CN110653001A - Catalytic cracking catalyst - Google Patents

Catalytic cracking catalyst Download PDF

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Publication number
CN110653001A
CN110653001A CN201810715238.0A CN201810715238A CN110653001A CN 110653001 A CN110653001 A CN 110653001A CN 201810715238 A CN201810715238 A CN 201810715238A CN 110653001 A CN110653001 A CN 110653001A
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molecular sieve
type molecular
rare earth
content
modified
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CN110653001B (en
Inventor
袁帅
周灵萍
田辉平
张蔚琳
沙昊
陈振宇
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Priority to CN201810715238.0A priority Critical patent/CN110653001B/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petrochemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to PCT/CN2019/093279 priority patent/WO2020001540A1/en
Priority to AU2019296826A priority patent/AU2019296826A1/en
Priority to US17/256,943 priority patent/US11504702B2/en
Priority to JP2020573127A priority patent/JP7352584B2/en
Priority to SG11202013116TA priority patent/SG11202013116TA/en
Priority to EP19825723.0A priority patent/EP3815784A4/en
Priority to TW108122866A priority patent/TWI805793B/en
Publication of CN110653001A publication Critical patent/CN110653001A/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
    • B01J29/085—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
    • B01J35/617—
    • B01J35/633—
    • B01J35/647—
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride

Abstract

A catalytic cracking catalyst contains modified Y-type molecular sieve, alumina binder and clay; the CaO content of the modified Y-type molecular sieve is 0.3-4 wt%, and RE content is2O3The content of the sodium oxide is 2-7 wt%, the content of the sodium oxide is 0.1-0.5 wt%, the total pore volume is 0.33-0.39 mL/g, the percentage of the pore volume of secondary pores with the pore diameter of 2-100 nm in the modified Y-type molecular sieve in the total pore volume is 10-25%, the unit cell constant is 2.440-2.455 nm, the percentage of non-framework aluminum content in the modified Y-type molecular sieve in the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, the acid B amount and the acid B amount are respectively equal toThe ratio of the L acid amount is not less than 2.30. The catalytic cracking catalyst has higher heavy oil conversion activity, lower coke selectivity, higher gasoline yield and isomeric C4 yield, and higher isomeric hydrocarbon content in gasoline.

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 isomeric hydrocarbon in the isomeric C4 and gasoline produced by the catalyst prepared in the conventional Y molecular sieve is stable in a certain range and is difficult to increase.
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, Si of NaY zeolite is used as the starting materialO2/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. 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. 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. However, gas phase ultrastable molecular sieves have few secondary pores.
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 but not effectively increase the content of isomeric hydrocarbon in gasoline under certain conditions.
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 which has higher thermal and hydrothermal stability, higher gasoline yield and good selectivity of more-produced isomeric C4 and isomeric hydrocarbon and coke in gasoline, and the catalyst contains a Y-type molecular sieve. The invention also aims to provide a preparation method and an application method of the catalyst.
The invention provides a catalytic cracking catalyst, which comprises 10-50 wt% of modified Y-type molecular sieve and 10-40 wt% of alumina on a dry basisA binder and 10 to 80 wt% clay on a dry basis; the modified molecular sieve has the calcium oxide content of 0.3-4 wt%, the rare earth oxide content of 2-7 wt%, the sodium oxide content of not more than 0.5 wt%, such as 0.1-0.5 wt%, the total pore volume of 0.33-0.39 mL/g, the percentage of the pore volume of secondary pores with the pore diameter of 2-100 nm in the total pore volume of the modified Y-type molecular sieve is 10-25%, the unit cell constant is 2.440-2.455 nm, and the framework silicon-aluminum ratio (SiO/Al)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 1050 ℃, 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 1050 ℃, preferably 1050-1080 ℃, for example 1052-1065 ℃ or 1050-1063 ℃.
In the catalytic cracking catalyst provided by the invention, the ratio of the B acid amount to the L acid amount 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, 2.4-3.5 or 2.3-5.0.
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 to 12.6.
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, 10-20% or 13-19% by weight.
In the catalytic cracking catalyst provided by the invention, the modified Y-type molecular sieve has a crystal retention of over 35%, such as 36-45%, 38-44%, 35-48% or 39-45%, 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-shaped molecular sieve is not less than 58%, such as 58-68%, 59-63%, 60-70% or 60-66%.
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, and preferably 15-21%, or 15-23%, or 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 or 0.28-0.31 mL/g.
In the catalytic cracking catalyst provided by the invention, the modified Y-type molecular sieve contains calcium and rare earth elements, the content of calcium oxide in the modified Y-type molecular sieve is 0.3-4 wt%, such as 0.5-3.5 wt% or 0.9-3 wt% or 0.9-4 wt% calculated by CaO, and Re is used in the modified Y-type molecular sieve2O3The rare earth content is preferably 2 to 7 wt%, for example 2.5 to 6.5 wt%, for example 2.5 to 4.5 wt%.
The modified Y-type molecular sieve provided by the invention has the sodium oxide content of not more than 0.5%, and can be 0.15-0.5 wt%, for example, 0.3-0.5 wt%, or 0.20-0.45 wt%, or 0.25-0.4 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 (AlPO 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 NaY molecular sieve with soluble calcium salt and rare earth salt solution to carry out ion exchange reaction
Filtering and washing to obtain the Y-type molecular sieve with conventional unit cell size and reduced sodium oxide content and containing calcium and rare earth;
wherein the soluble calcium salt solution is also called calcium salt solution, and the soluble rare earth salt solution is also called rare earth salt solution;
(2) sieving the calcium and rare earth-containing Y-type molecular sieve with conventional unit cell size and reduced sodium oxide content
Carrying out modification treatment, optionally drying to obtain the Y-type molecular sieve with reduced unit cell constant, wherein the modification treatment is
Subjecting said calcium and rare earth containing conventional unit cell size Y-type molecular sieve having a reduced sodium oxide content to temperature
An atmosphere containing 30 to 90 vol% of steam at 350 to 480 ℃ (also referred to as an atmosphere containing 30 to 90 vol% of steam or
Weighing 30-90% of water vapor) and roasting 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 contained4: weight of Y-type molecular sieve having reduced unit cell constant obtained in step (2) on a dry basisThe ratio 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 having a reduced unit cell constant is preferably not more than 1% by weight; if the water content in the Y-type molecular sieve obtained by modification treatment in the step (2) (in a Y-type molecular sieve sample obtained by roasting) is not more than 1 wt%, the Y-type molecular sieve can be directly used for contacting silicon tetrachloride to carry out the reaction, and if the water content in the Y-type molecular sieve obtained by roasting in the step (2) is more than 1 wt%, the Y-type molecular sieve with the reduced unit cell constant 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 hydrothermal stability, is used for heavy oil catalytic cracking, has higher heavy oil conversion activity and lower coke selectivity compared with the existing catalytic cracking catalyst containing the Y-type molecular sieve, has higher gasoline yield, light oil yield, total liquid yield and isomeric C4 yield, and has more isomeric hydrocarbons in gasoline. For example, the catalytic cracking catalyst SC3 having a modified Y molecular sieve SZ3 content of 30.0 wt%, a kaolin content of 42 wt%, a pseudoboehmite content of 25 wt%, and an alumina sol content of 3 wt% prepared by the method of the present invention was evaluated with heavy oil on a fixed fluidized bed ACE evaluation apparatus, and the SC3 catalyst had a heavy oil conversion rate of 74.61 wt%, a liquefied gas yield of 16.83 wt%, a gasoline yield of 52.05 wt%, an isomeric C4 hydrocarbon yield of 7.21 wt%, a hydrocarbon content in gasoline of 38.94 wt%, a light oil yield of 69.26 wt%, a total liquid yield of 86.09 wt%, and a coke selectivity of 5.91%, whereas the catalyst DC3 having the same content of the high-silica molecular sieve component prepared by the conventional method had a heavy oil conversion rate of 74.47 wt%, a liquefied gas yield of 15.79 wt%, a gasoline yield of 50.86 wt%, an isomeric C4 hydrocarbon yield of 5.58 wt%, the content of isomeric hydrocarbon in the gasoline is 36.82 percent by weight, the yield of light oil is 68.09 percent by weight, the total liquid yield is 83.88 percent by weight, and the selectivity of coke is 8.61 percent; therefore, the catalyst has higher heavy oil conversion capacity, higher yield of isomeric C4 and gasoline, higher content of isomeric hydrocarbon 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.
The catalytic cracking method provided by the invention has the advantages of higher heavy oil conversion capacity, higher liquefied gas yield and isomeric C4 yield, higher gasoline yield, higher content of isomeric hydrocarbon in gasoline, higher light oil yield and total liquid yield, and better coke selectivity. Can be used for increasing the yield of gasoline with higher content of isomeric hydrocarbon and simultaneously increasing the yield of C4 isomeric hydrocarbon.
In the present invention, the isoparaffin refers to a chain isoparaffin and a chain isoolefin. The increase of the content of the isomeric hydrocarbon is beneficial to improving the quality of the gasoline, for example, the octane number of the gasoline can be kept from being reduced under the condition of reducing the content of aromatic hydrocarbon and olefin.
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-shaped molecular sieve, and in one embodiment, the calcium oxide content of the modified Y-shaped molecular sieve is 0.3-4 wt%, preferably 0.5-3.5 wt%% of rare earth oxide is 2 to 7% by weight, preferably 2.5 to 6.5% by weight, for example 2.5 to 4.5% by weight. The content of sodium oxide is 0.1 to 0.5 wt%, for example, 0.3 to 0.5 wt% or 0.13 to 0.4 wt%, the total pore volume is 0.33 to 0.39mL/g, the percentage of the pore volume of the secondary pores having a pore diameter of 2 to 100nm to the total pore volume is 10 to 25%, preferably 15 to 21%, the unit cell constant is 2.440 to 2.455nm, and the framework silicon-aluminum ratio (SiO 2.440 to 2.455 nm)2/Al2O3Molar ratio) is: 7.3-14.0, 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 58%, the lattice collapse temperature is 1050-1080 ℃ or 1052-1065 ℃, 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 not lower 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, in the step (1), the NaY molecular sieve is contacted with a soluble calcium salt and a rare earth salt solution to carry out an ion exchange reaction, so that the Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content and containing calcium is obtained. The soluble calcium salt and the rare earth salt are a calcium salt capable of being dissolved in a solvent and a rare earth salt capable of being dissolved in a solvent, and the contacting can be carried out by contacting the NaY molecular sieve with a soluble calcium salt solution and a soluble rare earth salt for ion exchange (for example, contacting with a rare earth salt solution and then a calcium salt solution, or contacting with a calcium salt solution and then a rare earth salt solution), or contacting with a solution containing a soluble calcium salt and a soluble rare earth salt (also referred to as a mixed solution of a soluble calcium salt and a rare earth salt in the invention), and the mixed solution of the soluble calcium salt and the soluble rare earth salt can be obtained by mixing the soluble calcium salt and the soluble rare earth salt with a solvent such as water. The NaY molecular sieve can be purchased or prepared according to the existing method, and in one embodiment, the unit cell constant of the NaY molecular sieve is2.465-2.472 nm, 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, the soluble calcium salt and the rare earth 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 (calculated on a dry basis), calcium salt (calculated as CaO), rare earth salt (calculated as RE)2O3Meter): h2O is 1: 0.009-0.28: 0.005-0.09: 5-15 by weight. The rare earth salt is soluble rare earth salt, and the calcium salt is soluble calcium salt. In one embodiment, the ion exchange reaction of the NaY molecular sieve in contact with the soluble calcium salt and the rare earth salt solution comprises the following steps of2The method comprises the steps of mixing NaY molecular sieve (also called NaY zeolite), calcium salt, rare earth salt and water in a weight ratio of 1: 0.009-0.27: 0.005-0.09: 5-15, and carrying out exchange of calcium ions and rare earth ions with sodium ions by stirring at 15-95 ℃, such as 65-95 ℃, preferably for 30-120 minutes. The NaY molecular sieve, the calcium salt, the 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 the calcium salt and/or the calcium salt water solution, the rare earth salt and/or the rare earth salt water solution are added into the slurry. The calcium salt is preferably calcium chloride and/or calcium nitrate. The rare earth salt is preferably rare earth chloride and/or rare earth nitrate. The rare earth such as one or more of La, Ce, Pr, Nd and misch metal, preferably, the misch metal contains one or more of La, Ce, Pr and Nd, or further contains at least one of rare earth other than 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 calcium content of the calcium and rare earth containing Y-type molecular sieve with conventional unit cell size and reduced sodium oxide content obtained in step (1) is 0.3-10 wt% calculated on CaO, such as 0.4-9 wt%, or 0.4-6 wt%, or 1-5 wt%, or 2-4 wt%, or 0.3-4 wt%, or 3-6 wt%, or 3.5-5.5 wt%Or 4-9 wt%, the rare earth content being Re2O32 to 8 wt% or 2.1 to 7 wt% or 3 to 7 wt% or 4 to 6 wt%, sodium oxide content of not more than 9 wt%, for example, 5.5 to 8.5 wt% or 5.5 to 7.5 wt%, and unit cell constant of 2.465nm to 2.472 nm.
In the preparation method of the modified Y-type molecular sieve, the Y-type molecular sieve containing calcium and rare earth in the 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, Na in the washing liquid after washing in general+、Cl-And Al3+The content of each ion is not more than 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 mixed solution of soluble calcium salt and rare earth salt, filtering and washing to obtain a Y-type molecular sieve with conventional unit cell size, reduced sodium oxide content and containing calcium and rare earth; 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-and rare earth-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 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.
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 calcium chloride and the calcium nitrate are chemical pure reagents produced by national medicine group chemical reagent limited company (Hu test), and the rare earth chloride and the rare earth nitrate 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; kaolin is from China Gao SuzhouKaolin specially used for a cracking catalyst produced by RingTu company 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 × (a)0-2.42383)]Wherein, a0Is a unit cell constant in
Figure BDA0001717496550000091
(ii) a 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: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. 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 BDA0001717496550000092
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, and 345ml of Ca (NO) is added3)2The solution (248 g/L solution concentration in CaO) was then charged with 300ml of RE (NO)3)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 the crystal cell constant of 2.471nm, the content of sodium oxide of 6.6 wt%, the content of calcium of 4.9 wt% in terms of CaO, RE2O3Calculating Y-type molecular sieve with rare earth content of 4.4 wt%, calcining at 390 deg.C in atmosphere containing 50 vol% of water vapor and 50 vol% of air for 6 hr to obtain Y-type molecular sieve with unit cell constant of 2.455nm, 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 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, aging SZ1 in a naked state for 17 hours at 800 ℃, 1atm and 100 percent of water vapor, analyzing the relative crystallinity of the molecular sieve before and after the aging of SZ1 by using an XRD method, and calculating the relative junction after the agingCrystal retention, results are shown in table 2, where:
Figure BDA0001717496550000101
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
Adding 2000 g NaY molecular sieve (dry basis) into 25L of decationized aqueous solution, stirring to mix well, adding 368ml CaCl2Solution (solution concentration as CaO: 248g/L), 400ml of RECl3Solutions (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 product with the unit cell constant of 2.471nm, the sodium oxide content of 5.2 wt%, the calcium content of 8.7 wt% calculated by CaO, and the RE content2O3Calculating Y-type molecular sieve with rare earth content of 5.7 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 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 SZ2 is subjected to 100% water evaporation at 800 deg.C for 17 hr in an exposed stateAfter gas aging (17 hours 100% steam aging means aging under 100% steam atmosphere for 17 hours), the crystallinity of zeolite before and after SZ2 aging was analyzed by XRD method and the relative crystal retention after aging was calculated, and the results are shown in Table 2.
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
Adding 2000 g NaY molecular sieve (dry basis) into 22L of decationized aqueous solution, stirring to mix well, adding 214ml CaCl2Solution (solution concentration as CaO 248g/L), 285ml of RECl3Solutions (with RE)2O3319g/L) of rare earth solution, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, and drying a filter cake at 120 ℃ to obtain a crystal cell constant of 2.471nm, a sodium oxide content of 7.2 wt%, a calcium content of 3.8 wt% in terms of CaO, and a RE content2O3Calculating Y-type molecular sieve with rare earth content of 4.7 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 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 ℃ for 1 hour, filtering, washing, drying filter cake at 120 ℃, roasting at 650 ℃ for 5 hours under 100% of water vapor, and performing second hydrothermal modification treatment to obtain twice-separated productThe super-stable Y-shaped molecular sieve containing no calcium and rare earth is obtained by twice hydrothermal exchange 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 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 the filter cake at 120 ℃, performing hydrothermal modification treatment at 650 ℃ for 5 hours under 100% water vapor, adding into 20L of decationized aqueous solution, stirring, mixing well, adding 203ml of Ca (NO)3)2The solution (248 g/L solution concentration based on CaO) was added with 100ml of 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 ℃, 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 NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 243ml of Ca (NO) is added3)2The solution (248 g/L solution concentration in terms of CaO) was added with 325ml of RE (NO)3)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 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. Iso C4 hydrocarbon content (wt.%) iso-butane content (wt.%) + iso-butene content (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
As can be seen from Table 1, the modified Y-type molecular sieve which produces more isomeric C4 hydrocarbons and has high stability provided by the 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 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 content of certain calcium and rare earth is high, and the thermal stability is high.
TABLE 2
Figure BDA0001717496550000151
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 BDA0001717496550000152
TABLE 4
Figure BDA0001717496550000161
TABLE 5
Figure BDA0001717496550000162
As can be seen from the results shown in tables 3 and 5, the catalytic cracking catalyst prepared by using the molecular sieve provided by the present invention as an active component has high hydrothermal stability, significantly lower coke selectivity, significantly higher total liquid yield, significantly higher light oil yield, higher gasoline yield, higher heavy oil conversion activity, significantly higher content of iso-C4 hydrocarbon, and higher content of iso-hydrocarbon in gasoline.

Claims (13)

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 has the calcium oxide content of 0.3-4 wt%, the rare earth oxide content of 2-7 wt%, the sodium oxide content of no more than 0.5 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 10-25% of the total pore volume, the unit cell constant of 2.440-2.455 nm, the non-framework aluminum content of the modified Y-type molecular sieve accounting for no more than 20% of the total aluminum content, the lattice collapse temperature of no less than 1050 ℃, 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 determined by a pyridine adsorption infrared method at 200 ℃ of no less 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 2-100 nm, the pore volume of which accounts for 15-21% of the total pore volume, the non-framework aluminum content of which accounts for 13-19% of the total aluminum content, and the framework silicon-aluminum ratio which is SiO2/Al2O3The molar ratio is 7.3-14, the lattice collapse temperature of the molecular sieve is 1050-1080 ℃, for example 1050-1063 ℃, and the total acid of the modified Y-type molecular sieve is measured at 200 ℃ by a pyridine adsorption infrared methodThe ratio of the amount of the B acid to the amount of the L acid in the amount is 2.4-4.2.
3. The catalytic cracking catalyst according to claim 1, wherein the modified Y-type molecular sieve has a relative crystal retention of 35% or more, for example, 36 to 45%, after severe aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
4. The catalytic cracking catalyst of claim 1, wherein the modified Y-type molecular sieve has a relative crystallinity of 58 to 68%.
5. 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 0.3 to 4 wt%, a rare earth oxide content of 2 to 7 wt%, a sodium oxide content of 0.2 to 0.5 wt%, a unit cell constant of 2.442 to 2.452nm, and a framework Si/Al ratio of 8 to 12.6.
6. A preparation method of a catalytic cracking catalyst comprises the steps of preparing a modified Y-type molecular sieve, forming slurry comprising the modified Y-type molecular sieve, an alumina binder, clay and water, and spray drying, wherein the preparation method of the modified Y-type molecular sieve comprises the following steps:
(1) contacting the NaY molecular sieve with soluble calcium salt and rare earth salt to carry out ion exchange reaction, filtering, washing and optionally drying to obtain the Y-type molecular sieve with conventional unit cell size, wherein the content of sodium oxide is reduced, and the Y-type molecular sieve contains calcium and rare earth;
(2) roasting the calcium-and rare earth-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 weight ratio of the Y-type molecular sieve with reduced unit cell constant to silicon tetrachloride gas, the reaction temperature is 200-650 ℃, and the reaction is carried outThe reaction time is 10 minutes to 5 hours, and the modified Y-type molecular sieve is obtained by washing and filtering.
7. The process of claim 6, wherein said calcium and rare earth containing Y-type molecular sieve having a conventional unit cell size with 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 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 weight percent.
8. The method according to claim 7, wherein in the step (1), the calcium content of the calcium and rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size is 0.4 to 3.9 wt% in terms of CaO, and the rare earth content is Re in terms of Re2O32 to 7 wt%, a sodium oxide content of 4 to 8.8 wt%, for example, 5.5 to 8.5 wt%, and a cell constant of 2.465nm to 2.472 nm.
9. The method of claim 6, wherein the step (1) of contacting the NaY molecular sieve with the soluble calcium salt and the rare earth salt solution to perform the ion exchange reaction comprises the following steps of: soluble calcium salt: soluble rare earth salt: h2O is 1: 0.009-0.28: 0.005-0.09: 5-15, mixing the NaY molecular sieve, the soluble calcium salt, the soluble rare earth salt and water, and stirring.
10. The method of claim 6 or 9, wherein the step (1) of contacting the NaY molecular sieve with a soluble calcium salt and a rare earth 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 and soluble rare earth salt and/or soluble rare earth 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 ℃, and the exchange time is 30-120 minutes; the soluble calcium salt solution and the rare earth salt solution are aqueous solutions of soluble calcium salt and soluble rare earth salt; the soluble calcium salt is calcium chloride and/or calcium nitrate, and the soluble rare earth salt is rare earth chloride and/or rare earth nitrate.
11. The method of claim 6, wherein the roasting temperature in the step (2) is 380-460 ℃, the roasting atmosphere is 40-80% of water vapor atmosphere, and the roasting time is 5-6 hours.
12. The method of claim 6, wherein the washing method in 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 ℃.
13. 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 5; the FCC conditions are, for example: 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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PCT/CN2019/093279 WO2020001540A1 (en) 2018-06-29 2019-06-27 Modified y type molecular sieve, catalytic cracking catalyst having same, and preparation method therefor and application thereof
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707461A (en) * 1983-09-28 1987-11-17 Chevron Research Company Vanadium passivation in a hydrocarbon catalytic cracking process
CN1388064A (en) * 2001-05-30 2003-01-01 中国石油化工股份有限公司 Prepn of high-silicon Y-Zeolite
CN101745418A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation and application thereof
CN102029177A (en) * 2009-09-28 2011-04-27 中国石油化工股份有限公司 Cracking catalyst and preparation method thereof
CN103769192A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Catalytic cracking catalyst and preparation method therefor
CN103962176A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Cracking catalyst capable of increasing octane number of catalytic cracking gasoline

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707461A (en) * 1983-09-28 1987-11-17 Chevron Research Company Vanadium passivation in a hydrocarbon catalytic cracking process
CN1388064A (en) * 2001-05-30 2003-01-01 中国石油化工股份有限公司 Prepn of high-silicon Y-Zeolite
CN101745418A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation and application thereof
CN102029177A (en) * 2009-09-28 2011-04-27 中国石油化工股份有限公司 Cracking catalyst and preparation method thereof
CN103769192A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Catalytic cracking catalyst and preparation method therefor
CN103962176A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Cracking catalyst capable of increasing octane number of catalytic cracking gasoline

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱华元: "FCC催化材料上的氢转移反应研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

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