CN116251616A - Residuum catalytic cracking catalyst and its preparation method - Google Patents

Residuum catalytic cracking catalyst and its preparation method Download PDF

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Publication number
CN116251616A
CN116251616A CN202111502842.3A CN202111502842A CN116251616A CN 116251616 A CN116251616 A CN 116251616A CN 202111502842 A CN202111502842 A CN 202111502842A CN 116251616 A CN116251616 A CN 116251616A
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catalytic cracking
cracking catalyst
silicon
catalyst
alumina
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熊晓云
高雄厚
刘超伟
刘涛
王宝杰
胡清勋
王久江
赵红娟
刘宏海
张莉
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • B01J35/651—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B01J35/638—
    • B01J35/647—
    • B01J35/653—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a residual oil catalytic cracking catalyst, which comprises 50-85 parts of matrix, 15-50 parts of molecular sieve, 1-20 parts of silicon-aluminum material in the matrix, wherein the silicon-aluminum material has a pseudo-boehmite structure, and the anhydrous chemical expression is as follows: (0-0.2) Na 2 O:(4‑30)SiO 2 :(70‑96)Al 2 O 3 The specific surface area is more than 500 and not more than 650m 2 The ratio of the amount of pyridine infrared B acid to the amount of L acid measured at 200 ℃ is 0.10-0.38. The invention prepares the silicon-aluminum material with higher pore volume, larger specific surface area, B acid center and double pore distribution through cheap silicon-aluminum source, thereby constructing the catalytic cracking catalyst with high-efficiency heavy oil conversion capability.

Description

Residuum catalytic cracking catalyst and its preparation method
Technical Field
The invention belongs to the field of oil refining catalysts, and particularly relates to a residual oil catalytic cracking catalyst and a preparation method thereof.
Background
In order to maximize benefits, oil refining enterprises begin to blend more and more residual oil in a catalytic cracking device, and compared with distillate oil, the residual oil has the characteristics of large density, high boiling point, low H/C atomic ratio, high metal content and the like. The residual oil type catalytic cracking catalyst needs to have more mesoporous and macroporous distribution to meet the requirements of cracking and diffusion of macromolecules due to the large molecular diameter of heavy oil molecules and higher heavy metal content. Much research has been devoted to introducing macropores into catalytic cracking catalysts.
One of the main characteristics of the GO-ULTRA catalyst (NPRA, 2010 AM-10-175) newly introduced in 2009 by Albemarle company is that the macroporous structure is greatly improved, the macropores between 100 and 400nm are greatly increased, and the overcracking reaction, the excessive hydrogen transfer activity and the coke polymerization reaction are greatly reduced. Compared with the catalyst RUBY of the GO-ULTRA, the catalyst has high gasoline and diesel oil yields and better coke selectivity at the same catalyst-to-oil ratio, conversion rate and coke difference.
US 6776899 reports a method of adding sucrose during catalyst synthesis to introduce macropores into the matrix, resulting in improved catalyst activity and heavy metal resistance. CN1778676a discloses a preparation method of an in-situ crystallization catalyst, and the pore structure of the catalyst can be effectively improved by adding structural auxiliary agents such as starch and carboxymethyl cellulose.
US4624773 reports a process for preparing a large pore catalytic cracking catalyst using carbon black. At least 0.10cm can be produced by the introduction of carbon black 3 g -1 Macropores with the pore diameter larger than 100 nm. Qi Yanping et al (Energy Fuels,24 (5), 2010, 2825) synthesized a macroporous catalytic cracking catalyst by adding polystyrene pellets of different particle sizes and different contents, and found that the addition of polystyrene pellets not only introduced macropores but also increased catalyst activity.
DMS (Distributed Matrix Structures) technology of ENGHARD, the product has card type stacking morphology among particles, a highly dispersed matrix structure, and the highly dispersed zeolite crystal covers the surface of the matrix to improve the selectivity of the catalyst, and in addition, the DMS product contains a stable intermediate Kong Fu aluminum carrier in order to improve the cracking capability of heavy oil. The aluminum-rich carrier is obtained by roasting kaolin at high temperature through alkali modification (NPRA-AM-03-38).
CN201210062013.2 discloses a preparation method of a macroporous catalytic cracking catalyst, which comprises introducing a compound which is decomposed and completely converted into gas at a boiling point temperature of 150 ℃ or less in spray slurry, and introducing macropores in a catalyst spray drying process.
The zeolite molecular sieve in the catalytic cracking catalyst mainly provides microporous channels, macropores are mainly provided by catalyst matrix materials, and the synthesis of the matrix materials rich in the macropore structure is an important way for preparing the macroporous catalytic cracking catalyst and is also a hot spot for research in the current catalyst field.
Zheng Jinyu (Petroleum refining and chemical industry, 2015, 46 (9): 47-51) successfully prepares a disordered mesoporous silica alumina material (JSA) with a pseudo-boehmite structure through processes of gel forming, aging and the like, and the disordered mesoporous silica alumina material has higher specific surface area and pore volume, and the specific surface area reaches 300m 2 Above/g, pore volume greater than 0.7cm 3 Per g, several pore diametersAt 6-7 nm.
Maryam KhosraviMardkhe (Applied Catalysis, A: general, 2014, 482:16-23.) et al describe a silicon doped alumina material whose XRD shows that it still has alumina characteristic diffraction peaks. By adjusting the content of silicon, the silicon doped alumina with large pore volume and large aperture can be obtained, and the pore volume is 0.33-1.83 cm 3 In the range of/g, the pore diameter can reach 51.6nm.
CN03147975.8 describes a mesoporous alumino-silicate material having a phase structure of pseudo-boehmite, the anhydrous chemical expression by weight of oxide being: (0-0.3) Na 2 O·(40～90)Al 2 O 3 ·(10～60)SiO 2 The specific surface area is 200-400 m 2 Per g, pore volume of 0.5-2.0 ml/g, average pore diameter of 8-20 nm, and most probable pore diameter of 5-15 nm.
CN201110251792.6 the invention provides an acidic silica-alumina catalytic material with pseudo-boehmite crystalline phase structure; the anhydrous chemical expression of the catalyst is as follows, based on the weight of oxide: (0-0.2) Na 2 O·(44～46)SiO 2 ·(54～56)Al 2 O 3 The pore volume is 0.5-1.0 ml/g, and the average pore diameter is 8-15 nm.
The invention of CN201110251761.0 provides a mesoporous acidic silicon-aluminum catalytic material which has a pseudo-boehmite crystal phase structure, and the anhydrous chemical expression of the material is as follows, based on the weight of oxide: (0-0.2) Na 2 O·(16～20)SiO 2 ·(80～84)Al 2 O 3 The pore volume is 1.0-2.0 ml/g, the average pore diameter is 8-20 nm, and the ratio of pyridine infrared B acid to L acid measured at 200 ℃ of the material is 0.060-0.085.
CN201210409663.X provides a preparation method of a silicon-containing aluminum oxide dry adhesive, the prepared silicon-containing aluminum oxide dry adhesive is roasted for 2-6 hours at 500-950 ℃, and the properties of the obtained silicon-containing aluminum oxide are as follows: the pore volume is 0.55-1.10 mL/g, and the pore volume of the pores with the pore diameter of 10-50 nm accounts for 30-80% of the total pore volume.
Xubenjing et al (Microporous and Mesoporous materials 238 (2017): 84-89) introduced water glass as a silicon source into an alumina synthesis system to synthesize a silicon-containing alumina material, and examined the silicaThe effect on the pore structure of the product was found to be 3%,6%,12% and 24% for the addition. The pore volume of the synthetic material is up to 1.46cm 3 Per gram, specific surface area up to 427m 2 /g。
CN201510861407.8 describes an active mesoporous Si-Al catalytic material with a pseudo-boehmite crystal phase structure and a specific surface area of 200-600 m 2 Per g, pore volume of 0.5-2.0 ml/g, average pore diameter of 8-20 nm, and ratio of pyridine infrared B acid amount to L acid amount of 0.055-0.085 measured at 200 ℃.
CN201510864343.7, which provides a preparation method of an active catalytic material, the material has a pseudo-boehmite crystalline phase structure, and the anhydrous chemical expression thereof is as follows, based on the weight of oxide: (0-0.2) Na 2 O·(10～60)SiO 2 ·(40～90)Al 2 O 3 The specific surface area is 200-600 m 2 The pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, the particle size distribution of the catalytic material is D (V, 0.5) is less than or equal to 4 mu m, D (V, 0.9) is less than or equal to 12 mu m, and the ratio of the pyridine infrared B acid amount to the L acid amount measured under the condition of 200 ℃ is 0.055-0.085. The invention obtains better pore volume and smaller material granularity through the online addition of the silicon source. The preparation method of the material comprises the following steps: (1) Neutralizing an aluminum source and alkali solution sodium metaaluminate at room temperature to 85 ℃ to form glue, and controlling the pH value in the glue forming process to be 7-11; (2) According to SiO 2 :Al 2 O 3 The weight ratio of (0.6-9), adding the needed silicon source into the glue slurry in parallel flow mode in the process of neutralizing and forming glue, realizing the online addition of the silicon source, and aging for 1-10 hours at the temperature of room temperature to 90 ℃; (3) The resulting solid precipitate was taken as a solid precipitate (dry basis): ammonium salt: h 2 O=1: (0.1-1): (10-30) exchanging for 1-3 times at room temperature to 100 ℃ for 0.5-1 hour each time until the sodium content in the solid precipitate is lower than 0.2%. The active catalytic material obtained by the method provided by the invention has obvious mesoporous characteristic, smaller granularity, higher ratio of the B acid amount to the L acid amount and higher cracking activity of the material, and contains B acid and L acid centers.
CN201710382520.7 discloses a porous catalytic materialThe XRD spectrum of the catalytic material shows a diffuse diffraction peak at a 2 theta angle of 25-27 degrees, and simultaneously has a FAU crystalline phase structure, the chemical composition of the catalytic material contains 50-80% of silicon and 20-50% of aluminum by weight of oxide, and the total specific surface area is no more than 250m 2 The ratio of the specific surface area of the micropores to the total specific surface area is no more than 28 percent, and the ratio of the number of B acid centers to the number of L acid centers measured by pyridine infrared at 200 ℃ is not less than 0.30; when the surface Al/Si atomic ratio measured by XPS method is a and the bulk Al/Si atomic ratio measured by XRF method is b, a/b=1.1 to 1.6. The material is a mixture of amorphous silicon aluminum oxide and zeolite.
CN201710382478.9 discloses a high-activity catalytic material, its XRD spectrum has characteristic diffraction peaks of pseudo-boehmite structure at 2 theta angles of 14 deg., 28 deg., 38.5 deg., 49 deg. and 65 deg., the ratio of B acid center number to L acid center number measured by pyridine infrared at 200 deg.C is 0.10-0.23, the chemical composition contains 15-45% of silicon and 55-85% of aluminium, and its specific surface area is 300-500 m 2 And/g, wherein the average pore diameter is 5-18 nm, and when c is the surface Al/Si atomic ratio measured by an XPS method and d is the bulk phase Al/Si atomic ratio measured by an XRF method, c/d=1.2-1.6. The preparation method of the material comprises the following steps: simultaneously adding a silicon source and an alkaline aluminum source into a container in a parallel flow mode under the condition of stirring at the temperature of between room temperature and 60 ℃ to control the pH value to be 13-14 for mixing into glue, then adding an acidic aluminum source into the container, controlling the end point pH value of a slurry system to be 8.0-10.5, then carrying out constant temperature treatment at the temperature of between 40 and 80 ℃, washing and filtering, and carrying out ion exchange on the obtained solid precipitate to remove impurity ions, wherein the weight ratio of the silicon source to the aluminum source is 1: (1.2 to 5.7) a silicon source in terms of silicon oxide and an aluminum source in terms of aluminum oxide, being the sum of the basic aluminum source and the acidic aluminum source.
Alumina, silicon-containing alumina or its precursor and silica-alumina material are prepared through sol-gel process, and the pH value, reaction temperature and polycondensation speed of aluminum and silicon ion are all in great relation. At present, although a lot of reports on preparation of silicon-containing aluminum oxide, silicon-containing aluminum oxide precursors or silicon-aluminum materials are available, the pore volume of the materials is generally less than 2.0ml/g, and the specific surface area is generally smaller than that of the materialsGenerally at 500m 2 g -1 In the following, the pore size is small and is mainly single pore distribution, while for macromolecule cracking, such as catalytic cracking, the heavy oil molecular size distribution is wide, and the material is often required to have double pore or multi-stage pore distribution. The invention is based on the preparation of a silicon-aluminum material with higher pore volume, large specific surface area, B acid center and double pore distribution by using an inexpensive silicon-aluminum source, and the catalytic cracking catalyst with high-efficiency heavy oil conversion capability is constructed by using the silicon-aluminum material as a carrier material.
Disclosure of Invention
Based on the above, the main purpose of the invention is to prepare a silica-alumina material with higher pore volume and larger specific surface area, containing B acid center and having double pore distribution by using the silica-alumina source with low cost, and construct a catalytic cracking catalyst with high-efficiency heavy oil conversion capability by using the silica-alumina material as a carrier material.
The invention provides a residual oil catalytic cracking catalyst, which comprises, by mass, 100 parts of a catalyst composition, 50-85 parts of a matrix and 15-50 parts of a molecular sieve, wherein the matrix comprises, by mass, 100 parts of the catalyst, 1-20 parts of a silicon-aluminum material, the silicon-aluminum material has a pseudo-boehmite structure, and the anhydrous chemical expression of the silicon-aluminum material is as follows, by weight of oxide: (0-0.2) Na 2 O:(4-30)SiO 2 :(70-96)Al 2 O 3 It has a double pore distribution of 2-40nm and 70-300nm, a specific surface area of more than 500 and not more than 650m 2 The ratio of the amount of pyridine infrared B acid to the amount of L acid measured at 200 ℃ is 0.10-0.38.
The residual oil catalytic cracking catalyst of the invention preferably comprises 60-80 parts of matrix and 20-40 parts of molecular sieve, wherein the matrix comprises 4-15 parts of silicon-aluminum materials, based on 100 parts of catalyst mass composition.
The residual oil catalytic cracking catalyst disclosed by the invention has the advantages that the silicon-aluminum material has double-pore distribution of 2-40nm and 70-300 nm.
The residuum catalytic cracking catalyst of the present invention is preferably one in which the silica-alumina material is prepared by the steps of:
(1) Preheating an acidic aluminum source and a sodium metaaluminate solution to 45-70 ℃ respectively, adding the acidic aluminum source and the sodium metaaluminate solution into a reaction kettle in parallel flow, keeping the temperature at 45-70 ℃, and stirring for reaction, wherein the pH value of the reaction is 6-8;
(2) According to SiO 2 :Al 2 O 3 Adding a silicon source in a weight ratio of (0.05-0.43:1), adding an alcohol solvent, uniformly stirring, and aging for the first time, wherein the temperature of the first time is kept at 45-70 ℃, and the pH value of the first time is kept at (6-8);
(3) Heating to 80-100deg.C, adding alkaline solution to adjust pH to 8.5-10.0, and aging under stirring to obtain solid precipitate;
(4) The resulting solid precipitate was filtered, washed, exchanged and dried.
In the preparation method of the residual oil catalytic cracking catalyst, the preheating firstly heats the acidic aluminum source and the sodium metaaluminate reaction material to a certain temperature, and can be realized in various modes, such as water bath heating, steam heating and oil bath heating.
In the preparation method of the residual oil catalytic cracking catalyst, the filtering, washing, exchanging and drying of the obtained solid precipitate are conventional technical means in the field, and the exchanging refers to the ammonium exchange and/or acid exchange at 60-100 ℃ after the product is washed. The ammonium exchange recommends the following process conditions: solid precipitate as precipitate (dry basis): ammonium salt: h20 =1: (0.1-1): (5-10) exchanging at 60-100 ℃; exchanging for 1-3 times, each for 0.3-1 hour, until the sodium content in the solid precipitate is lower than 0.2wt%. The ammonium salt used for exchange is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate and ammonium bicarbonate. The acid exchange recommended the following process conditions: solid precipitate as precipitate (dry basis): h 2 0=1: (5-10), followed by ph=2.5-3.5 with an acid solution, exchanged at 60-100 ℃; exchanging for 1-3 times, each for 0.3-1 hour, until the sodium content in the solid precipitate is lower than 0.3wt%. The acidic solution used for exchange is one selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid solutionOne or more.
In the preparation method of the residual oil catalytic cracking catalyst, the drying is a general technology, and can be carried out in an oven or by adopting a spray drying or flash drying mode.
In the preparation method of the residual oil catalytic cracking catalyst, the acidic aluminum source is one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
In the preparation method of the residual oil catalytic cracking catalyst, the concentration of the acidic aluminum source is 50-150g/L calculated by alumina, and the concentration of the sodium metaaluminate solution is 20-130g/L calculated by alumina.
In the preparation method of the residual oil catalytic cracking catalyst, the silicon source is one or more selected from water glass, sodium silicate and silicate ester compounds.
In the preparation method of the residual oil catalytic cracking catalyst, in the preparation method of the silicon-aluminum material, in the step (2), the silicon source and the alcohol solvent are preferably added simultaneously, or the silicon source is added first and then the alcohol solvent is added.
In the preparation method of the residual oil catalytic cracking catalyst, the addition amount of the acidic aluminum source is 1-10 times, more preferably 2-5 times, of the addition amount of the alcohol solvent based on the weight of the aluminum oxide.
In the preparation method of the residual oil catalytic cracking catalyst, the alcohol solvent is a compound formed by substituting hydrogen atoms in saturated aliphatic hydrocarbon and/or alicyclic hydrocarbon with hydroxyl groups.
In the preparation method of the residual oil catalytic cracking catalyst, the alcohol solvent is monohydric alcohol, dihydric alcohol or trihydric alcohol of C1-C8, more preferably alcohol of C2-C4, and even more preferably the alcohol solvent is one or more selected from ethanol, glycol, propanol, glycerol, butanol and butanediol.
In the preparation method of the residual oil catalytic cracking catalyst, the primary aging time is 0.5-3h, and the secondary aging time is 0.5-3h.
In the preparation method of the residual oil catalytic cracking catalyst, the alkaline solution is preferably selected from one or more of ammonia water, sodium metaaluminate solution, sodium silicate and sodium hydroxide solution.
The residual oil catalytic cracking catalyst of the invention, wherein the substrate preferably further comprises one or more of alumina, clay, silica gel and silica gel, more preferably alumina and clay, more preferably, the clay is selected from one or more of kaolin, halloysite, montmorillonite and bentonite, and the alumina is selected from one or more of alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, eta-alumina, theta-alumina and precursor pseudo-boehmite of alumina, alumina sol and aluminum hydroxide.
The residuum catalytic cracking catalyst of the present invention, wherein the alumina is preferably a mixture of precursors of two kinds of alumina, more preferably a mixture of pseudo-boehmite and alumina sol, wherein the alumina from the pseudo-boehmite is 0 to 40 parts by mass of the catalyst, still more preferably 10 to 35 parts by mass; alumina from the alumina sol is 4-15 parts by mass of the catalyst.
The residual oil catalytic cracking catalyst is preferably various molecular sieves with acid centers, and more preferably one or more selected from Y-type, X-type, beta, ZSM-5, MOR, MCM-22 and HY, REY, USY, REHY, REUSY, HZSM-5.
Therefore, the invention also provides a preparation method of the residual oil catalytic cracking catalyst, which comprises the following steps: mixing and pulping a matrix containing a silicon-aluminum material with a molecular sieve, adding acid, heating and ageing; and then the slurry is molded, dried and roasted to obtain the catalyst.
The slurry of the present invention, the preparation method of which is known to those skilled in the art, is not particularly limited in the manner of adding the silicon-aluminum material, and may be added before or after acidification.
The preparation method of the residual oil catalytic cracking catalyst is characterized in that the acid is preferably inorganic acid and is selected from one or more of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid; further preferably, the aging conditions are: the temperature is 40-90 ℃ and the time is 0.5-3 hours.
The preparation method of the residual oil catalytic cracking catalyst is characterized in that the forming and drying is preferably spray forming and drying, and the process conditions are that the hearth temperature of a spray tower is controlled at 450-550 ℃, and the temperature of spray tail gas is controlled at 200-300 ℃.
The preparation method of the residuum catalytic cracking catalyst of the invention preferably further comprises the step of further removing impurity ions, including Na, from the obtained catalyst by ion exchange treatment + ，SO 4 2- ，Cl - Etc., further preferably, the ion exchange conditions are: acid exchange or ammonium exchange is adopted, the pH value is 2.5-3.5, and the exchange time is 0.3-2 hours.
The beneficial effects of the invention are as follows:
the residual oil catalytic cracking catalyst provided by the invention contains a silicon-aluminum material, and the material has the advantages of higher pore volume, larger specific surface area, double-pore distribution, higher thermal stability, higher acid quantity and B acid center. The residual oil catalytic cracking catalyst prepared by the material has better pore structure distribution, better heavy metal pollution resistance, stronger heavy oil conversion performance and higher total liquid yield.
Drawings
Figure 1 is an XRD spectrum of the silica alumina material prepared in example 3 and of an industrial pseudo-boehmite material. Fig. 1 shows that the silicon aluminum material prepared in example 3 has a pseudo-boehmite crystal phase structure, but has a lower crystallinity than industrial pseudo-boehmite.
Fig. 2 is an SEM picture of the silicon aluminum material prepared in example 3. Figure 2 shows that the silicon-aluminum material is formed by stacking nano short rods, and the distribution of two pore paths with mesopores and macropores can be obviously observed.
FIG. 3 is a BJH pore distribution curve of the silicon aluminum material AS-3 prepared in example 3. FIG. 3 shows that the silica-alumina material prepared in example 3 has a double pore distribution of 2-40nm and 70-300nm, respectively, whereas the comparative industrial pseudo-boehmite material has a single pore distribution of only 2-4nm, and the several pore diameters can be 3.4nm; DB-1, DB-2 are BJH pore distribution curves of the materials prepared in comparative example 1 and comparative example 2, respectively.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Analysis method
In various embodiments, na in the product 2 O、A1 2 O 3 、SiO 2 The content of (A) was measured by X-ray fluorescence (see "petrochemical analysis method (RIPP Experimental method)", yang Cuiding et al, scientific Press, 1990). The specific surface and the pore structure are measured by adopting a low-temperature nitrogen adsorption-desorption method, and the pore distribution curve is calculated by a BJH method. Scanning Electron Microscopy (SEM) was characterized using an ULTRA-Plus field emission scanning electron microscope from Zeiss, germany.
Pyridine adsorption infrared spectroscopy (Py-FTIR) the sample acid type was characterized using a TENSOR-27 fourier infrared spectroscopy manufactured by bruck corporation, usa. After 10mg of the sample was pressed into a tablet, it was placed in an in-situ detection cell, surface-purified for two hours in a vacuum environment at 350℃and then subjected to infrared analysis.
The abrasion strength of the spray microsphere is measured by adopting an air-borne method, the method standard is Q/SYLS 0518-2002, and the method is the standard of the national institute of petrochemical industry, and before the measurement, the spray microsphere is not subjected to any roasting: the sprayed microspheres were placed in an apparatus for measuring wear index, an MS-C type wear index analyzer, and impacted with an air stream for 5 hours, wherein the amount of fine powder collected in the first 1 hour was taken as the amount of fine powder produced (less than 15 μm) in the preparation of the microspheres, and the amount of fine powder collected in the last 4 hours was taken as the amount of fine powder produced, and the percentage of the mass of fine powder collected in the last 4 hours was the total mass of the sample, namely the wear index.
Water drop pore volume measurement: about 80g of catalyst sample is taken and placed in an evaporation dish, burned for 1 hour at 480 ℃, taken out and cooled in a dryer, 20g of sample is taken and added into a triangular flask, and the accuracy is 0.1g. Distilled water is added into a triangular flask by a burette, the fluidity of the catalyst is deteriorated along with the addition of water, the catalyst is continuously stirred and shaken uniformly by a glass rod until the sample loses fluidity, all the samples are polymerized together, the water consumption is recorded, and the pore volume of the sample is calculated by vp=v/m. Vp-sample pore volume, ml/g; v-consume titration water volume, ml; m-sample mass, g.
Raw material source
Aluminum chloride, sodium metaaluminate, aluminum sulfate, aluminum nitrate, propanol, ethanol, ethylene glycol, butanol, butanediol, ammonium nitrate, ammonium sulfate, ammonium chloride, methyl orthosilicate, ethyl orthosilicate, and sodium silicate are analytical reagents manufactured by national pharmaceutical chemicals, inc.
The industrial pseudo-boehmite is provided for petrochemical catalyst factories in the Lanzhou of China.
NaY zeolite directing agent, manufactured by catalyst plant, lanzhou petrochemical company;
kaolin, industrial products of chinese kaolin company, discounting by 20.43%;
pseudo-boehmite, produced by Shanxi aluminum factory, is reduced by 31.5 percent;
aluminum sol containing Al 2 O 3 23.7wt% produced by catalyst plant of Lanzhou petrochemical company;
REUSY molecular sieve, produced by catalyst plant of Lanzhou petrochemical company, na, accounting for 7.9% 2 O content 1.1 wt%, RE 2 O 3 The content is 7.0wt%;
example 1
Preparation of silicon-aluminum material
Preparing 150g/L aluminum nitrate solution (the same applies below based on the weight of aluminum oxide) and 70g/L sodium metaaluminate solution, heating to 55 ℃ and 60 ℃ respectively, then adding aluminum nitrate and sodium metaaluminate solution into a reaction kettle in parallel flow under stirring, keeping the gel forming temperature at 55 ℃ during the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=6.0, and continuing stirring after the feeding is finished 35 minutes, followed by SiO pressing 2 :Al 2 O 3 After the water glass is added, glycerol is added according to the weight of 5 times of the weight of the alumina, and then the mixture is continuously stirred and aged for 2.0 hours at 55 ℃, then the mixture is heated to 90 ℃, and the water glass is added to adjust the pH value to be 9.5, and the mixture is stirred and aged for 1.0 hour at 90 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated by the following steps of: solid precipitate (dry basis): mixing water=0.2:1:5, performing ion exchange at 70 ℃ to remove sodium ions, repeating the exchange for 0.5h each time, washing and filtering after each exchange, and drying at 110 ℃ for 20h to obtain the silicon-aluminum material AS-1 with the elemental analysis chemical composition of 0.06Na 2 O:74.1Al 2 O 3 :25.9SiO 2 。
Catalyst preparation
1.56 kg of kaolin (dry basis, product of Kaolin Co., ltd., hereinafter the same) and 1.475 kg of alumina sol (containing Al) 2 O 3 23.7wt%, produced by catalyst plant of Lanzhou petrochemical company, the same applies hereinafter) and 4.3 kg of deionized water are added into a pulping tank for pulping, then 1.62 kg of pseudo-boehmite (solid content 64.18%, product of Shanxi aluminum plant, the same applies hereinafter) is added, stirring is carried out for 1 hour, 145 g of concentrated nitric acid is added, stirring is carried out for 1.5 hours, aging is carried out for 2 hours at 65 ℃, then 468 g of medium and large pore silicon aluminum material AS-1 (dry basis, the same applies hereinafter) is added, and stirring is carried out for 1 hour.
1.127 kg of REUSY molecular sieve (solid content 71%, na) 2 O content 1.1 wt%, RE 2 O 3 The content of 7.1wt percent, the silicon-aluminum ratio of 5.1, produced by catalyst factories of Lanzhou petrochemical company, the same applies below), and 2.5 kg deionized water are mixed and pulped for 1 hour, and then added into a first-step pulping tank after mixing, pulping and homogenizing for 3 hours, and then spray drying.
Roasting the catalyst obtained by spray drying for 1.5 hours at 550 ℃, stirring for 60 minutes in a hydrochloric acid aqueous solution with pH=3.0, filtering, and drying for 6 hours at 160 ℃ to obtain the cracking catalyst CAT-1.
The catalyst CAT-1 comprises the following components: 39% by weight of kaolin, 26% by weight of alumina from pseudo-boehmite, 7.0% by weight of alumina from alumina sol, 20% by weight of silica alumina material AS-1 8% by weight of REUSY type molecular sieve.
Example 2
Preparation of silicon-aluminum material
Preparing 60g/L aluminum chloride solution and 90g/L sodium metaaluminate solution, heating to 70 ℃ and 45 ℃ respectively, then adding the aluminum chloride and sodium metaaluminate solution into a reaction kettle in parallel under stirring, keeping the gel forming temperature at 60 ℃ in the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=8.0, continuing stirring for 25 minutes after the feeding is finished, and then pressing SiO 2 :Al 2 O 3 Adding sodium silicate solution in a ratio of (1) to (0.42:1), adding butanediol in an amount which is 3 times the weight of aluminum oxide after the sodium silicate is added, continuously stirring and ageing for 3.0 hours at 60 ℃, then heating to 80 ℃, adding ammonia water to adjust the pH value to (10.0), and stirring and ageing for 0.5 hours at 80 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is prepared into solid precipitate (dry basis): mixing water=1:7, adding hydrochloric acid to adjust pH=3.0, performing ion exchange at 90 ℃ to remove sodium ions, performing exchange for 0.8h, performing water washing filtration after the exchange is finished, and then drying at 130 ℃ for 10h to obtain the silicon-aluminum material AS-2 with the elemental analysis chemical composition of 0.18Na 2 O:70.2Al 2 O 3 :29.6SiO 2 。
Catalyst preparation
1.771 kg of kaolin, 3.161 kg of alumina sol and 2.9 kg of deionized water are added into a pulping tank for pulping, then 1.091 kg of pseudo-boehmite is added, stirring is carried out for 1.5 hours, 171 g of concentrated hydrochloric acid is added, stirring is carried out for 2.0 hours, aging is carried out for 1.5 hours at 70 ℃, 292 g of silicon-aluminum material AS-2 is added, and stirring is carried out for 2 hours.
1.127 kg REUSY molecular sieve and 4.3 kg deionized water are mixed and pulped for 1.5 hours, then added into a first-step pulping tank after mixing, pulped and homogenized for 2 hours, and then spray-dried.
Roasting the catalyst obtained by spray drying for 2.0h at 500 ℃, stirring for 45 minutes in a hydrochloric acid aqueous solution with pH=2.8, filtering, and drying for 10 h at 130 ℃ to obtain the cracking catalyst CAT-2.
The catalyst CAT-2 comprises the following components: 30% by weight of kaolin, 14% by weight of alumina from pseudo-boehmite, 12% by weight of alumina from alumina sol, 40% by weight of a silica alumina material AS-2 4% by weight of REUSY molecular sieve.
Example 3
Preparation of silicon-aluminum material
Preparing 120g/L aluminum sulfate solution and 50g/L sodium metaaluminate solution, heating to 60 ℃ and 65 ℃ respectively, then adding the aluminum sulfate solution and the sodium metaaluminate solution into a reaction kettle in parallel under stirring, keeping the gel forming temperature at 63 ℃ in the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=7.5, continuously stirring for 15 minutes after the feeding is finished, and then pressing SiO 2 :Al 2 O 3 Methyl orthosilicate solution is added in a ratio of (1) to (0.15:1), after methyl orthosilicate is added, propanol is added according to 3 times of the weight of aluminum oxide, stirring and ageing are continued for 1.0 hour at 63 ℃, then the temperature is raised to 95 ℃, sodium metaaluminate solution is added to adjust the pH value to (8.5), and stirring and ageing are carried out for 2.0 hours at 95 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated with ammonium chloride: solid precipitate (dry basis): mixing water=1:0.4:7, performing ion exchange at 90 ℃ to remove sodium ions, repeating the exchange twice for 1.0h each time, washing and filtering after each exchange, and drying at 120 ℃ for 15h to obtain the silicon-aluminum material AS-3 with the elemental analysis chemical composition of 0.03Na 2 O:86.6Al 2 O 3 :13.4SiO 2 。
Catalyst preparation
Adding 0.765 kg of kaolin, 1.897 kg of aluminum sol and 3.1 kg of deionized water into a pulping tank for pulping, then adding 2.103 kg of pseudo-boehmite, stirring for 1.0 hour, adding 247 g of concentrated hydrochloric acid, stirring for 1.0 hour, aging for 1.2 hours at 60 ℃, then adding 450 g of silicon aluminum material AS-3, and stirring for 1.5 hours.
2.218 kg REUSY molecular sieve and 3.4 kg deionized water are mixed and pulped for 0.5 hours, then added into a first-step pulping tank after mixing, pulped and homogenized for 1.8 hours, and then spray dried.
Roasting the catalyst obtained by spray drying for 1.5 hours at 450 ℃, stirring for 80 minutes in a hydrochloric acid aqueous solution with pH=3.3, filtering, and drying for 16 hours at 120 ℃ to obtain the cracking catalyst CAT-3.
The catalyst CAT-3 comprises the following components: 17% by weight of kaolin, 30% by weight of alumina from pseudo-boehmite, 8% by weight of alumina from alumina sol, 35% by weight of a silica alumina material AS-2, and REUSY type molecular sieve.
Example 4
Preparation of silicon-aluminum material
Preparing 105g/L aluminum chloride solution and 110g/L sodium metaaluminate solution, heating to 45 ℃ and 50 ℃ respectively, then adding the aluminum chloride and sodium metaaluminate solution into a reaction kettle in parallel flow under stirring, keeping the gel forming temperature at 47 ℃ in the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=7.0, continuously stirring for 20 minutes after the feeding is finished, and then pressing SiO 2 :Al 2 O 3 After the addition of water glass, butanol is added according to 8 times of the weight of aluminum oxide, and then stirring and aging are continued for 1.5 hours at 47 ℃, then the temperature is raised to 100 ℃, sodium silicate solution is added to adjust the pH value to be 9.0, and stirring and aging are carried out for 3.0 hours at 100 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated by ammonium sulfate: solid precipitate (dry basis): mixing water=0.4:1:8, performing ion exchange at 80 ℃ to remove sodium ions, repeating the exchange for 0.75h each time, washing and filtering after each exchange, and drying at 150 ℃ for 14h to obtain the silicon-aluminum material AS-4 with the elemental analysis chemical composition of 0.09Na 2 O:79.8Al 2 O 3 :20.1SiO 2 。
Catalyst preparation
2.255 kg of kaolin, 2.898 kg of alumina sol and 4.5 kg of deionized water are added into a pulping tank for pulping, then 0.857 kg of pseudo-boehmite is added, stirring is carried out for 3.0 hours, 130 g of concentrated hydrochloric acid is added, stirring is carried out for 0.5 hours, aging is carried out for 2.0 hours at 75 ℃, 770 g of silicon-aluminum material AS-4 is added, and stirring is carried out for 3 hours.
1.937 kg REUSY molecular sieve and 2.6 kg deionized water are mixed and pulped for 1.7 hours, then added into a first step pulping tank after mixing, pulped and homogenized for 1.2 hours, and then spray dried.
Roasting the catalyst obtained by spray drying at 600 ℃ for 0.8h, stirring in a hydrochloric acid aqueous solution with pH=3.5 for 90 minutes, filtering, and drying at 160 ℃ for 7 hours to obtain the cracking catalyst CAT-4.
The catalyst CAT-4 comprises the following components: 41% by weight of kaolin, 10% by weight of alumina from pseudo-boehmite, 10% by weight of alumina from alumina sol, 25% by weight of a silica alumina material AS-4, and the REUSY type molecular sieve.
Example 5
Preparation of silicon-aluminum material
Preparing 85g/L aluminum sulfate solution and 20g/L sodium metaaluminate solution, heating to 65 ℃ and 70 ℃ respectively, then adding the aluminum sulfate solution and the sodium metaaluminate solution into a reaction kettle in parallel under stirring, keeping the gel forming temperature at 68 ℃ in the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=6.5, continuously stirring for 30 minutes after the feeding is finished, and then pressing SiO 2 :Al 2 O 3 Ethyl orthosilicate solution is added in a ratio of (1) =0.05:1, after the addition of the ethyl orthosilicate is completed, propanol is added according to 6 times of the weight of the aluminum oxide, and then stirring and ageing are carried out for 0.5 hour at 68 ℃, then the temperature is raised to 85 ℃, sodium hydroxide solution is added to adjust the pH value=9.8, and stirring and ageing are carried out for 2.5 hours at 85 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated by the following steps of: solid precipitate (dry basis): mixing water=0.9:1:6, performing ion exchange at 95 ℃ to remove sodium ions, repeating the exchange twice for 0.4h each time, washing and filtering after each exchange, and drying at 120 ℃ for 16h to obtain the silicon-aluminum material AS-5 with the elemental analysis chemical composition of 0.10Na 2 O:95.1Al 2 O 3 :4.8SiO 2 。
Catalyst preparation
Adding 0.99 kg of kaolin, 1.423 kg of alumina sol and 2.6 kg of deionized water into a pulping tank for pulping, then adding 0.841 kg of pseudo-boehmite, stirring for 1.6 hours, adding 109 g of concentrated hydrochloric acid, stirring for 1.4 hours, aging for 1.2 hours at 67 ℃, then adding 360 g of silicon-aluminum material AS-5, and stirring for 1.9 hours.
1.183 kg REUSY molecular sieve and 1.7 kg deionized water are mixed and pulped for 1.3 hours, then added into a first-step pulping tank after mixing, pulped and homogenized for 2.2 hours, and then spray dried.
Roasting the catalyst obtained by spray drying at 560 ℃ for 1.1h, stirring in a hydrochloric acid aqueous solution with pH=3.2 for 70 minutes, filtering, and drying at 135 ℃ for 12 hours to obtain the cracking catalyst CAT-5.
The catalyst CAT-5 comprises the following components: 33 wt% of kaolin, 18 wt% of alumina from pseudo-boehmite, 9 wt% of alumina from alumina sol, 28 wt% of REUSY type molecular sieve, and 5-5 wt% of silicon aluminum material AS.
Example 6
Preparation of silicon-aluminum material
Preparing 135g/L aluminum chloride solution and 80g/L sodium metaaluminate solution, heating to 50 ℃ and 55 ℃ respectively, then adding the aluminum chloride and sodium metaaluminate solution into a reaction kettle in parallel under stirring, keeping the gel forming temperature at 52 ℃ in the feeding process, controlling the feeding speeds of the two solutions to ensure that the gel forming pH value=7.8, continuously stirring for 10 minutes after the feeding is finished, and then pressing SiO 2 :Al 2 O 3 After the addition of water glass, ethanol is added according to the weight of 2 times of the weight of aluminum oxide, and then stirring and ageing are continued for 2.5 hours at 52 ℃, then the temperature is raised to 82 ℃, ammonia water solution is added to adjust the pH value to be 9.3, and stirring and ageing are carried out for 1.5 hours at 82 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated by the following steps of: solid precipitate (dry basis): mixing water=0.6:1:10, performing ion exchange at 85 ℃ to remove sodium ions, repeating the exchange for 0.6h each time, performing water washing filtration after each exchange, and drying at 140 ℃ for 12h to obtain the silicon aluminum material AS-6 with the elemental analysis chemical composition of 0.13Na 2 O:76.8Al 2 O 3 :23.1SiO 2 。
Catalyst preparation
1.86 kg of kaolin, 3.477 kg of alumina sol and 3.7 kg of deionized water are added into a pulping tank for pulping, 2.057 kg of pseudo-boehmite is added, stirring is carried out for 2.3 hours, 254 g of concentrated hydrochloric acid is added, stirring is carried out for 1.7 hours, aging is carried out for 1.6 hours at 73 ℃, 360 g of silicon aluminum material AS-6 is added, and stirring is carried out for 2.1 hours.
2.535 kg REUSY molecular sieve and 3.1 kg deionized water are mixed and pulped for 0.9 hours, then added into a first step pulping tank after mixing, pulped and homogenized for 1.6 hours, and then spray dried.
Roasting the catalyst obtained by spray drying for 1.3 hours at 590 ℃, stirring for 85 minutes in a hydrochloric acid aqueous solution with pH=2.7, filtering, and drying for 8 hours at 155 ℃ to obtain the cracking catalyst CAT-6.
The catalyst CAT-6 comprises the following components: 31 wt% of kaolin, 22 wt% of alumina from pseudo-boehmite, 11 wt% of alumina from alumina sol, 30 wt% of REUSY molecular sieve, and AS-5 6 wt% of silica alumina material.
Comparative example 1
Preparation of silicon-aluminum material
Comparative example 1 was prepared following the CN201510864343.7 preparation procedure.
Aluminum sulfate and sodium metaaluminate are used as raw materials, and are parallel-flow glued at 63 ℃, and the glue pH value is controlled to be 7.5, and meanwhile, according to SiO 2 :Al 2 O 3 Methyl orthosilicate solution was added online, mixed co-current with the cement slurry, and after the addition of the raw materials was completed, the slurry was aged for 2.0 hours at 90 ℃. After the obtained product is filtered and washed, the obtained solid precipitate is treated with ammonium chloride: solid precipitate (dry basis): mixing water=1:0.4:10, performing ion exchange at 90 ℃ to remove sodium ions, repeating the exchange twice for 1.0h each time, washing and filtering after each exchange, and drying at 120 ℃ for 15h to obtain the comparative silicon aluminum material DB-1, wherein the elemental analysis chemical composition is 0.04Na 2 O:86.8Al 2 O 3 :13.2SiO 2 。
Catalyst preparation
Adding 0.765 kg of kaolin, 1.897 kg of aluminum sol and 3.1 kg of deionized water into a pulping tank for pulping, then adding 2.103 kg of pseudo-boehmite, stirring for 1.0 hour, adding 247 g of concentrated hydrochloric acid, stirring for 1.0 hour, aging for 1.2 hours at 60 ℃, then adding 450 g of silicon aluminum material DB-1, and stirring for 1.5 hours.
2.218 kg REUSY molecular sieve and 3.4 kg deionized water are mixed and pulped for 0.5 hours, then added into a first-step pulping tank after mixing, pulped and homogenized for 1.8 hours, and then spray dried.
Roasting the catalyst obtained by spray drying for 1.5 hours at 450 ℃, stirring for 80 minutes in a hydrochloric acid aqueous solution with pH=3.3, filtering, and drying for 16 hours at 120 ℃ to obtain the cracking catalyst CAT-A.
The catalyst CAT-A comprises the following components: 17% by weight of kaolin, 30% by weight of alumina from pseudo-boehmite, 8% by weight of alumina from alumina sol, 10% by weight of silica alumina material DB-1 and 35% by weight of REUSY molecular sieve.
Comparative example 2
Preparation of silicon-aluminum material
Comparative example 2 was prepared following the preparation procedure of CN 201710382520.7.
Adding a small amount of deionized water into a beaker, then adding water glass (250 g/L, based on silica) and sodium metaaluminate solution (110 g/L, based on alumina) in a parallel flow mode by strong stirring at 47 ℃, controlling the flow rate to ensure that the water glass and the sodium metaaluminate are added at the same time, and the pH value is 13.0; 105g/L of aluminum chloride solution was then added and the final pH of the slurry system was controlled to 9.0, followed by a constant temperature treatment at 100℃for 3.0 hours. After the obtained product is filtered and washed, the obtained solid precipitate is treated by ammonium sulfate: solid precipitate (dry basis): mixing water=0.4:1:8, performing ion exchange at 80deg.C to remove sodium ions, repeating the exchange for 0.75 hr each time, washing with water, filtering, and drying at 150deg.C for 14 hr to obtain comparative silicon aluminum material DB-2 with elemental analysis chemical composition of 0.08Na 2 O:79.9Al 2 O 3 :20.0SiO 2 。
Catalyst preparation
2.255 kg of kaolin, 2.898 kg of alumina sol and 4.5 kg of deionized water are added into a pulping tank for pulping, then 0.857 kg of pseudo-boehmite is added, stirring is carried out for 3.0 hours, 130 g of concentrated hydrochloric acid is added, stirring is carried out for 0.5 hours, aging is carried out for 2.0 hours at 75 ℃, 770 g of silicon-aluminum material DB-2 is added, and stirring is carried out for 3 hours.
1.937 kg REUSY molecular sieve and 2.6 kg deionized water are mixed and pulped for 1.7 hours, then added into a first step pulping tank after mixing, pulped and homogenized for 1.2 hours, and then spray dried.
Roasting the catalyst obtained by spray drying at 600 ℃ for 0.8h, stirring in a hydrochloric acid aqueous solution with pH=3.5 for 90 minutes, filtering, and drying at 160 ℃ for 7 hours to obtain the cracking catalyst CAT-B.
The catalyst CAT-B comprises the following components: 41% by weight of kaolin, 10% by weight of alumina from pseudo-boehmite, 10% by weight of alumina from alumina sol, 14% by weight of silica alumina material DB-2 and 25% by weight of REUSY type molecular sieve.
Table 1 provides pore structure data and pyridine infrared acidity data for samples AS-1 through AS-6 prepared in examples 1-5, AS well AS for commercial pseudo-boehmite and comparative tests.
TABLE 1 physicochemical Properties of different samples
Figure BDA0003402181480000211
TABLE 2 catalyst composition
Figure BDA0003402181480000212
TABLE 3 physicochemical Properties of the catalyst
Figure BDA0003402181480000213
In table 3, pore volume was measured using the water drop method.
As is clear from Table 3, the analysis of the physicochemical properties of the catalyst shows that the catalyst of the present invention has a higher pore volume by the water drop method than the comparative catalyst by incorporating a silica alumina material with specific physicochemical properties.
Test example 1
Catalyst evaluation:
the reaction performance of the catalyst is evaluated by adopting a fixed fluidized bed device, and the raw oil is Xinjiang vacuum wide fraction wax oil and Xinjiang vacuum residuum, and the mixing ratio is 30%. The properties of the raw oil are shown in Table 4. Table 5 shows the catalyst after 10 hours of aging at 800℃with 100% steam; and the catalytic cracking reaction conditions are as follows: the reaction temperature is 500 ℃, and the mass ratio of the catalyst to the oil is 4.0.
TABLE 4 catalyst Selectivity assessment of the properties of the feedstock used
Figure BDA0003402181480000221
TABLE 5 evaluation results of catalyst reactions
Figure BDA0003402181480000231
As can be seen from table 5, in example 3, compared with comparative example 1, the slurry yield was reduced by 1.06 percentage points, and the total liquid yield was increased by 1.58 percentage points; example 4 compared to comparative example 2, the slurry yield was reduced by 1.31 percent and the total liquid yield was increased by 1.44 percent. For the catalytic device, the total liquid yield is increased by only 0.5 percent, so that great economic benefits can be brought to oil refining enterprises.
In conclusion, the evaluation result of the fixed fluidized bed shows that after the silicon-aluminum material with specific physicochemical properties is added into the catalyst, the reaction performance of the catalyst is improved, and compared with a comparative catalyst, the catalyst has the advantages of high conversion rate, strong heavy oil conversion capability and increased total liquid yield.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (17)

1. The residual oil catalytic cracking catalyst comprises 50-85 parts of matrix and 15-50 parts of molecular sieve based on 100 parts of catalyst mass, and is characterized in that the matrix comprises 1-20 parts of silicon-aluminum material based on 100 parts of catalyst mass, the silicon-aluminum material has a pseudo-boehmite structure, and the anhydrous chemical expression of the silicon-aluminum material based on the weight of oxide is as follows: (0-0.2) Na 2 O:(4-30)SiO 2 :(70-96)Al 2 O 3 The specific surface area is more than 500 and not more than 650m 2 The ratio of the amount of pyridine infrared B acid to the amount of L acid measured at 200 ℃ is 0.10-0.38.
2. The residuum catalytic cracking catalyst according to claim 1, wherein the residuum catalytic cracking catalyst comprises 60 to 80 parts of a matrix comprising 4 to 15 parts of a silica-alumina material, 20 to 40 parts of a molecular sieve, based on 100 parts of the catalyst mass composition.
3. Residual oil catalytic cracking catalyst according to claim 1, characterized in that the silicoaluminous material has a double pore distribution of 2-40nm and 70-300 nm.
4. The residuum catalytic cracking catalyst of claim 1 wherein the silica alumina material is prepared by:
(1) Preheating an acidic aluminum source and a sodium metaaluminate solution to 45-70 ℃ respectively, adding the acidic aluminum source and the sodium metaaluminate solution into a reaction kettle in parallel flow, keeping the temperature at 45-70 ℃, and stirring for reaction, wherein the pH value of the reaction is 6-8;
(2) According to SiO 2 :Al 2 O 3 Adding a silicon source in a weight ratio of (0.05-0.43:1), adding an alcohol solvent, uniformly stirring, and aging for the first time, wherein the temperature of the first time is kept at 45-70 ℃, and the pH value of the first time is kept at (6-8);
(3) Heating to 80-100deg.C, adding alkaline solution to adjust pH to 8.5-10.0, and aging under stirring to obtain solid precipitate;
(4) The resulting solid precipitate was filtered, washed, exchanged and dried.
5. The residuum catalytic cracking catalyst of claim 4 wherein the acidic aluminum source is one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.
6. The resid catalytic cracking catalyst of claim 4 wherein the acidic aluminum source has a concentration of 50-150g/L on alumina and the sodium metaaluminate solution has a concentration of 20-130g/L on alumina.
7. The residuum catalytic cracking catalyst of claim 4 wherein the silicon source is selected from one or more of water glass, sodium silicate, and silicate compounds.
8. The resid catalytic cracking catalyst of claim 4, wherein in step (2), the silicon source and the alcohol solvent are added simultaneously or the silicon source is added first and then the alcohol solvent is added.
9. The resid catalytic cracking catalyst of claim 4 wherein the acidic aluminum source is added in an amount of 1 to 10 times, preferably 2 to 5 times the amount of the acidic aluminum source based on the weight of the alumina.
10. The residuum catalytic cracking catalyst according to claim 4, wherein the alcohol solvent is a compound in which a hydrogen atom in a saturated aliphatic hydrocarbon and/or alicyclic hydrocarbon is substituted with a hydroxyl group.
11. The residuum catalytic cracking catalyst of claim 10 wherein the alcohol solvent is a C1-C8 monohydric, dihydric or trihydric alcohol, preferably a C2-C4 alcohol, more preferably the alcohol solvent is selected from one or more of ethanol, ethylene glycol, propanol, glycerol, butanol, butanediol.
12. The residuum catalytic cracking catalyst of claim 4 wherein the primary aging time is from 0.5 to 3 hours and the secondary aging time is from 0.5 to 3 hours.
13. The residuum catalytic cracking catalyst according to claim 4, wherein the alkaline solution is selected from one or more of ammonia water, sodium metaaluminate solution, water glass, sodium hydroxide solution.
14. The residuum catalytic cracking catalyst of claim 1 wherein the substrate further comprises one or more of alumina, clay, silica gel, silica alumina gel, preferably alumina and clay.
15. The residuum catalytic cracking catalyst of claim 1 wherein the molecular sieve is selected from one or more of Y-type, X-type, beta, ZSM-5, MOR, MCM-22, HY, REY, USY, REHY, REUSY, HZSM-5.
16. The preparation method of the residuum catalytic cracking catalyst is characterized by comprising the following steps: mixing and pulping a matrix containing a silicon-aluminum material with a molecular sieve, adding acid, heating and ageing; and then the slurry is molded, dried and roasted to obtain the catalyst.
17. The method for preparing a residuum catalytic cracking catalyst according to claim 16, further comprising subjecting the resulting catalyst to an acid exchange or an ammonium exchange treatment.
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CN106807352A (en) * 2015-12-01 2017-06-09 中国石油化工股份有限公司 A kind of active mesoporous Si-Al catalysis material
CN109304221A (en) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 A kind of catalyst for heavy oil catalytic cracking and preparation method thereof
CN109304223A (en) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 A kind of low coking type catalytic cracking catalyst and preparation method thereof
CN108745409A (en) * 2018-06-05 2018-11-06 中国石油天然气股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof improving gasoline yield
CN108786901A (en) * 2018-06-05 2018-11-13 中国石油天然气股份有限公司 A kind of preventing from heavy metal type catalytic cracking catalyst and preparation method thereof
JP2020032352A (en) * 2018-08-29 2020-03-05 日揮触媒化成株式会社 Fluid contact cracking catalyst for hydrocarbon oil

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