CN103506154B

CN103506154B - A kind of catalytic cracking catalyst

Info

Publication number: CN103506154B
Application number: CN201210217724.2A
Authority: CN
Inventors: 龙军; 朱玉霞; 罗一斌; 严加松; 任飞; 杨雪; 田辉平; 庄立; 李明罡; 欧阳颖; 舒兴田
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: 2012-06-27
Filing date: 2012-06-27
Publication date: 2015-08-26
Anticipated expiration: 2032-06-27
Also published as: CN103506154A

Abstract

A kind of catalytic cracking catalyst, contains in the Modified Zeolite Y of butt 10 % by weight ~ 50 % by weight, in other molecular sieve of butt 0 ~ 30 % by weight, in the clay of butt 10 % by weight ~ 70 % by weight with the inorganic oxide binder of oxide basis 10 % by weight ~ 40 % by weight; Described Modified Zeolite Y, lattice constant is 2.420 ~ 2.440nm, and by weight percentage, P is 0.05 ~ 6%, RE ₂o ₃be 0.03 ~ 10%, aluminium oxide is less than 22%, is less than 0.35mmol/g than hydroxyl nest concentration.Described catalytic cracking catalyst of the present invention shows good stability in catalytic cracking process, can reduce green coke, improves heavy oil utilization rate.

Description

A kind of catalytic cracking catalyst

Technical field

The present invention relates to a kind of hydrocarbon oil catalytic cracking catalyst, is furthermore about the catalytic cracking catalyst of one containing the Modified Zeolite Y of " three hand over three roastings "

Background technology

Along with the minimizing day by day of petroleum resources, petroleum heaviness, in poor quality become undisputable fact.As the main manufacturing process by heavy oil transformation being gasoline and diesel oil light-weight fuel oil, catalytic cracking inevitably needs to process more heavy oil feedstocks more inferior.The reduction of conversion ratio and the increase of coke yield are that feedstock oil heaviness in poor quality is to one of catalytic cracking performance bringing impact.Be directed to this, people from molecular sieve modified, catalyst be fabricated onto technological design aspect carried out large quantifier elimination (Liu Tao, Zhang Zhongdong, Haitao Zhang etc. China and foreign countries energy .2009,14(1): 71-77).But current most Catalyst Design and commercial plant operation are all the high yields realizing light oil and liquefied gas product by improving cracking reaction conversion ratio, cause coke yield obviously higher, cause the waste of feedstock oil resource.Improve heavy oil utilization rate, suitably can control conversion ratio, reduce coke yield, to improve coke selectivity.In the composition of FCC catalyst, the combined reaction performance of molecular sieve on catalyst has conclusive impact, and therefore carrying out modification to molecular sieve is improve one of the most effective means of catalytic cracking catalyst reactivity worth.

Coke is made up of the poor hydrogen compound that various scarce hydrogen degree is different, is the product of hydrogen transfer reaction, thus will reduces coke yield, needs suitably to reduce hydrogen transfer reaction.The main process of hydrogen transfer reaction is the absorption of protonated alkene at acidic zeolite center, reaction and desorption.Molecular sieve acid site density is high, and hydrogen transfer reaction increases.The sour density of molecular sieve is relevant with its framework si-al ratio.The molecular sieve that framework si-al ratio is low, aluminum-oxygen tetrahedron acid site is many, and the sour density of molecular sieve is high, and its hydrogen transfer reaction is many, and speed is fast, and coke yield is high; And the molecular sieve of high framework si-al ratio, acid site density is low, and hydrogen transfer reaction is relatively few, and coke yield reduces.The coke selectivity that active component has had to be ensured as can be seen here, active component must be made to have low lattice constant, appropriate sour density.

As everyone knows, cracking unit, in operation process, for maintaining the stable of reactivity, needs constantly to draw off old dose, fresh makeup catalyst.Thus there is age distribution in catalyst.Its reactivity worth of the catalyst of all ages and classes is different.Fresh catalyst Middle molecule sieve structure cell is comparatively large, and cracking activity is high, and hydrogen migration ability is strong, and coke yield is high; And the catalyst operated for a long time molecular sieve generation framework dealumination under hydrothermal conditions, structural breakdown, makes catalyst cracking activity decrease, and reaction selectivity is deteriorated.Obviously the catalyst of this two states is all unfavorable for the raising of heavy oil utilization rate.Improve catalyst heavy oil utilization rate, will start with from the reactivity worth of raising molecular sieve under different level of deactivation, use the molecular sieve of low unit cell dimension on the one hand, to reduce the coke selectivity of fresh molecular sieve, on the other hand, pass through modification, improve molecular sieve activity stability, to improve equilibrium activity, reduce the active difference of zeolite-water heat ageing when different phase as far as possible, to reduce the coke selectivity of catalyst on the whole, thus improve heavy oil utilization rate.

Use the Y zeolite of low unit cell dimension that catalyst activity and heavy oil conversion performance must be made to decline, other modifying element must be added to improve the performance of active component for this reason.Rare earth modified cracking activity and the hydrothermal stability that can significantly improve molecular sieve, but large quantity research shows, the molecular sieve coke selectivity of high rare-earth content is poor, in low content of rare earth comparatively suitable.In recent years, people adopt method of modifying phosphorus and rare earth being introduced jointly molecular sieve, to improve catalytic performance further.

CN1624079A discloses a kind of hydrocarbon cracking catalyzer containing modcfied faujasite, first the method for modifying of its mesolite for carrying out exchange reaction by faujasite and phosphorus compound and ammonium compounds, water and weight zeolite are than 2 ~ 25, pH2.0 ~ 6.5, temperature is 10 ~ 150 DEG C, swap time is 0.1 ~ 4 hour, then in exchange slurries, earth solution is introduced, reaction time is 1 ~ 60 minute, further reaction, after filtration, washing, through phosphorus and rare earth modified zeolite at 250 ~ 800 DEG C, roasting 0.1 ~ 3.5 hour under 1 ~ 100% steam and obtaining.Lattice constant 2.440 ~ the 2.465nm of the modified zeolite adopting this method of modifying to prepare, sodium oxide molybdena 2.0 ~ 6.5 % by weight, phosphorus content 0.01 ~ 3 % by weight, rare earth oxide 0.1 ~ 15 % by weight.Containing the catalyst activity good stability of this molecular sieve, yield of gasoline is high, and coke yield is low, heavy oil cracking ability and preventing from heavy metal pollution ability strong.The catalyst adopting this modified molecular screen to prepare has higher yield of gasoline and good coke selectivity.But the molecular sieve lattice constant obtained by this preparation method is comparatively large, will affect molecular sieve catalyst coke selectivity.

CN1506161A discloses a kind of hyperastable Y-type RE molecular sieve active component, and this modified molecular screen is containing the heavy % of rare earth oxide 8 ~ 25, and phosphorus 0.1 ~ 3.0 weighs %; The heavy % of sodium oxide molybdena 0.3 ~ 2.5, degree of crystallinity 30 ~ 55%, lattice constant 2.455 ~ 2.472 nanometer.Molecular sieve take NaY zeolite as raw material, through rare earth exchanged and first time roasting, obtains " one hands over a roasting " rare earth NaY; React with rare earth, phosphorus containg substances and ammonium salt again, carry out second time calcination process, acquisition phosphorus and rare earth modified modified Y zeolite.This modified molecular screen coke yield is moderate.Molecular sieve content of rare earth obtained is by this method higher, and lattice constant is large, and molecular sieve coke selectivity is affected.

CN1317547A discloses a kind of FCC catalyst, wherein containing a kind of phosphorus and the composite modified Y zeolite of rare earth, this molecular sieve by NaY zeolite through rare earth and ammonium salt hybrid switching again after hydrothermal calcine process, react with phosphorus compound, then the preparation of second time calcination process is carried out, wherein RE ₂o ₃the weight ratio of/Y zeolite is 0.02 ~ 0.18, and the weight ratio of ammonium salt/Y zeolite is the weight ratio of 0.1 ~ 1.0, P/Y zeolite is 0.003 ~ 0.05, sintering temperature 250 ~ 750 DEG C, water vapor condition 5 ~ 100%, 0.2 ~ 3.5 hour time.

CN101537366A reports a kind of modified molecular screen improving coking behavior, it is characterized in that this molecular sieve hands over the preparation method of two roastings to obtain by NaY molecular sieve through two, by weight percentage, and RE ₂o ₃be 0.05 ~ 4.0%, P is 0.05 ~ 5.0%, structure cell is 2.430 ~ 2.440nm, degree of crystallinity is 35 ~ 55%.This molecular sieve have more in macropore pore volume and good stability, while reduction catalyst coke productive rate, heavy oil pyrolysis ability improves further, thus total liquid yield is improved, and is particularly conducive to the raising of yield of light oil.

EP0421422 refer to a kind of faujasite for hydrocracking catalyst, it is characterized in that this faujasite is at wave number 3740 ± 10cm ^-1has the INFRARED ABSORPTION of 20% at least, at wave number 3560 ± 10cm ^-1have 5% INFRARED ABSORPTION at least, the former is at least 2 than the latter.This faujasite specific area at least 650m ²/ g, framework si-al ratio 20 ~ 50, lattice constant 24.15 ~ 23.50.

CN1951814A discloses a kind of modified Y zeolite, and its feature is 7 ~ 30 at the silica alumina ratio of this modified Y zeolite, specific area 700 ~ 900m ²/ g, lattice constant 2.425 ~ 2.445nm, relative crystallinity>=80%, Na ₂o content≤0.25%, the secondary pore of 1.7 ~ 10nm accounts for more than 45% of total pore volume, and non-framework aluminum accounts for more than 30% of whole alumiunum amount, infrared acidity 0.15 ~ 0.55mmol/g.This modified zeolite take NaY as raw material, obtains through the process such as ammonium exchange, hydrothermal treatment consists, de-non-framework aluminum, reaming, intermediate water heat treatment.Modified zeolite can as the acidic components of various catalyst, as middle oil type hydrocracking catalyst.

Several sections of patent documents improve the silica alumina ratio of Y zeolite by the method for hydrothermal dealumination and (or) chemical dealuminization above, through intermediate water thermal bake-out to realize the contraction of structure cell, but at deep sealumination modified (SiO ₂/ Al ₂o ₃mol ratio>=15) often cause zeolite structured destruction in process, zeolite crystallinity is declined.

US5013699 proposes a kind of processing method of Y zeolite, is by NaY zeolite through ammonium ion exchange, then carries out high-temperature vapor process, and sample carries out ammonium exchange again and removes aluminium under the condition of PH < 4, obtains zeolite product.This processing method adopts and processes zeolite sample at the low ph, and does not adopt safeguard measure, easily causes zeolitic frameworks to destroy, zeolite crystallinity is reduced.

US4503023 discloses a kind of LZ ~ 210 zeolite and preparation method thereof, and NaY zeolite fluosilicate is carried out dealumination complement silicon to improve the silica alumina ratio of zeolite, the product degree of crystallinity obtained is higher, but when adopting fluosilicate to carry out dealuminzation to Y zeolite, the SiO of zeolite product ₂/ Al ₂o ₃mol ratio usually can not higher than 13, otherwise the degree of crystallinity of zeolite product will significantly decline.In addition, the modified Y zeolite secondary pore adopting the fluosilicate method of carrying out dealumination complement silicon to prepare is few, is disadvantageous for being used as heavy oil catalytic cracking reaction.

Summary of the invention

The object of this invention is to provide a kind of stability high, coke yield is low, the catalytic cracking catalyst that high heavy oil utilization rate is high, containing a kind of novel Modified Zeolite Y in this catalyst.

The invention provides a kind of catalytic cracking catalyst, contain in the Modified Zeolite Y of butt 10 % by weight ~ 50 % by weight, in other molecular sieve of butt 0 ~ 30 % by weight, in the clay of butt 10 % by weight ~ 70 % by weight with the inorganic oxide binder of oxide basis 10 % by weight ~ 40 % by weight; Described Modified Zeolite Y, lattice constant is 2.420 ~ 2.440nm, and by weight percentage, P content is 0.05% ~ 6%, RE ₂o ₃content is 0.03% ~ 10%, and alumina content is less than 22%, is less than 0.35mmol/g than hydroxyl nest concentration, described

In formula, M _{200 DEG C}, M _{500 DEG C}and M _{800 DEG C}represent respectively sample temperature 200 DEG C, 500 DEG C and 800 DEG C time the percent weight loss that records, C is sample crystallinity.

Catalytic cracking catalyst provided by the invention, by by described Modified Zeolite Y, other molecular sieve, clay and inorganic oxide binder mixing are pulled an oar and the preparation of spray-dired method, described modified molecular screen can obtain through the preparation methods of three friendship three roastings, so-called " three hand over three roastings " is the general abbreviation of this area to a kind of molecular sieve modified technique, refer to NaY molecular sieve to be raw material, adopt the combination modified technique of three exchanges and three hydrothermal treatment consists, rare earth and phosphorus adopt exchanged form, add phosphorous exchange solution and exchange containing rare earth exchanged solution, phosphorus can add in arbitrary exchange operation, can once or several times add, rare earth can add in arbitrary exchange operation beyond a friendship.Exchange operation and also can add removing of dealumination agent promotion aluminium, chemical dealuminization process can be carried out in arbitrary exchange operation beyond a friendship.Filter after exchanging, washing is conventional method.

Described catalytic cracking catalyst of the present invention, can show good stability in catalytic cracking process, can reduce coking yield, improves heavy oil utilization rate.

Accompanying drawing explanation

Fig. 1 is the light oil microactivity (MA) of embodiment and comparative example gained phosphorus and rare earth modified Y zeolite.

The degree of crystallinity of Fig. 2 embodiment and comparative example gained phosphorus and rare earth modified Y zeolite.

The crystallization reservation degree of Fig. 3 embodiment and contrast row.

Detailed description of the invention

Catalytic cracking catalyst provided by the invention, phosphorous with the Modified Zeolite Y of rare earth, in other molecular sieve of butt 0-30 % by weight, in the clay of butt 10 % by weight-70 % by weight with the inorganic oxide binder of oxide basis 10 % by weight-40 % by weight containing " three hand over three roastings " in butt 10 % by weight-50 % by weight.

In the present invention, described Modified Zeolite Y, take NaY molecular sieve as raw material, preparation process through " three hand over three roastings " obtains, its born of the same parents' constant is 2.420 ~ 2.440nm, preferably lattice constant is 2.428 ~ 2.438nm, by weight percentage, P is 0.05% ~ 6%, is preferably 0.1% ~ 4.5%, RE ₂o ₃be 0.03% ~ 10%, be preferably 0.1% ~ 4.5%, aluminium oxide is less than and 22% is generally 10% ~ 22%, is preferably less than 20%, is less than 0.35mmol/g such as 0.01mmol/ ~ 0.35mmol/g, be preferably less than 0.3mmol/g than hydroxyl nest concentration, described

Zeolite molecular sieve framework dealumination, formed in its aluminium room " the hydroxyl nest " that be made up of four adjacent Si-OH, be the rejected region in zeolite molecular sieve lattice, its quantity and zeolite structured stability have direct relation." hydroxyl nest " quantity is more, and illustrate that the aluminium room because of framework dealumination formation on molecular sieve is more, the structural stability of molecular sieve is poorer.The aluminium room that Y zeolite is formed in hydro-thermal or chemical dealuminization process is filled by the silicon dissociated, in the modifying process of molecular sieve, dealumination process and treatment conditions directly have influence on the stability of modified molecular screen, inventor is on the basis of great many of experiments, be surprised to find that the Modified Zeolite Y after " three hand over three roastings ", the aluminium room that framework dealumination is formed can fully be filled by silicon, hydroxyl nest quantity reduces, and therefore stability improves greatly.

In modified Y molecular sieve of the present invention, than hydroxyl nest concentration adopt document (Liu Xingyun, Liu Hui, Li Xuanwen etc. Acta PhySico-Chimica Sinica .1998,14 (12): 1094 ~ 1097) method that provides characterizes.This characterizing method sample is carried out thermogravimetric analysis calculate.

On weight-loss curve, less than the 200 DEG C weightlessness corresponding to desorption attached water, 200 DEG C ~ 500 DEG C correspond to the weightlessness that zeolite takes off ammonium and the dehydration of hydroxyl nest, 500 DEG C ~ 800 DEG C weightlessness corresponding to dehydroxylation.NH on Y zeolite ₄ ⁺decompose and just produce acid hydroxy group, therefore the molal quantity of hydroxyl and NH ₃corresponding.After calculating hydroxyl moles by 500 DEG C ~ 800 DEG C weight-loss curves like this, be converted into NH ₃quality, then deduct NH from the weight loss that 200 DEG C ~ 500 DEG C weight-loss curves calculate ₃amount, just can calculate the molal quantity of hydroxyl nest.

In the calculating of hydroxyl nest concentration, hydroxyl nest disappears because de-two molecular waters, therefore its mole is 36, two hydroxyls takes off a part water, therefore its mole is 9.

The preparation method of above-mentioned Modified Zeolite Y, take NaY molecular sieve as raw material, preparation process through " three hand over three roastings " obtains, so-called " three hand over three roastings " is the general abbreviation of this area to a kind of molecular sieve modified technique, namely the combination modified technique of three exchanges and three hydrothermal treatment consists is adopted, rare earth and phosphorus adopt exchanged form, add phosphorous exchange solution and exchange containing rare earth exchanged solution, phosphorus can add in arbitrary exchange operation, can once or several times add, rare earth can add in arbitrary exchange operation beyond a friendship, exchange operation also can add dealumination agent and carry out chemical dealuminization to promote removing of aluminium, chemical dealuminization process can be carried out in arbitrary exchange operation beyond a friendship.

The preferred preparation process of one of described Modified Zeolite Y can be comprise the steps:

1) NaY zeolite and ammonium salt, phosphorus ammonium salt and water are according to NaY molecular sieve: ammonium salt: phosphorus ammonium salt: the part by weight of water=1:0.4 ~ 1.0:0 ~ 0.04:5 ~ 10 is mixed to get slurries, be 3.0 ~ 4.5 by the pH value of inorganic acid adjusting slurry, then at 70 DEG C ~ 95 DEG C, at least 0.5h is processed, wash after usual 0.5 ~ 10h, wherein, NaY molecular sieve is in butt, and phosphorus ammonium salt is in elemental phosphorous; One or more in the ammonium salt of the ammonium salt of described phosphorus ammonium salt such as pyrophosphoric acid, the ammonium salt of phosphoric acid, phosphorous acid, one or more in ammonium salt such as ammonium phosphate, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP) of described phosphoric acid;

2) product step 1) obtained roasting at least 0.5h, usual 0.5h ~ 10h, preferred 2-6 hour under temperature 350 DEG C ~ 650 DEG C, 1% ~ 100% steam (i.e. water vapour) atmosphere obtain a roasting molecular sieve;

3) by step 2) obtain one roasting molecular sieve roast molecular sieve with phosphoric acid, dealumination agent according to one: phosphoric acid: dealumination agent: the part by weight of water=1:0 ~ 0.04:0.02 ~ 0.3:5 ~ 10 mixes, with inorganic acid adjust pH 2.4 ~ 3.5, then at 50 DEG C ~ 90 DEG C, at least 0.5 hour is processed, usual 0.5 h ~ 10h, filters, washs, washing water temperature >=50 DEG C, usual 50 DEG C ~ 100 DEG C, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous;

4) product step 3) obtained temperature 350 DEG C ~ 650 DEG C, roasting at least 0.5 hour under 1% ~ 100% steam atmosphere, usual 0.5h ~ 10h, preferred 2-6 hour obtain two roasting molecular sieves;

5) two roasting molecular sieves step 4) obtained roast molecular sieve with rare earth chloride and water according to two: rare earth chloride: the part by weight of water=1:0.01 ~ 0.05:5 ~ 10 mixes, then at 70 ~ 90 DEG C, at least 0.5 hour is processed, usual 0.5 h ~ 10h, filters; Washing, DEG C usual 50 DEG C ~ 100 DEG C, washing water temperature>=50, wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE ₂o ₃meter;

6) product step 5) obtained is at 350 ~ 650 DEG C, roasting at least 0.5h, usual 0.5h ~ 10h under 1 ~ 100% steam atmosphere, and preferred 2-6 hour obtains Modified Zeolite Y.

Phosphorus containg substances in phosphorous exchange liquid of the present invention be selected from orthophosphoric acid, phosphorous acid, pyrophosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), aluminum phosphate one or more.

In described ammonium salt solution containing ammonium material be selected from ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, ammonium hydrogen sulfate one or more.

Described containing in rare earth exchanged liquid containing rare-earth substance be selected from lanthana, cerium oxide, lanthanum nitrate, cerous nitrate, lanthanum chloride, cerium chloride, nitric acid mishmetal, chlorination mishmetal one or more.

The inorganic acid that described adjustment exchanges liquid pH value be selected from hydrochloric acid, sulfuric acid, nitric acid one or more.

Described dealumination agent is selected from organic acid (comprising ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid), inorganic acid (comprising fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid), organic and inorganic salts (comprising ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate).

The present invention's " three hand over three roastings " technique prepares high silica alumina ratio, little structure cell modified molecular screen, roasting condition relaxes, and the aluminium room formed after dealuminzation can be filled by silicon as much as possible, and lattice defect is few, constitution water heat endurance and active water Heat stability is good, coke selectivity is good.

Modified Zeolite Y of the present invention, the aluminium room formed after dealuminzation can be filled by silicon as much as possible, and lattice defect is few, and stability is very excellent, constitution water heat endurance and active water Heat stability is good.This molecular sieve is applied to catalytic cracking catalyst as active component, can maintain long period stabilizing active, effectively control coke yield, improves heavy oil utilization rate.

According to catalytic cracking catalyst of the present invention, can contain other molecular sieve, its content is no more than 30 % by weight usually, such as, can be 0.5 ~ 30 % by weight.Other y-type zeolite conventional in other wherein said molecular sieve catalytic cracking catalyst, have in MFI structure zeolite, Beta zeolite, non-zeolite molecular sieve one or more.Other described y-type zeolite is other Y zeolite except described Modified Zeolite Y, such as, in REY, REHY, DASY, USY, REUSY molecular sieve one or more.One or more as one or more in ZSM-5, ZRP, ZSP molecular sieve, in said non-zeolite molecular sieve such as SAPO, HTS of described MFI structure molecular sieves.Preferably, other described molecular sieve comprises REY molecular sieve and/or DASY molecular sieve, containing the REY molecular sieve of 5 ~ 15 % by weight and/or DASY molecular sieve in described catalytic cracking catalyst, is conducive to improving yield of light oil.

According to catalytic cracking catalyst of the present invention, wherein said clay is selected from as one or more in the clay of cracking catalyst component, such as, in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite one or more.These clays are that those of ordinary skill in the art are known.

Binding agent of the present invention is one or more in the inorganic oxide binder commonly used of catalytic cracking catalyst, preferential oxidation al binder, described alumina binder is selected from one or more in the aluminium oxide of usual the used various forms of Cracking catalyst, hydrated alumina and Alumina gel.Such as, be selected from one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite), the double aluminium binder of preferred boehmite and Alumina gel.

Catalytic cracking catalyst of the present invention can be prepared according to the preparation method of any existing Cracking catalyst, such as by clay, molecular sieve, alumina binder mixing making beating, spraying dry and washing, filtration, dry step, these methods have detailed description in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C, CN1727445A, quote as a reference in the lump here.

Spraying dry, washing, drying are prior art, and the present invention does not have particular/special requirement.

The following examples will be further described the present invention, but content not thereby limiting the invention.

In embodiment and comparative example, raw material specification used is as follows:

NaY molecular sieve, industrial goods, silica alumina ratio > 4.7, degree of crystallinity > 85%

Mixed chlorinated rare earth, technical grade

Ammonium sulfate, chemical pure

Phosphoric acid, chemical pure

Ammonium dihydrogen phosphate (ADP), chemical pure

Sulfuric acid, chemical pure

Oxalic acid, solid, chemical pure

Fluosilicic acid, technical grade

Hydrochloric acid, chemical pure

REY molecular sieve is the commercially available prod of catalyst asphalt in Shenli Refinery of China Petrochemical Industry, solid content 85 % by weight, RE ₂o ₃content 12%

DASY-2.0 molecular sieve is the commercially available prod of catalyst asphalt in Shenli Refinery of China Petrochemical Industry, solid content 87 % by weight, RE ₂o ₃content 2%.

Kaolin is the commercial goods of Suzhou China Kaolin Co., Ltd, and solid content 78 % by weight Alumina gel is the commercial goods of catalyst asphalt in Shenli Refinery of China Petrochemical Industry, Al ₂o ₃content is 21.5 % by weight boehmites is the commercial goods of Shandong Aluminum Plant, solid content 60 % by weight

In embodiment and comparative example, analysis test method used is as follows:

Constituent content is by x-ray fluorescence spectrometry.

Lattice constant, degree of crystallinity by X-ray diffraction method (XRD) adopt respectively RIPP145-90 and RIPP146-90 standard method (see " Petrochemical Engineering Analysis method (RIPP test method) ", Yang Cuiding etc., Science Press, nineteen ninety version) measure.

Than in the concentration determination of hydroxyl nest, the thermogravimetric analysis data of sample adopts hereinbefore described thermogravimetric method to measure.

Catalytic cracking catalyst micro-activity (MA) measures with reference to RIPP 92-90 standard method.

What embodiment and the usage ratio described in comparative example did not have a specified otherwise is weight ratio.

Embodiment 1

(1) preparation of modified molecular screen

Be that raw material ammonium sulfate exchanges with NaY molecular sieve, treatment conditions are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:8(weight ratio), sulfuric acid adjust pH 3.5,85 DEG C exchanges 1h, washing.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one containing rare earth, treatment conditions are: roasting molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.042:8(weight ratio), 70 DEG C exchange 1h, and deionized water is washed.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% steam roasting time 2h.Rear sample is roasted by the solution-treated two of phosphoric acid and oxalic acid, treatment conditions are: two roastings molecular sieve (butt): phosphoric acid (by P): oxalic acid (containing two molecular crystalline water): water=1:0.014:0.14:8(weight ratio), with sulfuric acid adjust pH 2.8,70 DEG C process 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 70% steam roasting time 2h, obtain modified molecular screen, be designated as A1, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with deionized water in the boehmite of 20 weight portions of aluminium oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio (36 % by weight hydrochloric acid with in the weight ratio of the boehmite of aluminium oxide, lower same) be 0.20, be warming up to 65 DEG C to stir 1 hour, add respectively in the slurries of 30 parts by weight kaolin clay of butt (slurry solid content 45 % by weight, lower same), in the Alumina gel (Al of 10 weight portions of aluminium oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A1 molecular sieve of butt 35 weight portion with in the REY molecular sieve of 5 weight portions of butt afterwards more wherein, continue stirring 30 minutes, obtain the slurries of solid content 30 % by weight, spraying dry makes microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10 weight ratio) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C1 after filtration at 120 DEG C.

Comparative example 1

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 1000g exchange solution is housed (containing (NH of 0.63% ₄) ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=3.0 ~ 3.5 simultaneously, filter after exchanging, washing; 730 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.58% ₃with 6.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 730 DEG C, 70% steam exist under roasting 2h, obtained modified molecular screen, be designated as B1, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 1, difference is, replaces described modified molecular screen A1 with described modified molecular screen B1, thus obtained catalytic cracking catalyst DC1.

Embodiment 2

(1) preparation of modified molecular screen

Be that raw material ammonium chloride solution exchanges with NaY molecular sieve, treatment conditions are: NaY molecular sieve (butt): ammonium chloride: water=1:0.8:8, and hydrochloric acid adjust pH 4.0,90 DEG C exchanges 1h, washing.Hydrothermal calcine process, sintering temperature 550 DEG C, 80% steam roasting time 2h.Roast rear sample with phosphoric acid and silicate fluoride solution process one, treatment conditions are: roasting molecular sieve (butt): phosphoric acid (by P): fluosilicic acid: water=1:0.01:0.03:8, and hydrochloric acid adjusts pH2.8, and 70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 70% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment conditions are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.03:8,70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 100% steam roasting time 2h, obtain modified molecular screen, be designated as A2, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with deionized water in the boehmite of 20 weight portions of aluminium oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 32 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight portions of aluminium oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A2 molecular sieve of 30 weight portions of butt with in the REY molecular sieve of 8 weight portions of butt afterwards more wherein, stir 30 minutes, spraying dry makes microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o weight ratio=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C2 after filtration at 120 DEG C.

Comparative example 2

(1) preparation of modified molecular screen

Get 100 grams of (butt) NaY molecular sieve, pour into and 900g exchange solution is housed (containing (NH of 0.45% ₄) ₂hPO ₄salt and 10% (NH ₄) ₂sO ₄) reactor in, exchange 1h at 90 DEG C, simultaneously in exchange process, control pH value of solution=3.0 ~ 3.5, filter after exchanging, washing; 730 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.44% ₃with 7.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 730 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B2, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 2, difference is, replaces described modified molecular screen A2 with described modified molecular screen B2, thus obtained catalytic cracking catalyst DC2.

Embodiment 3

(1) preparation of modified molecular screen

Be that raw material ammonium sulfate exchanges with NaY molecular sieve, treatment conditions are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:10, and sulfuric acid adjust pH 3.5,90 DEG C exchanges 2h, washing.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one of phosphate-containing and oxalic acid, treatment conditions are: roasting molecular sieve (butt): diammonium hydrogen phosphate (by P): oxalic acid: water=1:0.018:0.03:8, and hydrochloric acid adjusts pH=3.0, and 70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment conditions are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.02:8.0,85 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% water steams roasting time 2h, and obtain modified molecular screen, be designated as A3, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with a certain amount of deionized water in the boehmite of 20 weight portions of aluminium oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 32 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight portions of aluminium oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A3 molecular sieve of 25 weight portions of butt, in the REY molecular sieve of 10 weight portions of butt with in the DASY-2.0 molecular sieve of 3 weight portions of butt afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C3 after filtration at 120 DEG C.

Comparative example 3

(1) preparation of modified molecular screen

Get 100 grams of (butt) NaY molecular sieve, pour into and 1000g exchange solution is housed (containing (NH of 0.63% ₄) ₂hPO ₄salt and 10% (NH ₄) ₂sO4) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=3.0 ~ 3.5 simultaneously, filter after exchanging, washing; 670 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 400g is housed exchanges solution (containing the RECl of 0.60% ₃with 6.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B3, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 3, difference is, replaces described modified molecular screen A3 with described modified molecular screen B3, thus obtained catalytic cracking catalyst DC3.

Embodiment 4

(1) preparation of modified molecular screen

Be that raw material ammonium phosphate and ammonium sulfate exchange with NaY molecular sieve, treatment conditions are: NaY molecular sieve (butt): ammonium dihydrogen phosphate (ADP) (by P): ammonium sulfate: water=1:0.05:1.0:8(weight ratio), sulfuric acid adjust pH 3.0,85 DEG C exchanges 1h, washing.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% steam, roasting time 2h.Roast rear sample by the solution-treated one containing oxalic acid, treatment conditions are: roasting molecular sieve (butt): oxalic acid: water=1:0.15:0.020:8(weight ratio), 70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment conditions are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.01:8(weight ratio), 70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 600 DEG C, 100% steam roasting time 2h, obtain modified molecular screen, be designated as A4, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with a certain amount of deionized water in the boehmite of 20 weight portions of aluminium oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 32 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight portions of aluminium oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A4 molecular sieve of 20 weight portions of butt, in the REY molecular sieve of 12 weight portions of butt with in the DASY-2.0 molecular sieve of 6 weight portions of butt afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10 weight ratio) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C4 after filtration at 120 DEG C.

Comparative example 4

(1) preparation of modified molecular screen

Get 100 grams of (butt) NaY molecular sieve, pour into and 1200g exchange solution is housed (containing (NH of 1.22% ₄) ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=5.0-5.5 simultaneously, filter after exchanging, washing; 620 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.055% ₃with 7.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B4, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 4, difference is, replaces described modified molecular screen A4 with described modified molecular screen B4, thus obtained catalytic cracking catalyst DC4.

Embodiment 5

(1) preparation of modified molecular screen

Be that raw material ammonium phosphate and ammonium sulfate exchange with NaY molecular sieve, treatment conditions are: NaY molecular sieve (butt): ammonium dihydrogen phosphate (ADP) (by P): ammonium sulfate: water=1:0.05:1.0:8, sulfuric acid adjust pH 3.5,90 DEG C exchanges 2h, washing.Hydrothermal calcine process, sintering temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one containing rare earth, treatment conditions are: roasting molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.02:8.0, hydrochloric acid adjusts pH2.9, and 85 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two of phosphate-containing and fluosilicic acid, treatment conditions are: two roastings molecular sieve (butt): diammonium hydrogen phosphate (by P): fluosilicic acid: water=1:0.006:0.03:8, and hydrochloric acid adjusts pH=3.0, and 70 DEG C exchange 1h, filter; Deionized water is washed.Hydrothermal calcine process, sintering temperature 550 DEG C, 100% water steams roasting time 2h, and obtain modified molecular screen, be designated as A5, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with deionized water in the boehmite of 20 weight portions of aluminium oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 32 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight portions of aluminium oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A5 molecular sieve of 15 weight portions of butt, in the REY molecular sieve of 10 weight portions of butt with in the DASY-2.0 molecular sieve of 13 weight portions of butt afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C5 after filtration at 120 DEG C.

Comparative example 5

(1) preparation of modified molecular screen

Get 100 grams of (butt) NaY molecular sieve, pour into and 1500g exchange solution is housed (containing (NH of 1.1 1% ₄) ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=4.5-5.0 simultaneously, filter after exchanging, washing; 650 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1000g is housed exchanges solution (containing the RECl of 0.35% ₃with 7.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 70% steam exist under roasting 2h, obtained modified molecular screen, be designated as B5, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 5, difference is, replaces described modified molecular screen A5 with described modified molecular screen B5, thus obtained catalytic cracking catalyst DC5.

Embodiment 6

According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike all using A1 molecular sieve, do not add REY molecular sieve, wherein the A1 molecular sieve of REY molecular sieve equivalent replaces.Obtain catalyst and be designated as C6.

Embodiment 7

According to the method for embodiment 1, Kaolinite Preparation of Catalyst, its proportioning is as follows: kaolin 15 % by weight, boehmite 25 % by weight, Alumina gel 15 % by weight, A1 molecular sieve 35 % by weight, REY molecular sieve 10 % by weight.

Embodiment 8

According to the method for embodiment 1, Kaolinite Preparation of Catalyst, its proportioning is as follows: kaolin 55 % by weight, boehmite 20 % by weight, A1 molecular sieve 20 % by weight, ZSP-1 molecular sieve 5 % by weight

Table 1

Test case 1

The present embodiment illustrates the hydrothermal stability adopting catalytic cracking catalyst of the present invention.

By above-described embodiment and obtained catalyst sample C2, DC2, C5, the DC5 of comparative example 2,5 800 DEG C, carry out hydrothermal aging process in 4 hours, 8 hours, 17 hours, 22 hours respectively under 100% water vapor conditions, measure light oil microactivity (MA), the results are shown in Figure 1, can find out, catalyst containing Modified Zeolite Y provided by the invention has better stability than comparative catalyst, in thermal and hydric environment, after initial stage rapid deactivation, reach equilibrium activity very soon, and equilibrium activity is higher than contrast sample.

Test case 2

The present embodiment illustrates the cracking reaction performance adopting catalytic cracking catalyst of the present invention.

By above-mentioned catalytic cracking catalyst C1-C5 and DC1-DC5, at 800 DEG C, under 100% water vapour condition aging 12 hours, the reactivity worth of catalyst is evaluated, catalyst filling amount 9g by small fixed flowing bed ACE R+ device (being manufactured by U.S. KayserTechnology Inc. company designs).At reaction temperature 500 DEG C, weight (hourly) space velocity (WHSV) 16h ^-1, oil ratio (weight) is under the condition of 8, using the catalytic mixing oil shown in table 2 as feedstock oil, inject described ACE R+ device and carry out catalytic cracking reaction, result is as shown in table 3.

Test case 3

The present embodiment illustrates the hydrothermal structural stability adopting modified Y molecular sieve of the present invention.

By above-described embodiment 2,3,4 and the obtained phosphorus of comparative example 2,3,4 and rare earth modified Y zeolite sample 800 DEG C, carry out hydrothermal aging process in 2 hours, 4 hours, 8 hours, 17 hours, 24 hours respectively under 100% water vapor conditions, and it is carried out to the mensuration of degree of crystallinity, degree of crystallinity and crystallization reservation degree the results are shown in Fig. 2 and Fig. 3.

As can be seen from Fig. 2, Fig. 3, modified Y molecular sieve provided by the invention is after hydrothermal aging process, and degree of crystallinity and crystallization reservation degree are significantly higher than comparative example.Illustrate that modified Y molecular sieve hydrothermal structural stability provided by the invention is better.

Table 2

Density, g/cm ³(20℃)	0.9044
		Viscosity (100C), mm ²/s	9.96
Condensation point, DEG C	40
		Carbon residue, % by weight	3.0
Constituent content, % by weight
		C	85.98
H	12.86
		S	0.55
N	0.18
		Tenor, μ g/g
Ca	28
		Fe	15.7
Na	3.4
		Ni	7.4
V	1.2
		Boiling range, DEG C
Initial boiling point	243
		10%	316
50%	429
		70%	473

Table 3

In table 3, Jiao turns than the weight ratio being coke and conversion ratio.

As can be seen from the data of table 3, catalytic cracking catalyst provided by the present invention shows relatively high catalytic cracking activity in hydrothermal aging process after 12 hours, can obtain higher conversion ratio, has better heavy oil conversion performance, coke selectivity is better, and yield of light oil is higher.

Claims

1. a catalytic cracking catalyst, contains in the Modified Zeolite Y of butt 10 ~ 50 % by weight, in other molecular sieve of butt 0 ~ 30 % by weight, in the clay of butt 10 ~ 70 % by weight with the inorganic oxide binder of oxide basis 10 ~ 40 % by weight; Wherein said Modified Zeolite Y, lattice constant is 2.420 ~ 2.440nm, and by weight percentage, P content is 0.05 ~ 6%, RE ₂o ₃content is 0.03 ~ 10%, and alumina content is less than 22%, is less than 0.35mmol/g than hydroxyl nest concentration, described

In formula, M _{200 DEG C}, M _{500 DEG C}and M _{800 DEG C}represent respectively sample temperature 200 DEG C, 500 DEG C and 800 DEG C time the percent weight loss that records, C is sample crystallinity;

Other described molecular screening from other y-type zeolite, have in MFI structure zeolite, Beta zeolite, non-zeolite molecular sieve one or more, other y-type zeolite described is one or more in REY, REHY, DASY, USY, REUSY molecular sieve, described MFI structure molecular sieve is one or more in ZSM-5, ZRP, ZSP molecular sieve, and described non-zeolite molecular sieve is one or more in SAPO, HTS.

2. according to catalytic cracking catalyst according to claim 1, it is characterized in that, described Modified Zeolite Y: lattice constant is 2.428 ~ 2.438nm, P is 0.1 ~ 4.5%, RE by weight percentage ₂o ₃be 0.1 ~ 4.5%, aluminium oxide is less than 20%, is less than 0.3mmol/g than hydroxyl nest concentration.

3. the preparation method of catalytic cracking catalyst described in claim 1, the method comprises the Modified Zeolite Y described in preparation, by prepared Modified Zeolite Y, clay and inorganic oxide binder mixing making beating or by prepared Modified Zeolite Y, clay, inorganic oxide binder and other molecular sieve mixing making beating, spray-dired step, described Modified Zeolite Y take NaY molecular sieve as raw material, three exchange operations and three hydrothermal treatment consists are adopted to obtain with containing rare-earth substance and phosphorus containg substances, wherein, exchanged form is adopted containing rare-earth substance and phosphorus containg substances, add phosphorus containg substances exchange solution and exchange containing rare-earth substance exchange solution, phosphorus containg substances once or several times adds in arbitrary exchange operation, add in arbitrary exchange operation beyond a friendship containing rare-earth substance, other described molecular screening is from other y-type zeolite, there is MFI structure zeolite, Beta zeolite, one or more in non-zeolite molecular sieve, other y-type zeolite described is REY, REHY, DASY, USY, one or more in REUSY molecular sieve, described MFI structure molecular sieve is ZSM-5, ZRP, one or more in ZSP molecular sieve, described non-zeolite molecular sieve is SAPO, one or more in HTS.

4. according to the preparation method of catalytic cracking catalyst according to claim 3, it is characterized in that, described exchange operation comprises further and adds dealumination agent and carry out chemical dealuminization to promote removing of aluminium, and chemical dealuminization process is carried out in arbitrary exchange operation beyond handing over one.

5., according to the preparation method of catalytic cracking catalyst according to claim 3, it is characterized in that, described phosphorus containg substances be selected from orthophosphoric acid, phosphorous acid, pyrophosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and aluminum phosphate one or more.

6., according to the preparation method of catalytic cracking catalyst according to claim 3, it is characterized in that, described containing rare-earth substance be selected from lanthana, cerium oxide, lanthanum nitrate, cerous nitrate, lanthanum chloride and cerium chloride one or more.

7. according to the preparation method of catalytic cracking catalyst according to claim 3, it is characterized in that, described is one or more in nitric acid mishmetal and chlorination mishmetal containing rare-earth substance.

8. according to the preparation method of catalytic cracking catalyst according to claim 4, it is characterized in that, described dealumination agent be selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid, fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid, ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate one or more.

9. according to the preparation method of the catalytic cracking catalyst described in any one of claim 3 ~ 8, it is characterized in that, the preparation method of described Modified Zeolite Y comprises the steps:

1) NaY molecular sieve and ammonium salt, phosphorus ammonium salt and water are according to NaY molecular sieve: ammonium salt: phosphorus ammonium salt: the ratio of water=1:0.4 ~ 1.0:0 ~ 0.04:5 ~ 10 is mixed to get slurries, be 3.0 ~ 4.5 by the pH value of inorganic acid adjusting slurry, then process at 70 ~ 95 DEG C and at least wash after 0.5h, wherein, NaY molecular sieve is in butt, and phosphorus ammonium salt is in elemental phosphorous;

2) by step 1) product that obtains under temperature 350 ~ 650 DEG C, 1 ~ 100% steam atmosphere roasting at least 0.5h obtain a roasting molecular sieve;

3) by step 2) obtain one roasting molecular sieve roast molecular sieve with phosphoric acid, dealumination agent according to one: phosphoric acid: dealumination agent: the ratio of water=1:0 ~ 0.04:0.02 ~ 0.3:5 ~ 10 mixes, with inorganic acid adjust pH 2.4 ~ 3.5, then at 50 ~ 90 DEG C, at least 0.5 hour is processed, filter, wash, washing water temperature >=50 DEG C, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous;

4) by step 3) product that obtains temperature 350 ~ 650 DEG C, under 1 ~ 100% steam atmosphere roasting at least 0.5h obtain two roasting molecular sieves;

5) by step 4) obtain two roasting molecular sieves roast molecular sieve with rare earth chloride and water according to two: rare earth chloride: the ratio of water=1:0.01 ~ 0.05:5 ~ 10 mixes, then processes at least 0.5 hour at 70 ~ 90 DEG C, filtration; Washing, washing water temperature>=50 DEG C, wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE ₂o ₃meter;

6) by step 5) product that obtains 350 ~ 650 DEG C, under 1 ~ 100% steam atmosphere roasting at least 0.5h obtain Modified Zeolite Y.

10. according to the preparation method of catalytic cracking catalyst according to claim 3, it is characterized in that, described binding agent be selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite) one or more; Described clay be selected from kaolin, imvite, diatomite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite one or more; Other described molecular screening from other Y zeolite, beta-molecular sieve, have in MFI structure molecular sieve and non-zeolite molecular sieve one or more, other y-type zeolite described is one or more in REY, REHY, DASY, USY, REUSY molecular sieve, described MFI structure molecular sieve is one or more in ZSM-5, ZRP, ZSP molecular sieve, and described non-zeolite molecular sieve is one or more in SAPO, HTS.

11. according to the preparation method of catalytic cracking catalyst according to claim 10, and it is characterized in that, described kaolin is halloysite.