CN108452826B - Catalytic cracking catalyst - Google Patents
Catalytic cracking catalyst Download PDFInfo
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- CN108452826B CN108452826B CN201710093369.5A CN201710093369A CN108452826B CN 108452826 B CN108452826 B CN 108452826B CN 201710093369 A CN201710093369 A CN 201710093369A CN 108452826 B CN108452826 B CN 108452826B
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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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- 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
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
A catalytic cracking catalyst contains modified Y-type molecular sieve containing magnesium, alumina binder and clay; the magnesium modified high-silicon ultrastable Y-type molecular sieve has the rare earth oxide content of 4-10 wt%, the magnesium oxide content of 0.1-4 wt%, the sodium oxide content of 0.3-0.8 wt%, the total pore volume of 0.33-0.39 mL/g, the pore volume of secondary pores with the pore diameter of 2-100 nm accounting for 10-30% of the total pore volume, the unit cell constant of 2.440-2.455 nm, the non-framework aluminum content accounting for the total aluminum content in the modified Y-type molecular sieve is not higher than 20%, and the lattice collapse temperature is not lower than 1045 ℃. The modified Y-type molecular sieve has higher heavy oil conversion activity, lower coke selectivity, higher diesel oil yield, light oil yield and total liquid yield.
Description
Technical Field
The invention relates to a magnesium-containing high-stability modified Y-type molecular sieve and a preparation method thereof.
Background
The catalytic cracking catalyst containing Mg-contained high-silicon Y-type zeolite is used for heavy oil conversion to increase diesel oil yield. At present, the industrial preparation of high-silicon Y-type zeolite mainly adopts a hydrothermal method: the rare earth-containing high-silicon Y-type zeolite can be prepared by carrying out multiple rare earth ion exchange and multiple high-temperature hydrothermal roasting on NaY zeolite, which is the most conventional method for preparing the high-silicon Y-type zeolite, but the defect of the hydrothermal method for preparing the rare earth high-silicon Y-type zeolite is that: 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 dealuminization 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 crystal retention of the zeolite is low; 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, and the crystallinity retention rate and the specific surface area retention rate are low after hydrothermal aging.
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 cost is higher. Said method, which also comprises rare earth exchange of NaY followed by hydrothermal treatment, has the same drawbacks as the aforementioned US4584287 and US 4429053.
Gas phase chemical processes are another important process for preparing high silica zeolites first reported by Beyer and Mankui in 1980. The gas phase 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. US4273753, US4438178, CN1382525A, CN1194941A, CN1683244A disclose the use of SiCl4A process for preparing ultra-stable Y-type zeolite by gas-phase chemical dealumination. However, the prior art does not suggest how to further improve the cracking activity of the gas phase ultrastable molecular sieve heavy oil.
The existing magnesium-containing high-silicon Y zeolite cracking catalyst has low heavy oil cracking activity and low diesel oil selectivity.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a catalytic cracking catalyst suitable for heavy oil catalytic cracking processing, wherein the catalyst contains a modified Y-type molecular sieve (Y-type molecular sieve is also called Y-type zeolite) containing magnesium, and has higher heavy oil cracking activity and higher diesel oil selectivity. The second technical problem to be solved by the invention is to provide a preparation method of the catalytic cracking catalyst.
The invention provides a catalytic cracking catalyst, which comprises 10-50 wt% of modified Y-type molecular sieve containing magnesium, 10-40 wt% of alumina binder and 10-80 wt% of clay on a dry basis, wherein the weight percentage of the modified Y-type molecular sieve is calculated by the dry basis: the magnesium-containing modified Y-type molecular sieve comprises, by weight, 4-11% of rare earth oxide, 0.1-4% of magnesium oxide, 0.3-0.8% 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 10-30% of the total pore volume of the modified Y-type molecular sieve, 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% of the total aluminum content, and the lattice collapse temperature is not lower than 1045 ℃.
The modified Y-type molecular sieve provided by the invention has the lattice collapse temperature of not less than 1045 ℃, preferably, the lattice collapse temperature of the molecular sieve is 1045-1075 ℃, for example, 1050-1070 ℃.
In the catalytic cracking catalyst provided by the invention, the content of magnesium oxide in the modified magnesium-containing Y-type molecular sieve is preferably 0.5-3 wt%.
In the catalytic cracking catalyst provided by the invention, the unit cell constant of the magnesium-containing modified Y-type molecular sieve is 2.440-2.455 nm, such as 2.441-2.453 nm or 2.442-2.451 nm.
In the catalytic cracking catalyst provided by the invention, the magnesium-containing modified Y-type molecular sieve is a high-silicon Y-type molecular sieve, and the framework silicon-aluminum ratio (SiO) of the high-silicon Y-type molecular sieve2/Al2O3Molar ratio) of 7.3 to 14, for example: 7.8 to 13.2 or 8.5 to 12.6.
In the catalytic cracking catalyst provided by the invention, the percentage of the non-framework aluminum content in the modified magnesium-containing Y-type molecular sieve in the total aluminum content is not higher than 20%, for example, 13-19 wt%.
In the catalytic cracking catalyst provided by the invention, the crystal retention of the modified magnesium-containing Y-type molecular sieve after aging for 17 hours at 800 ℃ under normal pressure and in a 100 volume percent steam atmosphere is more than 30 percent, such as 30-45 percent, 32-40 percent, 35-44 percent or 38-43 percent. The normal pressure is 1 atm.
In the catalytic cracking catalyst provided by the invention, the relative crystallinity of the modified magnesium-containing Y-type molecular sieve is not less than 55%, preferably, the relative crystallinity of the modified Y-type molecular sieve provided by the invention is 55-68%, for example, 58-66%.
In the catalytic cracking catalyst provided by the invention, the magnesium-containing modified Y-type molecular sieve has an implementation mode that the specific surface area is 600-670 m2The/g is, for example, 610 to 660m2The number of the particles is 620 to 655m2/g or 630 to 650m2/g。
In the catalytic cracking catalyst provided by the invention, preferably, the total pore volume of the modified magnesium-containing Y-type molecular sieve is 0.33-0.39 mL/g, such as 0.35-0.39 mL/g or 0.35-0.37 mL/g.
In the catalytic cracking catalyst provided by the invention, the modified magnesium-containing Y-type molecular sieve has the pore volume of secondary pores with the pore diameter (diameter) of 2.0-100 nm accounting for 10-30% of the total pore volume, for example, 15-25%, or 17-22%, or 20-28%.
In the catalytic cracking catalyst provided by the invention, the magnesium-containing modified Y-type molecular sieve contains rare earth elements, and RE is used in the magnesium-containing modified Y-type molecular sieve2O3The rare earth oxide content is 4 to 11 wt%, preferably 4.5 to 10 wt%, for example 5 to 9 wt%.
In the catalytic cracking catalyst provided by the invention, the content of sodium oxide in the modified magnesium-containing Y-type molecular sieve is not more than 0.8%, and can be 0.3-0.8 wt%, for example, 0.5-0.80 wt% or 0.4-0.6 wt%.
In the catalytic cracking catalyst provided by the invention, the content of the modified Y-type molecular sieve containing magnesium 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.
The content of the alumina binder in the catalytic cracking catalyst provided by the invention is 10-40 wt%, for example 20-35 wt%, the alumina binder of the invention is selected from one or more of alumina, hydrated alumina and alumina sol of various forms commonly used in cracking catalysts, for example, one or more selected from gamma-alumina, η -alumina, theta-alumina, chi-alumina, pseudoboehmite (pseudoboehmite), diaspore (Boehmite), Gibbsite (Gibbsite), bayer (bayer) or alumina sol, preferably pseudoboehmite and alumina sol, for example, the catalytic cracking catalyst contains 2-15 wt%, preferably 3-10 wt% of alumina sol, and 10-30 wt%, preferably 15-25 wt% of pseudoboehmite in terms of alumina.
The catalyst provided by the invention can also contain other molecular sieves except the magnesium-containing modified Y-type molecular sieve, and the content of the other molecular sieves is, for example, 0-40 wt% such as 0-30 wt% or 1-20 wt% based on the weight of the catalyst on a dry basis, the other molecular sieves are selected from the molecular sieves used in the catalytic cracking catalyst, such as one or more of zeolite with MFI structure, Beta zeolite, other Y-type zeolite and non-zeolite molecular sieve, preferably, the content of the other Y-type molecular sieves is not more than 40 wt% such as 1-40 wt% or 0-20 wt% based on the dry basis, the other Y-type zeolite is, for example, one or more of REY, REHY, DASY, SOY and PSRY, the MFI structure zeolite is, for example, one or more of HZSM-5, ZRP and ZSP, the Beta zeolite is, for example, H β, the non-zeolite molecular sieves are, for example, one or more of aluminum phosphate (AlPO molecular sieves) and phosphorus molecular sieves (molecular sieves).
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 a modified Y-type molecular sieve comprising magnesium, 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 invention provides a preparation method of a catalytic cracking catalyst, which comprises the steps of preparing a magnesium-containing modified Y-type molecular sieve, forming a slurry from raw materials comprising the magnesium-containing modified Y-type molecular sieve, an alumina binder, clay and water, and spray drying; the preparation method of the modified Y-type molecular sieve containing magnesium comprises the following steps:
(1) contacting the NaY molecular sieve with a rare earth solution to perform an ion exchange reaction, filtering and washing to obtain a Y-type molecular sieve containing rare earth with a conventional unit cell size and reduced sodium oxide content; wherein the rare earth solution is also called rare earth salt solution;
(2) modifying the rare earth-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 rare earth-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) mixing the Y-type molecular sieve sample with SiCl, wherein the unit cell constant is reduced4Gas is contacted and reacted at the temperature of 200-650 ℃, wherein SiCl is preferred4: 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, filtering and optionally drying to obtain the ultra-stable 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) (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) is more than 1 wt%, the Y-type molecular sieve sample obtained by roasting in the step (2) with a reduced unit cell constant is obtained by roasting in the step (2)Drying the molecular sieve sample to a water content of less than 1 wt.%;
(4) and (4) contacting the ultrastable modified Y-shaped molecular sieve obtained in the step (3) with a magnesium compound for magnesium modification treatment.
The catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking, has higher heavy oil conversion activity and lower coke selectivity, has higher diesel oil yield, and has higher light oil yield and total liquid yield compared with the existing cracking catalyst containing the magnesium Y-type molecular sieve. The catalytic cracking catalyst provided by the invention can be used for converting heavy oil or poor oil.
The preparation method of the catalytic cracking catalyst, provided by the invention, can be used for preparing the magnesium-containing high-silicon ultrastable Y-type molecular sieve with a certain secondary pore structure, high crystallinity, high thermal stability and high hydrothermal stability, wherein the molecular sieve is uniform in aluminum distribution and low in non-framework aluminum content.
Detailed Description
The catalytic cracking catalyst provided by the invention contains 10-50 wt% of modified Y-type molecular sieve containing magnesium, 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 modified Y-type molecular sieve containing magnesium on a dry basis, 20 to 35 wt% of 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 magnesium-containing Y-type molecular sieve, and in one embodiment, the modified magnesium-containing Y-type molecular sieve has a rare earth oxide content of 4-11 wt%, preferably 4.5-10 wt%, a magnesium oxide content of 0.1-4 wt%, for example 0.5-3 wt%, a sodium oxide content of 0.3-0.8 wt%, preferably 0.35-0.75 wt%, for example 0.4-0.6 wt%, a total pore volume of 0.33-0.39 mL/g, a percentage of secondary pores with a pore diameter of 2-100 nm in the total pore volume of 10-30%, preferably 15-25%, a unit cell constant of 2.440-2.455 nm, and a framework silica-alumina ratio (SiO 2-25%, 2.440-2.455 nm, 2.2/Al2O3Molar ratio) is: 7-14, the percentage of non-framework aluminum content in the molecular sieve in the total aluminum content is not higher than 20%, preferably 13-19, the relative crystallinity is not lower than 55%, for example 55-68%, and the lattice collapse temperature is 1045-1075 ℃, for example 1047-1065 ℃.
The preparation process of the magnesium-containing 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 catalytic cracking catalyst, in the step (1), the NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction to obtain the rare earth-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content. 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 rare earth 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) rare earth salt (RE)2O3Meter) H2O is 1:0.01 to 0.18:5 to 15 by weight. In one embodiment, the ion exchange reaction of the NaY molecular sieve and the rare earth solution comprises the following steps of mixing the NaY molecular sieve, rare earth salt and H2The exchange between rare earth ions and sodium ions is carried out by mixing NaY molecular sieve (also called NaY zeolite), rare earth salt and water at a weight ratio of 1: 0.01-0.18: 5-15, and stirring at 15-95 ℃, for example, 65-95 ℃, preferably 30-120 minutes. The NaY molecular sieve, rare earth salt and water are mixed to form a mixture, the NaY molecular sieve and the water can be formed into slurry, and then rare earth salt and/or aqueous solution of rare earth salt are added into the slurry, wherein the rare earth solution is solution of rare earth salt, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate. The rare earth such as La, Ce, Pr, Nd and mixtures thereofAnd one or more of La, Ce, Pr and Nd, or at least one of the rare earths except La, Ce, Pr and Nd. 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 rare earth content of the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content obtained in step (1) and the conventional unit cell size is calculated as RE2O34.5 to 13 wt%, for example 5.5 to 13 wt% or 5.5 to 12 wt%, sodium oxide content of not more than 9.5 wt%, for example 5.5 to 9.5 wt%, and a cell constant of 2.465nm to 2.472 nm.
In the preparation method of the catalytic cracking catalyst, in the step (2), the Y-type molecular sieve with the conventional unit cell size containing rare earth is roasted for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere of 30-90 vol% of water vapor, preferably, in the step (2), the roasting temperature is 380-460 ℃, the roasting atmosphere is 40-80 vol% of water vapor (the atmosphere contains 40-80 vol% of water vapor), and the roasting time is 5-6 hours. The water vapor atmosphere contains 30-90% 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 modified Y-shaped molecular sieve containing magnesium is prepared by the step (3) of SiCl4: 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: washing water and waterThe weight ratio of the sub-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, usually Na in washed molecular sieve samples+，Cl-And Al3+The respective contents of ions do not exceed 0.05 wt.%.
In the preparation method of the catalytic cracking catalyst, the magnesium-containing modified Y-shaped molecular sieve comprises the step (4) of performing magnesium modification treatment on the ultrastable modified Y-shaped molecular sieve obtained in the step (3) by using a magnesium compound. One embodiment comprises adding the filter cake sample or dried sample of the ultrastable modified Y-type molecular sieve obtained in step (3) into a solution containing a magnesium compound such as magnesium salt, stirring for 10-120 minutes at 5-50 ℃, then adding ammonia water, adjusting the pH of the solution to 7.5-10, stirring uniformly, filtering, leaching with neutral water, drying the filter cake, and then placing the dried filter cake in a muffle furnace to bake for more than 1 hour, such as 1-5 hours or 2-3 hours, thus obtaining the magnesium modified high-silicon ultrastable Y-type molecular sieve. Wherein, the dosage of the magnesium-containing compound solution and the molecular sieve is that the weight ratio of water to the molecular sieve (calculated by dry basis) is 1-6, preferably 1.5-3.5, and the weight ratio of magnesium (calculated by magnesium oxide) to the molecular sieve (calculated by dry basis) is as follows: 0.001-0.04, preferably 0.005-0.035; preferably, the magnesium salt is magnesium chloride and/or magnesium nitrate.
The preparation method of the catalytic cracking catalyst provided by the invention is a preparation method of a modified Y-type molecular sieve containing magnesium, and one embodiment of the preparation method comprises the following steps:
(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a rare earth solution, filtering and washing to obtain a Y-type molecular sieve containing rare earth and having a conventional unit cell size and reduced sodium oxide content; 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 rare earth-containing Y-type molecular sieve with the normal 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 a gas-phase ultrastable modified Y-type molecular sieve filter cake;
(4) and (3) mixing the gas-phase ultrastable modified Y-type molecular sieve filter cake obtained in the step (3) with a magnesium salt aqueous solution, stirring for 10-120 minutes at 5-50 ℃, then adding ammonia water, adjusting the pH of the solution to 7.5-10, stirring uniformly, filtering, leaching with neutral water, drying the filter cake, and roasting at 500-650 ℃ for 1-3 hours to obtain the magnesium-modified high-silicon ultrastable Y-type molecular sieve. Wherein, in a mixture formed by a magnesium salt aqueous solution and a gas-phase ultra-stable modified Y-type molecular sieve, the weight ratio of water to the molecular sieve is 1-6, preferably 1.5-3.5, and the weight ratio of magnesium (calculated as magnesium oxide) to the molecular sieve is as follows: 0.001 to 0.04, preferably 0.005 to 0.035.
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%; the chlorinated rare earth and the nitric acid rare earth are chemical pure reagents produced by Beijing chemical plants. The pseudoboehmite is an industrial product produced by Shandong aluminum factories, and has the solid content of 61 percent by weight; the kaolin is kaolin specially used for a cracking catalyst produced by Suzhou China kaolin company, and has the solid content of 76 weight percent; the alumina sol is provided by the company Qilu, China petrochemical catalyst, Inc.
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: SiO 22/Al2O3＝(2.5858-a0)×2/(a0-2.4191)]Wherein a is0Is the unit cell constant in nm; 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 of the comparative examples and examples, the secondary pore volume was determined as follows: measuring total pore volume of the molecular sieve according to adsorption isotherm, measuring micropore volume of the molecular sieve according to T mapping method from adsorption isotherm, subtracting micropore volume from total pore volume to obtain secondary 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, 600ml of RE (NO) is added3)3Solution (rare earth solution concentration in RE)2O3319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying filter cake at 120 ℃, obtaining crystal cell constant of 2.471nm, sodium oxide content of 7.0 wt%, RE2O3Y-type molecular sieve with rare earth content of 8.8 wt% is calcined at 390 deg.C in the atmosphere of 50 vol% water vapor and 50 vol% air for 6 hr to obtain molecular sieve with unit cell constant of 2.455nmY-type molecular sieve, drying to water content less than 1 wt%, and adding SiCl4: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating4Gas, at a temperature of 400 ℃, for 2 hours, after which it was washed with 20 litres of decationised water and then filtered, and a sample of the molecular sieve cake was added to a solution containing magnesium chloride, in a weight ratio of water to molecular sieve of 2.5, and magnesium (expressed as magnesium oxide) to molecular sieve: 0.01; stirring for 40 minutes at 25 ℃, then adding ammonia water, adjusting the pH value to 8.5, stirring uniformly, filtering, rinsing with deionized water, drying a filter cake, and roasting at 550 ℃ for 2 hours to obtain the magnesium-containing modified Y-type molecular sieve (also called as a magnesium-modified high-silicon ultrastable Y-type molecular sieve) provided by the invention, which is marked as SZ 1. The physicochemical properties are shown in table 1, after the exposed state of SZ1 is aged for 17 hours at 800 ℃, 1atm and 100% steam, the relative crystallinity of the molecular sieve before and after the aging of SZ1 is analyzed by XRD method and the relative crystallinity retention after the aging is calculated, the results are shown in table 2, wherein:
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 concentration of 36% by mass 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. 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.
Example 2
2000 g of NaY molecular sieve (calculated on a dry basis) is added into 25L of decationized aqueous solution and stirred to be uniformly mixed,800ml of RECl were added3Solutions (with RE)2O3The solution concentration is measured as: 319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying the filter cake at 120 ℃, and obtaining the crystal cell with the constant of 2.471nm, the content of sodium oxide of 5.5 weight percent and RE2O3Calculating Y-type molecular sieve with rare earth content of 11.3 wt%, calcining at 450 deg.C under 80% water vapor for 5.5 hr to obtain Y-type molecular sieve with unit cell constant of 2.461nm, drying to water content of less than 1 wt%, and adding SiCl4: y-type zeolite 0.6: 1, by weight, introducing SiCl vaporized by heating4Gas, at 480 ℃, for 1.5 hours, then washing with 20 liters of decationized water, then filtering, and adding a molecular sieve cake sample to a solution containing magnesium nitrate, wherein the ratio of the magnesium nitrate containing solution to the molecular sieve is 2.3 by weight, and the ratio of magnesium (in terms of magnesium oxide) to the molecular sieve is: 0.02, stirring for 35 minutes at 30 ℃, adding ammonia water, adjusting the pH value of the solution to 9, stirring uniformly, filtering, leaching with deionized water, drying a filter cake, and roasting in a muffle furnace at 590 ℃ for 2 hours to obtain the magnesium-modified high-silicon ultrastable Y-type molecular sieve recorded as SZ 2. Physical and chemical properties of SZ2 are shown in table 1, and the results are shown in table 2, in which after exposure of SZ2 at 800 ℃ for 17 hours and 100% steam aging (17 hours and 100% steam aging means aging for 17 hours in 100% steam atmosphere), the crystallinity of zeolite before and after SZ2 aging is analyzed by XRD and the relative crystal retention after aging is calculated.
714.5 g of alumina sol with an alumina content of 21 wt% was added to 1565.5 g of decationized water, stirring was started, and 2763 g of kaolin with a solids content of 76 wt% was added and dispersed for 60 minutes to obtain a kaolin slurry. 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 concentration of 36% by mass is added under the stirring state, the kaolin slurry is added after acidification for 60 minutes, then 1500 g (dry basis) of ground SZ2 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 2. 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.
Example 3
2000 g of NaY molecular sieve (dry basis) is added into 22L of decationized aqueous solution and stirred to be mixed evenly, and 570ml of RECl is added3Solutions (with RE)2O3The calculated concentration of the rare earth solution is 319g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and obtaining the rare earth solution with the unit cell constant of 2.471nm, the sodium oxide content of 7.5 weight percent and the RE content2O3Calculating Y-type molecular sieve with rare earth content of 8.5 wt%, calcining at 470 deg.C under 70 vol% steam for 5 hr to obtain Y-type molecular sieve with unit cell constant of 2.458nm, drying to water content lower than 1 wt%, and adding SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4Reacting gas for 1 hour at the temperature of 500 ℃, washing with 20 liters of decationized water, filtering, adding a molecular sieve filter cake sample into a solution containing magnesium chloride, stirring for 45 minutes at the temperature of 20 ℃, adding ammonia water, adjusting the pH value of the solution to 9.2, stirring uniformly, filtering, leaching with water, drying the filter cake, and roasting in a muffle furnace at the temperature of 580 ℃ for 2 hours to obtain the magnesium-modified high-silicon ultrastable Y-type molecular sieve. Wherein, in the mixture formed by the solution of magnesium chloride and the molecular sieve, the weight ratio of water to the molecular sieve is 3.2, and the weight ratio of magnesium (calculated as magnesium oxide) to the molecular sieve is as follows: 0.025, and is marked as 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.
714.5 g of alumina sol with the alumina content of 21 weight percent is taken and added into 1565.5 g of decationized water, stirring is started, 2763 g of kaolin with the solid content of 76 weight percent is added, and the kaolin is dispersed for 60 minutes to obtain well dispersed kaolin slurry. 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 concentration of 36% by mass 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 SZ3 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 3. 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.
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 at 120 deg.C, hydrothermal modifying (650 deg.C, baking with 100% water vapor for 5 hr), adding into 20L of decationized water solution, stirring to mix well, 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, then carrying out second hydrothermal modification treatment, roasting at 650 ℃ under 100% of water vapor for 5 hours, and obtaining the rare earth-free hydrothermal ultrastable Y-shaped molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and 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.
Comparative example 2
2000 g of NaY molecular sieve (dry basis) is added to 20 l of decationizingStirring the seed aqueous solution to mix the seed aqueous solution and adding 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out hydrothermal modification treatment, wherein the conditions of the hydrothermal modification treatment are as follows: calcining at 650 deg.C under 100% steam atmosphere for 5 hr, adding into 20L decationized water solution, stirring, mixing, adding 200ml RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth solution is measured as follows: 319g/L) and 900 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, then carrying out second hydrothermal modification treatment, roasting at 650 ℃ under 100% of water vapor for 5 hours, and obtaining the rare earth-containing hydrothermal ultrastable Y-shaped molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable and is marked as DZ 2. 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.
Comparative example 3
2000 g NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 650ml of RE (NO) is added3)3Stirring the solution (319g/L), 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 SiCl treatment4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4Gas, at 580 deg.C, reacting for 1.5 hrThen, washing with 20 liters of decationized ionic water, filtering, then adding a molecular sieve filter cake sample into a solution containing magnesium chloride, stirring for 45 minutes at 20 ℃, then adding ammonia water, adjusting the pH value of the solution to 9.2, stirring uniformly, filtering, rinsing with water, drying the filter cake, and then roasting in a muffle furnace at 580 ℃ for 2 hours to obtain the magnesium-modified high-silicon ultrastable Y-type molecular sieve. Wherein, in the mixture formed by the solution of magnesium chloride and the molecular sieve, the weight ratio of water to the molecular sieve is 3.2, and the weight ratio of magnesium (calculated as magnesium oxide) to the molecular sieve is as follows: 0.025, and is marked 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.
Examples 4 to 6
Examples 4-6 illustrate the catalytic cracking activity and stability of the modified Y-type molecular sieve provided by the invention.
The light oil micro-reactivities of the catalysts were evaluated after 100% steam aging at 800 ℃ for 4 hours or 17 hours for SC1, SC2, and SC3, respectively, 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
Comparative examples 4-6 illustrate the catalytic cracking activity and stability of the ultrastable Y-type molecular sieves prepared by the methods provided in comparative examples 1-3.
The light oil micro-reactivities of the DC1, DC2 and DC3 catalysts were evaluated after 100% steam aging at 800 ℃ for 4 hours or 17 hours. See example 6 for evaluation, and the results are shown in Table 3.
TABLE 1
As can be seen from table 1, the high-stability modified Y-type molecular sieve provided by the present invention has the following advantages: the content of sodium oxide 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 volume percentage of the total pores, the ratio of B acid/L acid (the total amount of B acid to the amount of L acid) is high, the crystallinity value measured when the content of rare earth is high when the unit cell constant of the molecular sieve is small is high, and the thermal stability is high.
TABLE 2
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
Examples 7 to 9
Examples 7 to 9 illustrate the catalytic cracking reaction performance of the catalytic cracking catalyst provided by the present invention.
After the catalysts SC1, SC2 and SC3 were aged with 100% steam at 800 ℃ for 17 hours, the catalytic cracking reaction performance was evaluated in a small fixed fluidized bed reactor (ACE), and cracked gas and product oil were collected separately and analyzed by gas chromatography. The catalyst loading is 9g, the reaction temperature is 500 ℃, and the weight hourly space velocity is 16h－1The weight ratio of the base oil is shown in Table 5, the properties of the raw materials for the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
Comparative examples 7 to 9
Comparative examples 7 to 9 illustrate the catalytic cracking reaction performance of the catalytic cracking catalysts provided in comparative examples 1 to 3.
After aging DC1, DC2 and DC3 catalysts at 800 ℃ for 17 hours in a 100% steam atmosphere, the catalytic cracking reaction performance was evaluated on a small fixed fluidized bed reactor (ACE), the evaluation method is shown in example 7, the properties of the raw materials for the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
TABLE 4 ACE evaluation of raw oil Properties
TABLE 5
| Example numbering | Example 7 | Example 8 | Example 9 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Sample numbering | SC1 | SC2 | SC3 | DC1 | DC2 | DC3 |
| The molecular sieve used | SZ1 | SZ2 | SZ3 | DZ1 | DZ2 | DZ3 |
| Ratio of agent to oil | 5 | 5 | 5 | 9 | 8 | 5 |
| Product distribution/weight% | ||||||
| Dry gas | 1.39 | 1.41 | 1.38 | 1.55 | 1.48 | 1.47 |
| Liquefied gas | 15.87 | 15.87 | 16.04 | 16.86 | 15.33 | 16.03 |
| Coke | 4.48 | 4.61 | 4.32 | 8.33 | 7.61 | 6.15 |
| Gasoline (gasoline) | 45.29 | 44.91 | 43.99 | 38.55 | 43.91 | 49.19 |
| Diesel oil | 25.35 | 26.69 | 26.46 | 20.17 | 19.25 | 18.88 |
| Heavy oil | 7.62 | 6.51 | 7.81 | 14.54 | 12.42 | 8.28 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion/weight% | 67.03 | 66.8 | 65.73 | 65.29 | 68.33 | 72.84 |
| Coke selectivity/weight% | 6.68 | 6.90 | 6.57 | 12.76 | 11.14 | 8.44 |
| Yield of light oil/weight% | 70.64 | 71.6 | 70.45 | 58.72 | 63.16 | 68.07 |
| Total liquid/weight% | 86.51 | 87.47 | 86.49 | 75.58 | 78.49 | 84.1 |
| Ratio of diesel to gasoline | 0.56 | 0.59 | 0.60 | 0.52 | 0.44 | 0.38 |
As can be seen from tables 3 and 5, the catalytic cracking catalyst provided by the present invention has the advantages of higher hydrothermal stability, obviously lower coke selectivity, obviously higher liquid yield, obviously higher light oil yield, higher diesel-gasoline ratio and higher heavy oil conversion activity.
Claims (22)
1. A catalytic cracking catalyst comprises 10-50 wt% of modified Y-type molecular sieve containing magnesium, 10-40 wt% of alumina binder and 10-80 wt% of clay; the magnesium-containing modified Y-type molecular sieve comprises, by weight, 4-11% of rare earth oxide, 0.1-4% of magnesium oxide, 0.3-0.8% 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 10-30% 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% of the total aluminum content, and the lattice collapse temperature is 1045-1075 ℃.
2. The catalytic cracking catalyst of claim 1, wherein the secondary pores of the magnesium-containing modified Y-type molecular sieve having a pore diameter of 2nm to 100nm have a pore volume percentage of 15% to 25% of the total pore volume.
3. The catalytic cracking catalyst of claim 1, wherein the modified magnesium-containing Y-type molecular sieve has a non-framework aluminum content of 13-19% of the total aluminum content, and the framework silica-alumina ratio is SiO2/Al2O3The molar ratio is 7-14.
4. The catalytic cracking catalyst of claim 1, wherein the modified magnesium-containing Y-type molecular sieve has a lattice collapse temperature of 1050-1070 ℃.
5. The catalytic cracking catalyst of claim 1, wherein the magnesium-containing modified Y-type molecular sieve has a magnesium oxide content of 0.5-3 wt.%.
6. The catalytic cracking catalyst of claim 1, wherein the modified Y-type molecular sieve containing magnesium has a relative crystal retention of 30% or more after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
7. The catalytic cracking catalyst of claim 1, wherein the modified magnesium-containing Y-type molecular sieve has a relative crystal retention of 30 to 45% after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
8. The catalytic cracking catalyst of claim 1, wherein the modified Y-type molecular sieve containing magnesium has a relative crystallinity of 55 to 68%.
9. The catalytic cracking catalyst of any one of claims 1 to 8, wherein the magnesium-containing modified Y-type molecular sieve has a rare earth oxide content of 4.5 to 10 wt%, a sodium oxide content of 0.4 to 0.6 wt%, a unit cell constant of 2.442 to 2.451nm, and a framework silica-alumina ratio of 8.5 to 12.6.
10. A preparation method of a catalytic cracking catalyst comprises the steps of forming a raw material comprising a modified Y-type molecular sieve containing magnesium, an alumina binder and clay and water into slurry, and performing spray drying; the preparation method of the modified Y-type molecular sieve containing magnesium comprises the following steps:
(1) contacting the NaY molecular sieve with a rare earth salt solution to perform an ion exchange reaction, filtering, washing, and optionally drying to obtain a rare earth-containing Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content;
(2) roasting the rare earth-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 of 30-90 vol% of water vapor, and optionally drying to obtain the Y-type molecular sieve with the reduced unit cell constant;
(3) the Y-shaped molecular sieve with the reduced unit cell constant is contacted with silicon tetrachloride gas for reaction, and the Y-shaped molecular sieve is washed and filtered to obtain a high-silicon ultrastable Y-shaped molecular sieve; the contact reaction, SiCl4: the weight ratio of the Y-type molecular sieve with reduced unit cell constant on a dry basis is 0.1-0.7: 1. the reaction temperature is 200-650 ℃, and the reaction time is 10 minutes to 5 hours;
(4) and (4) modifying the high-silicon ultrastable Y-type molecular sieve obtained in the step (3) by using a magnesium compound.
11. The process of claim 10, wherein the rare earth-containing Y-type molecular sieve having a conventional unit cell size and a reduced sodium oxide content in step (1) has a unit cell constant of 2.465 to 2.472nm and a sodium oxide content of not more than 9.5 wt.%.
12. The process of claim 10, wherein in step (1), the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content and a conventional unit cell size contains rare earth in an amount of RE2O34.5 to 13 wt%, sodium oxide content 5 to 9.5 wt%, and unit cell constant 2.465nm to 2.472 nm.
13. The method of claim 10, wherein the step (1) of contacting the NaY molecular sieve with the rare earth salt solution to perform the ion exchange reaction is performed according to the following formula: rare earth salt: h2O is 1: 0.01-0.18: 5-15, mixing the NaY molecular sieve, the rare earth salt and water to form a mixture, and stirring.
14. The method of claim 10 or 13, wherein the step (1) of contacting the NaY molecular sieve with the rare earth solution for ion exchange reaction comprises: mixing NaY molecular sieve with decationized water, stirring, adding rare earth salt and/or rare earth salt solution 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 rare earth salt solution is a rare earth salt water solution.
15. The method as claimed in claim 10, wherein the roasting temperature in step (2) is 380-460 ℃, the roasting atmosphere is 40-80% water vapor atmosphere, and the roasting time is 5-6 hours.
16. The method of claim 10, wherein the unit cell constant of the Y-type molecular sieve with reduced unit cell constant obtained in step (2) is 2.450nm to 2.462nm, and the water content of the Y-type molecular sieve with reduced unit cell constant is not more than 1 wt%.
17. The method according to claim 10, wherein the washing method in the step (3) is washing with water under the washing conditions that the molecular sieve: h2O is 1: 6-15, the pH value is 2.5-5.0, and the washing temperature is 30-60 ℃.
18. The method according to claim 10, wherein the modification treatment with a magnesium compound in the step (4) comprises: adding a molecular sieve into a solution containing magnesium salt, stirring for 10-120 minutes at 5-50 ℃, then adding ammonia water, adjusting the pH of the solution to 7.5-10, uniformly stirring, filtering, leaching with water, drying a filter cake, roasting at 500-650 ℃ for at least 1 hour to obtain the magnesium modified high-silicon ultrastable Y-type molecular sieve, wherein in a mixture formed by the solution containing the magnesium salt and the molecular sieve, the weight ratio of the water to the molecular sieve is 1-6, and the weight ratio of the magnesium salt to the molecular sieve calculated by magnesium oxide is as follows: 0.001 to 0.04.
19. The method of claim 12, wherein the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content and a conventional unit cell size has a sodium oxide content of 5.5 to 9.0 wt.%.
20. The method of claim 18, wherein the weight ratio of water to molecular sieve in step (4) is 1.5-3.5.
21. The method of claim 18, wherein the weight ratio of the magnesium salt to the molecular sieve is 0.005-0.035.
22. The method of claim 10, wherein the rare earth salt is a rare earth chloride and/or a rare earth nitrate; the magnesium compound is magnesium chloride and/or magnesium nitrate.
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| PCT/CN2018/076431 WO2018153303A1 (en) | 2017-02-21 | 2018-02-12 | Modified y-type molecular sieve containing magnesium, preparation method therefor, and catalyst containing modified y-type molecular sieve |
| MYPI2019004663A MY195283A (en) | 2017-02-21 | 2018-02-12 | Magnesium Modified Y-Type Molecular Sieve, Preparation Thereof and Catalyst Comprising the same |
| JP2019545357A JP7163298B2 (en) | 2017-02-21 | 2018-02-12 | MAGNESIUM-MODIFIED Y-TYPE MOLECULAR SIEVE, METHOD FOR PRODUCTION THEREOF, AND CATALYST CONTAINING THE SAME |
| RU2019127289A RU2770421C2 (en) | 2017-02-21 | 2018-02-12 | Magnesium-modified y-type molecular sieve, production thereof and catalyst containing same |
| US16/484,880 US11053129B2 (en) | 2017-02-21 | 2018-02-12 | Magnesium modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
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