CN106140256B - A kind of modified Y zeolite and preparation method thereof - Google Patents

Abstract

A kind of modified Y zeolite and preparation method thereof, the modified Y zeolite contains Group IVB metal oxide and phosphorus, and the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is 0.2~0.8 in the modified Y zeolite lattice structure：1, zeolite surface Group IVB tenor and the ratio of zeolite interior Group IVB tenor are not higher than 0.5.The zeolite preparation method include the steps that acid processing zeolite materials, dehydration, in organic solvent impregnating metal, handle the impregnating metal in organic solvent zeolite, handle metal-modified Y zeolite with phosphorous compound and roast.The modified Y zeolite has for residual oil cracking compared with high cracking activity, higher yield of gasoline, lower coke yield.

Description

A kind of modified Y zeolite and preparation method thereof

Technical field

The present invention relates to a kind of modified Y zeolites, more specifically to one kind for hydrocarbon ils in the absence of hydrogen Y zeolite, preparation method and the application in catalytic cracking of the metal containing Group IVB of processing.

Background technique

Rare earth modified Y zeolite is largely paid close attention to, people for a long time as most common FCC catalyst active component Trial is adopted to be made improvements in various manners, to improve the activity, selectivity and stability of catalyst.Rare earth ion can be significant The structural stability for enhancing Y zeolite, has obtained common recognition, it is generally accepted that rare earth ion exists in the form of hydrated ion, such as RE (H₂O)_n ³⁺, in roasting and hydrothermal treatment process, part rare earth ion goes hydration to generate RE (OH)²⁺, and from Y zeolite supercage to β It migrates and positions in cage, support and stabilization are played to Y skeleton structure of zeolite.Rare earth ion can also modulation Y zeolite acidity, Generally, it is considered that rare earth ion effectively attracts OH by polarization to hydrone and inducing action^-, while discharging H⁺。

However, rare earth is as important strategic resource and its non-renewable, rare earth rapid rise of price, makes in causing in recent years FCC catalyst cost steeply rises.How to reduce the content of rare earth in FCC catalyst and make obtained molecular sieve have compared with High hydrothermal stability becomes current problem in the urgent need to address.

CN1350887A is disclosed a kind of while being contained noble metal and non-noble metal modified Y zeolite and preparation method thereof, is led to It crosses and noble metal and non-noble metal ion exchange, hydro-thermal process and ammonium salt exchange is carried out to NaY zeolite raw material, finally make Obtain the noble metal containing 0.05 weight %~2.0 weight %, the non-noble metal modified Y zeolite of 0.5 weight %~15.0 weight %. CN1765492A discloses a kind of alumina support and preparation method thereof of zeolite containing Y, and wherein modified Y zeolite is using Section VI B What race and/or one or more of group VIII metal W, Ni, Co, Fe, Mo were modified by way of cation exchange. US2007010698A1 discloses a kind of carbon monoxide-olefin polymeric, is boiled comprising a kind of with lanthanide series and the Y of group VIIIB metal exchange Stone, the group VIIIB metal are mainly selected from platinum and palladium, using ion exchange and dipping method by lanthanide series saline solution and Group VIIIB aqueous metal salt handles Y zeolite.

The preparation method for the metal-modified Y zeolite that the above patent of invention provides mainly uses ion exchange and dipping method Y zeolite is handled with aqueous metal salt.Obtained metal-modified Y zeolite hydrothermal stability is not high, is used for cracking hydrocarbon oil gasoline Yield is not high.

CN101898144A and CN101134576A, which provides a kind of appropriate hetero atom of selection, to carry out skeleton to Y zeolite and changes Property, the method for raising Y zeolite heat and hydrothermal stability.This method includes using Direct Hydrothermal crystallization synthetic method, is added suitable Hetero atom prepares the MY type zeolite containing cage heteroatom, and MY zeolite is carried out secondary NH₄ ⁺Ion exchange and after baking, A small amount of hetero atom of the same race is added before after baking processing, obtains super steady heteroatom zeolite USMY, thermal stability and hydrothermally stable Property significantly improved than conventional USY zeolite.The non-rare-earth metal modified Y zeolite that above method obtains is used for its gasoline of catalytic cracking Yield is not high.

Also have in the prior art using P Modification Y zeolite, to change cracking activity, stability or the selectivity of Y zeolite.Example Such as, EP 397183 exchanges NaY using ammonium sulfate in advance makes Na in zeolite₂O is 1~5 heavy %, then and selected from H₃PO₄、(NH₄)₂HPO₄、NH₄H₂PO₄And NaH₂PO₄Phosphorus-containing compound, in pH=4~7, temperature be 20~350 DEG C at mix, drying P- is made NaHNH₄Y, P₂O₅Content be 0.1~4%, and roasted under 500~700 DEG C, 10~100% vapor, obtain P Modification Y zeolite.CN1104955C discloses a kind of hydrocarbon cracking catalyzer containing new modified Y zeolite, wherein new modified Y zeolite Using NaY zeolite as raw material, by primary phosphorous ammonium salt solution exchange and a superheated vapor roasting, i.e., " one hands over a roasting " preparation is Technique is made phosphorous Y zeolite, thereby simplifies the preparation process of Cracking catalyst molecular sieve active component.It is existing only to pass through Its hydrothermal stability of the Y molecular sieve of P Modification is not high.

CN 101823726B discloses a kind of modified Y molecular sieve, is carried out once by NaY molecular sieve and earth solution Then exchange reaction introduces phosphorus compound in exchange slurries, further reacts, by being filtered, washed, filter cake is in water vapor condition What lower roasting obtained.2.450~2.479 sodium rice of lattice constant of the modified Y molecular sieve, wherein 2.0~6.0 weight containing sodium oxide molybdena Measure %, 0.01~2.5 weight % of phosphorus, 11~23 weight % of rare earth oxide.CN 1111136C discloses a kind of phosphorous and rare earth The preparation method of Y type molecular sieve, this method include that NaY molecular sieve is first used to ammonium ion and rare earth ion exchanged and hydrothermal calcine, Then by the P of itself and 0.2~10 weight % in phosphorus compound reaction bonded₂O₅, then carry out hydrothermal calcine.It is replaced with other metals The molecular sieve performance containing metal and phosphorus that rare earth is modified according to the method described above is poor.

Molecular sieve needs hydrothermal stability with higher for catalytic cracking process, however, with rare earth modified Y zeolite phase Than the heat of other metal-modified Y zeolites and hydrothermal stability are poor outside existing rare earth, are catalyzed to affect it in catalytic cracking Application in agent.

Summary of the invention

The technical problem to be solved by the present invention is to the metal-modified Y zeolite of existing IV B race there are aiming at the problem that, one kind is provided Modified Y zeolite and preparation method thereof containing Group IVB metal and phosphorus, the Group IVB metal which prepares than existing methods Modified Y zeolite has higher heat and hydrothermal stability.The present invention further provides the application methods of the modified Y zeolite.

The present invention provides a kind of modified Y zeolite, and on the basis of the weight of the modified Y zeolite, the modified Y zeolite contains The Group IVB metal oxide of 1~15 weight % such as 1~10 weight %, contains in terms of P 0.1~10.0 weight % phosphorus；It is described to change Property Y zeolite lattice structure in the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum be (0.2~0.8)：1, zeolite surface The ratio of Group IVB tenor and zeolite interior Group IVB tenor is not higher than 0.5.

Preferably, the modified Y zeolite, cell parameter are 2.448~2.458nm, and specific surface area is 600~850m²/ g, Crystallinity is not less than 60%.

Modified Y zeolite (also referred to as IV B race metal and the composite modified Y zeolite of phosphorus) provided by the invention, contains modified metal, institute The modified metal stated is Group IVB metal, and the Group IVB metal is selected from one or more of Ti, Zr, Hf, Rf, preferably Ti, Zr One or both of.The modified Y zeolite contains in terms of oxide (with MO₂Meter, M represent IV B race metal) 1~15 weight The IV B race metallic element of % is measured, the content of IV B race metallic element is preferably 1~10 weight %.The modified Y zeolite Contain 0.1~10.0 weight % of phosphorus (in terms of P), preferably 0.5~6.0 weight %.

In the modified Y zeolite lattice structure ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum be (0.2~ 0.8)：1, for example, 0.2~0.7:1 or (0.3~0.6):1.The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is used²⁷The ratio of spectral peak area and spectral peak area at chemical shift 60 indicates at the chemical shift 40 that Al MAS NMR method measures.

The modified Y zeolite provided by the invention, IV B race metal ion are predominantly located in zeolite interior, a small amount of to be located at boiling The ratio of stone surface, IV B race tenor of zeolite surface and IV B race tenor of zeolite interior is not higher than 0.5, for example, 0.001~0.5 is, for example, 0.2~0.5 for example, 0.01~0.35.IV B race tenor of zeolite surface refers to using X-ray light Electronic spectroscopy (XPS) analyzes the IV B race tenor measured within the scope of 2~5nm of zeolite surface.IV B race of zeolite interior gold Belong to the difference that content refers to IV B race tenor of zeolite ontology Yu IV B race tenor of zeolite surface, wherein IV B of zeolite ontology Race's tenor is the content of IV B race metal in the zeolite analyzed by chemical method.

The modified Y zeolite, 2.448~2.458nm of cell parameter are, for example, 2.450~2.455nm, specific surface area 600 ~850m²/ g is preferably 600~750m²/ g, crystallinity are, for example, 60~120% not less than 60% or are 60~95%.

The preparation method of modified Y zeolite provided by the invention includes the following steps：

(1) Y zeolite is contacted with acid solution and/or EDTA aqueous solution contact treatment；The acid is organic acid and/or nothing Machine acid；

(2) step (1) products therefrom is dehydrated in 400 DEG C or less, makes the water content in zeolite not higher than 5 weight %；

(3) zeolite for obtaining step (2) impregnating metal in organic solvent；

(4) the Y zeolite for the impregnating metal for obtaining step (3) and organic solvent are according to solid and liquid weight than 1：(5~50) in It is mixed in reactor, is filled with one of inert gas such as nitrogen, helium or a variety of, in 0.0~2.0MPa of pressure (gauge pressure) Such as at least 1 hour, such as 1~48 hour are kept at 0.1~2MPa, room temperature~200 DEG C；Optionally filtering, optionally drying, preferably It is filtered and dries；

(5) zeolite by step (4) processing roasts in an inert gas atmosphere, and 300~700 DEG C of maturing temperature, roasting Time is 0.5 hour or more, such as 0.5~5 hour.

(6) the Y zeolite obtained by the aqueous solution contact procedure (5) containing phosphorus compound, phosphorus (in terms of P) and Y zeolite are (with butt Meter) weight ratio 0.001~0.1, it is small that the Y zeolite after contact is roasted to 0.5~5 under 300~800 DEG C, 100% water vapour When, obtain the composite modified Y zeolite containing IV B race metal and phosphorus.

In the preparation method of the modified Y zeolite provided by the invention, make in step (1) Y zeolite and acid solution and/or The contact of EDTA aqueous solution, handles Y zeolite.Contact described in step (1) can be for according to solid-to-liquid ratio 1：5~20 weight Amount than make Y zeolite (in terms of butt) and acid solution and/or EDTA aqueous solution contacted at 0~100 DEG C of such as room temperature~100 DEG C to It is such as 0.5~3 hour 0.5 hour few, then it is filtered, washed；Sour concentration is in the acid solution with H⁺It is calculated as 0.1~1mol/ L, such as 0.2~0.5mol/L or can be 0.5~1mol/L.In the EDTA aqueous solution concentration of EDTA be 0.1~ 1mol/L is, for example, 0.2~0.8mol/L.The washing can with water for example with deionized water, distillation water washing, to wash away zeolite In acid, such as the mass ratio of water and zeolite can be 5~20：1.The acid solution is the aqueous solution of acid.The acid is inorganic Acid and/or organic acid, the inorganic acid such as one of hydrochloric acid, sulfuric acid and nitric acid or a variety of；The organic acids such as formic acid, One or more of acetic acid, oxalic acid, citric acid.The wherein Y zeolite materials, can be selected from NaY, NaHY, NaNH₄Y、NH₄Y、 HY, USY, one hand over a roasting Y zeolite, DASY zeolite, two that two roasting Y zeolites, two is handed over to hand over one of roasting Y zeolite or a variety of.Wherein Described one hands over a roasting Y zeolite to be, for example, NaY zeolite by primary exchange and once roast obtained Y zeolite, and DASY zeolite is for example For the Y zeolite that Y zeolite roasts in the presence of water vapor, two hand over two roasting Y zeolites be, for example, NaY zeolite by exchange twice and The Y zeolite that double roasting obtains；Two hand over a roasting Y zeolite to be, for example, NaY zeolite by exchange twice and once roast obtained Y boiling Stone, it is preferred that described to be exchanged for using H⁺And/or NH₄ ⁺It swaps.The room temperature is 15~40 DEG C.

In the preparation method of modified Y zeolite of the present invention, in treated the zeolite that step (1) obtains Na₂O content is preferably no greater than 4.0 heavy %, Na in more preferable zeolite₂O content is not higher than 2.0 heavy %.

By the zeolite dehydration after being contacted obtained by step (1) with acid solution and/or EDTA aqueous solution in step (2), it is preferable over It is roasted at 200~400 DEG C such as 300~350 DEG C to remove absorption water, the roasting makes the water content in zeolite not higher than 5 weights % is measured, such as not higher than 3 weight %, calcining time can be 2~10 hours, for example, 2~4 hours；Zeolite consolidates after roasting Content (calcination alkali number) is not less than 95 weight %, such as not less than 97 weight %, for example, 97~99.9 weight %.

The zeolite for obtaining step (2) described in step (3) impregnating metal in organic solvent, including will be dissolved with IV B The organic solvent of race's metallic compound is mixed with the zeolite that step (2) obtains, and holding 0.5 is small under stirring or standing (without stirring) When more than such as 0.5~12 hour, such as under stiring keep 0.5~12 hour, then carry out next step process for example into Row step (4) repeats dipping described in step (3).Wherein the solid-to-liquid ratio (for weight ratio) of Y zeolite and organic solvent can be 1：(0.5~5) is, for example, 1：(1~2).Modified metal i.e. IV B can be introduced in Y zeolite by one or many be immersed in Race's metal.The Group IVB metal is selected from one or more of Ti, Zr, Hf, Rf, preferably one or both of Ti, Zr, institute State one of compound that IV B race metallic compound is the compound of Ti, the compound of Zr, the compound of Hf, Rf or a variety of The for example, compound of the compound of Ti and/or Zr.The IV B race metallic compound can be the inorganic salts of IV B race metal And/or organo-metallic compound, such as the compound of titanium can be titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, titanium One of sour four butyl esters, ammonium titanium fluoride are a variety of.The compound of zirconium can be zirconium chloride, zirconium sulfate, zirconium nitrate, oxychlorination One of zirconium, acetic acid zirconium, zirconium iso-propoxide are a variety of.The water content of the organic solvent be lower than 5 weight %, preferably more than 3 Weight % is for example no more than 1 weight %.Organic solvent can be alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, one in halogenated alkane Kind is a variety of, and preferably 40~100 DEG C of the normal boiling point of the organic solvent.The preferred n-hexane of the organic solvent, hexamethylene, One of heptane, benzene, toluene, methanol, ethyl alcohol, isopropanol, acetone, butanone, chloroform are a variety of.Step (3) described leaching Stain, wherein the solid-to-liquid ratio of zeolite and organic solvent can be 1:(1~4) weight ratio, for example, 1：(1.1~1.6).When dipping Temperature makes organic solvent liquid.The dipping can use equi-volume impregnating or excessive impregnation method.Dipping temperature does not have Particular/special requirement can for example impregnate at room temperature.

Step (4) handles the zeolite sample after dipping that step (3) obtains, including the leaching for obtaining step (3) Zeolite and organic solvent after stain are set in a reaction vessel such as an autoclave, and one of inert gas such as nitrogen, helium is filled with Or it is a variety of, it is kept at least under standing or stir at pressure (gauge pressure) 0.0~2.0MPa preferably 0.1~2MPa, room temperature~200 DEG C 1 hour, usually 1~48 hour was, for example, 2~24 hours；The pressure is preferably 0.5~1.5MPa, and the temperature is for example It is room temperature~150 DEG C such as room temperature to 90 DEG C, the retention time is preferably 4~24 hours.Then it optionally filters and/or dry It is dry, it preferably filters and dry, zeolite is separated with organic solvent, the filtering, drying can be carried out according to existing method, can Can be using existing drying means such as pneumatic conveying drying, flash drying, spray drying, drying, such as the temperature of the drying 100~200 DEG C, the time of the drying can be 1s~2 day, such as can dry 6~24 hours.Wherein molecular sieve with it is organic The weight ratio (solid-to-liquid ratio of molecular sieve and organic solvent) of solvent is 1：(5~50), such as 1：(5~30) or 1：(5~10).Step Suddenly organic solvent used in (4) may be the same or different with organic solvent used in step (3)；In general, step (4) is used to be had Organic solvent used in solvent and step (3) is organic solvent of the same race.

The obtained product of step (4) is roasted in step (5), the roasting carries out in an inert gas atmosphere, roasts Temperature is 300~700 DEG C, and calcining time is 0.5~5 hour, such as maturing temperature is 450~650 DEG C or 500~600 DEG C, roasting Burning the time is 1~4 hour.One of described inert gas such as nitrogen, helium is a variety of.

The Y zeolite obtained by aqueous solution contact procedure (5) containing phosphorus compound described in step (6), including by step (5) Gained Y zeolite, phosphorus compound and deionized water are according to zeolite (butt)：P：Water=1：(0.001~0.10)：The weight of (5~40) Amount ratio is mixed with beating, and slurry temperature is raised to 40~100 DEG C and stirs 0.5~5 hour, is filtered and is washed with water, after then handling Y zeolite roasted 0.5~5 hour under 300~800 DEG C, 100% water vapour, obtain containing IV B race metal (such as titaniferous or/ Zirconium) and the composite modified Y zeolite of phosphorus obtain modified Y zeolite provided by the present invention.

Phosphorus compound described in step (6) for example can be orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen Diammonium, aluminum phosphate, pyrophosphoric acid can be one of or a variety of.

The present invention also provides a kind of catalytic cracking catalysts, on the basis of the total catalyst weight, contain 10~60 weights The heat-resisting of the modified Y zeolite of % such as 20~60 weight % aforementioned present invention offer, the clay of 10~60 weight % and 5~50 weight % is provided Inorganic oxide matrix, it is preferred that the catalytic cracking catalyst contains the modification Y of 20~55 weight % aforementioned present invention offer Zeolite, the heat-resistant inorganic oxide matrix of the clay of 15~60 weight % and 10~40 weight %.

The present invention also provides the preparation method of the catalytic cracking catalyst, including formed include the modified Y zeolite, The step of slurries of clay, heat-resistant inorganic oxide matrix and water, spray drying optionally includes calcination steps.The formation packet The slurries for including the modified Y zeolite, clay, heat-resistant inorganic oxide matrix and water, can in any way, for example, will go Then ionized water, clay and heat-resistant inorganic oxide matrix, which are mixed with beating, is added modified Y zeolite into gained slurries.The present invention The prior art can be used in spray drying described in the catalytic cracking catalyst preparation method, roasting, this is those skilled in the art Well known to member.

The present invention is provided in the catalytic cracking catalyst, and the clay can be selected from clay well known to the technical staff of field It is one or more, such as in kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite, sepiolite One or several kinds of mixtures；.

Catalytic cracking catalyst preparation method provided by the invention, the heat-resistant inorganic oxide matrix is optional cracking to urge One of common inorganic oxide matrix of agent or a variety of, such as being customarily used in the binder of catalytic cracking catalyst one Kind is a variety of.The binder is the substance that heat-resistant inorganic oxide can be formed after roasting, and wherein heat-resistant inorganic oxide is oxygen Change one or more of aluminium, silica, amorphous silicon aluminium, preferably aluminium oxide.The preferred hydrated alumina of the binder, aluminium are molten One of glue, boehmite, boehmite, hibbsite, monohydrate alumina, amorphous hydroted alumina are several Kind, with γ-Al after these various forms of binder roastings₂O₃Form exists.

Modified Y zeolite provided by the invention, contains IV B race metallic element and P elements, and IV B race metallic element of surface contains Amount is lower than the Group IVB tenor of zeolite interior, and IV B race modified metal element a part is another in zeolite surface high degree of dispersion Part enters zeolite interior and skeleton [AlO₄] interaction, without in zeolite surface aggregation characteristic, distorted tetracoordinate skeleton aluminum ratio Example is higher, and crystallinity is high, large specific surface area, has high heat and hydrothermal stability, has good coke selectivity, have compared with High cracking activity and selectivity.In the preparation method of modified Y zeolite provided by the invention, to treated Y zeolite, first adopt The IV B race metal is introduced with the method that organic solvent impregnates, is then carried out P Modification, last hydrothermal calcine can be with The Y zeolite with high thermal stability and hydrothermal stability is obtained, the cracking activity and selectivity of zeolite can be significantly improved, is improved burnt Charcoal selectivity.Compared with IV B race metallic element modified Y zeolite of existing method preparation, the zeolite that the method for the present invention obtains has Higher crystallinity, higher hydrothermal stability and bigger specific surface area.Compared with existing rare earth modified Y zeolite, work as metal When oxide content is suitable, modified Y zeolite provided by the invention has quite even preferably hydrothermal stability.The present invention is mentioned The modified Y zeolite of confession is suitable for preparing catalytic cracking catalyst, can substitute rare earth modified Y zeolite, can significantly reduce catalyst Production cost.

Cracking catalyst provided by the invention, cracking activity with higher, gasoline yield with higher have higher Liquid receive, coke selectivity is preferable.And the Cracking catalyst for using modified Y zeolite provided by the invention to prepare for active component There is lower coke yield for hydrocarbon oil catalytic cracking.

Cracking catalyst provided by the invention can be used for the catalytic cracking of hydro carbons.Compared with prior art, the present invention provides Modified Y zeolite Cracking catalyst heavy oil yield reduce, gasoline yield increase, while coke yield decline, coke selectivity It significantly improves.With it is existing containing the Cracking catalyst of rare earth modified Y zeolite compared with, Cracking catalyst provided by the invention has suitable Even higher heavy oil conversion performance and gasoline yield, and coke yield significantly reduces.

Detailed description of the invention

Fig. 1 is embodiment 3, the XRD spectra of modified Y zeolite prepared by embodiment 6, comparative example 3~4.

Fig. 2 is the XRD spectra of modified Y zeolite prepared by embodiment 6 and comparative example 6.

Fig. 3 is modified Y zeolite prepared by standard Y zeolite (in figure label be), embodiment 3, embodiment 5, comparative example 5 FT-IR spectrogram.

The modified Y zeolite that Fig. 4 is embodiment 3, prepared by comparative example 3, comparative example 6²⁷Al-NMR spectrogram.

Specific embodiment

The following examples illustrate the present invention further, it is intended to reader be helped to more fully understand reality of the invention Matter place and brought beneficial effect, but should not be construed as any restriction to enforceable range of the invention.

In each embodiment and comparative example, the lattice constant (cell parameter) and crystallinity of zeolite use PHILIPSX ' The measurement of Pert type x-ray powder diffraction instrument, Cu K alpha ray, tube voltage 40kV, tube current 40mA, 2 °/min of scanning speed, scanning 2 θ=5~70 ° of range；Wherein crystal retention is the ratio of crystallinity and crystallinity before aging after zeolite aging, specific surface area Reservation degree be zeolite aging before with the ratio after aging.Constituent content is by x-ray fluorescence spectrometry.Crystal structure avalanche temperature Degree is measured by differential thermal analysis (DTA).The room temperature can be 15-40 DEG C.

The ratiometric method of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum in the modified Y zeolite lattice structure It is：It uses first²⁷Al MAS NMR method obtains the spectrogram of sample, then measures spectral peak area and chemistry at chemical shift 40 It is displaced spectral peak area at 60, the ratio of the two indicates the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum.Wherein²⁷Al MAS NMR analysis condition is with reference to as follows：Using U.S.'s VARIAN INOVA 300M type NMR spectrometer with superconducting magnet, solid double resonance Probe, 6mm ZrO₂Rotor, magic angle rotating speed 4kHz,²⁷It is 78.155MHz, sampling time 0.02s, arteries and veins that Al, which detects nuclear resounce frequency, 0.3 μ s is rushed, is scanned 2000 times.

It is raw materials used in embodiment and comparative example：The one roasting Y boiling of the super steady zeolite DASY (0.0) of NaY zeolite, hydro-thermal and a friendship Stone, is provided by Sinopec catalyst asphalt in Shenli Refinery, and property is shown in Table 1.

Prepare raw materials used in catalyst be described as follows：Kaolin is produced by Kaolin of Suzhou company, solid content 76 Weight %；Alumina content in Aluminum sol is 21.5 heavy %；Boehmite is produced by Shandong Aluminum Plant, solid content 62.0 Weight %；Acidification pseudo-boehmite solid content is 12.0 heavy %, and the molar ratio of acid and aluminium oxide is 0.15 when acidification；NaY used Molecular sieve is that Shandong catalyst plant is produced, solid content 75.0%, lattice constant 2.466nm, in terms of weight percent content, Na₂O content is 12.8%, Si/Al molar ratio 2.5.Remaining reagent is produced by Sinopharm Chemical Reagent Co., Ltd., and specification is equal It is pure to analyze.

Embodiment 1

(1) under room temperature (26 DEG C, similarly hereinafter), 200gNaY zeolite (75 weight % of butt) is taken, is 0.5mol/L with molar concentration Hydrochloric acid solution 1500ml mixing, stir 30 minutes, filtering wash with 1500ml deionized water, is obtained acid treated NaY and is boiled Stone, sodium oxide content are 3.5 weight %；

(2) by gained acid, treated that NaY zeolite roast 3 hours at 300 DEG C, and obtaining solid content is 96 boilings for weighing % Stone is denoted as F1；

(3) by 5.23g zirconium nitrate Zr (NO₃)₄·5H₂O is dissolved in 200g ethyl alcohol (analyzing pure, 99.9 weight % of ethanol content) In maceration extract is made, gained maceration extract is uniformly mixed with the zeolite F1 that step (2) obtains, and stands 1h at room temperature；

(4) step (3) products therefrom is mixed with 800ml ethyl alcohol, is transferred in autoclave, and pour nitrogen, makes pressure For 0.5MPa, then stand and kept for 12 hours at room temperature, filtering, 100 DEG C dry 24 hours,

(5) product for obtaining step (4) roasts 4 hours at nitrogen atmosphere, 500 DEG C.The Y zeolite of modified zirconia is obtained, It is denoted as Zr (1) Y；

(6) ZrY (1) zeolite that step (5) obtains is mixed with beating with 2000g deionized water, 8.38g (NH is added₄) H₂PO₄, 90 DEG C of stirring 2h are warming up to, are then filtered, washed.Filter cake is roasted into 2h under 600 DEG C, 100% water vapor conditions.Most Zirconium and composite modified Zr (the 1)-P-Y zeolite of phosphorus are obtained afterwards.Its property is shown in Table 2.

Embodiment 2~7

Prepare modified Y zeolite according to the method provided by the invention, the property of operating condition and product, which is shown in Table 2, (can join Examine embodiment 1).

Embodiment 8

Modified zeolite is prepared according to the method for embodiment 1, the difference is that pouring nitrogen in step (4), makes pressure (gauge pressure) For 0MPa.Obtained modified molecular screen is denoted as Zr (1)-P-Y-1. its property and is shown in Table 2.

Embodiment 9

Modified zeolite is prepared according to the method for embodiment 1, the difference is that in step (1)：

(1) under room temperature (26 DEG C, similarly hereinafter), 200gNaY zeolite (75 weight % of butt) is taken, is 0.5mol/L with molar concentration EDTA solution 1500ml mixing, stir 30 minutes, filtering wash with 1500ml deionized water, is obtained acid treated NaY and is boiled Stone, sodium oxide content are 3.5 weight %；Step (2)~(6) obtain modified molecular screen and are denoted as Zr (1)-P-Y- with embodiment 1 2.Its property is shown in Table 2

Comparative example 1

This comparative example illustrates the preparation method of conventional rare modified Y zeolite.

200gNaY zeolite (with embodiment 1) is taken, after the mashing of 2000g deionized water, 60g ammonium sulfate is added, uses dilute hydrochloric acid PH=4.0 is adjusted, 80 DEG C is warming up to and exchanges 1 hour, filter and eluted with water, then by filter cake in 550 DEG C, 100% water vapour Middle roasting 2 hours, repeats the above steps 2 times, obtains modified Y zeolite.

Then after gained Y zeolite being beaten with 2000g deionized water, 270g/l RECl is added₃45 milliliters of solution, use is dilute Hydrochloric acid adjusts pH=3.8, after being warming up to 80 DEG C of exchanges 1 hour, 45g ammonium sulfate is added and continues stirring 1 hour, then filters, wash It washs, filter cake is roasted 2 hours in 550 DEG C, 100% water vapour.Rare earth modified RE-Y zeolite is finally obtained, property is shown in Table 3。

Comparative example 2

This comparative example illustrates the preparation method of conventional rare and P Modification Y zeolite.

According to the method for patent CN 1111136C, takes 200gNaY zeolite to be placed in 2000g deionized water and stir evenly, add Enter 80g NH₄Cl adds concentration 270g/l RECl₃It 45 milliliters of solution, is exchanged 1 hour at 90 DEG C, filters and eluted with water, it will Filter cake roasts 2 hours in 600 DEG C, 100% water vapour, obtains REUSY molecular sieve.

Above-mentioned molecular sieve 2000g deionized water is beaten, 40g NH is added₄After Cl, 9.6g (NH is added₄)H₂PO₄, It exchanges 1 hour at 90 DEG C, filter and is eluted with water, filter cake is roasted 3 hours in 600 DEG C, 100% water vapour, obtains rare earth With the composite modified Y zeolite of phosphorus, property is shown in Table 3.

Comparative example 3

The comparative example illustrates the zirconium and P Modification Y zeolite using conventional method preparation.

According to the method for embodiment 3, the difference is that the zirconium iso-propoxide of equivalent is dissolved in 200g deionized water.It finally obtains Zr (W)-P-Y zeolite, property are shown in Table 3.

Comparative example 4

The comparative example illustrates the titanium and P Modification Y zeolite using the preparation of conventional method aqueous solution exchange process.

After taking 200gNaY zeolite to be beaten with 2000 grams of deionized waters, 7.13g titanium tetrachloride is added, is warming up to 90 DEG C of exchanges 2 Hour, it filters and is eluted with water, then roast filter cake 2 hours under 600 DEG C, 100% water vapour.

Molecular sieve after roasting is continued to be beaten with 2000 grams of deionized waters, 45g ammonium chloride and 15.38g (NH is added₄)₂HPO₄, it is warming up to 90 DEG C and exchanges 3 hours, be then filtered, washed, filter cake is roasted 2 hours under 600 DEG C, 100% water vapour, Ti (W)-P-Y zeolite is finally obtained, property is shown in Table 3.

Comparative example 5

The comparative example illustrates disclosed in CN101134576A using the modified zirconia Y zeolite of hydrothermal crystallization method preparation.

Modified zirconia Y zeolite is prepared according to the method for embodiment 1 in CN101134576A, finally obtains Zr (G)-Y zeolite, Property is shown in Table 3.

Comparative example 6

By 200 grams of DASY0.0 zeolites, it is added in 500 grams of dehydrated alcohols with vigorous stirring and forms suspension, acutely stirred Lower butyl titanate-ethanol solution that 50 grams per liter of concentration is added is mixed (with TiO₂Meter), it is dried under stiring in ambient temperature overnight, Sample roasts 5 hours in 500 DEG C, obtains the titanium modified zeolite of the weight of Ti content 7.9 %, is denoted as Ti (D) Y.Property is shown in Table 3.

Comparative example 7

The Y molecular sieve that comparative example 6 obtains is contacted with phosphoric acid solution, phosphorus and transition metal modified Y molecular sieve is obtained, is denoted as Ti (D) Y-P, property are shown in Table 3.

It can be seen that the modified Y zeolite prepared using the method for the invention from the XRD spectra of Fig. 1 modified Y zeolite, and The spectrogram of standard Y zeolite is almost the same, does not find Group IVB metal oxide (such as TiO₂、ZrO₂) characteristic peak, show Group IVB gold Belong in zeolite surface high degree of dispersion or enter zeolite interior, does not assemble in zeolite surface.With the modification Y using conventional method preparation Zeolite is compared, and the metal-modified Y zeolite of IV B race using the method for the present invention preparation has higher crystallinity.

From figure 2, it is seen that there is TiO in the spectral peak of modified Y zeolite prepared by comparative example 6₂Characteristic peak (2 25.3 ° of the angles θ, 48.0 °), it is seen that metal is more advantageous in the high degree of dispersion of molecular sieve surface using modified Y zeolite prepared by the method for the present invention.

Find out from the FT-IR spectrogram of Fig. 3 modified Y zeolite, Zr (G)-Y zeolite that existing Y zeolite such as comparative example 5 provides Anti-symmetric vibration frequency (1050~1150cm^-1) and symmetrical stretching vibration frequency (750~820cm^-1) sent out to low frequency direction Red shift has been given birth to, has shown that Zr enters Y skeleton structure of zeolite.Modified Y zeolite provided by the invention does not find Red Shift Phenomena, shows Zr Zeolite skeleton is not entered into Ti, IV B race metal of modified Y zeolite provided by the invention does not enter Y zeolite skeleton.

From Fig. 4 modified Y zeolite²⁷Al-NMR spectrogram finds out that the present invention provides modified Y zeolite and is primarily present four-coordination skeleton Al (chemical shift 60), a small amount of hexa-coordinate non-skeleton Al (chemical shift is 0).Compared with existing Y zeolite, Zr (6)-P-Y boiling The peak four-coordination skeleton Al of stone is significantly broadened, and mobile to low chemical shift direction, shows Zr and P and boiling into zeolite interior Stone skeleton [AlO₄] interacted, this interaction causes four-coordinate framework AL spectrum peak to shift to High-Field, distorts simultaneously Four-coordinate framework AL spectrum peak (chemical shift 40) significantly, modified zeolite distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum of the present invention Ratio be preferably 0.2~0.8.Zr (W)-P-Y and Ti (D) the Y boiling prepared using aqua-solution method and 6 the method for comparative example Stone, the variation of the four-coordination peak skeleton Al is not significant, shows modifying element and zeolite skeleton [AlO₄] interaction it is smaller, distortion four The ratio of co-ordinating backbone aluminium and four-coordinate skeleton aluminum is lower than 0.1.It can be seen that the modified Y zeolite prepared using the method for the present invention, is more had Enter zeolite interior conducive to modifying element, with zeolite skeleton [AlO₄] interaction, to play molecular sieves stabilized skeleton knot The effect of structure.

The modified Y zeolite that it can be seen from 3 data of table 2 and table prepared by 1~embodiment of embodiment 9 compares table with biggish Area.Compared with rare earth modified Y zeolite (comparative example 1 and 2), the modified Y zeolite of the method for the present invention preparation has quite even more Good thermal stability.Compared with comparative example 3 and 4, the lattice damage temperature of modified Y zeolite prepared by the present invention is significantly improved, table The bright modified Y zeolite using the method for the present invention preparation has more high thermal stability.

Modified Y zeolite preparation method provided by the invention, the composite modified Y zeolite of obtained IV B metal and phosphorus, metal from Son is predominantly located at zeolite interior, and the tenor of zeolite surface and the ratio of zeolite interior tenor are not higher than 0.5, existing side The metal-modified Y zeolite of IV B race of method preparation, zeolite surface tenor and the ratio of zeolite interior tenor are considerably higher, As it can be seen that the method for the present invention, which is more advantageous to, plays the role of stable skeleton structure of zeolite and adjusting Catalytic Cracking Performance.

Table 1

Raw material	NaY	DASY(0.0)	One hands over a roasting
				Element composition, weight %
Na2O	12.8	1.2	3.7
				Al2O3	21.9	23.6	23.4
SiO2	64.4	71.7	72.0
				Lattice constant, nm	2.466	2.448	2.453
Crystallinity, %	81.6	65.6	78.0
				Total specific surface area, m2/g	762	620	644
Total pore volume, ml/g	0.377	0.353	0.352

Table 2

Remarks：In table 2~8, w% indicates weight %

2 (Continued) of table

Table 3

Embodiment 10~18

Embodiment 10~18 illustrates the hydrothermal stability of modified Y zeolite prepared by the present invention.

By the modified Y zeolite of Examples 1 to 9 preparation respectively under the conditions of 800 DEG C, 100% water vapour after aging 17 hours, Its crystallinity and specific surface area are measured, and calculates crystal retention and specific surface area reservation degree, and carries out light oil microactivity and comments As a result valence is listed in table 4.Light oil microactivity evaluation, using RIPP92-90 standard method (see《Petrochemical analysis method》 (RIPP test method) Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) light oil microactivity of evaluation sample, catalyst Loading amount is 5.0g, and 460 DEG C of reaction temperature, feedstock oil is 235~337 DEG C of straight distillation light diesel oils of boiling range, and product is formed by gas-chromatography Analysis calculates light oil microactivity according to product composition.

Light oil microactivity (MA)=(gasoline production+gas yield+coke output for being lower than 216 DEG C in product)/charging Total amount × 100%

Comparative example 8~14

After 1~7 modified Y zeolite of comparative example is distinguished aging 17 hours under the conditions of 800 DEG C, 100% water vapour respectively, survey Its fixed crystallinity and specific surface area, and crystal retention and specific surface area reservation degree are calculated, as a result it is listed in table 4.And according to implementation The light oil microactivity of the method evaluation sample of example 10, the results are shown in Table 4.

From table 4, it can be seen that compared with rare earth modified Y zeolite (comparative example 8 and 9), when tenor and content of rare earth phase At that time, there is modified Y zeolite (embodiment 10) provided by the invention quite even slightly higher crystal retention, specific surface area to retain Degree and micro-activity show that modified Y zeolite provided by the invention has quite even slightly higher hydrothermal stability.With existing method The metal-modified Y zeolite of IV B of preparation compares (9~comparative example of comparative example 12), and the modified Y zeolite that the method for the present invention provides not only has There are higher crystal retention and specific surface area reservation degree, and micro-activity also significantly improves.As it can be seen that prepared by the present invention change Property Y zeolite have high hydrothermal stability.

Table 4

4 (Continued) of table

Embodiment 19

Using modified Y zeolite Zr (6)-P-Y provided by the invention as active component, according to conventional catalytic cracking catalyst side Method prepares catalyst.Preparation method is as follows：According to molecular sieve (in terms of butt)：Kaolin (in terms of butt)：Boehmite (with Al₂O₃Meter)：Aluminum sol is (with Al₂O₃Meter) it is 38：34：20：8 ratio will add after kaolin and the mashing uniformly of decationized Y sieve water Enter Aluminum sol, is separately added into boehmite under constant stirring and is added to the slurries containing molecular sieve after stir about 30 minutes In colloid, after remixing uniformly, spray drying forming obtains catalyst C1.

Heavy oil cracking performance evaluation：Through 800 DEG C, 100% steam aging 8 is small for evaluation on small fixed fluidized bed unit When after catalyst, feedstock oil be Zhenghai VGO and the normal slag (80 of grand celebration:20 weight ratios) miscella, feedstock property is shown in Table 5, instead Answering temperature is 500 DEG C, weight (hourly) space velocity (WHSV) 16h^-1, agent oil weight ratio is 45, and evaluation result is shown in Table 6.

Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield

Coke selectivity=coke yield × 100/ conversion ratio

Comparative example 15~19

Comparative catalyst is prepared according to the method for embodiment 19, the difference is that respectively with equivalent REY zeolite, equivalent RE-P- Y, equivalent Zr (W)-P-Y zeolite, equivalent Ti (D) Y zeolite, Ti (D) Y-P zeolite replace Zr therein (6)-P-Y zeolite, respectively To comparative catalyst DC1, DC2, DC3, DC4, DC5, then DC1~DC5 is evaluated according to the method for embodiment 19.Evaluation It the results are shown in Table 6.

Table 5

Table 6

By table 6 as it can be seen that compared with the catalyst containing rare earth modified Y zeolite, the present invention provides the heavy oil yield phase of catalyst When even slightly lower, gasoline yield increase, while coke yield is remarkably decreased, and coke selectivity is obviously improved, and shows that the present invention mentions The Cracking catalyst of confession has the catalytic performance quite or even slightly good with conventional rare Cracking catalyst.With the existing method system of use The catalyst of standby modified Y zeolite is compared, and the present invention provides the heavy oil conversion performance of catalyst and yield of gasoline significantly mentions Height shows that the Cracking catalyst of the method for the present invention preparation has higher activity and product selectivity.

Embodiment 20

Zr (2)-P (1)-Y zeolite is prepared according to the method for embodiment 1, and wherein zirconium nitrate is (with ZrO₂Meter) with the weight of Y zeolite Amount is than being 0.02:The 1, (NH in terms of P₄)H₂PO₄Weight ratio with Y zeolite is 0.01:1.

323g boehmite and 1343g deionized water are mixed, after stirring 15 minutes, obtain pseudoboehmite slurry, The pH value that slurries are adjusted with dilute hydrochloric acid (concentration is 15 weight %) is 3.5, at room temperature aging 6 hours；Slurries after weathering In, 421g kaolin and 465g Aluminum sol is added, stirs 60 minutes；It states then up and is added that 380g (butt) is above-mentioned changes in slurries Property Zr (2)-P (1)-Y zeolite and 800g deionized water be beaten the slurries to be formed, stirring obtains catalyst slurry after sixty minutes, will Obtained slurries spray drying forming roasts 2 hours in 550 DEG C, obtains Cracking catalyst C20 provided by the invention.XRF is measured The ZrO of catalyst C20₂Content is 0.75 weight %, 0.38 weight % of P content.

Embodiment 21

Zr (4)-P (0.5)-Y zeolite is prepared according to the method for embodiment 3, wherein zirconium iso-propoxide is (with ZrO₂Meter) and Y zeolite Weight ratio be 0.04:The 1, (NH in terms of P₄)₃PO₄Weight ratio with Y zeolite is 0.005:1.

421g kaolin, 465g Aluminum sol and 732g deionization are added in mashing tank and are beaten, 1667g acid is then added Change boehmite, continue stirring after sixty minutes, 380g (butt) above-mentioned modified Zr (4)-P (0.5)-Y zeolite and 800g is added Deionized water is beaten the slurries to be formed, and stirs 60 minutes, obtains catalyst slurry, be then spray dried to obtained slurries Type roasts 1 hour in 550 DEG C, obtains Cracking catalyst C21 provided by the invention.XRF measures the ZrO of catalyst C21₂Content For 1.51 weight %, 0.18 weight % of P content.

Embodiment 22

421g kaolin, 558g Aluminum sol and 800g deionized water are mixed with beating 60 minutes, 1500g acidification is then added Boehmite, stirring after sixty minutes, are added 380g (butt) modified Zr (10)-P-Y zeolite and 800g deionized water are beaten shape At slurries, stir the slurries spray drying forming that will obtain after sixty minutes, roasted 2 hours in 650 DEG C, offer of the present invention is provided Cracking catalyst C22.XRF measures the ZrO of catalyst C22₂Content is 3.52 weight %, 0.10 weight % of P content.

Embodiment 23

The method of reference implementation example 5 prepares titanium and P Modification Y zeolite, is denoted as Ti (8)-P (4)-Y, wherein in step (3) Titanium tetrachloride is (with TiO when dipping₂Meter) it with the weight ratio of zeolite is 0.08:The 1, (NH in terms of P₄)₂HPO₄With the weight ratio of Y zeolite It is 0.04:1.

421g kaolin and 380g deionized water are mixed with beating 60 minutes, 1667g acidification pseudo-boehmite is then added, After continuing stirring 30 minutes, 380g (butt) above-mentioned modified Ti (8)-P (4)-Y zeolite is added and is beaten to be formed with 800g deionized water Slurries, stir 60 minutes, continue into gained slurries be added 465g Aluminum sol stir 30 minutes, finally by obtained slurries spray Mist drying and moulding roasts 2 hours in 700 DEG C, obtains Cracking catalyst C23 provided by the invention.XRF measures catalyst C23's TiO₂Content is 3.02 weight %, 1.50 weight % of P content.

Embodiment 24

The method of reference implementation example 6 prepares titanium and P Modification Y zeolite, is denoted as Ti (4)-P (3)-Y, wherein in step (3) Butyl titanate is (with TiO when dipping₂Meter) it with the weight ratio of zeolite is 0.04:1, the NH in terms of P₄H₂PO₄With the weight ratio of Y zeolite It is 0.03:1.

323g boehmite and 1478g deionized water are mixed, stirring obtained pseudoboehmite slurry after 30 minutes, used The pH value that suitable dilute hydrochloric acid adjusts entire slurries is 3.8, aging 2 hours at 60 DEG C；In the aged slurry, it is added 421g kaolin and 465g Aluminum sol continue stirring 60 minutes；Addition 380g (butt) above-mentioned modification in slurries is stated then up Ti (4)-P (3)-Y zeolite and 800g deionized water are beaten the slurries to be formed, and obtained slurries are spray-dried by stirring after sixty minutes Molding roasts 3 hours in 600 DEG C, obtains Cracking catalyst C24 provided by the invention.XRF measures the TiO of catalyst C24₂Contain Amount is 1.48 heavy %, 1.11 weight % of P content.

Embodiment 25

The method of reference implementation example 5 prepares hafnium and P Modification Y zeolite, is denoted as Hf (6)-P (1.5)-Y, wherein step (3) Hafnium nitrate is (with HfO when middle dipping₂Meter) it with the weight ratio of zeolite is 0.06:The 1, (NH in terms of P₄)₂HPO₄With the weight ratio of Y zeolite It is 0.015:1.

421g kaolin and 380g deionized water are mixed with beating 60 minutes, 1667g acidification pseudo-boehmite is then added, After stirring 30 minutes, 380g (butt) above-mentioned modified Hf (6)-P (1.5)-Y zeolite and 800g deionized water is added and is beaten to be formed Slurries stir 60 minutes, and 465g Aluminum sol is added into gained slurries and stirs 30 minutes, is finally spray-dried obtained slurries Molding roasts 2 hours in 700 DEG C, obtains Cracking catalyst C25 provided by the invention.XRF measures the HfO of catalyst C25₂Contain Amount is 2.11 heavy %, 0.56 weight % of P content.

Embodiment 26

421g kaolin and 380g deionized water are mixed with beating 60 minutes, 1667g acidification pseudo-boehmite is then added, After continuing stirring 30 minutes, 380g (butt) above-mentioned modified Ti-Zr-P-Y zeolite and 800g deionized water is added and is beaten to be formed Slurries stir 60 minutes, continue that 465g Aluminum sol stirring 30 minutes is added into gained slurries, are finally sprayed obtained slurries Drying and moulding roasts 2 hours in 700 DEG C, obtains Cracking catalyst C26 provided by the invention.XRF measures catalyst C26's TiO₂Content is 1.50 heavy %, ZrO₂Content is 1.48 heavy %, 0.52 weight % of P content.

Comparative example 20

The method of reference implementation example 7 prepares titanium, zirconium and the composite modified Y zeolite of phosphorus, unlike：By four fourth of metatitanic acid of equivalent Ester and zirconium nitrate are dissolved in 225g deionized water.Finally obtain Zr (W)-Ti (W)-P-Y zeolite.

Catalyst is prepared referring to the method for embodiment 26, unlike, Zr (W)-Ti (W)-P-Y zeolite of equivalent is replaced Ti-Zr-P-Y zeolite.Obtain comparison Cracking catalyst DC20 provided by the invention.XRF measures the TiO of catalyst DC20₂Content For 1.49 heavy %, ZrO₂Content is 1.51 heavy %, 0.51 weight % of P content.

Comparative example 21

The method of reference implementation example 7 prepares titanium, zirconium and the composite modified Y zeolite of phosphorus, unlike：By equivalent in step (3) Butyl titanate and zirconium nitrate be dissolved in 225g deionized water, step is added without (NH in (6)₄)H₂PO₄.Finally obtain Zr (W)-Ti (W)-Y zeolite.

Cracking catalyst is prepared according to the method for embodiment 26, unlike：With Zr (W)-Ti (the W)-Y zeolite generation of equivalent For Ti-Zr-P-Y zeolite.Finally obtain DC21 catalyst.XRF measures the TiO of catalyst DC21₂Content is 1.50 heavy %, ZrO₂ Content is 1.50 heavy %.

Comparative example 22

The method of reference implementation example 7 prepares titanium, zirconium and the composite modified Y zeolite of phosphorus, unlike：Step is added without in (6) (NH₄)H₂PO₄.Finally obtain Zr-Ti-Y zeolite.

According to the method for embodiment 26, the difference is that：Ti-Zr-P-Y zeolite is replaced with the Zr-Ti-Y zeolite of equivalent.Finally Obtain DC22 catalyst.XRF measures the TiO of catalyst DC22₂Content is 1.51 heavy %, ZrO₂Content is 1.52 heavy %.

Comparative example 23

This comparative example illustrates the catalytic cracking catalyst using conventional rare and P Modification Y zeolite.

200gNaY zeolite is taken, after the mashing of 2000g deionized water, 270g/l RECl is added₃45 milliliters of solution, with dilute salt Acid for adjusting pH=3.8 are warming up to 80 DEG C and exchange 1 hour, roast filter cake 3 hours at 500 DEG C after filtration washing.Then by gained After Y zeolite is beaten with 2000g deionized water, 45g ammonium sulfate and 9.6g (NH is added₄)H₂PO₄, it is small to be warming up to 90 DEG C of exchanges 1.5 When, it is then filtered, washed, filter cake is roasted 1 hour in 550 DEG C, 100% water vapour.Finally obtain rare earth and P Modification RE (8)-P-Y zeolite.

Catalyst is prepared according to the method for embodiment 26, unlike：Ti-Zr- is replaced with RE (8)-P-Y zeolite of equivalent P-Y zeolite.Finally obtain DC23 catalyst.XRF measures the RE of catalyst DC23₂O₃Content is 2.95 heavy %, P content 0.53 Weight %.

By the catalysis of catalyst C20~C25, DC20~DC23 after 800 DEG C, 100% steam aging 17 hours Agent is evaluated on small fixed fluidized bed unit ACE, and feedstock oil force mixed three, raw material oil nature is shown in Table 7, reaction temperature 500 DEG C, agent oil weight ratio is 5.Evaluation result is shown in Table 8.

Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield

Coke selectivity=100/ conversion ratio of coke yield *

Table 7

Table 8

8 (Continued) of table

Catalyst source	Comparative example 20	Comparative example 21	Comparative example 22	Comparative example 23
					Catalyst number	DC20	DC21	DC22	DC23
Modified Y boiling	Zr(W)-Ti(W)-P-Y	Zr(W)-Ti(W)-Y	Zr-Ti-Y	RE(8)-P-Y
					Reaction temperature, DEG C	500	500	500	500
Oil ratio (weight ratio)	5	5	5	5
					Weight space velocity, h-1	16	16	16	16
Product distribution, w%
					Dry gas	1.2	1.17	1.2	1.23
Liquefied gas	11.78	12.03	12.35	12.42
					Coke	4.97	5.36	4.99	5.52
Gasoline	51.54	50.33	54.11	54.79
					Diesel oil	22.07	22.14	21.36	20.56
Heavy oil	8.44	8.97	5.99	5.48
					It is total	100	100	100	100
Conversion ratio, w%	69.49	68.89	72.65	73.96
					Coke selectivity	7.15	7.78	6.87	7.46

By table 8 as it can be seen that compared with the catalyst containing rare earth and P Modification Y zeolite, the heavy oil that the present invention provides catalyst is split Change ability and gasoline yield are suitable, but coke selectivity significantly improves.With the IV B group 4 transition metal for using existing method to prepare The catalyst of modified Y zeolite is compared, and the present invention provides the heavy oil conversion performance of catalyst and gasoline yield increases substantially, table The Cracking catalyst of bright the method for the present invention preparation has higher activity and product selectivity.

Claims (30)

1. a kind of modified Y zeolite, which is characterized in that on the basis of the weight of the modified Y zeolite, the modified Y zeolite contains 1 The Group IVB metal oxide of~15 weight %, containing in terms of P 0.1~10 weight % phosphorus, in the modified Y zeolite lattice structure The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is 0.2~0.8:1, zeolite surface Group IVB tenor and zeolite The ratio of internal Group IVB tenor is not higher than 0.5；IV B race tenor of zeolite surface refers to using x-ray photoelectron spectroscopy Method analyzes the IV B race tenor measured within the scope of 2~5nm of zeolite surface；IV B race tenor of zeolite interior refers to zeolite The difference of IV B race tenor of ontology and IV B race tenor of zeolite surface, wherein IV B race tenor of zeolite ontology is logical Cross the content of IV B race metal in the zeolite that chemical method is analyzed.

2. modified Y zeolite described in accordance with the claim 1, which is characterized in that the modified Y zeolite：Cell parameter 2.448~ 2.458nm, 600~850m of specific surface area²/ g, crystallinity are not less than 60%.

3. modified Y zeolite described in accordance with the claim 1, which is characterized in that distort four in the modified Y zeolite lattice structure and match The ratio of position framework aluminum and four-coordinate skeleton aluminum is 0.2~0.7:1.

4. modified Y zeolite described in accordance with the claim 1, which is characterized in that the modified Y zeolite surface Group IVB tenor Ratio with zeolite interior Group IVB tenor is 0.01~0.35:1.

5. modified Y zeolite described in accordance with the claim 1, which is characterized in that IV B race gold in terms of the oxide of IV B metal The content of category is 1~10 weight %.

6. modified Y zeolite described in accordance with the claim 1, which is characterized in that in terms of P, the content of the phosphorus is 0.5~6 weight Measure %.

7. modified Y zeolite described in accordance with the claim 1, which is characterized in that IV B race's metal is in Ti, Zr, Hf and Rf It is one or more.

8. a kind of preparation method of modified Y zeolite, includes the following steps：

(1) Y zeolite is contacted with acid solution and/or EDTA aqueous solution；The acid is organic and or inorganic acids；

(2) zeolite obtained by step (1) is dehydrated in 400 DEG C or less, makes the water content in zeolite not higher than 5 weight %；

(3) zeolite for obtaining step (2) impregnating metal in organic solvent；

(4) the Y zeolite for the impregnating metal for obtaining step (3) and organic solvent are according to solid-to-liquid ratio 1:5~50 weight ratio is added In container, it is filled with inert gas, is kept for 1 hour or more at 0~2.0MPa of pressure, room temperature~200 DEG C；Optionally filtering and/or It is dry；

(5) the Y zeolite for obtaining step (4) roasts；The roasting carries out in an inert gas atmosphere, maturing temperature be 300~ 700 DEG C, calcining time is 0.5 hour or more；

(6) the Y zeolite obtained by the aqueous solution contact procedure (5) containing phosphorus compound, the weight ratio 0.001 of phosphorus and the Y zeolite ~0.1, the Y zeolite after contact is roasted 0.5~5 hour under 300~800 DEG C, 100% water vapour, obtains modified Y zeolite.

9. according to the method for claim 8, which is characterized in that Y zeolite described in step (1) is NaY, NaHY, NaNH₄Y、 NH₄Y, HY, USY, DASY zeolite, one hand over a roasting Y zeolite, two that two roasting Y zeolites, two is handed over to hand over one of roasting Y zeolite or a variety of.

10. according to the method for claim 8, which is characterized in that step contacts Y zeolite with acid solution described in (1) And/or EDTA aqueous solution contact treatment is：According to solid-to-liquid ratio 1:5~1:20 weight ratio makes Y zeolite and acid solution and/or EDTA Solution contacts 0.5 hour or more at room temperature~100 DEG C, is then filtered, washed；Sour concentration is in the acid solution with H⁺It is calculated as 0.1~1mol/L, the concentration of the EDTA solution are 0.1~1mol/L.

11. according to the method for claim 10, which is characterized in that make described in step (1) Y zeolite and acid solution and/or The time of EDTA aqueous solution contact treatment is 0.5~3 hour；The inorganic acid is one of hydrochloric acid, sulfuric acid and nitric acid or more Kind；The organic acid is one or more of formic acid, acetic acid, oxalic acid, citric acid.

12. according to the method for claim 8, which is characterized in that dehydration described in step (2), for step (1) is obtained Zeolite in 200-400 DEG C roast, calcining time be 2~10 hours.

13. according to the method for claim 8, which is characterized in that impregnating metal in organic solvent described in step (3) Including：It will mix, kept at least 0.5 hour with the zeolite that step (2) obtains dissolved with the organic solvent of IV B race metallic compound, Wherein the solid-to-liquid ratio of Y zeolite and organic solvent is 1：(0.5~5) weight ratio.

14. according to the method for claim 13, which is characterized in that step (3) holding carries out under standing or stirring, Retention time is 0.5~12 hour.

15. according to the method for claim 8, which is characterized in that the zeolite that step (3) step (2) obtains with it is organic The solid-to-liquid ratio of solvent is 1:1~2 weight ratio.

16. according to the method for claim 13, which is characterized in that IV B race's metallic compound be titanium compound and/ Or the compound of zirconium；The compound of the titanium is titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, butyl titanate, fluorine One of titanium acid ammonium is a variety of, the compound of the zirconium be zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, One of zirconium iso-propoxide is a variety of.

17. according to the method for claim 8, which is characterized in that the time of step (4) described holding is 1~48 hour.

18. according to the method for claim 8, which is characterized in that in step (4), the pressure is 0.5~1.5MPa, temperature Degree is room temperature~150 DEG C, and the retention time is 4~24 hours, and the liquid-solid ratio of organic solvent and zeolite is 5~30:1 weight ratio.

19. according to the method for claim 8, which is characterized in that in step (5), maturing temperature is 450~650 DEG C, roasting Time is 1~4 hour.

20. according to the method for claim 8, which is characterized in that the water of step (3) and step (4) described organic solvent contains Amount is no more than 5 weight %.

21. according to the method for claim 20, which is characterized in that the water content of the organic solvent is no more than 3 weight %； The water content of the Y zeolite is no more than 3 weight %.

22. according to the described in any item methods of claim 8~21, which is characterized in that step (3) organic solvent is alkane One or more of hydrocarbon, aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane, step (4) organic solvent are alkane, fragrance One or more of hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane；Organic solvent used in step (3) and step (4) can phase It is same to can also be different.

23. according to the method for claim 20, which is characterized in that the normal boiling point of the organic solvent is 40~100 DEG C.

24. according to the method for claim 20, which is characterized in that step (3) organic solvent is n-hexane, hexamethylene One of alkane, heptane, benzene, toluene, methanol, ethyl alcohol, isopropanol, acetone, butanone, chloroform are a variety of；Step (4) is described Organic solvent is n-hexane, in hexamethylene, heptane, benzene, toluene, methanol, ethyl alcohol, isopropanol, acetone, butanone, chloroform It is one or more.

25. according to the method for claim 8, which is characterized in that phosphorus compound described in step (6) is orthophosphoric acid, phosphorous One or more of acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid.

26. according to the method for claim 8, which is characterized in that pressure described in step (4) is 0.1~2Mpa.

27. according to the method for claim 8, which is characterized in that calcining time described in step (5) is 0.5~5 hour.

28. a kind of catalytic cracking catalyst, including Y type molecular sieve, which is characterized in that the Y type molecular sieve is claim 1 ~7 described in any item modified Y zeolites.

29. according to the catalytic cracking catalyst described in claim 28, which is characterized in that based on the total catalyst weight, contain There is the heat-resistant inorganic oxide matrix of modified Y zeolite described in 10~60 weight %, the clay of 10~60 weight % and 5~50 weight %.

30. the preparation method of catalytic cracking catalyst described in claim 28, which is characterized in that including being formed including claim 1~7 described in any item modified Y zeolites, clay, heat-resistant inorganic oxide matrix and water slurries, the step of spray drying.