CN110193377A

CN110193377A - A kind of catalytic cracking petroleum hydrocarbons catalyst

Info

Publication number: CN110193377A
Application number: CN201810159805.9A
Authority: CN
Inventors: 王鹏; 田辉平; 周灵萍; 姜秋桥; 孙言; 严加松; 宋海涛; 张久顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-02-26
Filing date: 2018-02-26
Publication date: 2019-09-03
Anticipated expiration: 2038-02-26
Also published as: CN110193377B

Abstract

A kind of catalytic cracking petroleum hydrocarbons catalyst, the molecular sieve for being 0.59-0.73 nanometers containing carrier, Y type molecular sieve, the mesopore molecular sieve with M41S structure and channel openings diameter；Described Y type molecular sieve includes the super-stable Y molecular sieves containing rare earth, its total pore volume is 0.33~0.39mL/g, aperture is that the pore volume of the second hole of 2~100nm accounts for the 10~25% of total pore volume, lattice constant is 2.440~2.455nm, the total aluminium content ratio of non-framework aluminum content Zhan is not higher than 20%, lattice collapse temperature is not less than 1050 DEG C, and the ratio of the B acid amount and L acid amount that are measured with pyridine adsorption infrared method at 200 DEG C is not less than 2.50.The catalyst heavy oil conversion activity is high, and coke selectivity is good, and yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield are high.

Description

A kind of catalytic cracking petroleum hydrocarbons catalyst

Technical field

The present invention relates to a kind of catalytic cracking petroleum hydrocarbons catalyst.

Background technique

Catalytic cracking is the important means of hydrocarbon ils processing, and catalytically cracked material slag-mixing amount increases in recent years, since residual oil is big Ratio shared by molecule is big, and arene content is high, is easy to coking in reaction process, proposes to the heavy oil cracking activity of Cracking catalyst Requirements at the higher level.In order to improve the processing performance of residual oil, in the prior art to catalytic cracking is carried out after residual hydrogenation again, with production The fuel such as gasoline, diesel oil.

The Cracking catalyst of heavy oil conversion depth is improved at present in the catalyst using super steady Y type molecular sieve.For example, CN1060976、CN1060977、CN1128673、CN1005405、CN1119206、CN1065844、US5340957、 The hydro-thermal of super-stable Y molecular sieves is provided in US5206194, US4273753, US4438178, US4584287 and US4429053 Preparation method, but the above method is easy that the crystal structure of molecular sieve is made to generate defect, obtained super-stable Y molecular sieves, and heavy oil is split Change activity is not high, and coke selectivity is bad.

CN1382525A, CN1194941A, CN1683244A, which are disclosed, utilizes SiCl₄Gas chemistry dealuminzation prepares super steady Y The method of type molecular sieve.But existing gas phase super stable molecular sieve still has the not high problem of activity, Bu Nengman for residual oil cracking The processing of sufficient mink cell focus and poor oil needs, and affects the product distribution and economic benefit of catalytic cracking unit.

CN106268932A provides a kind of catalytic cracking catalyst and the preparation method and application thereof.The catalyst contains base The IM-5 molecular sieve of matter, the USY molecular sieve of super stabilizing and super stabilizing, on the basis of the weight of the catalyst, the super stabilizing USY molecular sieve and the total weight content of IM-5 molecular sieve of super stabilizing be 50wt%~90wt%, and the IM-5 of super stabilizing point The weight ratio of the USY molecular sieve of son sieve and super stabilizing is (0.01~0.25): 1.The catalyst is suitable for plus the conversion of hydrogen wax oil, uses It is converted in hydrogenated residue, cracking activity and yield of gasoline be not high, and coke selectivity is bad.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of catalytic cracking petroleum hydrocarbons catalyst, and the catalyst is for weight Oily cracking has higher heavy oil cracking activity and better coke selectivity.The invention solves second technical problem be A kind of preparation method and application method of catalyst is provided.

The present invention provides a kind of catalytic cracking of petroleum hydrocarbon catalyst, and with dry basis, the catalytic cracking of petroleum hydrocarbon is urged Agent contains the carrier of 40-80 weight % such as 50~70 weight %, the Y type point of 10~50 weight % such as 20-50 weight % Son sieve, the mesopore molecular sieve with M41S structure of 5-15 weight %, the channel openings diameter of 5-15 weight % are 0.59-0.73 The molecular sieve of nanometer, the Y type molecular sieve include super-stable Y molecular sieves (the referred to as modified Y type molecule of the present invention containing rare earth Sieve), which is 5~12 weight %, and sodium oxide content is 0.1~0.7 weight % is measured, total pore volume is 0.33~0.39mL/g, the second hole which is 2nm~100nm Pore volume to account for the percentage of the super-stable Y molecular sieves total pore volume containing rare earth be 10%~25%, lattice constant is 2.440nm~2.455nm, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) it can be 7.3~14.0:1, non-skeleton in molecular sieve The percentage of the total aluminium content of aluminium content Zhan is not higher than 20%, and lattice collapse temperature is not less than 1050 DEG C, also, red with pyridine adsorption B acid amount and the ratio of L acid amount are not less than in the super-stable Y molecular sieves total acid content for containing rare earth that outer method is measured at 200 DEG C 2.50。

The superstable gamma-type molecule containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, lattice collapse temperature are not less than 1050 DEG C, it is preferred that 1055 DEG C~1080 DEG C of the molecular sieve lattice collapse temperature, for example, 1057~1075 DEG C.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, B acid amount and L acid amount in the super-stable Y molecular sieves total acid content for containing rare earth measured with pyridine adsorption infrared method at 200 DEG C It is, for example, 2.7~3.3 that ratio, which is preferably 2.6~4.0,.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, Lattice constant is that 2.440nm~2.455nm is, for example, 2.442~2.450nm.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, For high-Si Y-type molecular sieve, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) it is 7.3~14.0, for example, 8.5~12.6.

The super-stable Y molecular sieves containing rare earth used in catalyst provided by the invention, non-skeleton in molecular sieve The percentage of the total aluminium content of aluminium content Zhan is not higher than 20 weight %, for example, 13~19 weight %.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, It is, for example, 38 that crystal retention under 800 DEG C, normal pressure, 100 volume % water vapour atmospheres after aging 17 hours, which is 38% or more, ~48% or 39~45%.The normal pressure is 1atm.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, Relative crystallinity is not less than 60%, it is preferred that the opposite crystallization of the super-stable Y molecular sieves containing rare earth provided by the invention Degree is 60~70%, for example, 60~66%.In the present invention measuring method of described relative crystallinity (abbreviation crystallinity) referring to RIPP in " petrochemical egineering analysis method (RIPP test methods) " (Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) 146-90 standard method.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, A kind of embodiment, specific surface area are 620~670m²/ g is, for example, 630~660m²/g。

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, Preferably, it is, for example, 0.36~0.375mL/g that total pore volume, which is 0.35~0.39mL/g,.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, The percentage that the pore volume for the second hole that aperture (referring to diameter) is 2.0nm~100nm accounts for total pore volume is 10%~25%, preferably It is 15~21%.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, Containing rare earth element, this contains in the super-stable Y molecular sieves of rare earth with RE₂O₃The rare earth oxide content of meter is that 5~12 weight % are preferred For 5.5~10 weight %.

The super-stable Y molecular sieves containing rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, Sodium oxide content is no more than 0.7%, can be, for example, 0.35~0.60 weight % or 0.4~0.55 weight for 0.3~0.7 weight % Measure %.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, the used super-stable Y molecular sieves containing rare earth Preparation method the following steps are included:

(1) NaY molecular sieve is contacted with earth solution and carries out ion-exchange reactions, be filtered, washed, obtain sodium oxide content The Y type molecular sieve of the conventional unit cell dimension containing rare earth reduced；Wherein earth solution is also referred to as rare-earth salt solution；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content reduces is modified processing, Optionally drying, obtains the Y type molecular sieve of lattice constant reduction, and the modification is to reduce the sodium oxide content containing dilute The Y type molecular sieve of the conventional unit cell dimension of soil is in 350~480 DEG C of temperature, the atmosphere (also referred to as 30 containing 30~90 volume % water vapours ~90 volume % water vapour atmospheres or 30~90% water vapours) under roast 4.5~7 hours；

Wherein, the water content for the Y type molecular sieve that the lattice constant reduces is preferably more than 1 weight %；

(3) Y type molecular sieve and SiCl that the lattice constant for obtaining step (2) reduces₄Gas is 200 in temperature Haptoreaction under conditions of~650 DEG C, wherein SiCl₄: the Y type point that the lattice constant that (2) obtain the step of in terms of butt reduces Weight ratio=0.1~0.7:1 of son sieve, the reaction time 10 minutes to 5 hours, then washed, filtering obtained described containing rare earth Super-stable Y molecular sieves.

Catalytic cracking of petroleum hydrocarbon catalyst provided by the present invention, containing carrier, wherein described carrier can be it is existing Conventional carrier, the present invention used in catalytic cracking catalyst are not particularly limited it, such as can be clay, oxidation One of alumina supporter, silica support, silicaalumina carrier are a variety of.The clay such as kaolin, more Hydrokaolinite, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, one in bentonite Kind is several.The alumina support can be one of aluminium oxide, hydrated alumina and Aluminum sol of various forms Or it is several；For example, one in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, hydrated alumina or Aluminum sol Kind or several, the hydrated alumina such as boehmite (Pseudoboemite), a diaspore (Boehmite), three One of diaspore (Gibbsite), bayerite (Bayerite) are a variety of.The alumina support preferably intends thin water aluminium Stone and Aluminum sol.A kind of embodiment, on the basis of the weight of catalyst, containing with oxidation in the catalytic cracking catalyst 2~15 weight % of aluminium the meter preferably Aluminum sol of 3~10 weight %, the weight of the 5-40 in terms of aluminium oxide % or 10~30 weight % are preferred The boehmite of 15~25 weight %.The silica support can be Silica hydrogel, waterglass and/or silica solution, preferably , the silica support includes silica solution, on the basis of the weight of catalyst, with SiO₂The content of silica solution is counted as 1-30 weight Measuring % or 0.5~25 weight % is, for example, 0.5-20 weight % or 1-15 weight %, and it is molten that the silica solution can be neutral silicon Glue, acidic silicasol or alkaline silica sol.Silicaalumina carrier such as silicon-aluminum sol, silica-alumina gel, amorphous One of silicon-aluminium oxide is a variety of.

Contain the mesopore molecular sieve with M41S structure in catalytic cracking petroleum hydrocarbons catalyst provided by the present invention, with On the basis of catalytic cracking petroleum hydrocarbons catalyst weight, the mesopore molecular sieve content with M41S structure is calculated as 5- with butt 15 weight %.One of described mesopore molecular sieve such as MCM-41, MCM-48 and MCM-50 with M41S structure is a variety of. In general, the M41S structure molecular screen sial atomic molar ratio be 10~400:1 such as 50~350:1 or 100-300:1 or 10-200:1 or 10-100:1 or 20~80:1 or 15~50:1.The M41S structure molecular screen sodium oxide content is no more than 0.1 weight %, the M41S structure molecular screen can be Hydrogen M41S structure molecular screen, for example, HMCM-41, H-Al- One of MCM-48 and HMCM-50 or a variety of.Hydrogen M41S molecular sieve can be passed through by the sodium form M41S molecular sieve synthesized Peracid and/or ammonium exchange, roasting obtain, this is known to the skilled person.

On the basis of catalytic cracking petroleum hydrocarbons catalyst weight, catalytic cracking petroleum hydrocarbons catalyst provided by the invention In the channel openings diameter containing 5-15 weight % be 0.59-0.73 nanometers of molecular sieve.The channel openings diameter is 0.59- 0.73 nanometer of molecular sieve, which is selected from, has AFR structure molecular screen, AFS structure molecular screen, AFI structure molecular sieve, BEA structural molecule Sieve, BOG structure molecular screen, CON structure molecular screen, GME structure molecular screen, LTL structure molecular screen, MEI structure molecular screen, MOR At least one of structure molecular screen and the molecular sieve of OFF structure.It is preferred that are as follows: Beta molecular sieve, SAPO-5 molecular sieve, SAPO- In 40 molecular sieves, SSZ-24 molecular sieve, CIT-1 molecular sieve, ZSM-18 molecular sieve, modenite, sodium chabazite and offretite At least one.Preferably, described channel openings diameter be 0.59-0.73 nanometers of molecular sieve include ZSM-18 molecular sieve, One of SAPO-5 molecular sieve, Beta molecular sieve are a variety of.Channel openings diameter is that 0.59-0.73 nanometers of molecular sieve is preferred The molecular sieve for being 0.59-0.73 nanometers for Hydrogen channel openings diameter, sodium oxide content are no more than 1.5 weight % and are, for example, 0.01-1.5wt% or 0.1~1 weight % or 0.2~0.5 weight %, sial atomic molar ratio are that 0.1-500 is, for example, 0.1- 300:1 or 0.5-200:1 or 1~100:1.For example, it is preferable to channel openings diameter be 0.59-0.73 nanometers molecular sieve be silicon Aluminium zeolite, for example, Beta molecular sieve, SAPO-40 molecular sieve, SSZ-24 molecular sieve, CIT-1 molecular sieve, ZSM-18 molecular sieve, One of modenite, sodium chabazite and offretite are a variety of, and sial atomic molar is than being respectively 0.1-100 or 1- 100:1 or 5~80:1 or 10~50:1 or 20~40:1.

In catalytic cracking petroleum hydrocarbons catalyst provided by the invention, the Y type molecular sieve includes described super containing rare earth Stabilization Y-type molecular sieve, on the basis of catalytic cracking petroleum hydrocarbons catalyst weight, the super-stable Y molecular sieves containing rare earth contain Amount is 10~50 weight %, preferably 20-40 weight %.The Y type molecular sieve can also include other types of Y type molecule Sieve, such as the Y type molecular sieve that existing method obtains, other types of Y type molecular sieve content are preferably more than 30 weight %, such as For 0-20 weight % or 0-10 weight %.Preferably, the Y type molecular sieve is the superstable gamma-type molecule of the present invention containing rare earth Sieve.

The present invention also provides a kind of catalytic cracking of petroleum hydrocarbon method for preparing catalyst, comprising: by carrier, Y type molecular sieve, tool There is the mesopore molecular sieve of M41S structure, the molecular sieve that channel openings diameter is 0.59-0.73 nanometer and water formation slurries, drying Step；Wherein the Y type molecular sieve preferably includes or for the super-stable Y molecular sieves containing rare earth, this contains the super of rare earth Stabilization Y-type molecular sieve preparation method the following steps are included:

(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains The Y type molecular sieve of the conventional unit cell dimension containing rare earth reduced to sodium oxide content；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content temperature 350~ 480 DEG C, roast 4.5~7 hours under 30~90 volume % water vapour atmospheres, optionally drying obtains the Y type point of lattice constant reduction Son sieve, water content are preferably more than 1 weight %；

(3) Y type molecular sieve for reducing the lattice constant and silicon tetrachloride gas haptoreaction, washing and filtering, it is excellent Choosing, according to SiCl₄: Y type molecular sieve=0.1~0.7:1 weight ratio that the lattice constant in terms of butt reduces is by institute The Y type molecular sieve and silicon tetrachloride gas haptoreaction of lattice constant reduction are stated, reaction temperature is 200 DEG C~650 DEG C, when reaction Between be 10 minutes to 5 hours, washing and filtering obtain the super-stable Y molecular sieves containing rare earth.

Catalytic cracking of petroleum hydrocarbon method for preparing catalyst provided by the invention, optional further includes that will dry for example spraying do Dry obtained catalyst microspheres washing and dry step.The formation slurries, spray drying, washing and drying are existing skill Art, the present invention do not have particular/special requirement.

It can be with or without rare earth element, with petroleum in the carrier of catalytic cracking of petroleum hydrocarbon catalyst provided by the present invention On the basis of the weight of hydrocarbon catalytic cracking catalyst, the catalyst carrier can the rare earth containing 0-5 weight % (with RE₂O₃Meter), In described rare earth element be, for example, mixed rare-earth elements based on lanthanum and/or cerium, wherein the content of lanthanum and/or cerium is total dilute The 50 weight % or more of soil amount, such as 60 weight % or more.Rare earth element is added in the carrier can improve the stabilization of catalyst Property.When containing rare earth element in carrier, during forming catalyst slurry, rare earth compound, Ke Yixian is added Rare earth compound is mixed with carrier, then carrier and molecular sieve first can also be mixed to form slurry with molecular sieve mixture again Then liquid adds rare earth compound, or rare earth compound is mixed with Component Vectors, then add mixture to part In the slurries that carrier and molecular sieve are formed.

Catalytic cracking of petroleum hydrocarbon catalyst of the present invention is converted suitable for hydrocarbon oil catalytic cracking, is particularly suitable for heavy oil and is urged Change cracking.For this purpose, the present invention provides a kind of Heavy oil conversion method, including urging heavy oil and the catalytic cracking of petroleum hydrocarbon Agent is under catalytic cracking condition the step of haptoreaction, and wherein reaction temperature is 400-600 DEG C, weight (hourly) space velocity (WHSV) 5-30 hours^-1, Oil ratio 1-10 (weight ratio)；Preferable reaction temperature is 450-550 DEG C or 480-530 DEG C, and weight (hourly) space velocity (WHSV) is preferably 8-25 small When^-1, the preferred 2-7 of oil ratio.The heavy oil such as reduced crude, decompression residuum, wax tailings, deasphalted oil or this above-mentioned hydrocarbon One of hydrotreating oil that oil obtains after hydrotreating is a variety of.Heavy oil conversion method provided by the invention is especially Suitable for hydrogenated residue catalyzed conversion.A kind of embodiment, the heavy oil are hydrogenated residue, the arene content of the hydrogenated residue For 40~75 weight % such as 45~65 weight % or 50~70 weight %, paraffinicity is that 1~25 weight % is, for example, 5- 20 weight % or 8-15 weight %, naphthene content be 15~45 weight % such as 20~45 weight % or 25~35 weight %, Specific gravity is 0.92~0.95g/cm³, such as 0.925~0.945g/cm³Or 0.93~0.942g/cm³, oil ratio refer to catalyst with The weight ratio of feedstock oil.

Super-stable Y molecular sieves in catalyst provided by the invention containing described containing rare earth and described there is M41S knot The molecular sieve that the mesopore molecular sieve and channel openings diameter of structure are 0.59-0.73 nanometers has superior heavy oil macromolecular cracking Ability and good product selectivity, heavy oil conversion rate and yield of light oil are high, and coke selectivity is good, can obtain than existing methods The catalytic cracking catalyst arrived has higher heavy oil conversion activity and lower coke selectivity, higher for arene content Hydrogenated residue conversion, can have higher yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield.

Catalytic cracking catalyst preparation method provided by the invention will be described including preparing the stabilization Y-type molecular sieve containing rare earth Super-stable Y molecular sieves containing rare earth and carrier, the mesopore molecular sieve with M41S structure, channel openings diameter be 0.59- 0.73 nanometer of molecular sieve and water forms the step of slurries, drying, can prepare catalytic cracking of petroleum hydrocarbon provided by the invention Catalyst.

Heavy oil conversion method provided by the invention, heavy oil conversion rate is high, and coke yield is low, and yield of light oil is high, more existing Heavy oil conversion method has higher yield of gasoline, yield of liquefied gas and total liquid yield.

Specific embodiment

Catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, using catalytic cracking of petroleum hydrocarbon catalyst dry weight as base Standard, the catalytic cracking of petroleum hydrocarbon catalyst contain the carrier by dry basis 40-80 weight %, by dry basis 10~ The Y type molecular sieve of 50 weight %, the mesopore molecular sieve by dry basis 5-15 weight % with M41S structure and press butt The molecular sieve that the channel openings diameter of poidometer 5-15 weight % is 0.59-0.73 nanometers, it is preferred that press dry basis, institute State catalytic cracking of petroleum hydrocarbon catalyst to contain: carrier 50-75 weight % is preferably 50-70 or 55-75 weight %, Y type molecular sieve 15-50 weight % is preferably 20~40 weight % or 25-45 weight %, the mesopore molecular sieve 5-15 weight % with M41S structure Preferably 5-10 weight %, molecular sieve (present invention is also referred to as shape-selective molecular sieve) 5- that channel openings diameter is 0.59-0.73 nanometers 15 weight % are preferably 5-10 weight %.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, the oxidation of the super-stable Y molecular sieves containing rare earth is dilute Native content is 5~12 weight %, preferably 5.5~10 weight %；The super-stable Y molecular sieves containing rare earth, sodium oxide content are 0.1~0.7 weight %, preferably 0.3~0.7 weight %, total pore volume are 0.33~0.39mL/g, and aperture is 2nm~100nm The pore volume of second hole to account for the percentage of total pore volume be 10%~25%, preferably 15%~21%, lattice constant is 2.440nm~2.455nm, framework si-al ratio (SiO2/Al2O3 molar ratio) are as follows: 7.3~14.0, non-framework aluminum contains in molecular sieve The percentage for measuring the total aluminium content of Zhan is not higher than 20%, preferably 13~19, and relative crystallinity is not less than 60%, lattice collapse temperature Be 1055 DEG C~1080 DEG C, also, measured with pyridine adsorption infrared method at 200 DEG C this contain the super-stable Y molecular sieves of rare earth The ratio of B acid amount and L acid amount is not less than 2.50, preferably 2.6~4.0 in total acid content.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, the super-stable Y molecular sieves containing rare earth, for containing rare earth The super steady Modified Zeolite Y of gas phase, include contacting Y type molecular sieve with silicon tetrachloride to carry out dealumination complement silicon in preparation process The step of reaction.The molecular sieve has high-crystallinity, has second level pore structure, and thermal stability and hydrothermal stability are high.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves preparation containing rare earth In method, NaY molecular sieve and earth solution are subjected to ion-exchange reactions in step (1), to obtain sodium oxide content reduction The Y type molecular sieve of conventional unit cell dimension containing rare earth.The NaY molecular sieve, can be commercially available or prepares, one according to existing method Kind embodiment, the NaY molecular sieve lattice constant are 2.465~2.472nm, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) It is 4.5~5.2, it is, for example, 85~95% that relative crystallinity, which is 85% or more, and sodium oxide content is 13.0~13.8 weight %.Step Suddenly NaY molecular sieve described in (1) and earth solution carry out ion-exchange reactions, and it is, for example, 65 that exchange temperature, which is preferably 15~95 DEG C, ~95 DEG C, swap time is preferably such as 45~90 minutes 30~120 minutes.NaY molecular sieve (in terms of butt): rare-earth salts (with RE₂O₃Meter): H₂The weight ratio of O=1:0.01~0.18:5~15.A kind of embodiment, the NaY molecular sieve and earth solution Carrying out ion-exchange reactions includes, according to NaY molecular sieve: rare-earth salts: H₂The weight ratio of O=1:0.01~0.18:5~15 will NaY molecular sieve (also referred to as NaY zeolite), rare-earth salts and water form mixture, preferably stir in 15~95 DEG C of such as 65~95 DEG C stirrings It mixes and carries out within 30~120 minutes exchanging for rare earth ion and sodium ion, the water such as decationized Y sieve water, deionized water or it is mixed Close object.NaY molecular sieve, rare-earth salts and water are formed into mixture, NaY molecular sieve and water can be formed into slurries, then described Slurries in the aqueous solution of rare-earth salts and/or rare-earth salts is added, the earth solution is the solution of rare-earth salts, the rare earth Salt is preferably rare earth chloride and/or nitric acid rare earth.The rare earth such as one of La, Ce, Pr, Nd and mischmetal or It is a variety of, it is preferred that containing one of La, Ce, Pr and Nd or a variety of in the mischmetal, or also containing except La, Ce, Pr With at least one of the rare earth other than Nd.A kind of embodiment, the rare earth are mischmetal.Step is washed described in (1) It washs, it is therefore an objective to wash away the sodium ion being swapped out, it is, for example, possible to use deionized water or decationized Y sieve water washings.It is preferred that step (1) content of rare earth of the Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content obtained reduces is with RE₂O₃It is calculated as 5.5~14 weight % are, for example, 7~14 weight or 5.5~12 weight %, and it is, for example, 5.5 that sodium oxide content, which is no more than 9 weight %, ~8.5 weight % or 5.5~7.5 weight %, lattice constant are 2.465nm~2.472nm.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves preparation containing rare earth Method, by the Y type molecular sieve of the conventional unit cell dimension containing rare earth at 350~480 DEG C of temperature in step (2), 30~90 volume % It roasting 4.5~7 hours and is handled under water vapour atmosphere, it is preferred that maturing temperature described in step (2) is 380~460 DEG C, Calcination atmosphere is 40~80 volume % water vapour atmospheres, and calcining time is 5~6 hours.Contain 30 in the water vapour atmosphere ~90 volume % vapor also contain other gases such as one of air, helium or nitrogen or a variety of.Institute in step (2) The Y type molecular sieve that the lattice constant stated reduces, lattice constant are 2.450nm~2.462nm.

The water content in Y type molecular sieve that lattice constant described in step (2) reduces is preferably more than 1 weight %.It can The water content in molecular sieve is reduced by the method for roasting or drying, such as the drying, existing method can be used, such as adopt With pneumatic conveying drying, drying, expansion drying method.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves preparation containing rare earth In method, in step (3), SiCl₄: the weight ratio of Y type molecular sieve (in terms of butt) is preferably 0.3~0.6:1, the reaction Temperature is preferably 350~500 DEG C, and example can be washed with water using conventional washing methods in washing methods described in step (3) As decationized Y sieve water or deionized water wash, it is therefore an objective to remove Na remaining in zeolite⁺, Cl^-And Al³⁺Equal soluble by-products, Such as wash conditions can be with are as follows: the weight ratio of washing water and molecular sieve can be 5~20:1, usual molecular sieve: H₂O weight ratio= 1:6~15, pH value are preferably 2.5~5.0, and wash temperature is 30~60 DEG C.Preferably, the washing, the washing after making washing Detected in liquid do not go on a tour from Na⁺, Cl^-And Al³⁺Plasma, usually Na in the sieve sample after washing⁺, Cl^-And Al³⁺Ion Respective content is no more than 0.05 weight %.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves preparation containing rare earth Method, a kind of embodiment the following steps are included:

(1) NaY molecular sieve (also referred to as NaY zeolite) and earth solution are subjected to ion-exchange reactions, filtered, washing obtains The Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium oxide content reduces；The ion exchange usually stirring, temperature be It is exchanged 30~120 minutes under conditions of 15~95 DEG C preferably 65~95 DEG C；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing the sodium oxide content temperature 350~ It 480 DEG C, roasts 4.5~7 hours under the atmosphere containing 30~90 volume % water vapours, it is dry, obtain the Y type point of lattice constant reduction Son sieve；The lattice constant for the Y type molecular sieve that the lattice constant reduces is 2.450nm~2.462nm；

The water content for the Y type molecular sieve that the lattice constant reduces is lower than 1 weight %；

(3) SiCl of the Y type molecular sieve for reducing the lattice constant and heated vaporization₄Gas contacts, wherein SiCl₄: Weight ratio=0.1~the 0.7:1 for the Y type molecular sieve (in terms of butt) that lattice constant reduces, the item for being 200~650 DEG C in temperature Haptoreaction 10 minutes to 5 hours under part, washed and filtering, obtain the super-stable Y molecular sieves of the present invention containing rare earth.

The stabilization Y-type molecular sieve preparation method containing rare earth, available high-crystallinity, high thermal stability and high hydro-thermal are steady Qualitatively there is the high-Si Y-type molecular sieve of certain second level pore structure, aluminium is evenly distributed in the molecular sieve, and non-framework aluminum content is few.

In fluidized cracking catalysts preparation method provided by the invention, the carrier can be clay, alumina support, oxygen One of SiClx carrier, silicaalumina carrier are a variety of.The alumina support such as gama-alumina, η-oxidation Aluminium, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite), one or more of bayerite (Bayerite) or Aluminum sol；The silica support such as silica gel, silicon One of gel, silica solution, waterglass are a variety of；The silicaalumina carrier, for example, it is silica-alumina gel, amorphous One of silica-alumina, silicon-aluminum sol are a variety of, and the clay such as kaolin, halloysite, illiteracy is de- One or more of soil, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite, preferably One or more of kaolin, halloysite, montmorillonite, diatomite, tired de- soil, more preferable kaolin.Preferably, described Carrier includes the substance of commonly referred to as binder, such as al binder and/or silicon bonding, and the al binder can be selected from being hydrated Aluminium oxide and/or Aluminum sol, the hydrated alumina such as boehmite (Pseudoboemite), a diaspore (Boehmite), one or more of gibbsite (Gibbsite), bayerite (Bayerite), the hydrated alumina Acidification (acidizing product is also referred to as acidified hydrated alumina) is generally gone through as binder, wherein the acidification includes that will be hydrated oxygen Change the step of aluminium is contacted with acid, wherein the acid-aluminum ratio (36 weight % hydrochloric acid and the aqua oxidation in terms of aluminium oxide that are preferably acidified The weight ratio of aluminium) it is 0.15~0.25:1, preferably 0.18~0.22:1；In the silicon bonding such as silica solution, waterglass One or more, preferably silica solution, the silica solution is, for example, that acidic silicasol (usual pH value is 2~4), neutral silicon are molten One or more of glue (usual pH value is 6~8), alkaline silica sol (usual pH value is 9~10.5).

In fluidized cracking catalysts preparation method provided by the invention, in terms of oxide, silicon bonding accounts for carrier, Y type molecule Point that sieve, the mesopore molecular sieve (abbreviation mesopore molecular sieve) with M41S structure and channel openings diameter are 0.59-0.73 nanometers The ratio of the total dry weight (dry weight that the present invention is known as catalyst slurry) of son sieve (abbreviation shape-selective molecular sieve) is no more than 30 Weight % is, for example, that 0-15 weight % or 1-15 weight % is preferably 5-15 weight %；In terms of oxide, al binder account for carrier, The total butt of molecular sieve that Y type molecular sieve, the mesopore molecular sieve with M41S structure and channel openings diameter are 0.59-0.73 nanometers It is, for example, 0~40 weight % or 12~35 weight % that the ratio of weight, which is no more than 40 weight %,.A kind of embodiment, described is viscous Knot agent is one of boehmite, Aluminum sol and silica solution or a variety of, and binder accounts for carrier, Y type molecule in terms of oxide The total dry weight of molecular sieve that sieve, the mesopore molecular sieve with M41S structure and channel openings diameter are 0.59-0.73 nanometers Ratio is 12~35 weight % preferably 15~30 weight % or 18-28 weight % or 20-25 weight %.In general, other than binder The carrier present invention be known as inorganic oxide matrix, account for the dry weight of catalyst slurry ratio be 0-80 weight %, example For example 10-70 weight % or 20-50 weight % or 25-45 weight %, the inorganic oxide matrix are common selected from Cracking catalyst One or more of inorganic oxide matrix, preferred inorganic oxide matrix is that clay such as kaolin group's clay is preferred Kaolin, it is preferred that it is, for example, 20~50 weight % that clay, which accounts for the ratio of the dry weight of catalyst slurry as 10-60 weight %, Or 30~45 weight %.

Catalytic cracking of petroleum hydrocarbon method for preparing catalyst provided by the invention: will include the superstable gamma-type containing rare earth point Son sieve Y type molecular sieve, the mesopore molecular sieve with M41S structure, channel openings diameter be 0.59-0.73 nanometers molecular sieve, Inorganic oxide matrix, binder and deionized water are mixed with beating to form catalyst slurry, dry, obtain catalytic cracking catalysis Agent.The solid content for being beaten the catalyst slurry formed is generally 10-50 weight %, preferably 15-30 weight %.It is dry after mashing Dry condition is common drying condition in catalytic cracking catalyst preparation process.In general, drying temperature is 100-350 DEG C, Preferably 200-300 DEG C.The drying can use the method for drying, forced air drying or spray drying, the side of preferably spray drying Method.

The following examples illustrate the present invention further, but these embodiments should not be understood as to limit of the invention It is fixed.

In embodiment and in comparative example, NaY molecular sieve (also referred to as NaY zeolite) is Sinopec catalyst Co., Ltd Shandong Branch company provides, and sodium oxide content is 13.5 weight %, framework si-al ratio (SiO₂/Al₂O₃Molar ratio)=4.6, lattice constant is 2.470nm, relative crystallinity 90%；Rare earth chloride and nitric acid rare earth are the chemically pure reagent of Beijing Chemical Plant's production.

Analysis method: in each comparative example and embodiment, the constituent content of zeolite is by x-ray fluorescence spectrometry；Boiling The lattice constant of stone, relative crystallinity (crystallinity) use RIPP145-90, RIPP146- by x-ray powder diffraction (XRD) 90 standard methods (are compiled, Science Press, nineteen ninety goes out see " petrochemical analysis method " (RIPP test method) Yang Cui is surely equal Version) it measures, the framework si-al ratio of zeolite is calculated by following formula and is obtained: SiO₂/Al₂O₃=(2.5858-a₀)×2/(a₀-2.4191)] Wherein, a₀For lattice constant, unit nm；Si and Al element of the total silica alumina ratio of zeolite according to x-ray fluorescence spectrometry What content calculated, total silica alumina ratio of framework si-al ratio and the XRF measurement measured by XRD method can calculate the ratio of skeleton Al and total Al Value, and then calculate the ratio of non-skeleton Al and total Al.Crystal structure collapse temperature is measured by differential thermal analysis (DTA).

In each comparative example and embodiment, the acid site type and its acid amount of molecular sieve are divided using the infrared method of pyridine adsorption Analysis measurement.Laboratory apparatus: the U.S. Bruker company IFS113V type FT-IR (fourier-transform infrared) spectrometer.Use pyridine adsorption Infrared method measures acid amount experimental method at 200 DEG C: by sample self-supporting tabletting, being placed in the Chi Zhongmi in situ of infrared spectrometer Envelope.400 DEG C are warming up to, and is evacuated to 10^-3Pa, constant temperature 2h, the gas molecule of removing sample absorption.It is down to room temperature, imports pressure Power is that 2.67Pa pyridine steam keeps adsorption equilibrium 30min.200 DEG C are then heated to, is evacuated to 10^-330min is desorbed under Pa, It is down to room temperature and takes the photograph spectrum, scan wave-number range: 1400cm^-1~1700cm^-1, it is infrared to obtain the pyridine adsorption that sample is desorbed through 200 DEG C Spectrogram.According to 1540cm in Pyridine adsorption IR spectra figure^-1And 1450cm^-1The intensity of feature adsorption peak, obtains in molecular sieve TotalThe relative quantity in acid site (acid site B) and the acid site Lewis (acid site L).

In each comparative example and embodiment, wherein the measuring method of described second level pore volume is as follows: according to RIPP151-90 Standard method " petrochemical egineering analysis method (RIPP test methods) " (Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) root The total pore volume of molecular sieve is determined according to adsorption isotherm, then determines molecular sieve from adsorption isotherm according to T graphing method Total pore volume is subtracted micro pore volume and obtains second level pore volume by micro pore volume,

Chemical reagent used is not specifically specified in comparative example and embodiment, and specification is that chemistry is pure.

Embodiment 1

Taking 2000 grams of NaY molecular sieves (in terms of butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions keeps its mixing equal It is even, the RE (NO of 600ml is added₃)₃(earth solution concentration is with RE for solution₂O₃It is calculated as 319g/L), stirring is warming up to 90~95 DEG C It is kept for 1 hour, is then filtered, washed, for filter cake in 120 DEG C of dryings, obtaining lattice constant is 2.471nm, 7.0 weight of sodium oxide content Measure %, with RE₂O₃The Y type molecular sieve for counting 8.8 weight % of content of rare earth, later at 390 DEG C of temperature, containing 50 volume % water vapours and It is roasted 6 hours under the atmosphere of 50 volume % air, obtains the Y type molecular sieve that lattice constant is 2.455nm and be dried later Processing makes its water content lower than 1 weight %, then according to SiCl₄: the weight ratio of Y type molecular sieve (butt meter)=0.5:1 is led to Enter the SiCl of heated vaporization₄Gas reacts 2 hours, under conditions of temperature is 400 DEG C later, with 20 liters of decationized Y sieve water Washing, then filters, obtains Modified Zeolite Y provided by the invention, be denoted as SZ1, physico-chemical property is listed in Table 1 below, by SZ1 Naked state through 800 DEG C, 1atm, after 100% vapor aging 17 hours, point before and after SZ1 aging is analyzed with the method for XRD The relative crystallinity of son sieve simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2, in which:

Embodiment 2

Taking 2000 grams of NaY molecular sieves (in terms of butt) to be added to stirring in 25 liters of decationized Y sieve aqueous solutions keeps its mixing equal It is even, the RECl of 800ml is added₃Solution is (with RE₂O₃The solution concentration of meter are as follows: 319g/L), stirring is warming up to 90~95 DEG C and keeps 1 Hour, it is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 5.5 weights in 120 DEG C of dryings Measure %, with RE₂O₃The Y type molecular sieve that content of rare earth is 11.3 weight % is counted, is roasted under 450 DEG C of temperature, 80% water vapour later It 5.5 hours, obtains the Y type molecular sieve that lattice constant is 2.461nm and is dried later, make its water content lower than 1 weight % is measured, then according to SiCl₄: y-type zeolite=0.6:1 weight ratio is passed through the SiCl of heated vaporization₄Gas is in temperature It under conditions of 480 DEG C, reacts 1.5 hours, later, with 20 liters of decationized Y sieve water washings, then filters, obtain modified Y type molecule Sieve, is denoted as SZ2.Its physico-chemical property is listed in Table 1 below, by SZ2 in naked state through 800 DEG C, 100% vapor aging in 17 hours Afterwards, the crystallinity of the zeolite before and after analyzing SZ2 aging with the method for XRD simultaneously calculates the opposite crystal retention after aging, It the results are shown in Table 2.

Embodiment 3

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve aqueous solutions is uniformly mixed it, adds Enter the RECl of 570ml₃Solution is (with RE₂O₃The earth solution concentration of meter is 319g/L), stirring is warming up to 90~95 DEG C of holdings and stirs It mixes 1 hour, is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 7.5 weights in 120 DEG C of dryings Measure %, with RE₂O₃The Y type molecular sieve that content of rare earth is 8.5 weight % is counted, later under 470 DEG C of temperature, 70 volume % water vapours Roasting 5 hours obtains the Y type molecular sieve that lattice constant is 2.458nm and is dried later, makes its water content lower than 1 Weight %, then according to SiCl₄: y-type zeolite=0.4:1 weight ratio is passed through the SiCl of heated vaporization₄Gas is in temperature Under conditions of 500 DEG C, reacts 1 hour, later, with 20 liters of decationized Y sieve water washings, then filters, obtain Modified Zeolite Y, It is denoted as SZ3.Its physico-chemical property is listed in Table 1 below, and by SZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, is used The crystallinity of zeolite before and after the method analysis SZ3 aging of XRD simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2。

Comparative example 1

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions is uniformly mixed it, adds Enter 1000 grams of (NH₄)₂SO₄, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it It carries out afterwards hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours), later, is added to 20 liters of decationized Y sieves Stirring is uniformly mixed it in aqueous solution, and 1000 grams of (NH are added₄)₂SO₄, stir, be warming up to 90~95 DEG C of holdings 1 hour, then It being filtered, washed, second of hydrothermal modification treatment is carried out after filter cake is dry in 120 DEG C, hydrothermal conditions are 650 DEG C of temperature, It is roasted 5 hours under 100% water vapour, obtaining ion exchange twice, the super steady hydro-thermal superstable gamma-type without rare earth of hydro-thermal divides twice Son sieve, is denoted as DZ1.Its physico-chemical property is listed in Table 1 below, by DZ1 in naked state through 800 DEG C, 100% vapor aging in 17 hours Afterwards, the crystallinity of the zeolite before and after analyzing DZ1 aging with the method for XRD simultaneously calculates the opposite crystal retention after aging, It the results are shown in Table 2.

Comparative example 2

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions is uniformly mixed it, adds Enter 1000 grams of (NH₄)₂SO₄, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it After carry out hydrothermal modification treatment, hydrothermal modification treatment is roasted 5 hours under 650 DEG C of temperature, 100% water vapour, later, is added to Stirring is uniformly mixed it in 20 liters of decationized Y sieve aqueous solutions, and the RE (NO of 200ml is added₃)₃Solution is (with RE₂O₃Count earth solution Concentration are as follows: 319g/L) and 900 grams of (NH₄)₂SO₄, stir, be warming up to 90~95 DEG C and kept for 1 hour, is then filtered, washed, filter cake In 120 DEG C it is dry after carry out second of hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours), obtain Ion exchange super steady hydro-thermal super-stable Y molecular sieves containing rare earth of hydro-thermal twice twice, are denoted as DZ2.Its physico-chemical property is listed in table 1 In, by DZ2 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, before analyzing DZ2 aging with the method for XRD The crystallinity of zeolite afterwards simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.

Comparative example 3

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions is uniformly mixed it, adds Enter the RE (NO of 650ml₃)₃Solution (319g/L), stirring are warming up to 90~95 DEG C and are kept for 1 hour, be then filtered, washed, later The super steady modification of gas phase is carried out, molecular sieve drying process is first carried out, makes its water content lower than 1 heavy %, then according to SiCl₄: Y Type zeolite=0.4:1 weight ratio, is passed through the SiCl of heated vaporization₄Gas, under conditions of temperature is 580 DEG C, reaction 1.5 Hour, it later, with 20 liters of decationized Y sieve water washings, then filters, obtains the high silicon super-stable Y molecular sieves of gas phase, be denoted as DZ3.Its Physico-chemical property is listed in Table 1 below, by DZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, with the method for XRD It analyzes the crystallinity of the zeolite before and after DZ3 aging and calculates the opposite crystal retention after aging, the results are shown in Table 2.

Embodiment 4~7

Embodiment 4~7 illustrates method for preparing catalyst provided by the invention and its stability.

Super-stable Y molecular sieves SZ1, SZ2, SZ3 containing rare earth prepared by Examples 1 to 3 is prepared into catalyst respectively, is urged Agent is numbered successively are as follows: A1, A2, A3 and A4.

Kaolin is China Kaolin Co., Ltd's industrial products in embodiment 4-7, and solid content is 84 weight %；It is used intend it is thin Diaspore is Chinese Aluminium Co., Ltd Shandong branch company product, and alumina content is 35 weight %；During Aluminum sol is Asphalt in Shenli Refinery, Effect of Catalysis In Petrochemistry agent Co., Ltd, state produces, and alumina content is 21 weight %, MCM-41 molecular sieves and MCM- 48 molecular sieves are Nanjing Ji Cang nanosecond science and technology Co., Ltd product, and MCM-41 molecular sieve silica alumina ratio is 300 (sial atomic molars Than), crystallinity 90%, 0.1 weight % of sodium oxide content, Hydrogen；100 (sial atomic molar of Al-MCM-48 molecular sieve silica alumina ratio Than), crystallinity 91%, 0.08 weight % of sodium oxide content, Hydrogen；Beta zeolite, modenite are that Sinopec catalyst has Asphalt in Shenli Refinery, limit company commercial product, Beta (β) molecular sieve: asphalt in Shenli Refinery, Sinopec catalyst Co., Ltd product, Sial atomic molar ratio is 20,0.02 weight % of sodium oxide content；H-mordenite: the limited public affairs of Shanghai Shen environmental friendly material covered with clouds Department's production, sial atomic molar ratio are 10；0.05 weight % of sodium oxide content, Hydrogen.

Acidic silicasol is produced by Beijing Chemical Plant, and silica content is 25 weight %.

Method for preparing catalyst:

(1) it weighs quantitative boehmite (abbreviation aluminium stone) and quantitative water is uniformly mixed, be added under stiring quantitative Concentration be 36 weight % concentrated hydrochloric acid (chemistry pure, Beijing Chemical Plant produce), acid-aluminum ratio (36 weight % hydrochloric acid and aluminium stone (with Aluminium oxide meter) weight ratio) be 0.18, gained mixture is warming up to 70 DEG C of agings 1.5 hours, obtain aging intends thin water aluminium Stone, the alumina content of the boehmite of the aging are 12 weight %.

(2) super-stable Y molecular sieves SZ1, SZ2, SZ3 by quantitative containing rare earth, quantitative Aluminum sol and/or silica solution, (i.e. channel openings diameter is for quantitative mesopore molecular sieve (i.e. with the mesopore molecular sieve of M41S structure) and shape-selective molecular sieve 0.59-0.73 nanometers of molecular sieve), the boehmite of quantitative kaolin and above-mentioned aging add deionized water to be uniformly mixed, The slurries of 30 weight % of solid content are obtained, are spray-dried.

Table 3 gives type, the dosage of y-type zeolite used in (2) step, Aluminum sol, silica solution and kaolinic dosage. Table 4 gives the composition of catalyst A1~A4.Y-type zeolite, binder, mesopore molecular sieve, shape-selective molecule in catalyst composition Sieve, kaolinic content are calculated by inventory and are obtained, and the content of rare earth oxide uses x-ray fluorescence spectrometry.

By catalyst after 800 DEG C, 4 hours or 17 hours 100% vapor agings, the light oil micro-reactor for evaluating catalyst is living Property, evaluation result is listed in Table 5 below.

Table 1

Seen from table 1, the Modified Zeolite Y of high stability provided by the invention, is provided simultaneously with following advantages: sodium oxide molybdena Content is low, and the non-framework aluminum content when sial of molecular sieve is relatively high is less, 2.0nm~100nm second hole in aperture in molecular sieve Pore volume accounts for that total pore volume percentage is relatively high, also, B acid/L acid the ratio between (total B acid acid amount with L acid acid measure) is higher, in molecule The crystallinity value that the sieve smaller content of rare earth of lattice constant measures when higher is higher, has high thermal stability.

Table 2

As shown in Table 2, Modified Zeolite Y provided by the invention passes through 800 DEG C under sieve sample naked state, After harsh conditions aging in 17 hours, sample opposite crystal retention with higher shows modified Y type provided by the invention point Sub- sifter device has high hydrothermal stability.

Table 3

Table 4

The catalyst percentage composition of table 4 is weight percentage composition

Light oil microactivity evaluation method:

Using RIPP92-90 standard method (compiled see " petrochemical analysis method " (RIPP test method) Yang Cui is surely equal, Science Press, nineteen ninety publish) evaluation sample light oil microactivity, catalyst loading 5.0g, reaction temperature 460 DEG C, feedstock oil is 235~337 DEG C of huge port light diesel fuels of boiling range, and product composition is calculated by gas chromatographic analysis according to product composition Light oil microactivity.

Light oil microactivity (MA)=(product mid-boiling point is lower than 216 DEG C of gasoline production+gas yield+coke output)/ Total feed × 100%.

Comparative example 4~6

Comparative example 4~6 illustrates the cracking petroleum hydrocarbons being prepared using the super-stable Y molecular sieves that comparative example 1~3 provides The activity and its stability of catalyst.

Super-stable Y molecular sieves DZ1, the DZ2 for respectively preparing comparative example 1~3 according to the method for preparing catalyst of embodiment 4 And DZ3 (respectively instead of SZ1 molecular sieve) and boehmite, kaolin, mesopore molecular sieve, shape-selective molecular sieve, water and Aluminum sol Mixing, spray drying are prepared into microspherical catalyst, and catalyst is numbered successively are as follows: B1, B2 and B3, Y type molecular sieve in each catalyst The content of (also referred to as y-type zeolite) is 30 weight %, and the composition of remaining component is the same as embodiment 4.By catalyst through 800 DEG C, 4 hours Or after 100% vapor aging in 17 hours, evaluate its light oil microactivity.Evaluation method is shown in embodiment 4~7, evaluation result column In table 5.

Table 5

Embodiment 8~11

Embodiment 8~11 illustrates the cracking reaction performance of catalyst provided by the invention.

By A1, A2, A3 and A4 catalyst through 800 DEG C, after 100% vapor aging in 17 hours, in small fixed flowing bed Its catalytic cracking reaction performance is evaluated on reactor (ACE), cracked gas and product oil Shou Ji not be by gas chromatographic analysis.Catalysis Agent loading amount be 9g, 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 16h^-1, oil ratio (weight ratio) be shown in Table 7, ACE experiment raw material oiliness Matter is shown in Table 6, and evaluation result is shown in Table 7.

Comparative example 7~9

Comparative example 7~9 illustrates B1, B2 and B3 catalyst through 800 DEG C, after 100% vapor aging in 17 hours, small-sized solid Its catalytic cracking reaction performance is evaluated on constant current fluidized bed reactor (ACE), evaluation method is shown in embodiment 7, and ACE is tested feed stock Matter is shown in Table 6, and evaluation result is shown in Table 7.

Table 6

Table 7

Example number	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Comparative example 7	Comparative example 8	Comparative example 9
								Sample number into spectrum	A1	A2	A3	A4	B1	B2	B3
Molecular sieve used	SZ1	SZ1	SZ2	SZ3	DZ1	DZ2	DZ3
								Oil ratio	5	5	5	5	9	8	5
Product distribution/weight %
								Dry gas	1.35	1.34	1.37	1.49	1.55	1.48	1.49
Liquefied gas	16.83	16.12	16.75	16.93	16.86	15.33	16.21
								Coke	4.72	4.75	4.93	4.80	8.33	7.61	6.35
Gasoline	52.83	55.93	56.37	53.62	38.55	43.91	50.79
								Diesel oil	16.96	15.98	15.69	15.97	20.17	19.25	16.88
Heavy oil	7.31	5.88	4.89	7.19	14.54	12.42	8.28
								It is total	100	100	100	100	100	100	100
Conversion ratio/weight %	75.83	78.1	79.4	76.8	65.29	68.33	74.84
								Coke selectivity/weight %	6.22	6.08	6.21	6.25	12.76	11.14	8.48
Yield of light oil/weight %	69.79	72.05	73.12	70.55	58.72	63.16	67.67
								Total liquid yield/weight %	86.72	88.03	88.81	86.52	75.58	78.49	83.88

By table 5 and table 7 as it can be seen that catalytic cracking catalyst provided by the invention has very high hydrothermal stability, for weight Oil converts the hydrogenated residue conversion of for example high arene content, has significantly lower coke selectivity, with considerably higher total Liquid is received, and yield of light oil is considerably higher, and yield of gasoline significantly improves, and heavy oil conversion activity is higher.

Claims

1. a kind of catalytic cracking of petroleum hydrocarbon catalyst, with dry basis, the catalytic cracking of petroleum hydrocarbon catalyst contains 40-80 The carrier of weight %, the Y type molecular sieve of 10-50 weight %, the mesopore molecular sieve and 5- with M41S structure of 5-15 weight % The molecular sieve that the channel openings diameter of 15 weight % is 0.59-0.73 nanometers；Described Y type molecular sieve includes super steady containing rare earth Y type molecular sieve, this contains the content of rare earth of the super-stable Y molecular sieves of rare earth with RE₂O₃It is calculated as 5~12 weight %, Na₂O content is 0.1~0.7 weight %, total pore volume are 0.33~0.39mL/g, and aperture is the total hole pore volume Zhan of the second hole of 2~100nm The 10~25% of volume, lattice constant are 2.440~2.455nm, and the total aluminium content ratio of non-framework aluminum content Zhan is not higher than 20%, Lattice collapse temperature is not less than 1050 DEG C, and the ratio of the B acid amount and L acid amount that are measured with pyridine adsorption infrared method at 200 DEG C is not Lower than 2.50.

2. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that the superstable gamma-type containing rare earth The percentage that the pore volume for the second hole that aperture is 2nm~100nm in molecular sieve accounts for total pore volume is 15%~21%.

3. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that the superstable gamma-type containing rare earth The percentage of the total aluminium content of non-framework aluminum content Zhan is 13%~19% in molecular sieve, and framework si-al ratio is with SiO₂/Al₂O₃Mole Than being calculated as 7.3~14.

4. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that the superstable gamma-type containing rare earth 1055 DEG C~1080 DEG C of molecular sieve lattice collapse temperature.

5. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that existed with pyridine adsorption infrared method The ratio of B acid amount and L acid amount is 2.6~4.0 in the super-stable Y molecular sieves total acid content containing rare earth measured at 200 DEG C.

6. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that in 800 DEG C, normal pressure, 100% water After vapor atmosphere aging in 17 hours, the opposite crystal retentions of the super-stable Y molecular sieves containing rare earth is 38% or more for example It is 38%~48%；Preferably, the relative crystallinity of the super-stable Y molecular sieves for containing rare earth is 60%~70%.

7. according to any catalytic cracking of petroleum hydrocarbon catalyst of claim 1~7, which is characterized in that described containing rare earth The rare earth oxide content of super-stable Y molecular sieves is 5.5~10 weight %, and sodium oxide content is 0.3~0.7 weight %, and structure cell is normal Number is 2.442~2.450nm, and framework si-al ratio is 8.5~12.6.

8. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that mesoporous point of the M41S structure Son sieve is at least one of MCM-41, MCM-48 and MCM-50, and preferred its sodium oxide content of M41S structure molecular screen does not surpass Cross 0.1 weight %, it is preferred that its sial atomic molar ratio is 10~400:1 such as 10~100:1；The channel openings diameter For 0.59-0.73 nanometers of molecular sieve, being selected from has AFR, AFS, AFI, BEA, BOG, CON, GME, LTL, MEI, MOR and OFF At least one of molecular sieve of structure, preferably Beta, SAPO-5, SAPO-40, SSZ-24, CIT-1, ZSM-18, mercerising boiling At least one of stone, sodium chabazite and offretite, in general, point that the channel openings diameter is 0.59-0.73 nanometers The sodium oxide content of son sieve is 0.01~1.5 weight %, it is preferred that the channel openings diameter is 0.59-0.73 nanometers The sial atomic molar ratio of molecular sieve is 0.1~100；Described carrier be, for example, clay, alumina support, silica support, One of silicaalumina carrier is a variety of.

9. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that the catalytic cracking of petroleum hydrocarbon is urged Agent contains the carrier of the weight of the 50-70 in terms of butt %, the Y type molecular sieve of the weight of the 20-40 in terms of butt %, the 5-15 in terms of butt The mesopore molecular sieve with M41S structure of weight %, the channel openings diameter of the weight of the 5-15 in terms of butt % is 0.59-0.73 The molecular sieve of nanometer.

10. a kind of preparation method of catalytic cracking catalyst, including by carrier, Y type molecular sieve, mesoporous point with M41S structure Son sieve, the molecular sieve that channel openings diameter is 0.59-0.73 nanometers and water form the step of slurries, drying, wherein the Y type Molecular sieve includes the super-stable Y molecular sieves containing rare earth, this contain the super-stable Y molecular sieves preparation method of rare earth the following steps are included:

(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains oxygen Change the Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium content reduces；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content 350~480 DEG C of temperature, It is roasted 4.5~7 hours under 30~90 volume % water vapour atmospheres, optionally drying, obtains the Y type molecular sieve of lattice constant reduction；

(3) Y type molecular sieve and silicon tetrachloride gas haptoreaction that the lattice constant for obtaining step (2) reduces, washing and mistake Filter；Preferably, SiCl₄: the weight ratio=0.1~0.7:1 for the Y type molecular sieve that the lattice constant in terms of butt reduces is by four The Y type molecular sieve haptoreaction that silicon chloride gas and the lattice constant reduce, reaction temperature are 200 DEG C~650 DEG C, when reaction Between be 10 minutes to 5 hours, washing and filtering obtain the super-stable Y molecular sieves containing rare earth.

11. according to method described in any one of claim 10, which is characterized in that sodium oxide content described in step (1) reduced contains rare earth Conventional unit cell dimension Y type molecular sieve, lattice constant be 2.465~2.472nm, sodium oxide content be no more than 9.0 weights Measure %.

12. according to the method for claim 10, which is characterized in that in step (1), what the sodium oxide content reduced contains dilute In the Y type molecular sieve of the conventional unit cell dimension of soil, content of rare earth is with RE₂O₃It is calculated as 5.5~14 weight %, sodium oxide content is 4~ 9 weight % are, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.

13. according to the method for claim 10, which is characterized in that step (1) is described by NaY molecular sieve and rare-earth salt solution Contact carries out ion-exchange reactions, according to NaY molecular sieve: rare-earth salts: H₂The weight ratio of O=1:0.01~0.18:5~15 will NaY molecular sieve, rare-earth salts and water form mixture, stirring.

14. according to method described in claim 10 or 13, which is characterized in that step (1) is described molten with rare earth by NaY molecular sieve Liquid contact carries out ion-exchange reactions, comprising: mixes NaY molecular sieve with water, is added with stirring rare-earth salts and/or rare-earth salts is molten Liquid carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions are as follows: exchange temperature is 15~95 DEG C, swap time It is 30~120 minutes, the rare-earth salt solution is the aqueous solution of rare-earth salts.

15. according to the method for claim 10, which is characterized in that the rare-earth salts is that rare earth chloride and/or nitric acid are dilute Soil.

16. according to the method for claim 10, which is characterized in that step (2) maturing temperature is 380~460 DEG C, institute Stating calcination atmosphere is 40~80% water vapour atmospheres, and the calcining time is 5~6 hours.

17. according to the method for claim 10, which is characterized in that the Y that the lattice constant reduces obtained in step (2) The lattice constant of type molecular sieve is 2.450nm~2.462nm.

18. according to the method for claim 10, which is characterized in that the Y type point that the obtained lattice constant of step (2) reduces Water content in son sieve is no more than 1 weight %.

19. according to the method for claim 10, which is characterized in that washing methods described in step (3) is to be washed with water, and is washed Wash condition are as follows:

Molecular sieve: H₂O weight ratio=1:6~15, pH value are 2.5~5.0, and wash temperature is 30~60 DEG C.

20. according to the method for claim 10, which is characterized in that described carrier is clay, alumina support, oxidation Silicon-one of alumina support and silica support is a variety of；Preferably, described silica support is silica solution, described SiO in silica solution₂Content is 1-30 weight %, and the silica solution can be neutral silica solution, acidic silicasol or alkaline silicon Colloidal sol；Preferably, the alumina support is gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, Aluminum sol, water Close one of aluminium oxide or a variety of, the hydrated alumina such as boehmite, a diaspore, gibbsite, Bayer One or more of stone；The channel openings diameter is 0.59-0.73 nanometer of molecular sieve, selected from have AFR, AFS, AFI, At least one of the molecular sieve of BEA, BOG, CON, GME, LTL, MEI, MOR and OFF structure；Preferably Beta, SAPO-5, At least one of SAPO-40, SSZ-24, CIT-1, ZSM-18, modenite, sodium chabazite and offretite；Preferred institute The molecular sieve sial atomic molar ratio that the channel openings diameter said is 0.59-0.73 nanometers is 0.1~100:1；Belonging to preferred Silicaalumina carrier is one or more of silicon-aluminum sol, silica-alumina gel and amorphous silica-alumina.

21. a kind of Heavy oil conversion method, including by heavy oil and catalyst according to any one of claims 1 to 9 in catalytic cracking Under the conditions of haptoreaction the step of, reaction temperature be 400-600 DEG C, weight (hourly) space velocity (WHSV) 5-30 hours^-1, oil ratio 1-10 weight ratio； Preferable reaction temperature is 450-550 DEG C or 480-530 DEG C, and weight (hourly) space velocity (WHSV) is preferably 8-25 hours^-1, oil ratio 2-7.

22. according to the method for claim 21, which is characterized in that the heavy oil is hydrogenated residue, the hydrogenated residue Arene content is 40~75 weight %, and paraffinicity is 1-25 weight %, and naphthene content is 15~45 weight %, and specific gravity is 0.92~0.95g/cm³。