CN110653002B - Catalytic cracking catalyst - Google Patents

Catalytic cracking catalyst Download PDF

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Publication number
CN110653002B
CN110653002B CN201810715455.XA CN201810715455A CN110653002B CN 110653002 B CN110653002 B CN 110653002B CN 201810715455 A CN201810715455 A CN 201810715455A CN 110653002 B CN110653002 B CN 110653002B
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molecular sieve
type molecular
modified
catalytic cracking
unit cell
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CN110653002A (en
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袁帅
周灵萍
田辉平
沙昊
陈振宇
张蔚琳
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201810715455.XA priority Critical patent/CN110653002B/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to US17/256,938 priority patent/US11517886B2/en
Priority to EP19827156.1A priority patent/EP3815785A4/en
Priority to AU2019296817A priority patent/AU2019296817B2/en
Priority to PCT/CN2019/093250 priority patent/WO2020001531A1/en
Priority to SG11202013118VA priority patent/SG11202013118VA/en
Priority to JP2020573291A priority patent/JP7371033B2/en
Priority to TW108122873A priority patent/TWI802718B/en
Publication of CN110653002A publication Critical patent/CN110653002A/en
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    • 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
    • B01J29/084—Y-type faujasite
    • B01J35/633—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • 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
    • B01J2029/081—Increasing the silica/alumina ratio; Desalumination
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination

Abstract

A catalytic cracking catalyst contains modified Y-type molecular sieve, alumina binder and clay; the modified Y-type molecular sieve has CaO content of 0.7-6.3 wt%, sodium oxide content of 0.1-0.5 wt%, total pore volume of 0.33-0.39 mL/g, pore volume of secondary pores with pore diameter of 2-100 nm accounting for 10-25 wt%, unit cell constant of 2.440-2.455 nm, non-skeleton aluminum content accounting for not more than 20 wt%, lattice collapse temperature not lower than 1040 deg.c and ratio of B acid amount to L acid amount not lower than 2.30. The catalytic cracking catalyst has high heavy oil conversion activity, low coke selectivity, high gasoline yield, high liquefied gas yield, high liquid yield and high light oil yield, and the gasoline has high content of isomeric hydrocarbon and high content of dimethyl isomeric hydrocarbon.

Description

Catalytic cracking catalyst
Technical Field
The invention relates to a heavy oil catalytic cracking catalyst and a preparation method thereof.
Background
At present, the hydrothermal method is mainly adopted for industrially preparing the high-silicon Y-type zeolite. The rare earth-containing high-silicon Y-type zeolite can be prepared by carrying out multiple rare earth ion exchange and multiple high-temperature roasting on NaY zeolite, which is the most conventional method for preparing the high-silicon Y-type zeolite, but the rare earth high-silicon Y-type zeolite prepared by a hydrothermal method has the following defects: because the structure of the zeolite can be damaged by too harsh hydrothermal treatment conditions, the Y-type zeolite with high silica-alumina ratio can not be obtained; while the production of extra-framework aluminum is beneficial for improving the stability of the zeolite and forming new acid centers, the excess extra-framework aluminum reduces the selectivity of the zeolite; in addition, many dealumination cavities in the zeolite cannot be timely supplemented by silicon migrated from the framework, so that lattice defects of the zeolite are often caused, and the crystallization retention of the zeolite is low. And because the conventional Y molecular sieve only contains rare earth, silicon, aluminum and other elements, the adjustment of the structure and the performance of the conventional Y molecular sieve is limited in a certain range, and the composition of a product is often stabilized in a certain range. Therefore, the thermal and hydrothermal stability of the rare earth-containing high-silicon Y-type zeolite prepared by the hydrothermal method is poor, which is shown in that the lattice collapse temperature is low, the crystallinity retention rate and the specific surface area retention rate are low after hydrothermal aging, and the selectivity is poor. Moreover, the content of the isomeric hydrocarbon in the gasoline produced by the catalyst prepared in the conventional Y molecular sieve is stabilized in a certain range and is difficult to improve, the content of the isomeric hydrocarbon in the gasoline is mainly monomethyl isomeric hydrocarbon generally, and the ratio of the monomethyl isomeric hydrocarbon to the dimethyl isomeric hydrocarbon is low, so that the improvement of the quality of the catalytic cracking gasoline is limited, and the competitiveness of the catalytic cracking gasoline product is reduced.
In U.S. Pat. Nos. 4,849,287 and 4,4429053, NaY zeolite is exchanged with rare earth ions and then treated with water vapor, in the method, the aluminum removal of zeolite is difficult in the water vapor treatment process due to the shielding effect and support of the rare earth ions, the unit cell parameters of zeolite before the water vapor treatment are increased to 2.465-2.475 nm, the unit cell parameters after the treatment are 2.420-2.464 nm, and the temperature required for reducing the unit cell parameters is high (593-733 ℃).
In the processes provided in US5340957 and US5206194, SiO of NaY zeolite is used as the starting material2/Al2O3The ratio is 6.0, and the method is to perform rare earth exchange of NaY and then perform hydrothermal treatment, and has the disadvantages of the aforementioned U.S. Pat. Nos. 4,849,287 and 4429053.
Gas phase chemical processes are another important process for preparing high silica zeolites first reported by Beyer and Mankui in 1980. Gasification of gas phaseThe chemical method generally adopts SiCl under the protection of nitrogen4Reacting with anhydrous NaY zeolite at a certain temperature. Fully utilizes SiCl in the whole reaction process4The supplied foreign Si source completes dealuminization and silicon supplement reaction at one time through isomorphous substitution. U.S. Pat. Nos. 4,42737,178, U.S. Pat. No. 4,4438178, Chinese patent Nos. CN1382525A, CN1194941A and CN1683244A disclose the use of SiCl4A process for preparing ultra-stable Y-type zeolite by gas-phase chemical dealumination. The existing gas phase ultra-stable molecular sieve is not beneficial to the isomerization reaction in the hydrocarbon catalytic cracking process.
Zhuhuayuan (Petroleum institute, 2001, 17(6):6-10) et al proposed the effect of magnesium-containing modified molecular sieve on the performance of FCC catalyst. Researches find that the FCC catalyst containing the Mg and Ca molecular sieves has strong heavy oil conversion capability, high hydrogen transfer reaction activity and higher isobutane product content. However, the Y molecular sieve prepared by the method has poor thermal and hydrothermal stability, and can only increase the content of isobutane under certain conditions, but cannot effectively increase the content of the isomeric hydrocarbon in the gasoline, and the ratio of the dimethyl isomeric hydrocarbon to the monomethyl isomeric hydrocarbon is difficult to increase.
The performance of the ultra-stable molecular sieve prepared by a hydrothermal method or a gas phase method in the prior art cannot well meet the requirements of processing heavy oil and poor oil and improving the quality of gasoline at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalytic cracking catalyst with better selectivity of the dimethyl isomeric hydrocarbon and good coke selectivity in gasoline, wherein the catalyst contains a Y-type molecular sieve. The invention also aims to provide a preparation method and an application method of the catalytic cracking catalyst.
The invention provides a catalytic cracking catalyst, which comprises 10-50 wt% of modified Y-type molecular sieve, 10-40 wt% of alumina binder and 10-80 wt% of clay on a dry basis, wherein the modified Y-type molecular sieve is calculated on the dry basis; the modified molecular sieve has calcium oxide content of 0.7-6.3 wt%, sodium oxide content of 0.1-0.5 wt%, total pore volume of 0.33-0.39 mL/g, and pore volume of secondary pores with pore diameter of 2-100 nm accounting for the modified Y-type molecular sieveThe percentage of the total pore volume of the modified Y-type molecular sieve is 10 to 25 percent, the unit cell constant is 2.440 to 2.455nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) is: 7.3-14.0, the percentage of non-framework aluminum content in the molecular sieve to the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1040 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.30.
In the catalytic cracking catalyst provided by the invention, the lattice collapse temperature (also called structure collapse temperature) of the modified Y-type molecular sieve is not lower than 1040 ℃, such as 1040-1080 ℃ or 1041-1055 ℃.
In the catalytic cracking catalyst provided by the invention, the ratio of the amount of B acid to the amount of L acid in the total acid amount of the modified Y-type molecular sieve determined by a pyridine adsorption infrared method at 200 ℃ is preferably 2.4-4.2, for example 2.4-3.5.
In the catalytic cracking catalyst provided by the invention, the unit cell constant of the modified Y-type molecular sieve is 2.440-2.455 nm, such as 2.442-2.452 nm.
In the catalytic cracking catalyst provided by the invention, the modified Y-type molecular sieve is a high-silicon Y-type molecular sieve, and the framework silicon-aluminum ratio (SiO) of the modified Y-type molecular sieve2/Al2O3Molar ratio) of 7.3 to 14.0, for example: 8.5-12.6 or 8.1-12.
In the catalytic cracking catalyst provided by the invention, the non-framework aluminum content of the modified Y-type molecular sieve accounts for not more than 20% of the total aluminum content, for example, 13-19 wt%.
In the catalytic cracking catalyst provided by the invention, the modified Y-type molecular sieve has a crystal retention of over 33%, such as 36-40%, 39-45% or 35-45%, after aging for 17 hours at 800 ℃ under normal pressure and in a 100 volume% steam atmosphere. The normal pressure is 1 atm.
In the catalytic cracking catalyst provided by the invention, the relative crystallinity of the modified Y-type molecular sieve is not less than 58%, such as 58-75% or 58-68%, preferably, the relative crystallinity of the modified Y-type molecular sieve provided by the invention is 59-70%, such as 59-63%.
In the catalytic cracking catalyst provided by the invention, according to an implementation mode, the specific surface area of the modified Y-shaped molecular sieve is 620-670 m2The/g is, for example, 630 to 660m2/g。
In the catalytic cracking catalyst provided by the invention, preferably, the total pore volume of the modified Y-type molecular sieve is 0.35-0.39 mL/g, for example, 0.35-0.375 mL/g.
In the catalytic cracking catalyst provided by the invention, the pore volume of the modified Y-type molecular sieve with the secondary pores with the pore diameter (diameter) of 2.0-100 nm accounts for 10-25% of the total pore volume, preferably 15-21%, such as 17-21%.
In one embodiment, the modified Y-type molecular sieve has a micropore volume of 0.25-0.35 mL/g, such as 0.26-0.32 mL/g.
In the catalytic cracking catalyst provided by the invention, the modified Y-shaped molecular sieve contains calcium element, and the content of calcium oxide in the modified Y-shaped molecular sieve is 0.7-6.3 wt% calculated by CaO, preferably 0.9-5.9 wt%, or 1.5-6.0 wt%, or 0.7-4.3 wt%.
In the catalytic cracking catalyst provided by the invention, the content of the modified Y-type molecular sieve sodium oxide is not more than 0.5 wt%, and can be 0.15-0.5 wt%, for example, 0.20-0.5 wt% or 0.3-0.46 wt%.
The catalyst provided by the invention can also contain other molecular sieves except the modified Y-type molecular sieve, and the content of the other molecular sieves is, for example, 0-40 wt%, for example, 0-30 wt% or 1-20 wt% in terms of dry basis based on the weight of the catalyst. The other molecular sieve is selected from one or more of molecular sieves used in catalytic cracking catalysts, such as zeolite with MFI structure, zeolite Beta, other Y-type zeolite, and non-zeolite molecular sieves. Preferably, the content of the other Y-type molecular sieve is not more than 40 wt% on a dry basis, for example, 1 to 40 wt% or 0 to 20 wt%. Such as one or more of REY, REHY, DASY, SOY, PSRY, MFI structure zeolites such as one or more of HZSM-5, ZRP, ZSP, beta zeolites such as H β, non-zeolitic molecular sieves such as one or more of aluminum phosphate molecular sieves (Al PO molecular sieves), silicoaluminophosphate molecular sieves (SAPO molecular sieves).
In the catalytic cracking catalyst provided by the invention, the content of the modified Y-type molecular sieve is 10-50 wt% on a dry basis, preferably 15-45 wt%, for example 25-40 wt%.
In the catalytic cracking catalyst provided by the invention, the clay is selected from one or more of clays used as a cracking catalyst component, such as one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. These clays are well known to those of ordinary skill in the art. Preferably, the content of the clay in the catalytic cracking catalyst provided by the invention is 20-55 wt% or 30-50 wt% on a dry basis.
In the catalytic cracking catalyst provided by the invention, the content of the alumina binder is 10-40 wt%, for example 20-35 wt%. The alumina binder of the present invention is one or more selected from various forms of alumina, hydrated alumina and alumina sol generally used in cracking catalysts. For example, one or more selected from gamma-alumina, eta-alumina, theta-alumina, chi-alumina, pseudo-Boehmite (Pseudobioemite), diaspore (Boehmite), Gibbsite (Gibbsite), Bayer stone (Bayerite) and alumina sol, preferably pseudo-Boehmite and alumina sol, for example, the catalytic cracking catalyst contains 2-15 wt% of alumina sol, preferably 3-10 wt% of alumina sol, and 10-30 wt% of alumina sol, preferably 15-25 wt% of pseudo-Boehmite.
The catalyst of the present invention can be prepared by the methods disclosed in patents CN1098130A and CN 1362472A. Typically comprising the steps of forming a slurry comprising the modified Y-type molecular sieve, a binder, clay and water, spray drying, optionally washing and drying. Spray drying, washing and drying are the prior art, and the invention has no special requirements.
The preparation method of the catalytic cracking catalyst comprises the steps of preparing a modified Y-shaped molecular sieve, forming slurry comprising the modified Y-shaped molecular sieve, an alumina binder, clay and water, and spray drying, wherein the preparation method of the modified Y-shaped molecular sieve comprises the following steps:
(1) contacting the NaY molecular sieve with a soluble calcium salt solution to perform an ion exchange reaction, filtering and washing to obtain a Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content and containing calcium; wherein the soluble calcium salt solution is also called calcium salt solution;
(2) modifying the calcium-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size, and optionally drying to obtain a Y-type molecular sieve with a reduced unit cell constant, wherein the modifying is to roast the calcium-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size at the temperature of 350-480 ℃ in an atmosphere containing 30-90 vol% of water vapor (also called 30-90 vol% of water vapor atmosphere or 30-90 vol% of water vapor) for 4.5-7 hours;
(3) reducing the unit cell constant of the Y-type molecular sieve and SiCl4Gas is contacted and reacted at the temperature of 200-650 ℃, wherein SiCl is contained4: the weight ratio of the Y-type molecular sieve with reduced unit cell constant obtained in the step (2) on a dry basis is 0.1-0.7: 1, reacting for 10 minutes to 5 hours, and then washing and filtering to obtain the modified Y-type molecular sieve. Wherein the water content of the Y-type molecular sieve sample with reduced unit cell constant is preferably not more than 1 wt%; if the water content in the Y-type molecular sieve sample obtained by modification treatment in the step (2) (i.e. in the Y-type molecular sieve sample obtained by roasting) is not more than 1 wt%, the Y-type molecular sieve sample can be directly used for contacting silicon tetrachloride to carry out the reaction, and if the water content in the Y-type molecular sieve sample obtained by roasting in the step (2) exceeds 1 wt%, the Y-type molecular sieve obtained by roasting in the step (2) is dried to ensure that the water content is less than 1 wt%.
The invention also provides a catalytic cracking method, which comprises the step of carrying out contact reaction on heavy oil and the catalytic cracking catalyst provided by the invention under the condition of heavy oil FCC. The heavy oil such as one or more of vacuum wax oil, atmospheric residue oil, vacuum residue oil and heavy deasphalted oil, the FCC condition is a reaction condition of fluidized catalytic cracking of the heavy oil, and generally, the reaction temperature of the reaction is 480-530 ℃, the reaction time is 1-10 seconds, and the agent-oil ratio is 3-20: 1 weight ratio.
The catalytic cracking catalyst provided by the invention contains the modified Y-type molecular sieve with high thermal and hydrothermal stability, has higher thermal and hydrothermal stability, is used for heavy oil catalytic cracking, has higher activity stability and lower coke selectivity than the existing catalytic cracking catalyst containing the Y-type molecular sieve, has higher gasoline yield and liquefied gas yield, has higher light oil yield and higher total liquid yield, and has higher content of dimethyl isohydrocarbon in gasoline. For example, the catalytic cracking catalyst SC3 containing 30.0 wt% of modified Y molecular sieve SZ3, 42 wt% of kaolin, 25 wt% of pseudo-boehmite, and 3 wt% of alumina sol prepared by the method of the present invention was evaluated with heavy oil on a fixed fluidized bed ACE evaluation apparatus, and the heavy oil conversion rate of the SC3 catalyst was 73.94 wt%, the liquefied gas yield was 16.01 wt%, the gasoline yield was 52.24 wt%, the content of the dimethylisohydrocarbon in the gasoline was 7.25 wt%, the light oil yield was 69.78 wt%, the total liquid yield was 85.79 wt%, the coke selectivity was 5.90%, whereas the catalyst DC3 having the same content of the high-silica molecular sieve component prepared by the conventional method had the same catalyst DC3, the liquefied gas conversion rate was 74.26 wt%, the yield was 15.53 wt%, the gasoline yield was 50.98 wt%, and the content of the dimethylisohydrocarbon in the gasoline was 6.01 wt%, the yield of light oil is 68.81 wt%, the total liquid yield is 84.34 wt%, and the coke selectivity is 8.60%; therefore, the catalyst has higher heavy oil conversion capacity, higher liquefied gas yield and gasoline yield, higher content of the dimethyl isohydrocarbon in the gasoline and better coke selectivity. The light oil micro-reverse evaluation result shows that the catalytic cracking catalyst prepared by the invention has higher activity and hydrothermal stability.
In the present invention, the isoparaffin refers to a chain isoparaffin and a chain isoolefin. The term "bis-methyl isomeric hydrocarbons" means that the carbon chain contains two methyl branches, and the term "mono-methyl isomeric hydrocarbons" means that the carbon chain contains one methyl branch. Increasing the amount of the dimethylisohydrocarbon can improve the FCC gasoline quality, for example, by maintaining a higher gasoline octane number with a reduced olefin or aromatics content.
The catalytic cracking method provided by the invention has the advantages of higher heavy oil conversion capacity, higher liquefied gas yield, higher light oil yield, higher total liquid yield, higher gasoline yield, higher content of the dimethyl isohydrocarbon in the gasoline, higher ratio of the content of the dimethyl isohydrocarbon to the content of the monomethyl isohydrocarbon, and better coke selectivity.
Detailed Description
The catalytic cracking catalyst provided by the invention contains 10-50 wt% of modified Y-type molecular sieve, 10-40 wt% of alumina binder and 10-80 wt% of clay on a dry basis, wherein the weight of the catalyst is taken as a reference. Preferably, the catalytic cracking catalyst contains 25 to 40 wt% of the modified Y-type molecular sieve on a dry basis, 20 to 35 wt% of an alumina binder on an alumina basis, and 30 to 50 wt% of clay on a dry basis.
The catalytic cracking catalyst provided by the invention contains a modified Y-type molecular sieve, and according to one embodiment, the modified Y-type molecular sieve has a calcium oxide content of 0.7-6.3 wt%, preferably 0.9-5.9 wt% or 1.5-6 wt%, a sodium oxide content of 0.1-0.5 wt%, for example 0.13-0.4 wt% or 0.3-0.5 wt%, a total pore volume of 0.33-0.39 mL/g, a pore volume of secondary pores with a pore diameter of 2-100 nm accounting for 10-25%, preferably 15-21%, a unit cell constant of 2.440-2.455 nm, and a framework silica-alumina ratio (SiO/Al ratio)2/Al2O3Molar ratio) is: 7.3-14.0, the percentage of non-framework aluminum content in the molecular sieve to the total aluminum content is not higher than 20%, preferably 13-19, the relative crystallinity is not lower than 58%, the lattice collapse temperature is 1040-1060 ℃, and the B acid amount and the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 DEG CThe ratio of the acid amount is not less than 2.30, preferably 2.4-4.2.
In the catalytic cracking catalyst provided by the invention, the preparation process of the modified Y-type molecular sieve comprises the step of contacting the Y-type molecular sieve with silicon tetrachloride to carry out dealuminization and silicon supplementation reaction.
In the preparation method of the modified Y-type molecular sieve, the NaY molecular sieve and soluble calcium salt solution are subjected to ion exchange reaction in the step (1) to obtain the Y-type molecular sieve with conventional unit cell size and reduced sodium oxide content and containing calcium. The NaY molecular sieve can be purchased commercially or prepared according to the existing method, and in one embodiment, the unit cell constant of the NaY molecular sieve is 2.465-2.472 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85 to 95%, and a sodium oxide content of 13.0 to 13.8% by weight. The NaY molecular sieve and the soluble calcium salt solution are subjected to ion exchange reaction, the exchange temperature is preferably 15-95 ℃, for example 65-95 ℃, and the exchange time is preferably 30-120 minutes, for example 45-90 minutes. NaY molecular sieve (dry basis), soluble calcium salt (CaO) and H2O is 1: 0.009-0.28: 5-15 by weight. In one embodiment, the ion exchange reaction of the NaY molecular sieve with the soluble calcium salt solution comprises the following steps of2The method comprises the steps of mixing NaY molecular sieve (also called NaY zeolite), soluble calcium salt and water in a weight ratio of 1: 0.009-0.27: 5-15, and carrying out exchange of calcium ions and sodium ions by stirring at 15-95 ℃, for example, 65-95 ℃, preferably for 30-120 minutes, wherein the water is decationized water, deionized water or a mixture thereof. The NaY molecular sieve, the soluble calcium salt and the water are mixed to form a mixture, the NaY molecular sieve and the water can be formed into slurry, and then the soluble calcium salt and/or a soluble calcium salt solution are added into the slurry, wherein the soluble calcium salt solution is an aqueous solution of the soluble calcium salt, and the soluble calcium salt can be one or two of calcium chloride and calcium nitrate. The washing in step (1) is intended to wash out exchanged sodium ions, and for example, deionized water or decationized water may be used for washing. Preferably, the step (A)1) The obtained calcium-containing Y-type molecular sieve with a conventional unit cell size and a reduced sodium oxide content has a calcium content of 0.7-11 wt%, such as 0.8-10 wt% or 4-10 wt% or 0.9-7.5 wt% or 1.5-6 wt% or 0.7-4.5 wt%, calculated as CaO, a sodium oxide content of not more than 9 wt%, such as 4-8.8 wt% or 4.5-8.5 wt% or 5-7.5 wt%, and a unit cell constant of 2.465 nm-2.472 nm.
In the preparation method of the modified Y-type molecular sieve, the Y-type molecular sieve with the calcium-containing conventional unit cell size is roasted for 4.5-7 hours at the temperature of 350-480 ℃ under the atmosphere of 30-90 vol% of water vapor in step (2), preferably, the roasting temperature in step (2) is 380-460 ℃, the roasting atmosphere is 40-80 vol% of water vapor, and the roasting time is 5-6 hours. The water vapor atmosphere contains 30-90% by volume, preferably 40-80% by volume of water vapor, and also contains other gases, such as one or more of air, helium or nitrogen. The Y-type molecular sieve with the reduced unit cell constant in the step (2) has the unit cell constant of 2.450 nm-2.462 nm. Preferably, the calcined molecular sieve is also dried in step (2) so that the water content in the Y-type molecular sieve having a reduced unit cell constant is preferably not more than 1 wt%.
In the preparation method of the catalytic cracking catalyst, the SiCl is added in the step (3)4: the weight ratio of the Y-type zeolite (on a dry basis) is preferably 0.3-0.6: 1, the reaction temperature is preferably 350-500 ℃, and the washing method in the step (3) can adopt a conventional washing method, and can be washed by water, such as decationized water or deionized water, so as to remove Na remained in the zeolite+，Cl-And Al3+Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h2The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, and the washing temperature is 30-60 ℃. Preferably, the washing is performed such that no free Na is detected in the washing solution after washing+，Cl-And Al3+Plasma, washing after general washingNa in the liquid+、Cl-And Al3+The respective contents of ions do not exceed 0.05 wt.%.
In the preparation method of the catalytic cracking catalyst provided by the invention, one embodiment of the preparation method of the modified Y-type molecular sieve comprises the following steps:
(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a soluble calcium salt solution, filtering and washing to obtain a Y-type molecular sieve with conventional unit cell size and reduced sodium oxide content and containing calcium; the ion exchange is carried out for 30-120 minutes under the conditions of stirring and the temperature of 15-95 ℃, preferably 65-95 ℃;
(2) roasting the calcium-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere containing 30-90 vol% of water vapor, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant and the water content of less than 1 wt%; the unit cell constant of the Y-type molecular sieve with the reduced unit cell constant is 2.450 nm-2.462 nm;
(3) mixing said reduced unit cell constant Y-type molecular sieve sample having a water content of less than 1 wt% with heat vaporized SiCl4Gas contact of SiCl4: the weight ratio of the Y-type molecular sieve with the water content lower than 1 wt% and the reduced unit cell constant (calculated by dry basis) is 0.1-0.7: 1, carrying out contact reaction for 10 minutes to 5 hours at the temperature of 200-650 ℃, and washing and filtering to obtain the modified Y-type molecular sieve provided by the invention.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the examples and comparative examples, the NaY molecular sieve (also called NaY zeolite) was supplied by the chinese petrochemical catalyst co, zeuginese, inc, and had a sodium oxide content of 13.5 wt% and a framework silica to alumina ratio (SiO) of2/Al2O3Molar ratio) of 4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; calcium chloride and calcium nitrate are chemically pure reagents produced by national pharmaceutical group chemical reagent limited company (Hu test). The pseudoboehmite is an industrial product produced by Shandong aluminum factories, and has the solid content of 61 percent by weight; kaolin is Suzhou China Kaolin CorpThe produced kaolin special for the cracking catalyst has the solid content of 76 weight percent; the alumina sol was provided by the Qilu division of China petrochemical catalyst, Inc., in which the alumina content was 21% by weight.
The analysis method comprises the following steps: in each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy; the unit cell constants and relative crystallinity of the zeolite were measured by X-ray powder diffraction (XRD) using RIPP 145-90 and RIPP146-90 standard methods (compiled by petrochemical analysis method (RIPP test method), Yankee et al, scientific Press, published in 1990), and the framework silica-alumina ratio of the zeolite was calculated from the following formula:
Si/Al＝192/[1124×(a0-2.42383)]wherein, a0Is a unit cell constant in
Figure BDA0001717496670000081
The total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated. The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).
In each comparative example and example, the acid center type of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption. An experimental instrument: american Bruker IFS113V type FT-IR (Fourier transform Infrared)
A spectrometer. Experimental method for measuring acid content at 200 ℃ by using pyridine adsorption infrared method: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 200 ℃, and vacuumizing to 10 DEG C-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400cm-1～1700cm-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 200 ℃. According to pyridine absorption infrared spectrogram of 1540cm-1And 1450cm-1The strength of the adsorption peak is characterized to obtain the total content in the molecular sieve
Figure BDA0001717496670000092
Relative amount of acid center (B acid center) to Lewis acid center (L acid center).
In each of the comparative examples and examples, the secondary pore volume was determined as follows: the total pore volume of the molecular sieve was determined from the adsorption isotherm according to RIPP151-90 Standard method, "petrochemical analysis method (RIPP test method)," compiled by Yankee corporation, published in 1990 ", then the micropore volume of the molecular sieve was determined from the adsorption isotherm according to the T-plot method, and the secondary pore volume was obtained by subtracting the micropore volume from the total pore volume.
The chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.
Example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 689ml of Ca (NO) is added3)2Stirring the solution (the concentration of the solution is 248g/L in terms of CaO), heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying the filter cake at 120 ℃ to obtain a Y-type molecular sieve with a unit cell constant of 2.471nm, a sodium oxide content of 6.6 wt% and a calcium content of 9.8 wt% in terms of CaO, roasting for 6 hours at 390 ℃ in an atmosphere containing 50 vol% of water vapor and 50 vol% of air to obtain the Y-type molecular sieve with the unit cell constant of 2.454nm, drying to make the water content of the Y-type molecular sieve lower than 1 wt%, and then carrying out SiCl4: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating4Reacting gas at 400 ℃ for 2 hours, washing the reacted gas with 20 liters of decationized water, and filtering the washed gas to obtain the modified Y-type molecular sieve, which is marked as SZ1 and has the physicochemical properties shown in Table 1, wherein the relative crystallinity of the molecular sieve before and after the aging of SZ1 is analyzed by an XRD method after the exposed SZ1 is aged for 17 hours at 800 ℃, 1atm and 100 percent of water vapor, and the relative crystallinity retention after the aging is calculated, and the result is shown in Table 2, wherein:
Figure BDA0001717496670000091
714.5 g of an alumina sol having an alumina content of 21% by weight were added to 1565.5 g of decationized water, stirring was started, and 2763 g of kaolin having a solids content of 76% by weight were added and dispersed for 60 minutes. 2049 g of pseudo-boehmite with the alumina content of 61 wt% is taken and added into 8146 g of decationized water, 210ml of hydrochloric acid with the mass concentration of 36% is added under the stirring state, dispersed kaolin slurry is added after acidification is carried out for 60 minutes, 1500 g (dry basis) of ground SZ1 molecular sieve is added, after uniform stirring, spray drying and washing treatment are carried out, and the catalyst is obtained after drying and is marked as SC 1. Wherein the obtained SC1 catalyst contains 30 wt% of SZ1 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Example 2
2000 g of NaY molecular sieve (dry basis) is added into 25L of decationized aqueous solution and stirred to be mixed evenly, 734ml of CaCl is added2Stirring the solution (the concentration of the solution is 248g/L in terms of CaO), heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying the filter cake at 120 ℃ to obtain a Y-type molecular sieve with a unit cell constant of 2.471nm, a sodium oxide content of 5.2 wt% and a calcium content of 8.7 wt% in terms of CaO, then roasting for 5.5 hours at a temperature of 450 ℃ and 80% water vapor to obtain the Y-type molecular sieve with the unit cell constant of 2.460nm, then drying to ensure that the water content is lower than 1 wt%, and then carrying out SiCl4: y-type zeolite 0.6: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at 480 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to give a modified Y molecular sieve, noted SZ 2. The physicochemical properties are shown in table 1, and the results are shown in table 2, in which the crystallinity of zeolite before and after aging of SZ2 was analyzed by XRD after aging of SZ2 in the bare state at 800 ℃ for 17 hours with 100% water vapor (17 hours with 100% water vapor aging means aging for 17 hours in 100% water vapor atmosphere).
Referring to the preparation method of example 1, SZ2 molecular sieve, kaolin, water, pseudo-boehmite binder, and alumina sol were slurried and spray-dried to prepare a microspherical catalyst according to a conventional preparation method of a catalytic cracking catalyst, and the prepared catalytic cracking catalyst was designated as SC 2. Wherein the obtained SC2 catalyst contains 30 wt% of SZ2 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Example 3
2000 g of NaY molecular sieve (dry basis) is added into 22L of decationized aqueous solution and stirred to be mixed evenly, 428ml of CaCl is added2Stirring the solution (the concentration of the solution is 248g/L in terms of CaO), heating to 90-95 ℃, keeping stirring for 1 hour, filtering, washing, drying a filter cake at 120 ℃ to obtain a Y-type molecular sieve with a unit cell constant of 2.471nm, a sodium oxide content of 7.2 wt% and a calcium content of 4.8 wt% in terms of CaO, roasting at 470 ℃ and 70 vol% of water vapor for 5 hours to obtain the Y-type molecular sieve with the unit cell constant of 2.457nm, drying to ensure that the water content is lower than 1 wt%, and then carrying out SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at a temperature of 500 ℃ for 1 hour, then washed with 20 liters of decationized water and filtered to obtain a modified Y-type molecular sieve, noted SZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ3 is analyzed by XRD method after aging of SZ3 in a naked state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.
Slurry is formed by using an SZ3 molecular sieve, kaolin, water, a pseudo-boehmite binder and an aluminum sol according to a conventional preparation method of a catalytic cracking catalyst, and the slurry is spray-dried to prepare a microspherical catalyst, wherein the prepared catalytic cracking catalyst is marked as SC3 (refer to the preparation method of example 1). Wherein the obtained SC3 catalyst contains 30 wt% of SZ3 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Example 4
The SZ2 molecular sieve, kaolin, water, pseudo-boehmite binder and aluminum sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as SC4 (refer to the preparation method of example 1). Wherein the obtained SC4 catalyst contains 25 wt% of SZ2 molecular sieve, 47 wt% of kaolin, 24 wt% of pseudo-boehmite and 4 wt% of alumina sol on a dry basis.
Example 5
The SZ2 molecular sieve, kaolin, water, pseudo-boehmite binder and aluminum sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as SC5 (refer to the preparation method of example 1). Wherein the obtained SC5 catalyst contains 40 wt% of SZ2 molecular sieve, 30 wt% of kaolin, 20 wt% of pseudo-boehmite and 10 wt% of alumina sol on a dry basis.
Comparative example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying filter cake at 120 deg.C, calcining at 650 deg.C under 100% water vapor for 5 hr for hydrothermal modification, adding into 20L decationized water solution, stirring, mixing, adding 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, roasting for 5 hours at 650 ℃ under 100% of water vapor, and carrying out second hydrothermal modification treatment to obtain the twice-ion-exchange twice-hydrothermal ultrastable calcium-free hydrothermal ultrastable Y-shaped molecular sieve, which is marked as DZ 1. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ1 is analyzed by XRD method after aging DZ1 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
DZ1 molecular sieve, kaolin, water, pseudo-boehmite binder and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as DC1 (refer to the preparation method of example 1). Wherein the obtained DC1 catalyst contains 30 wt% of DZ1 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Comparative example 2
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 ℃ for 1 hour, filtering, washing, drying filter cake at 120 ℃, performing hydrothermal modification treatment, roasting at 650 ℃ under 100% water vapor for 5 hours, adding into 20L of decationized aqueous solution, stirring to mix uniformly, and adding 406ml of Ca (NO)3)2The solution (solution concentration as CaO: 248g/L) and 900 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then performing second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-containing hydrothermal ultrastable Y-type molecular sieve marked as DZ2, wherein the hydrothermal ultrastable Y-type molecular sieve is hydrothermally ultrastable twice through ion exchange twice. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ2 is analyzed by XRD method after aging DZ2 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
DZ2 molecular sieve, kaolin, water, pseudo-boehmite binder and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as DC2 (refer to the preparation method of example 1). Wherein the obtained DC2 catalyst contains 30 wt% of DZ2 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Comparative example 3
2000 g of NaY molecular sieve (dry basis) is added to 20 l of the mixtureStirring the cation aqueous solution to mix well, adding 486ml Ca (NO)3)2Stirring the solution (the concentration of the solution is 248g/L in terms of CaO), heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, then carrying out gas phase ultra-stable modification treatment, firstly carrying out molecular sieve drying treatment to ensure that the water content is lower than 1 weight percent, and then carrying out SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at 580 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to obtain a gas phase high silicon ultrastable Y-type molecular sieve designated as DZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ3 is analyzed by XRD method after aging DZ3 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
DZ3 molecular sieve, kaolin, water, pseudo-boehmite binder and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as DC3 (refer to the preparation method of example 1). Wherein the obtained DC3 catalyst contains 30 wt% of DZ3 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Examples 6 to 10
The catalysts SC1, SC2, SC3, SC4 and SC5 prepared in examples 1 to 5 were subjected to 100% steam aging at 800 ℃ for 4 hours or 17 hours, respectively, and then the light oil micro-reactivity of the catalysts was evaluated, and the evaluation results are shown in table 3.
Evaluation method of light oil micro-inverse activity:
the light oil micro-reverse activity of the sample is evaluated by adopting a standard method of RIPP92-90 (see the edition of petrochemical analysis method (RIPP test method), Yangcui et al, scientific publishing company, published in 1990), the catalyst loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is Hongkong light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the light oil micro-reverse activity is calculated according to the product composition.
Light oil Microreactivity (MA) (gasoline production at less than 216 ℃ in product + gas production + coke production)/total feed × 100%.
Comparative examples 4 to 6
The catalysts DC1, DC2 and DC3 prepared in comparative examples 1 to 3 were subjected to 100% steam aging at 800 ℃ for 4 hours or 17 hours, respectively, and then the light oil micro-reactivities thereof were evaluated. See example 6 for evaluation, and the results are shown in Table 3.
Examples 11 to 15
Examples 11-15 illustrate the catalytic cracking reaction performance of the modified Y-type molecular sieve provided by the invention.
After the catalysts SC1, SC2, SC3, SC4 and SC5 are aged by 100% steam for 17 hours at 800 ℃, the catalytic cracking reaction performance of the catalysts is evaluated on a small fixed fluidized bed reactor (ACE), and cracked gas and product oil are respectively collected and analyzed by gas chromatography. The catalyst loading is 9g, the reaction temperature is 500 ℃, and the weight hourly space velocity is 16h－1The oil-to-agent ratio (weight ratio) is shown in Table 5, the properties of the raw oil in the ACE test are shown in Table 4, and the evaluation results are shown in Table 5. The content (weight,%) of isoparaffin in gasoline + the content (weight,%) of isoolefin in gasoline. The content of the dimethylisoolefin (wt.%) is the content of the dimethylisoalkane (wt.%) + the content of the dimethylisoolefin (wt.%).
Comparative examples 7 to 9
Comparative examples 7-9 illustrate the catalytic cracking reaction performance of the ultrastable Y-type zeolite prepared by the methods provided in comparative examples 1-3.
After aging of DC1, DC2 and DC3 catalysts at 800 ℃ for 17 hours with 100% steam, the catalytic cracking reaction performance of the catalysts was evaluated in a small fixed fluidized bed reactor (ACE), the evaluation method is shown in example 11, the properties of the raw oil in the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
TABLE 1
Figure BDA0001717496670000141
As can be seen from table 1, the modified Y-type molecular sieve provided by the present invention has the following advantages: the sodium oxide content is low, the non-framework aluminum content is low when the silicon-aluminum content of the molecular sieve is high, the pore volume of 2.0-100 nm secondary pores in the molecular sieve accounts for the high volume percentage of the total pores, the B acid/L acid (the ratio of the total B acid content to the L acid content) is high, the crystallinity value measured when the unit cell constant of the molecular sieve is small and the molecular sieve contains a certain calcium content is high, and the thermal stability is high.
TABLE 2
Figure BDA0001717496670000142
As can be seen from Table 2, the modified Y-type molecular sieve provided by the invention has higher relative crystal retention after being aged under the harsh conditions of 800 ℃ and 17 hours in the exposed state of the molecular sieve sample, which indicates that the modified Y-type molecular sieve provided by the invention has high hydrothermal stability.
TABLE 3
Figure BDA0001717496670000151
TABLE 4
Figure BDA0001717496670000152
TABLE 5
Figure BDA0001717496670000161
As can be seen from the results shown in tables 3 and 5, the catalytic cracking catalyst provided by the present invention has high hydrothermal stability, significantly lower coke selectivity, significantly higher liquid yield, significantly higher light oil yield, and improved gasoline yield, and the content of iso-hydrocarbons and the content of di-methyl iso-hydrocarbons in gasoline are also significantly higher, and the ratio of the content of di-methyl iso-hydrocarbons/the content of mono-methyl iso-hydrocarbons in gasoline is also improved.

Claims (15)

1. A catalytic cracking catalyst comprises 10-50 wt% of modified Y-type molecular sieve calculated by dry basis, 10-40 wt% of alumina binder calculated by alumina, and 10-80 wt% of clay calculated by dry basis; the modified Y-type molecular sieve comprises 0.7-6.3 wt% of calcium oxide, 0.1-0.5 wt% of sodium oxide and 0.33-0.39 mL/g of total pore volume, wherein the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 10-25% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the non-framework aluminum content in the modified Y-type molecular sieve accounts for not more than 20 wt% of the total aluminum content, the lattice collapse temperature is not lower than 1040 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.30.
2. The catalytic cracking catalyst of claim 1, wherein the modified Y-type molecular sieve has secondary pores with a pore diameter of 2nm to 100nm, the pore volume of which accounts for 15% to 21% of the total pore volume, the non-framework aluminum content of which accounts for 13% to 19% of the total aluminum content, and the framework silicon-aluminum ratio is SiO2/Al2O3The molar ratio is 7.3-14, the lattice collapse temperature of the molecular sieve is 1040-1080 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured at 200 ℃ by using a pyridine adsorption infrared method is 2.4-4.2.
3. The catalytic cracking catalyst of claim 1, wherein the modified Y-type molecular sieve has a relative crystal retention of 33% or more after severe aging at 800 ℃ under normal pressure in a 100 vol% steam atmosphere for 17 hours.
4. The catalytic cracking catalyst of claim 3, wherein the modified Y-type molecular sieve has a relative crystal retention of 35 to 45% after severe aging at 800 ℃ under normal pressure in a 100 vol% steam atmosphere for 17 hours.
5. The catalytic cracking catalyst of claim 1, 2, 3 or 4, wherein the modified Y-type molecular sieve has a relative crystallinity of 58 to 75%.
6. The catalytic cracking catalyst according to any one of claims 1 to 4, wherein the modified Y-type molecular sieve has a calcium oxide content of 0.9 to 5.9 wt%, a sodium oxide content of 0.2 to 0.5 wt%, a unit cell constant of 2.442 to 2.450nm, and a framework silica-alumina ratio of 8.5 to 12.6.
7. The method for preparing a catalytic cracking catalyst according to any one of claims 1 to 6, comprising the steps of preparing a modified Y-type molecular sieve, forming a slurry comprising the modified Y-type molecular sieve, an alumina binder, clay and water, and spray-drying, wherein the method for preparing the modified Y-type molecular sieve comprises the following steps:
(1) contacting the NaY molecular sieve with a soluble calcium salt solution to perform an ion exchange reaction, filtering, washing, and optionally drying to obtain a calcium-containing Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content;
(2) roasting the calcium-containing Y-type molecular sieve with the conventional unit cell size and reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere of 30-90 vol% of water vapor, and optionally drying to obtain the Y-type molecular sieve with the reduced unit cell constant;
(3) according to SiCl4: the Y-type molecular sieve with reduced unit cell constant is 0.1-0.7: 1, carrying out contact reaction on the Y-shaped molecular sieve with the reduced unit cell constant and silicon tetrachloride gas at the reaction temperature of 200-650 ℃ for 10 minutes to 5 hours, washing and filtering to obtain the modified Y-shaped molecular sieve.
8. The process of claim 7, wherein said reduced sodium oxide calcium containing conventional unit cell size Y-type molecular sieve of step (1) has a unit cell constant of 2.465 to 2.472nm and a sodium oxide content of no more than 8.8 wt.%; the unit cell constant of the Y-type molecular sieve with the reduced unit cell constant obtained in the step (2) is 2.450 nm-2.462 nm, and the water content in the Y-type molecular sieve with the reduced unit cell constant is not more than 1 wt%.
9. The method according to claim 8, wherein in the step (1), the calcium oxide content of the calcium-containing Y-type molecular sieve having a conventional unit cell size and a reduced sodium oxide content is 0.8 to 10% by weight in terms of CaO, the sodium oxide content is 4 to 8.8% by weight, and the unit cell constant is 2.465nm to 2.472 nm.
10. The method of claim 9, wherein in the step (1), the calcium-containing Y-type molecular sieve having a reduced sodium oxide content has a sodium oxide content of 5 to 7.5% by weight.
11. The method of claim 7, wherein the step (1) of contacting the NaY molecular sieve with the soluble calcium salt solution is carried out by ion exchange reaction according to the following formula: soluble calcium salt: h2O is 1: 0.009-0.28: 5-15, mixing the NaY molecular sieve, the soluble calcium salt and water to form a mixture, and stirring.
12. The method of claim 7 or 11, wherein the step (1) of contacting the NaY molecular sieve with a soluble calcium salt solution to perform an ion exchange reaction comprises: mixing NaY molecular sieve with water, adding soluble calcium salt and/or soluble calcium salt solution under stirring to perform ion exchange reaction, filtering and washing; the conditions of the ion exchange reaction are as follows: the exchange temperature is 15-95 ℃, the exchange time is 30-120 minutes, and the soluble calcium salt is calcium chloride and/or calcium nitrate.
13. The method according to claim 7, wherein the roasting temperature in the step (2) is 380 to 460 ℃, the roasting atmosphere is 40 to 80 vol% of water vapor atmosphere, and the roasting time is 5 to 6 hours.
14. The method of claim 7, wherein the washing of step (3)The washing method is washing with water, and the washing conditions are that the molecular sieve: h2The weight ratio of O =1: 6-15, the pH value is 2.5-5.0, and the washing temperature is 30-60 ℃.
15. A catalytic cracking method comprises the step of carrying out contact reaction on heavy oil and a catalytic cracking catalyst under FCC conditions, wherein the catalytic cracking catalyst is the catalytic cracking catalyst according to any one of claims 1 to 6; the FCC conditions are as follows: the reaction temperature is 480-530 ℃, the reaction time is 1-10 seconds, and the ratio of the solvent to the oil is 3-20: 1 weight ratio.
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