the aluminum source solution is 60-120 g / L, based on the volume of the aluminum source solution.

7. The method according to claim 6, wherein, The aluminum source content in the aluminum source solution is 60-100 g / L.

8. The method according to claim 1, wherein, The pH value of the mixture is 8-9.

5.

9. The method according to claim 1, wherein, The molar ratio of SiO2 in the mother liquor of NaY molecular sieve crystallization to Al2O3 in the aluminum source solution is 4-34:

1.

10. The method according to claim 1 or 9, wherein, The molar ratio of the pore-expanding agent to Al2O3 in the aluminum source solution is in the range of 0.01-0.1:

1.

11. The method according to claim 1, wherein, The acidic solution includes at least one of hydrochloric acid, sulfuric acid, nitric acid, and acidic ammonium salt solutions.

12. The method according to claim 1, wherein, The pore-expanding agent includes at least one of hexadecyltrimethylammonium bromide, block copolymer P123, polyquaternium-6, and urea.

13. The acidic mesoporous material prepared by the method according to any one of claims 1-12; in, The acidic mesoporous material has a Brønsted acid content of 100-200 µmol / g, an average pore size of 6-12 nm, and a pore volume of 0.7-1.1 cm³. 3 / g, specific surface area of ​​460-560m² 2 / g.

14. The application of the acidic mesoporous material of claim 13 as a matrix material component in heavy oil catalytic cracking / pyrolysis catalysts.

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