CN1167505C - Catalytic cracking catalyst containing super-stable Y zeolite and its preparing process - Google Patents

Abstract

The present invention relates to a catalytic cracking catalyst containing super stabilized Y zeolite, which comprises 5 to 60 wt% of rare earth containing super stabilized Y zeolite and 40 to 95 wt% of catalyst carrier or substrate. The rare earth containing super stabilized Y zeolite is prepared with the following method: super stabilized Y zeolite having a sodium oxide content of 3 to 5 wt% is mixed with a solution of a rare earth compound to obtain slurry; the obtained slurry is ground; the weight ratio of the super stabilized Y zeolite, the rare earth compound and water is 1: (0.001 to 0.5): (1 to 10), the grinding shearing stress is at least 10 kg/cm<2>, and the milling time is at least 1 minute. The catalyst has the advantages of high activity and high activity stability.

Description

A kind of catalytic cracking catalyst that contains overstable gamma zeolite and preparation method thereof

Technical field

The invention relates to a kind of catalytic cracking catalyst that contains faujasite and preparation method thereof, more particularly, is about a kind of catalytic cracking catalyst that contains overstable gamma zeolite and preparation method thereof.

Background technology

At present, the active component of catalytic cracking catalyst rare earth Y type zeolite commonly used and overstable gamma zeolite, some catalytic cracking catalyst is an active component with the overstable gamma zeolite that contains rare earth.

CN1034680A discloses a kind of rich silicon molecular sieve by crystal Cracking catalyst that contains rare earth, and this catalyst is an active component with the Silicon-rich HY zeolite that contains rare earth of the heavy % of 5-40, is aided with the Al that comprises of the heavy % of 95-60 ₂O ₃, SiO ₂, SiO ₂-Al ₂O ₃At interior full synthesis carrier, or contain the semi-synthetic carrier of the silica gel of the heavy % of 15-30 or aluminium glue stick and constitute, contain in the Silicon-rich HY zeolite of rare earth, rare earth is all with RE ₂O ₃State exist, the exchangeable cations position is H ⁺Or Na ⁺Occupy, the similar conventional ultrastable of the X light powder diffraction spectrogram of this zeolite, but be the RE that a disperse is arranged on the 27-29 ° of position at 2 θ angles ₂O ₃Characteristic peak.The described rich silicon molecular sieve by crystal that contains rare earth can be by two kinds of method preparations, and first method comprises with NaOH or NH ₄OH precipitates RECl ₃Mixed solution obtains gluey rare-earth hydroxide, and what obtain during with hydrochloric acid or sulfuric acid precipitation waterglass or Ludox or synthetic A, X, Y molecular sieve contains SiO ₂Mother liquor obtains amorphous gluey SiO ₂Then, with gluey rare-earth hydroxide, amorphous gluey SiO ₂Press RE with the NaY molecular sieve ₂O ₃: SiO ₂: the NaY weight ratio is 0.05-0.5: 0.02-0.3: 1 ratio mixes, and the pH to 10-13 with NaOH solution adjusting slurries filters, and is (the NH of the heavy % of 1-30 again with concentration ₄) ₂SO ₄Solution is by (NH ₄) ₂SO ₄: NaY is the weight ratio of 0.5-2.0, carries out ion-exchange 1-3 time 35 to the temperature of boiling, each 5-60 minute, and filtration, at 450-650 ℃, in the 20-100% water vapour atmosphere roasting 0.5-4 hour.Second method comprises RECl ₃Solution and 20-80 ℃ the NaY zeolite slurry that contains mother liquor is by RE ₂O ₃: SiO ₂: NaY is 0.05-0.5: 0.02-0.3: 1 weight ratio mixes, with NaOH solution the pH value of mixed serum is transferred to 10-13, filter, with concentration is that the ammonium sulfate of the heavy % of 1-30 is that the weight ratio of 0.5-2.0 is 35 ℃ of exchanges 1-3 time to the boiling temperature by ammonium sulfate: NaY, each 5-60 minute, filter cake after the ammonium exchange is at 450-650 ℃, under the 20-100% steam roasting 0.5-4 hour.

CN1127161A discloses a kind of preparation method of rare earth-containing rich silicon ultra stabilization Y molecular sieve, this method comprise (1) with silica alumina ratio greater than 3.5 the NaY molecular sieve and the solid RECl of porphyrize ₃Make its water content be lower than 10 heavy %, NaY molecular sieve and RECl after (2) will handle through hydrothermal treatment consists respectively ₃Press RECl ₃: NaY=0.02-0.60: 1 weight ratio mixes while hot or mixes under dry atmosphere, and (3) feed the SiCl that dry atmosphere is carried in said mixture ₄Gas, in 150-550 ℃ of reaction 10 minutes to 5 hours, wherein, the water content of dry air was lower than 900ppm, SiCl in reactor ₄Consumption press SiCl ₄: NaY=0.10-0.80: 1 weight ratio is calculated, and the reaction back purged in reactor 10 minutes to 2 hours with this dry air, and the Na in the molecular sieve is removed in (4) washing ⁺, Cl ^-, Al ³⁺Etc. the solubility accessory substance.

In catalytic cracking catalyst, the activity of active component overstable gamma zeolite and activity stability are the focuses that everybody pays close attention to always, contain the sodium oxide molybdena about 4 heavy % mostly in the overstable gamma zeolite, sodium ion in the contained sodium oxide molybdena occupies the exchangeable cations position in the overstable gamma zeolite, and basically in the supercage of zeolite, the existence of this part sodium oxide molybdena has reduced structural stability, activity and the activity stability of overstable gamma zeolite.If the major part of this part sodium oxide molybdena is replaced by rare earth ion, will structural stability, activity and the activity stability of overstable gamma zeolite be improved.Yet, if adopt the described method of CN1034680A, prepare the overstable gamma zeolite that contains rare earth from the overstable gamma zeolite that contains sodium oxide molybdena, because the rare earth component adopts the method for precipitation to introduce, obvious, rare earth ion can not be replaced the Na that is positioned at the zeolite cation-bit ⁺And adopt the CN1127161A disclosed method, on the one hand, rare earth ion can not be replaced the Na on the cation position equally well ⁺, on the other hand, SiCl ₄Mend the silica alumina ratio of silicon effect will change overstable gamma zeolite, cause the change of overstable gamma zeolite catalytic property and the decline significantly of degree of crystallinity, obviously, the overstable gamma zeolite that also is not suitable for to contain about sodium oxide molybdena 4 heavy % is a raw material, the preparation super-stable Y zeolite containing rare-earth elements.

Another method of introducing the rare earth component in zeolite commonly used is an ion-exchange, in general, this method comprises ultrastable and a kind of solution that contains rare earth ion carries out ion-exchange at least 30 minutes at liquid-solid ratio 5-20 under temperature 60-100 ℃ the condition.Adopt the method for ion-exchange, though can make rare earth ion replacing section sodium ion,, the time of first ion-exchange is longer, and temperature is also higher, and second, even under higher temperature and longer swap time such condition, the content of sodium oxide molybdena also is difficult to be reduced to gratifying degree.Just because of this, adopt prior art, the sodium content of the super-stable Y zeolite containing rare-earth elements that obtains when preparing super-stable Y zeolite containing rare-earth elements with the overstable gamma zeolites of the left and right sides sodium oxide molybdena that contains 4 heavy % is higher, and hydrothermal stability, activity, activity stability are relatively poor.Activity of such catalysts, the activity stability of super-stable Y zeolite containing rare-earth elements that contains the preparation of useful art methods is also relatively poor.

Summary of the invention

The purpose of this invention is to provide higher catalytic cracking catalyst of a kind of new activity, activity stability and preparation method thereof.

Catalytic cracking catalyst provided by the invention contains a kind of overstable gamma zeolite and a kind of catalyst carrier or matrix, wherein, described overstable gamma zeolite is a kind of overstable gamma zeolite that contains rare earth, with the catalyst total amount is benchmark, the content of described super-stable Y zeolite containing rare-earth elements is the heavy % of 5-60, the content of catalyst carrier is the heavy % of 40-95, described super-stable Y zeolite containing rare-earth elements adopts the preparation of following method: with sodium oxide content is that the overstable gamma zeolite of the heavy % of 3-5 mixes with a kind of rare earth compound solution, make a kind of slurries, the slurries that obtain are ground, wherein, in the described slurries, overstable gamma zeolite, the weight ratio of rare earth compound and water is 1: 0.001-0.5: 1-10, the shear stress of grinding is at least 10 kilograms per centimeter ², milling time is no less than 1 minute.

Preparation of catalysts method provided by the invention comprises and will form the material of catalyst carrier or their precursor, a kind of overstable gamma zeolite or the slurries and the water that contain this overstable gamma zeolite are pulled an oar together, dry, washing and dry once more, wherein, described overstable gamma zeolite is the overstable gamma zeolite that contains rare earth as mentioned above, and described super-stable Y zeolite containing rare-earth elements adopts as above method preparation.

Catalyst provided by the invention has following advantage:

1. catalyst provided by the invention has higher cracking activity, and lower coke selectivity and the gasoline selective of Geng Gao are as shown in table 5.

2. because the used super-stable Y zeolite containing rare-earth elements of the present invention has higher hydrothermal stability and activity stability, therefore, catalyst provided by the invention also has higher activity stability.For example, as Figure 1-3, compare with the super-stable Y zeolite containing rare-earth elements for preparing with ion-exchange, after 800 ℃ of 100% steam aging handled, crystallization reservation degree, specific surface reservation degree and the pore volume reservation degree of the super-stable Y zeolite containing rare-earth elements of the used employing polishing preparation of the present invention with the decrease speed of ageing time will be slowly many.Again for example, as shown in Figure 4, identical with zeolite content, be used zeolite be to compare with the reference catalyst of the super-stable Y zeolite containing rare-earth elements of ion-exchange preparation, after 800 ℃ of 100% steam aging handled, prolong with ageing time, the light oil microactivity of catalyst provided by the invention underspeeds obviously slowly manyly.

3. catalyst provided by the invention has stronger anti-sodium pollution capacity and preventing from heavy metal pollution ability.For example, as shown in Figure 5, the sodium of 0.5 heavy %, 1.0 heavy % and 1.5 heavy % in catalyst, flooding respectively, and at 800 ℃ with 100% steam treatment 4 hours, all identical with other component and content, being used zeolite compares for the reference catalyst with the super-stable Y zeolite containing rare-earth elements of ion-exchange preparation, and with the increase that sodium in the catalyst pollutes content, the light oil microactivity reservation degree decrease speed of catalyst provided by the invention is much more slowly than reference catalyst.

Again for example, in catalyst, sneak into 5000 and the V of 10000ppm respectively ₂O ₅And at 800 ℃ with 100% steam treatment 4 hours, identical with constituent content, the reference catalyst of super-stable Y zeolite containing rare-earth elements that is the ion-exchange preparation of used zeolite is compared, and the light oil microactivity reservation degree of the catalyst provided by the invention after pollution of vanadium is much higher than reference catalyst.

Description of drawings

Fig. 1 is when carrying out hydrothermal treatment consists for 800 ℃, and the crystallization reservation degree of different super-stable Y zeolite containing rare-earth elements is with the variation diagram of the time of processing;

Fig. 2 is when carrying out hydrothermal treatment consists for 800 ℃, and the specific surface reservation degree of different super-stable Y zeolite containing rare-earth elements is with the variation diagram of the time of processing;

Fig. 3 is when carrying out hydrothermal treatment consists for 800 ℃, and the pore volume reservation degree of different super-stable Y zeolite containing rare-earth elements is with the variation diagram of the time of processing;

Fig. 4 is when carrying out hydrothermal aging for 800 ℃, and the light oil microactivity of different catalysts is with the variation diagram of ageing time;

Fig. 5 is the variation diagram of different catalysts light oil microactivity reservation degree with the sodium content on polluting.

The specific embodiment

According to catalyst provided by the invention, the content of described super-stable Y zeolite containing rare-earth elements is preferably the heavy % of 5-35, and the content of catalyst carrier is preferably the heavy % of 65-95.

In the preparation of described super-stable Y zeolite containing rare-earth elements, the overstable gamma zeolite of the heavy % of described sodium oxide content 3-5 can be purchased and get, and also can prepare with the following method: sodium oxide content 13-14 is weighed the NaY zeolite of % and contains NH ₄ ⁺Aqueous solution, under 60-100 ℃ temperature, carry out ion-exchange at least 30 minutes, contain NH ₄ ⁺The aqueous solution in, NH ₄ ⁺Concentration is the 0.1-2.0 mol, when carrying out ion-exchange, liquid-solid ratio is 5-20, and the zeolite after the ion-exchange is spent deionised water to there not being acid ion, under 650 ℃ of 100% water vapour atmosphere, carried out hydrothermal treatment consists 1-3 hour, and obtained the overstable gamma zeolite of the heavy % of sodium oxide content 3-5.Wherein, the described NH that contains ₄ ⁺The aqueous solution in NH ₄ ⁺By water soluble salt of ammonia, provide as ammonium chloride, ammonium nitrate, ammonium sulfate etc.

Described rare earth compound is selected from one or more in the water-soluble rare earth compound of energy, is preferably rare earth-iron-boron and/or nitrate, the chloride of preferred especially rare earth.Described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium, be preferably in lanthanum, cerium, lanthanum rich mischmetal, the cerium-rich mischmetal one or more, because lanthanum rich mischmetal and cerium-rich mischmetal more are easy to get, therefore more preferably lanthanum rich mischmetal or cerium-rich mischmetal.

Described grinding can be adopted various Ginding process, as the method for underhand polish, the method for mechanical lapping, preferably adopts the method for mechanical lapping, as carry out abrasive method in colloid mill.Grind shear stress and be at least 10 kilograms per centimeter ², be preferably the 10-100 kilograms per centimeter ², 10-50 kilograms per centimeter more preferably ²

Milling time is longer, and ion-exchange effect can be better, and still in general, milling time just can reach good effect at 15 minutes with interior, and therefore, milling time is preferably 1-15 minute, more preferably 2-10 minute.

The raising of grinding temperature helps the carrying out of ion-exchange, but difference and not obvious, and grinding temperature can be 5-100 ℃, carries out under 10-50 ℃ usually for reducing energy consumption, more preferably carries out under 10-40 ℃ temperature.。

The weight ratio of described overstable gamma zeolite, rare earth compound and water is very important, slurries are too rare, grinding effect is bad, too dense being difficult to again operates, and do not reach the purpose of fully carrying out ion-exchange, in general, the weight ratio of overstable gamma zeolite, rare earth compound and water is 1 in the slurries: 0.001-0.5: 1-10 is preferably 1: 0.05-0.3: 1-4.5.

In the preparation process of described super-stable Y zeolite containing rare-earth elements, if wish in zeolite, to introduce more rare earth component, perhaps wish in zeolite, to introduce the rare earth component of deposition form, can after grinding, add a kind of alkaline solution, make the pH value of slurries rise to 5-10, be preferably 6-8, the rare earth ion in the solution be deposited on the zeolite with the form of rare-earth hydroxide, and continue to grind at least 1 minute, preferred 1-15 minute, more preferably 2-10 minute.Wherein, described alkaline solution can be selected from one or more in the various inorganic and organic base solution, as in alkali-metal hydroxide solution, ammonia spirit, the organic amine solution one or more, is preferably ammonia spirit.

According to catalyst provided by the invention, described catalyst carrier or matrix are carrier or the matrix that is commonly used for catalytic cracking catalyst.As being amorphous aluminum silicate, also can be the mixture of al binder and clay.

According to specific embodiment of the present invention, described catalyst carrier is an amorphous aluminum silicate, with the total catalyst weight is benchmark, the content of super-stable Y zeolite containing rare-earth elements is the heavy % of 5-60, be preferably the heavy % of 5-35, the heavy % of silica content 30-70 is preferably the heavy % of 40-60, alumina content is the heavy % of 10-50, is preferably the heavy % of 20-40.

According to embodiment preferred of the present invention, described catalyst carrier is the mixture of al binder and clay, is benchmark with the total catalyst weight, and the content of super-stable Y zeolite containing rare-earth elements is the heavy % of 5-60, is preferably the heavy % of 5-35, with Al ₂O ₃Meter, the content of al binder are the heavy % of 10-45, are preferably the heavy % of 20-40, and the content of clay is the heavy % of 30-60, are preferably the heavy % of 40-60.

Silicon in the described amorphous aluminum silicate is provided by Ludox and/or waterglass, and the aluminium in the described amorphous aluminum silicide is provided by aluminium colloidal sol and/or boehmite.

Described al binder is selected from aluminium colloidal sol and/or boehmite.Described clay is selected from one or more in the various clays that are commonly used for the catalytic cracking catalyst component.As in kaolin, halloysite, imvite, the diatomite etc. one or more, be preferably kaolin.

In order to improve catalyst strength and to improve quality of gasoline in the catalytic cracking reaction product, can also contain phosphorus in the catalyst provided by the invention, with P ₂O ₅Meter, phosphorus content are the heavy % of 0.4-8, are preferably the heavy % of 0.5-5.

Can also partly replace the overstable gamma zeolite that contains rare earth of the present invention with other zeolite in the catalyst provided by the invention, described other zeolite is selected from one or more in the hydrogen Y zeolite (HY) that is commonly used for the catalytic cracking catalyst active component, rare earth exchanged Y zeolite (REY), rare earth hydrogen Y zeolite (REHY), overstable gamma zeolite (USY), phosphorous y-type zeolite, ZSM-5 zeolite, Beta zeolite, the modenite.If contain other zeolite, the weight ratio of super-stable Y zeolite containing rare-earth elements of the present invention and other zeolite is 1: 0.1-10 is preferably 1: 0.2-5.

According to Preparation of catalysts method provided by the invention, as previously mentioned, the material of forming catalyst carrier or matrix is selected from the mixture of amorphous aluminum silicate or al binder and clay.The precursor of silicon is selected from Ludox and/or waterglass in the amorphous aluminum silicide, and the precursor of aluminium is selected from aluminium colloidal sol and/or boehmite, and al binder is selected from aluminium colloidal sol and/or boehmite.

The preferred a kind of aging boehmite slurries of described boehmite, the preparation method of these slurries comprises boehmite and deionized water by 1: 1-10, be preferably 1: the weight ratio of 1-5 is mixed making beating, adding HCl and boehmite weight ratio is 1: 0.01-0.4, be preferably 1: the hydrochloric acid of 0.1-0.3, be warming up to 40-80 ℃, preferred 50-60 ℃ aging 10-60 minute, preferred 20-30 minute, promptly get described aging boehmite slurries.

According to Preparation of catalysts method provided by the invention, in pulping process, the conventional amount used when consumption of each material is the preparation catalytic cracking catalyst.As when adopting amorphous aluminum silicate as catalyst carrier or matrix, the consumption of super-stable Y zeolite containing rare-earth elements should make and contain the heavy % of 5-60 in the final catalyst, be preferably the super-stable Y zeolite containing rare-earth elements of the heavy % of 5-35, the consumption of Ludox or waterglass should make and contain the heavy % of 30-70 in the final catalyst, be preferably the silica of the heavy % of 40-60, the consumption of aluminium colloidal sol or boehmite should make and contain the heavy % of 10-50 in the final catalyst, is preferably the aluminium oxide of the heavy % of 20-40.As to adopt al binder and clay be catalyst carrier or matrix, the consumption of super-stable Y zeolite containing rare-earth elements should make and contain the heavy % of 5-60 in the final catalyst, be preferably the super-stable Y zeolite containing rare-earth elements of the heavy % of 5-35, the consumption of aluminium colloidal sol and/or boehmite should make and contain the heavy % of 10-45 in the final catalyst; Be preferably the al binder (in aluminium oxide) of 20-40, the consumption of clay should make and contain the heavy % of 30-60 in the final catalyst, is preferably the clay of the heavy % of 40-60.It is the heavy % of 20-40 that the consumption of deionized water should make the solid content of the slurries that obtain.

If partly replace the overstable gamma zeolite that contains rare earth of the present invention with aforesaid other zeolite, can with described other zeolite and super-stable Y zeolite containing rare-earth elements of the present invention together with form catalyst carrier or matrix or its precursor and deionization and mix making beating.

When containing phosphorus in the catalyst provided by the invention, can in slurries, add a kind of phosphorus-containing compound at pulping process, described phosphorus-containing compound can be selected from one or more in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate.The consumption of described phosphorus-containing compound should make and contain the heavy % of 0.4-8 in the final catalyst, the P2O5 of the heavy % of preferred 0.5-5.Also can in washing process as described below, introduce phosphorus.

The described dry drying means of routine when using the preparation catalytic cracking catalyst, as airing, oven dry and spray-dired method, dry temperature can be preferably 120-650 ℃ from room temperature to 700 ℃.

The purpose of described washing is to remove the wherein Na of solubility ⁺, materials such as acid ion, the method for washing can adopt conventional washing methods, as with deionized water and the making beating of dried catalyst, filters then, or directly uses the deionized water rinsing catalyst.

By washing, can also in catalyst, introduce phosphorus, method is with containing P ₂O ₅0.1-10 heavy % is preferably the heavy % of 0.1-5, pH value be 2.5-10, be preferably 3.5-5.5 phosphorus-containing compound the solution washing catalyst at least once, in catalyst, introduce 0.4-8 and weigh %, be preferably 0.5-5 and weigh the phosphorus of % (with P ₂O ₅Meter), the 5-20 that described phosphorus-containing compound solution is catalyst weight when washing at every turn doubly is preferably 10-15 doubly.Described phosphorus-containing compound can be any one water-soluble phosphorus-containing compound, is preferably the ammonium salt of phosphoric acid.

The following examples will the present invention will be further described.

Example 1

The preparation of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention.

Take by weighing overstable gamma zeolite that 500 gram sodium oxide contents are 4.3 heavy % (lattice constant is 2.468 nanometers, and Qilu Petrochemical company Zhou village catalyst plant is produced) and RECl ₃(produce in the chemical plant, packet header, wherein, in oxide, La ₂O ₃, CeO ₂With the weight ratio of other rare-earth oxides be 1: 2: 0.2.) the solution mixing, zeolite, RECl ₃With the weight ratio of water be 1: 0.135: 1.5.The slurries that obtain are placed JTM-50 vertical colloid mill (Xinguang Motive Power Machine Corp., Shenyang of Ministry of Astronautics Industry product), ground 5 minutes under 20 ℃ temperature, the shear stress of grinding is 20 kilograms per centimeter ²Filter, spend the deionised water solid product to there not being chlorion, 120 ℃ of oven dry obtain the used super-stable Y zeolite containing rare-earth elements B of catalyst provided by the invention.Its chemical composition and physico-chemical property are listed in the table 1.

Wherein, Na ₂O content adopts aas determination, the content of rare earth oxide, silica, aluminium oxide adopts the x-ray fluorescence spectrometry method to measure, the avalanche temperature adopts Differential scanning calorimetry to measure on Du Pont's 2100 type differential thermal analyzers, crystallization reservation degree and lattice constant adopt X-ray diffraction method to measure, and pore volume, specific surface adopt nitrogen adsorption capacity method to measure.

Example 2

The preparation of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention.

Taking by weighing sodium oxide content is overstable gamma zeolite (with example 1) 500 gram and the RECl of 4.3 heavy % ₃(with example 1) solution mixes zeolite, RECl ₃With the weight ratio of water be 1: 0.2: 2.0.The slurries that obtain are placed JTM-50 vertical colloid mill (with example 1), ground 5 minutes under 12 ℃ of temperature, grinding shear stress is 40 kilograms.Add 1: 1 ammoniacal liquor, regulate the pH value to 6.0 of slurries, continue to grind 5 minutes, filter, spend the deionised water solid product to there not being chlorion, 120 ℃ of oven dry obtain the used super-stable Y zeolite containing rare-earth elements C of catalyst provided by the invention.Its chemical composition and physico-chemical property are listed in the table 1.

Comparative Examples 1

Prepare super-stable Y zeolite containing rare-earth elements with ion-exchange.

Take by weighing described overstable gamma zeolite 500 grams that contain sodium oxide molybdena 4.3 heavy % of example 1, with 5000 ml concns be the RECl of 5 heavy % ₃(with example 1) solution mixes, and is warming up to 90 ℃, under agitation carries out ion-exchange 60 minutes, filters, and spends the deionised water solid product to there not being chlorion, and 120 ℃ of oven dry obtain reference super-stable Y zeolite containing rare-earth elements D.Its chemical composition and physico-chemical property are listed in the table 1.

Comparative Examples 2

Adopt the ion-exchange and the precipitation method to prepare the reference super-stable Y zeolite containing rare-earth elements.

Take by weighing described overstable gamma zeolite 500 grams that contain sodium oxide molybdena 4.3 heavy % of example 1, with 5000 ml concns be the RECl of 5 heavy % ₃(with example 1) solution mixes, be warming up to 90 ℃, under agitation carry out ion-exchange 60 minutes, be cooled to room temperature, add 1: 1 ammoniacal liquor, regulate the pH value to 6.0 of slurries, stirred 15 minutes, and filtered, spend the deionised water solid product to there not being chlorion, 120 ℃ of oven dry obtain reference super-stable Y zeolite containing rare-earth elements E.It is formed and physico-chemical property is listed in the table 1.

Table 1

The example deviation	The zeolite numbering	The chemical composition of zeolite, heavy %				The avalanche temperature, ℃	Crystallization reservation degree, %	Lattice constant, nanometer
									Na 2O	RE 2O 3	SiO 2	Al 2O 3
		1	B	0.8	5.8								74.5	18.9	1020	75	2.449
2	C					0.9	9.0	73.7	16.4	1015	76	2.449
		Comparative Examples 1	D	1.4	5.2								74.6	18.8	1009	75	2.450
Comparative Examples 2	E					1.3	8.5	73.5	16.7	1019	77	2.451

The result of table 1 shows, compare with Comparative Examples, adopt abrasive method, though the reaction time is short, temperature is also low, and the sodium oxide content of the super-stable Y zeolite containing rare-earth elements that obtains but obviously reduces, this explanation, adopt abrasive method, have more rare earth ion to substitute the sodium ion on the cation position, ion-exchange effect is better.

Example 3-4

Following example illustrates the hydrothermal stability of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention.

The super-stable Y zeolite containing rare-earth elements B and the C of example 1 and 2 preparations are handled with 100% water vapour at 800 ℃, crystallization reservation degree is over time successively shown among Fig. 11 and 2, successively shown among Fig. 25 and 6, pore volume reservation degree is successively shown among Fig. 39 and 10 over time for specific surface reservation degree.

Wherein, degree of crystallinity * 100% of the preceding zeolite of the degree of crystallinity/hydrothermal aging of zeolite behind crystallization reservation degree=hydrothermal aging; Specific surface * 100% of zeolite before the specific surface/hydrothermal aging of zeolite behind specific surface reservation degree=hydrothermal aging; Pore volume * 100% of zeolite before the pore volume/hydrothermal aging of zeolite behind pore volume reservation degree=hydrothermal aging.

Comparative Examples 3-4

The hydrothermal stability of following Comparative Examples explanation reference super-stable Y zeolite containing rare-earth elements.

Method by example 3 is carried out hydrothermal treatment consists to zeolite, different is with Comparative Examples 1 and the 2 reference zeolite D that prepare and E replacement B and C, crystallization reservation degree is over time successively shown among Fig. 13 and 4, successively shown among Fig. 27 and 8, pore volume reservation degree is successively shown among Fig. 3 11 and 12 over time for specific surface reservation degree.

The result of Fig. 1-3 shows that (1) and reference contain rare earth zeolite facies ratio, after hydrothermal treatment consists, the crystallization reservation degree of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention, specific surface reservation degree and pore volume reservation degree all are higher than the reference zeolite, (2) contain rare earth zeolite facies ratio with reference, with the prolongation of hydrothermal treatment consists time, the decrease speed of the crystallization reservation degree of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention, specific surface reservation degree and pore volume reservation degree is slower.This illustrates that the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention has the hydrothermal stability higher than prior art.

Example 5-6

Following example illustrates catalyst provided by the invention, its preparation and hydrothermal stability thereof.

(1) (solid content is 34.8 heavy % to take by weighing 24.4 gram (dry basis) boehmites, Shandong Aluminum Plant produces) and 70 gram deionized waters mixing making beating, adding 20 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, be warming up to 70 ℃ and wore out the boehmite slurries that obtain wearing out 1.5 hours.

(2) super-stable Y zeolite containing rare-earth elements 32 grams (dry basis), 50 with example 1 and 2 preparations restrain (dry basis) kaolin (solid content 85 heavy %, Suzhou kaolin company produces) respectively the aging boehmite with the preparation of (1) method of employing mix, obtain a kind of slurries, the solid content of these slurries is 30 heavy %, with these slurries 110 ℃ of oven dry, with the deionized water washing that is equivalent to 10 times of weights of solid particle once, 110 ℃ of oven dry, the solid product that obtains is ground into 20-40 purpose particle, obtains catalyst C provided by the invention ₁And C ₂Catalyst is formed and physico-chemical property is listed in the table 2.The catalyst composition is got by calculating.

(3) 800 ℃ with 100% water vapour to catalyst C ₁And C ₂Carrying out hydrothermal aging, is the catalyst C that raw material is estimated the processing of different hydrothermal aging time with straight distillation light diesel oil shown in the table 3 ₁And C ₂Light oil microactivity, be reflected in the small stationary bed bioreactor and carry out, reaction temperature is 460 ℃, weight (hourly) space velocity (WHSV) is 16 hours ^-1, agent weight of oil ratio is 3.2.Under the different ageing times, catalyst C ₁And C ₂Micro-activity shown among Fig. 4 13 and 14.Product adopts gas chromatographic analysis.

Wherein, light oil microactivity (MA) is calculated by following formula:

In the formula: W ₁It is heavy that-liquid is received oil, gram

W-feed oil is heavy, gram

A ₁-gasoline fraction spectrogram area

A ₂-fraction of diesel oil spectrogram area

Comparative Examples 5-6

Following Comparative Examples explanation reference catalyst, its preparation and hydrothermal stability thereof.

(1) presses the boehmite that (1) preparation among the example 5-6 is worn out.

(2) (2) of pressing among the example 5-6 prepare catalyst, and different just replaces super-stable Y zeolite containing rare-earth elements B and C respectively with Comparative Examples 1 and 2 reference zeolite D and the E that prepare respectively, obtains reference catalyst CB ₁And CB ₂, CB ₁And CB ₂Composition and physico-chemical property tabulation 2 in.

(3) press (3) hydrothermal aging catalyst CB among the example 5-6 ₁And CB ₂, and estimating its light oil microactivity in the same way, the result is successively shown among Fig. 4 15 and 16.

Table 2

Example number	The catalyst numbering	Contain the rare earth zeolite type	Catalyst is formed, heavy %			Specific surface, rice 2/ gram	Pore volume, milliliter/gram
								Zeolite	Al binder (in aluminium oxide)	Kaolin
			5	C 1	B						30.5	22.4	47.1	250	0.29
6	C 2	C				29.6	23.2	47.2	233	0.26
			Comparative Examples 5	CB 1	D						30.4	22.6	47.0	240	0.25
Comparative Examples 6	CB 2	E				30.1	22.4	47.5	222	0.23

Table 3

The feedstock oil title	Straight distillation light diesel oil
		Proportion (d 4 20), gram per centimeter 3	0.8620
Condensation point, ℃	-10
		Carbon residue, heavy %	0.128
S, heavy %	0.855
		Boiling range, the heavy % 5 10 30 50 80 90 95 of ℃ initial boiling point does	235 259 266 280 290 308 318 326 337

The result of table 2 and Fig. 4 shows, under 800 ℃ of situations with 100% water vapour hydrothermal aging different time, and catalyst C provided by the invention ₁And C ₂Micro-activity all be higher than reference catalyst CB ₁And CB ₂, and, with the prolongation of hydrothermal treatment consists time, reference catalyst CB ₁And CB ₂Active decrease speed is very fast, and catalyst C provided by the invention ₁And C ₂Activity descend slower.This has illustrated that catalyst provided by the invention has the hydrothermal stability higher than prior art.

Example 7-10

Following example illustrates the catalytic performance of catalyst provided by the invention.

With catalyst C ₁And C ₂Wore out 4 hours and 17 hours at 800 ℃ respectively.With vacuum gas oil (VGO) shown in the table 4 is the aging rear catalyst C of raw material evaluation ₁And C ₂Catalytic performance.Be reflected on the small stationary bed bioreactor and carry out, reaction temperature is 482 ℃, and weight (hourly) space velocity (WHSV) is 16 hours ^-1, agent weight of oil ratio is 4.The result is as shown in table 5.

Comparative Examples 7-10

The catalytic performance of following Comparative Examples explanation reference catalyst.

Press the method aging catalyst of example 7-10 and the performance of evaluate catalysts, different is to use catalyst CB ₁And CB ₂Replace catalyst C ₁And C ₂, the result is as shown in table 5.

Table 4

The feedstock oil title	Vacuum gas oil (VGO)
		Density (20 ℃), gram per centimeter 3	0.8652
Viscosity (50 ℃), millimeter 2/ second	14.58
		Viscosity (100 ℃), millimeter 2/ second	4.37
C 5Insoluble matter, heavy %	0.60
		C 7Insoluble matter, heavy %	0.026
Carbon residue, heavy %	0.04
		Sulfur content, heavy %	0.42
Boiling range, the heavy % 5 10 20 30 40 60 80 95 of ℃ initial boiling point does	227 274 289 322 347 373 401 431 458 475

Table 5

Example number	7	8	9	10	Comparative Examples 7	Comparative Examples 8	Comparative Examples 9	Comparative Examples 10
									Catalyst	C 1Aging 4 hours	C 1Aging 17 hours	C 2Aging 4 hours	C 2Aging 17 hours	CB 1Aging 4 hours	CB 1Aging 17 hours	CB 2Aging 4 hours	CB 2Aging 17 hours
Conversion ratio, heavy %	84.8	72.2	85.5	72.1	83.2	61.8	82.6	62.0
									Yield of light oil, heavy %	81.4	73.0	79.8	71.7	78.6	62.2	77.9	62.0
Product distributes, heavy %
									Gas	14.5	13.8	16.0	14.3	15.8	12.6	16.2	13.0
Gasoline	68.2	56.6	67.5	55.8	65.1	47.3	64.0	47.0
									Diesel oil	13.2	16.4	12.3	15.9	13.5	14.9	13.9	15.5
Heavy oil	2.0	11.4	2.2	12.0	3.3	23.3	3.5	22.5
									Coke	2.1	1.8	2.0	2.0	2.3	1.9	2.4	2.0

Wherein, conversion ratio=gas recovery ratio+yield of gasoline+coking yield; Yield of light oil=yield of gasoline+diesel yield, yield of gasoline=gasoline fraction weight/feedstock oil weight * 100%, the rest may be inferred by analogy.Here the boiling range of gasoline is C ₅-204 ℃, the diesel oil boiling range is 204-330 ℃, and heavy oil refers to boiling point greater than 330 ℃ cut, and gas is C ₅Following cut.

Example 11-12

Following example illustrates catalyst provided by the invention, its preparation and catalytic performance thereof.

Press the method for example 1, condition and each material proportioning will contain overstable gamma zeolite, RECl ₃Ground 5 minutes with the slurries of water, obtain containing the slurries of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention, 5.8 kilograms of (dry basis) slurries obtaining and 5.4 kilograms (dry basises) are mixed by the aging boehmite of the described method preparation of example 5-6 and 8.2 kilograms of described kaolin of (dry basis) example 5-6 and deionized water, obtaining a kind of solid content is the slurries of 32 heavy %, with these slurries at 650 ℃ of following spray drying formings, obtain the catalyst microballoon, with the P that contains of pH=3.4 ₂O ₅0.4 80 liters of washings of the ammonium phosphate solution of heavy % 2 times, 120 ℃ of oven dry obtain catalyst C provided by the invention ₃, its composition and physico-chemical property are shown in Table 6.

Press the method aging catalyst C of example 7-10 ₃, and evaluate catalysts C ₃The catalytic performance result as shown in table 7.

Example 13-14

Following example illustrates catalyst provided by the invention, its preparation and catalytic performance thereof.

Press the method for example 2, condition and each material proportioning will contain overstable gamma zeolite, RECl ₃Ground 5 minutes with the slurries of water, ground again 5 minutes after adding ammoniacal liquor, obtain containing the slurries of the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention, the slurries that 5.8 kilograms (dry basises) are obtained and 5.4 kilograms (dry basises) mix by the aging boehmite of the described method preparation of example 5-6 and 8.2 kilograms of described kaolin of (dry basis) example 5-6 and deionized water, obtaining a kind of solid content is the slurries of 28 heavy %, with these slurries at 650 ℃ of following spray drying formings, obtain the catalyst microballoon, use the method washing identical with example 11, drying obtains catalyst C provided by the invention ₄Catalyst C ₄Composition and physico-chemical property list in the table 6.

Press the method aging catalyst C of example 7-10 ₄, and evaluate catalysts C ₄Catalytic performance, the result is as shown in table 7.

Comparative Examples 11-12

The explanation of this Comparative Examples reference catalyst, its preparation and catalytic performance thereof.

Method by example 11 prepares catalyst, and different just replaces the example 11 described slurries that contain the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention with the slurries before the filtration of Comparative Examples 1 preparation, obtains reference catalyst CB ₃Catalyst CB ₃Composition and physico-chemical property list in the table 6.

Press the method aging catalyst CB of example 7-10 ₃, and evaluate catalysts CB ₃Catalytic performance, evaluation result is listed in the table 7.

Comparative Examples 13-14

The explanation of this Comparative Examples reference catalyst, its preparation and catalytic performance thereof.

Method by example 12 prepares catalyst, and different just replaces the example 12 described slurries that contain the used super-stable Y zeolite containing rare-earth elements of catalyst provided by the invention with the slurries before the filtration of Comparative Examples 2 preparations, obtains reference catalyst CB ₄Catalyst CB ₄Composition and physico-chemical property list in the table 6.

Press the method aging catalyst CB of example 7-10 ₄And evaluate catalysts CB ₄Catalytic performance, evaluation result is listed in the table 7.

Table 6

Example number	The catalyst numbering	Contain the rare earth zeolite type	Catalyst is formed, heavy %				Specific surface, rice 2/ gram	Pore volume, milliliter/gram
									Zeolite	Binding agent	Kaolin	P 2O 5
			11	C 3	B	29.7							26.5	40.7	3.1	260	0.28
12	C 4	C					29.9	26.8	40.4	2.9	255	0.25
			Comparative Examples 11	CB 3	D	29.8							27.3	40.2	2.7	235	0.27
Comparative Examples 12	CB 4	E					29.7	26.9	40.6	2.8	240	0.28

Table 7

Example number	11	12	13	14	Comparative Examples 11	Comparative Examples 12	Comparative Examples 13	Comparative Examples 14
									Catalyst	C 3Aging 4 hours	C 3Aging 17 hours	C 4Aging 4 hours	C 4Aging 17 hours	CB 3Aging 4 hours	CB 3Aging 17 hours	CB 4Aging 4 hours	CB 4Aging 17 hours
Conversion ratio, heavy %	85.6	74.0	86.5	73.1	83.3	63.3	84.9	63.1
									Yield of light oil, heavy %	80.3	74.9	79.6	73.8	78.4	63.5	78.1	64.9
Product is formed, heavy % casing head gasoling diesel oil heavy oil coke	15.7 67.9 12.4 2.0 2.0	13.7 58.4 16.5 9.5 1.9	16.3 68.1 11.5 2.0 2.1	13.5 57.8 15.2 11.7 1.8	16.7 64.3 14.1 2.6 2.3	13.2 48.0 15.5 21.2 2.1	17.0 65.7 12.4 2.7 2.2	12.7 48.4 16.5 20.4 2.0

Example 15

Following example illustrates the anti-sodium pollutant performance of catalyst provided by the invention.

Take by weighing the catalyst C of 50 gram examples, 13 preparations respectively ₄Be 6 heavy % with concentration respectively, 4 heavy %, this catalyst of NaCl solution impregnation of 2 heavy %, 120 ℃ of oven dry, obtain containing sodium oxide molybdena 0.5 heavy %, 1.0 the catalyst after the polluting of heavy % and 1.5 heavy % with sodium, with the catalyst before and after polluting respectively 800 ℃ with 100% steam treatment 4 hours, be raw material with straight distillation light diesel oil shown in the table 3, estimate the light oil microactivity of the catalyst of hydrothermal treatment consists after stain front and back, reaction unit and condition are with (3) among the example 5-6.Active reservation degree with the variation of sodium content shown among Fig. 5 17.

Comparative Examples 15

The anti-sodium pollutant performance of following Comparative Examples explanation reference catalyst.

Press the method NaCl solution impregnation catalyst of example 15, the light oil microactivity of the catalyst before and after sodium polluted after catalyst was carried out hydrothermal treatment consists and estimates hydrothermal treatment consists, different is that catalyst system therefor is reference catalyst CB ₄, active reservation degree with the variation of sodium content shown among Fig. 5 18.

From the result of Fig. 5 as can be seen, improve reference catalyst CB with the sodium content that pollutes in the catalyst ₄Activity reservation degree descend and catalyst C provided by the invention fast ₄Active reservation degree descends slower, and this has illustrated that catalyst provided by the invention has higher anti-sodium pollutant performance.

Example 16-17

With anti-vanadium performance is example, and the preventing from heavy metal pollution ability of catalyst provided by the invention is described.

Take by weighing 2 parts of catalyst C ₃Each 100 gram, mix with 0.9 milligram and 1.8 milligrams of vanadic anhydrides respectively, grind into powder, is smashed to pieces, is sieved and get 20-40 purpose particle compression molding, the particle that obtains was handled 4 hours under 800 ℃ of 100% water vapour atmosphere respectively, obtained catalyst with pollution of vanadium.With straight distillation light diesel oil shown in the table 3 is the micro-activity of raw material evaluation with the catalyst of pollution of vanadium, and compares with the untainted light oil microactivity of handling 4 hours catalyst under 800 ℃ of 100% water vapour atmosphere, obtains light oil microactivity reservation degree.Content of vanadium in the catalyst and light oil microactivity reservation degree are listed in the table 8.

Wherein, light oil microactivity evaluating apparatus and reaction condition are with (3) among the example 5-6.The light oil microactivity of the catalyst of light oil microactivity reservation degree=usefulness pollution of vanadium/through light oil microactivity * 100% of the pollution of vanadium procatalyst of similarity condition hydrothermal treatment consists.

Comparative Examples 16-17

With anti-vanadium performance is example, and the preventing from heavy metal pollution ability of reference catalyst is described.

Catalyst is carried out pollution of vanadium and measure its light oil microactivity reservation degree by the method for example 16-17, different is to use reference catalyst CB ₃Replaced C ₃, the results are shown in Table 8.

Table 8

Example number	Catalyst	Content of vanadium in the catalyst, ppm	Light oil microactivity reservation degree, %
				16	C 3	5000	95
17	C 3	10000	90
				Comparative Examples 16	CB 3	5000	85
Comparative Examples 17	CB 3	10000	76

From the result of table 8 as can be seen, after polluting 5000ppm and 10000ppm vanadium, activity of such catalysts reservation degree provided by the invention is respectively up to 95% and 90%, and the activity reservation degree of reference catalyst drops to 85% and 76% respectively, this result shows, compared with prior art, catalyst provided by the invention has stronger preventing from heavy metal pollution ability.

Claims (28)

1. catalytic cracking catalyst that contains overstable gamma zeolite, contain a kind of overstable gamma zeolite and a kind of catalyst carrier or matrix, it is characterized in that, described overstable gamma zeolite is a kind of super-stable Y zeolite containing rare-earth elements, with the total catalyst weight is benchmark, and the content of described super-stable Y zeolite containing rare-earth elements is the heavy % of 5-60, and the content of catalyst carrier or matrix is the heavy % of 40-95, this catalyst also contains, with P ₂O ₅Meter, the phosphorus of the heavy % of 0-8, described super-stable Y zeolite containing rare-earth elements adopts following method preparation: the overstable gamma zeolite of the heavy % of sodium oxide content 3-5 is mixed with a kind of rare earth compound solution, make a kind of slurries, the slurries that obtain are ground, wherein, in the described slurries, the weight ratio of overstable gamma zeolite, rare earth compound and water is 1: 0.001-0.5: 1-10, the shear stress of grinding is at least 10 kilograms per centimeter ²Grinding temperature is 5-100 ℃, milling time is no less than 1 minute, described catalyst carrier or matrix are carrier or the matrix that is commonly used for catalytic cracking catalyst, described rare earth compound is selected from one or more in the water-soluble rare earth compound of energy, and described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium.

2. catalyst according to claim 1 is characterized in that, the content of described super-stable Y zeolite containing rare-earth elements is the heavy % of 5-35, and the content of catalyst carrier or matrix is the heavy % of 65-95.

3. catalyst according to claim 1 is characterized in that, the shear stress of described grinding is the 10-100 kilograms per centimeter ²

4. catalyst according to claim 3 is characterized in that, the shear stress of described grinding is the 10-50 kilograms per centimeter ²

5. catalyst according to claim 1 is characterized in that, described milling time is 2-10 minute.

6. catalyst according to claim 1 is characterized in that described rare earth compound refers to the chloride of rare earth.

7. according to claim 1 or 6 described catalyst, it is characterized in that described rare earth is selected from lanthanum rich mischmetal or cerium-rich mischmetal.

8. catalyst according to claim 1 is characterized in that, the weight ratio of described overstable gamma zeolite, rare earth compound and water is 1: 0.05-0.3: 1-4.5.

9. catalyst according to claim 1 is characterized in that, in the super-stable Y zeolite containing rare-earth elements preparation process, also is included in after the grinding, adds a kind of alkaline solution, makes the pH value of slurries rise to 5-10, and continues to grind at least 1 minute.

10. catalyst according to claim 9 is characterized in that, the amount that adds alkaline solution makes the pH value of slurries rise to 6-8, and milling time is 2-10 minute.

11., it is characterized in that described alkaline solution is an ammonia spirit according to claim 9 or 10 described catalyst.

12. catalyst according to claim 1 is characterized in that, described catalyst carrier is the mixture of al binder and clay, with the total catalyst weight is benchmark, the content of super-stable Y zeolite containing rare-earth elements is the heavy % of 5-60, and the content of al binder is the heavy % of 10-45, and clay content is the heavy % of 30-60.

13. catalyst according to claim 12 is characterized in that, the content of described super-stable Y zeolite containing rare-earth elements is the heavy % of 5-35, and the content of al binder is the heavy % of 20-40, and clay content is the heavy % of 40-60.

14. according to claim 12 or 13 described catalyst, it is characterized in that described al binder is selected from aluminium colloidal sol and/or boehmite, described clay refers to kaolin.

15. claim 1 Preparation of catalysts method, this method comprises and will form the material of catalyst carrier or their precursor, a kind of overstable gamma zeolite or the slurries and the water that contain a kind of overstable gamma zeolite are pulled an oar together, dry, washing is also dry once more, it is characterized in that, described overstable gamma zeolite is a kind of overstable gamma zeolite that contains rare earth, it is that the overstable gamma zeolite of the heavy % of 3-5 mixes with a kind of rare earth compound solution that this preparation method who contains the overstable gamma zeolite of rare earth comprises sodium oxide content, make a kind of slurries, the slurries that obtain are ground, wherein, in the described slurries, overstable gamma zeolite, the weight ratio of rare earth compound and water is 1: 0.001-0.5: 1-10, grind shear stress and be at least 10 kilograms per centimeter ²Grinding temperature is 5-100 ℃, milling time is no less than 1 minute, described catalyst carrier or matrix are carrier or the matrix that is commonly used for catalytic cracking catalyst, described rare earth compound is selected from one or more in the water-soluble rare earth compound of energy, and described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium.

16. method according to claim 15, it is characterized in that, the material of described composition catalyst carrier is al binder and clay, al binder is selected from aluminium colloidal sol and/or boehmite, described clay refers to kaolin, it is the heavy % of 20-40 that the consumption of aluminium colloidal sol and/or boehmite, kaolin, super-stable Y zeolite containing rare-earth elements and deionized water makes the solid content of slurries, and make the super-stable Y zeolite containing rare-earth elements that contains the heavy % of 5-60 in the final catalyst, in aluminium oxide, the kaolin of the al binder of the heavy % of 10-45 and the heavy % of 30-60.

17. method according to claim 16, it is characterized in that, the consumption of described aluminium colloidal sol and/or boehmite, kaolin, super-stable Y zeolite containing rare-earth elements and deionized water makes the super-stable Y zeolite containing rare-earth elements that contains the heavy % of 5-35 in the final catalyst, in aluminium oxide, the kaolin of the al binder of the heavy % of 20-40 and the heavy % of 40-60.

18. method according to claim 15, it is characterized in that, this method also is included in when forming material or their precursor, a kind of overstable gamma zeolite of catalyst carrier or containing a kind of slurries making beating of overstable gamma zeolite, add a kind of phosphorus compound in slurries, the addition of phosphorus compound makes the P that contains the heavy % of 0.4-8 in the catalyst ₂O ₅

19. method according to claim 18 is characterized in that, the addition of phosphorus compound makes the P that contains the heavy % of 0.5-5 in the catalyst ₂0 ₅

20. method according to claim 15 is characterized in that, described washing comprises with containing P ₂O ₅0.1-10 the phosphorus-containing compound solution washing that heavy %pH value is 2.5-10 at least once, when washing, the consumption of phosphorus-containing compound solution is 5-20 a times of catalyst weight at every turn.

21. method according to claim 20 is characterized in that, described phosphorus-containing compound contains P ₂O ₅0.1-5 heavy %, the consumption of phosphorus-containing compound solution are 10-15 times of catalyst weight.

22. method according to claim 15 is characterized in that, the shear stress of described grinding is the 10-100 kilograms per centimeter ²

23. method according to claim 22 is characterized in that, the shear stress of described grinding is the 10-50 kilograms per centimeter ²

24. method according to claim 15 is characterized in that, described milling time is 2-10 minute.

25. method according to claim 15 is characterized in that, the weight ratio of described overstable gamma zeolite, rare earth compound and water is 1: 0.05-0.3: 1-4.5.

26. method according to claim 15 is characterized in that, in the preparation process of super-stable Y zeolite containing rare-earth elements, also comprises, after grinding, adds a kind of alkaline solution, makes the pH value of slurries rise to 5-10, and continues to grind at least 1 minute.

27. method according to claim 26 is characterized in that, adds the amount of alkaline solution, makes the pH value of slurries rise to 6-8, milling time 2-10 minute.

28., it is characterized in that described alkaline solution refers to ammonia spirit according to claim 26 or 27 described methods.

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