CN106890675A - Preparation method of rare earth-containing catalytic cracking catalyst - Google Patents

Abstract

A preparation method of a catalytic cracking catalyst containing rare earth. The preparation method comprises the following steps: (1) synthesizing catalyst precursor microspheres by a semisynthesis method or a total synthesis method; (2) dissolving a compound containing IIIB metal ions in the periodic table of elements in water or acid to form a solution, mixing the solution with (a) an organic complexing agent and/or a dispersing agent and (B) a precipitating agent, and stirring for at least 10 minutes at the temperature of 5-100 ℃ to form a precipitate containing IIIB elements; (3) mixing the obtained precipitate containing the IIIB element with catalyst precursor microspheres, stirring at the temperature of 5-100 ℃ for at least 10 minutes, filtering, and drying to prepare a catalytic cracking catalyst containing the IIIB element precipitate; wherein the weight ratio of IIIB element to catalyst dry base is 0.002-0.06: 1. The catalyst prepared by the method has good heavy metal resistance.

Description

Preparation method containing rare earth catalyst Cracking catalyst

Technical field

The present invention relates to a kind of preparation method of oil refining catalyst, and in particular to a kind of catalytic cracking catalyst Preparation method.

Background technology

Crude oil heaviness, in poor quality degree are increasingly sharpened, highly-efficient processing heavy oil, mix refining residual oil turn into oil refining Enterprise improves working ability, obtains the active demand of more high profit.Catalytic cracking is most important processing of heavy oil Technique, because its heavy oil transformation efficiency is high, good product quality, non-hydrogen and operating pressure it is low significantly Advantage, makes it occupy very important status in refinery's processing heavy oil technique, is the master of oil plant profit Originate.According to statistics, current whole world catalytic cracking unit has 420 sets or so, the catalytic cracking of single set Up to 10,000,000 tons/year, about 7.37 hundred million tons of total working ability occupies the head of secondary operation to unit scale maximum Position.

Due to the macromolecular compound of coke is easily produced in heavy oil and residual oil containing colloid, asphalitine etc., And containing heavy metal nickel, vanadium etc., cause nickel content of vanadium on catalytic cracking equilibrium catalyst to exist 10000 μ g/g are relatively common, and the up to serious pollution of 15000 μ g/g is not also rare, and vanadium is in catalysis The structure of the molecules of active components sieve under cracking high temperature thermal and hydric environment in heavy damage catalyst, causes catalysis Agent activity is reduced, and is distributed catalytic cracking product and is deteriorated.Accordingly, it would be desirable to develop with excellent activity, The molecular sieve catalyst of hydrothermal stability and preventing from heavy metal pollution, to meet heavy oil, slag oil cracking to catalysis The strict demand of agent performance.

It is general in the prior art to use at rare earth or P Modification in order to improve the activity and stability of catalyst Reason molecular sieve or catalytic cracking catalyst, such as Chinese patent CN1111136 C disclose it is a kind of phosphorous and The preparation method of the Y type molecular sieve of rare earth, is that NaY molecular sieve is first handed over ammonium ion and rare earth ion Change, be calcined, then the P with 1~10 weight % in phosphorus compound reaction bonded₂O₅, then be calcined Obtain.Chinese patent CN1209288 C disclose the preparation side of the faujasite of a kind of phosphorous and rare earth Method, is after faujasite first is carried out into an exchange reaction with ammonium compounds and phosphorus compound, then to hand over Change introducing earth solution in slurries further to react, through filtering, washing, then be calcined.Containing this The catalyst activity good stability of zeolite, yield of gasoline is high, and coke yield is low, heavy oil cracking ability and anti- Heavy metal pollution ability is strong.

The mode that rare earth introduces catalyst includes 3 kinds substantially：

One is that such as Chinese patent CN1169717C is public for catalyst with the system with molecular sieve for preparing after rare earth modified Method and product that a kind of Y zeolites rare earth ion is modified, the method NaY molecular sieve are opened It is raw material, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H⁺、NH₄ ⁺And RE³⁺Solution After treatment, scrubbed, dry, roasting obtains modified molecular screen product.Chinese patent CN1026225 C disclose a kind of preparation method of rare-earth Y molecular sieve, be by NaY molecular sieve with it is dilute After native ion carries out ion exchange in aqueous, filtering, filter cake is calcined in the water vapour of flowing Obtain.Chinese patent CN1069553 C disclose a kind of method for preparing rare earth Y type molecular sieve, are After NaY molecular sieve and rare earth ion are carried out into ion exchange, filtering, filter cake is calcined again, is calcined The 1~40% of product afterwards is recycled back into continuing operations described above in next group rare earth exchanged slurries, Remaining is used to prepare catalyst as REY zeolite products, is so carried out continuously, and obtains Y-type rare earth Molecular sieve.Chinese patent CN103058217 A disclose a kind of preparation side of the Y molecular sieve containing rare earth Method, the method NaY molecular sieve is raw material, is first exchanged through ammonium, then carries out hydro-thermal process, then use Containing H⁺、NH₄ ⁺、RE³⁺After the mixed solution treatment of organic solvent, mother liquor is separated, filter cake roasting, Obtain modified molecular screen product.Chinese patent CN1159101 C disclose a kind of containing hyperastable Y-type RE boiling The preparation method of stone, the method is dilute with one kind by the overstable gamma zeolite that sodium oxide content is 3~5 weight % Earth compounds solution mixes, and is made a kind of slurries, and the slurries that will be obtained are in shear stress at least 10 kilograms/li Rice²Under conditions of grind at least 1 minute, obtain modified molecular screen product.Zeolite tool prepared by the method There is the ability of hydrothermal stability high, anti-sodium and preventing from heavy metal pollution.CN99105792.9 discloses one Molecular sieve containing rare earth and preparation method thereof is planted, its preparation method is included in 25~120 DEG C, by one kind with oxygen Compound meter, rare-earth type molecular sieve and a kind of at least one material containing in (I) containing the weight of rare earth 0.1~40 % (II) solution of at least one material in is contacted at least 0.1 hour；(I) including inorganic acid, inorganic Alkali, organic acid or can with aluminium formed complex compound reagent, (II) including soluble ammonium salt, acylate and Amine, alcohol, aldehyde, ketone；The pH value of the solution is 3~12.Loaded first on the method molecular sieve Rare earth, afterwards just with containing (I) at least one material and (II) at least one material treatment, its Purpose is that, in order to obtain skeleton rare earth containing zeolite, its rare earth is present on the skeleton of molecular sieve, be instead of point Partial cation on sub- sieve skeleton frame.CN200510114495.1 discloses a kind of superstable gamma-type that improves and boils The method of stone content of rare earth, the method includes：By the acid that ultrastable and concentration are 0.01~2N Solution is sufficiently mixed with the ratio of liquid-solid ratio 4~20 under 20~100 DEG C of temperature range, and treatment 10~ Washed after 300 minutes, filtered, adding rare earths salt carries out rare earth ion exchanged, is washed after exchange Wash, filter, drying, obtaining the rare earth superstable Y-type boiling that duct is unobstructed, content of rare earth is significantly improved Stone.First using acid solution cleaning y-type zeolite duct, after filtering, zeolite molecular sieve is carried out the method Rare earth exchanged, its purpose is to improve the content of rare earth in molecular sieve, its rare earth is present in molecular sieve On skeleton, the partial cation on framework of molecular sieve is instead of.In the prior art, precipitating rare earth also changes The report of property molecular sieve, for example, CN200610087535.2 discloses a kind of system of REY molecular sieves Preparation Method, NaY molecular sieve is exchanged with the aqueous solution contact containing rare earth ion, is connect with additional precipitating reagent Touching makes part rare-earth precipitation over a molecular sieve, then carries out hydro-thermal process, is finally contacted with ammonium salt aqueous solution, Precipitating reagent therein is solvable carbonate aqueous solution or alkaline aqueous solution.The essence of the preparation method is to pass through Rare earth exchanged and ammonium salt exchange the Na in removal NaY molecular sieve⁺Content, while introducing rare earth ion； Molecular sieve is first carried out rare earth exchanged by the preparation, is dividing part rare-earth precipitation using additional precipitating reagent afterwards On son sieve, molecular sieve filtration, washing afterwards, filter cake carries out hydro-thermal process again, and ammonium is exchanged.Preparing Cheng Zhong, rare earth is mainly loaded on molecular sieve in the form of ion exchange, and part does not exchange to molecular sieve On the effect of rare earth and precipitating reagent precipitate, the Y types containing rare earth point prepared using this precipitation method The particle of son sieve, although form the sediment of rare earth, the rare earth containing independent phase, but rare-earth precipitation thing It is larger, it is unfavorable for being dispersed in molecular sieve surface, also it is unfavorable for effectively being contacted with heavy metal, catches in time Collection heavy metal, therefore its preventing from heavy metal pollution scarce capacity.Simultaneously as its raw material is NaY, Filtering, washing, hydro-thermal process, ammonium after rare earth exchanged exchange the utilization that drop sodium process also results in rare earth Rate is substantially reduced.Chinese patent CN02103909.7 disclose it is a kind of for RFCC, contain The novel rare-earth ultra-steady Y molecular sieve preparation method of anti-vanadium component, be with NaY type molecular sieves as raw material, Contain oxalic acid or oxalates and its mixture in chemical dealuminization complexing agent, while reacting the later stage in chemical dealuminization Rare earth ion is introduced, rare-earth precipitation is formed, then by hydro-thermal process, you can realize super stabilizing and introduce dilute The purpose of native ion and independent phase oxidation rare earth.The method first using chemical dealuminization complexing agent (oxalic acid and / or oxalates) treatment molecular sieve, make molecular sieve dealuminzation, then formed with complexing agent using rare earth and included The rare-earth precipitation thing of rare earth oxalate, in the method, chemical dealuminization complexing agent (oxalic acid and/or oxalates) Can be complexed with the aluminium in molecular sieve, but can not be sunk with rare earth complex, and the rare earth that the method is formed Starch particle is big, and the distribution in molecular sieve is not uniform enough, therefore preventing from heavy metal effect relative mistake.

Two is to add rare earth, such as Chinese patent during conventional semi-synthetic catalytic cracking catalyst plastic CN1291787C discloses a kind of hydrocarbon cracking catalyzer containing molecular sieve and preparation method thereof, the catalysis Agent contains molecular sieve, heat-resistant inorganic oxide matrix, clay and a kind of metal component, the metal component Substantially to reduce valence state presence, it is selected from periodic table of elements Group IIIA non-aluminum metal, IVA races gold Category, VA races metal, IB races metal, Group IIB metal, VB races metal, group vib metal, VIIB One or more in race's metal, VIII base metal, the catalyst is also containing being present in molecular sieve Rare earth metal outside duct, the molecular sieve is selected from y-type zeolite or y-type zeolite and has MFI structure Zeolite, β zeolites at least one mixture, the content of molecular sieve is 1-90 weight %, resistance to The content of hot inorganic oxide is 2-80 weight %, and the content of clay is 2-80 weight %, is present in point The content of the rare earth metal outside sub- sieve aperture road is 0.1-10 weight %, and the content of metal component is 0.1-30 weights Amount %.The catalyst has desulphurizing ability higher, anti-vanadium ability higher and heavy oil cracking activity higher. Chinese patent CN1224455C discloses a kind of Cracking catalyst, containing molecular sieve, manganese additive and Rare earth addition, also contains phosphorus additive.The catalyst has cracking activity higher, preferable coke Selectivity, can be greatly lowered the olefin(e) centent in gasoline, and yield of light oil is dramatically increased.

Three is that rare earth is introduced in catalyst microspheres, and such as Chinese patent CN1179734A discloses one kind The method that original position prepares improved fluid catalytic cracking zeolite catalyst, the method includes that spray drying is hydrated Kaolin, zirlite and the spinelle kaolin mixture of metakaolin is substantially free of, roasting generation Microballoon, hydrous kaolin is transformed into metakaolin, and zirlite hydrothermal transformation into transitional alumina, By the mixture of spinelle kaolin, transitional alumina and the metakaolin microballoon for constituting and the alkali for adding crystal seed Property sodium silicate solution reaction, obtain the microballoon containing Y type molecular sieve, then carry out ammonium, rare earth plasma Drop sodium treatment is exchanged, the invention catalyst is obtained.Chinese patent CN1179734A discloses a kind of height The preparation method of active fluidized catalytic cracking catalyst, it is characterized in that being that primary raw material passes through original with kaolin Position crystallization technology prepares highly active catalytic Cracking catalyst, and its preparation process is that kaolin, solid is brilliant Kind, auxiliary agent, organic dispersing agent and bonding agent etc. are spray-dried to be shaped to kaolin microsphere A, through high temperature Roasting obtains metakaolin microballoon, then carries out crystallization with sodium metasilicate, NaOH etc., obtains NaY zeolite content is 20-70%, the crystallization microballoon of Zeolite 4.0-6.0.By once roasting and NH₄ ⁺、RE³⁺Three exchanges obtain catalyst prod.The catalyst has that preventing from heavy metal ability is strong, splits The features such as changing active height, good activity stability, low cost.

Compared with 3 kinds of modes that catalytic cracking catalyst middle rare earth is introduced, with ion-exchanged molecular sieve Form introduce rare earth, it is possible to increase the activity of catalyst, but catalyst preventing from heavy metal pollution performance not Foot；With Y molecular sieve prepared by the rare-earth precipitation method for adding precipitating reagent, although make molecular sieve catalyst Preventing from heavy metal pollution performance increases, but because rare-earth precipitation composition granule is big, the distribution in molecular sieve It is not uniform enough, therefore preventing from heavy metal effect relative mistake；With molecular sieve, matrix, rare earth etc., each component is mixed The mode (semi-synthetic catalyst preparation mode) of aftershaping is closed, rare earth is introduced in the catalyst, although can To improve the stability and preventing from heavy metal performance of catalyst, but rare earth is moved to more easily by ion exchange On molecular sieve, play a part of exchanged rare earth, make the preventing from heavy metal effect relative mistake of catalyst, or, Rare earth skewness (such as rare earth is added in the form of an oxide) in the catalyst, rare earth are buried in In the matrix of catalyst, can also make the preventing from heavy metal performance of catalyst not enough；After catalyst microspheres shaping Introduce rare earth, the in-situ crystallization type for typically synthesizing through high-temperature roasting, in-situ crystallization with kaolin atomized microball Based on catalyst, rare earth is introduced with ion-exchange method or coprecipitation mode, wherein being drawn with ion-exchange method The rare earth for entering, improves catalyst activity, but catalyst preventing from heavy metal performance is not enough, and with coprecipitation mode The rare earth of introducing, prior art is not related to reduce the granularity of precipitating rare earth, is unfavorable for precipitating rare earth with weight Metal is effectively contacted, timely trap heavy metals, therefore, the modified in-situ crystallization type catalyst of precipitating rare earth Preventing from heavy metal performance is also required to further raising.

In catalytic cracking process, heavy metal nickel, vanadium in feedstock oil etc. are constantly deposited on a catalyst, its In, deposition vanadium on a catalyst forms vanadic acid under the aerobic of regenerator, high temperature and water vapour environment, The structure of the active component-molecular sieve in destruction catalyst, causes the avalanche of crystal structure of molecular sieve and divides The inactivation of son sieve.Deposition heavy metal nickel on a catalyst, can participate in reacting as dehydrogenation activity center Journey, makes catalytic cracking reaction selectively be deteriorated, produces more coke and dry gas.Accordingly, it would be desirable to will The capture in time such as nickel, vanadium, passivation, are allowed to be converted into stabilization, inert compound, are carried so as to reach The purpose of the preventing from heavy metal pollution of macromolecule sieve.It has been found that the sun such as sodium of rare earth ion and molecular sieve from There is ion exchange in son, migrate into molecular sieve, play a part of to improve molecular sieve activity and stability, But the rare earth after ion exchange is once contacted with vanadium, the skeleton structure of molecular sieve is easily separated from, forms vanadic acid Rare earth, makes the structural stability of molecular sieve be deteriorated on the contrary；And the rare earth existed in independent phase form, due to The difference of existence position and existence, can be used for trap heavy metals during catalytic cracking reaction, play The effect of preventing from heavy metal.Therefore the rare earth containing zeolite that prepared by above-mentioned use rare earth ion exchanged, without independence The rare earth of phase, the scarce capacity of its preventing from heavy metal pollution.

Y type molecular sieve containing rare earth prepared by the above-mentioned use precipitation method, even if foring the precipitation of rare earth Thing, the rare earth containing independent phase, but the particle of rare-earth precipitation thing is larger, is unfavorable for being dispersed in molecule Sieve surface, is also unfavorable for effectively being contacted with heavy metal, timely trap heavy metals.Therefore, in order to meet point Requirement of the sub- sieve catalyst to activity stability and preventing from heavy metal pollution ability, despite recent molecule Sieve catalyst technology of preparing, but still need the catalysis with excellent activity stability and preventing from heavy metal pollution Agent new preparation technology.

The content of the invention

It is an object of the invention to provide a kind of preparation method containing rare earth catalyst Cracking catalyst, the method is made Standby catalyst has good preventing from heavy metal pollution performance, is provided simultaneously with preferably activity and stability.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, including：

(1) semi-synthetic or total synthesis method synthetic catalyst predecessor microballoon is used；

(2) in the compound containing the B metal ions of the periodic table of elements III being dissolved in into water or acid, formed Containing the B metal ion solutions of the periodic table of elements III, with (a) organic complexing agent and/or dispersant, (b) Precipitant mix, at 5~100 DEG C of temperature, stirs at least 10 minutes, is formed containing III B element precipitation Thing, described organic complexing agent and the mol ratio of III B metal ions are 0.3~10:1, preferably 0.5~6:1, more preferably 1.0~4:1, the dispersant is with the mol ratio of III B metal ions 0.2~16:1, preferably 1~11:1, more preferably 2~7:1；

(3) gained is mixed containing III B element sediment with catalyst precursors microballoon, in temperature Stirred at 5~100 DEG C at least 10 minutes, filter, dry, prepared the catalysis containing III B element sediment and split Change catalyst；Wherein, III B element in terms of oxide is with the weight ratio of catalyst butt 0.002~0.06:1, preferably 0.004~0.03:1, more preferably 0.006~0.015:1.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, step (2) is containing III The preparation of B element sediment, it is described containing the B metal ion solutions of the periodic table of elements III and organic complexing agent And/or during dispersant, precipitant mix, containing B metal ion solutions of the periodic table of elements III, organic Complexing agent and/or dispersant, the addition sequence of precipitating reagent, addition number of times are not particularly limited.Can select Realized by one of following modes：Mode 1, will contain the B metal ion solutions of the periodic table of elements III and have After machine complexing agent and/or dispersant are uniform, precipitating reagent is added, stirred at least 10 minutes, formed Containing III B element sediment；Mode 2 is uniform with organic complexing agent and/or dispersant by precipitating reagent Afterwards, the solution of the compound containing the B metal ions of the periodic table of elements III is added, at least 10 points are stirred Clock, forms and contains III B element sediment；Mode 3, by precipitating reagent with containing the B metals of the periodic table of elements III from After the solution mixing of the compound of son, organic complexing agent and/or dispersant are added, stir at least 10 points Clock, forms and contains III B element sediment；Mode 4, will contain the B metal ion solutions of the periodic table of elements III with Organic complexing agent and/or dispersant, precipitating reagent add mixing simultaneously, stir at least 10 minutes, and formation contains III B element sediment.These are formed in the mode of sediment, and sediment is formed with mode 1 and mode 2 Granularity it is minimum, scheme is optimal.Organic complexing agent and/or dispersant play peptizaiton, and it is mainly made With the granular size for being III B element sediment in the reduction periodic table of elements；Precipitating reagent is mainly used in precipitation III B element in the periodic table of elements.Organic complexing agent, precipitating reagent can be used directly, or be dissolved in water In, used after forming solution.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described use is semi-synthetic Or total synthesis method synthetic catalyst predecessor microballoon, refer to catalyst precursors microballoon or by existing skill Semisynthesis synthesis catalytic Cracking catalyst used by art, i.e.,：Will be comprising molecular sieve, matrix, bonding The catalytic cracking catalyst each component of agent is mixed to form mixed serum, spray drying, forms complex catalyst precursor Thing microballoon；Catalyst precursors microballoon or by the total synthesis method synthesis catalytic cracking used by prior art Catalyst, i.e.,：With kaolin as raw material, the original position containing matrix and molecular sieve of hydrothermal crystallizing synthesis is brilliant Change type catalytic cracking catalyst.Either semisynthesis or total synthesis method are those skilled in the art It is known, such as CN02155601.6, CN00105235.7, CN200910092838.7, CN201110419922.2、CN02103907.0、CN03156915.3、CN1334318、 There is description in detail in CN200810102244.5.

Specifically, the general semisynthesis of prior art include：Will be including molecular sieve, matrix, viscous The mixing of knot agent component, plastic, are then spray-dried, solidify, wash, and obtain catalyst precursors Grain.Described total synthesis method refers to that clay slurry spray shaping is atomized microball, and atomized microball is fired into Roasting microballoon, then sodium metasilicate, directed agents, roasting microballoon, water are mixed, mixed system is in alkalescence condition Lower hydrothermal crystallizing, makes clay in-situ crystallization synthetic zeolite in microballoon, then drop by ion exchange repeatedly Sodium, roasting obtain complex catalyst precursor composition granule.

The preparation method of catalytic cracking catalyst disclosed in this invention, the catalyst precursors microballoon is adopted Synthesized with semi-synthetic or total synthesis method, using in semisynthesis synthetic catalyst predecessor microballoon Na₂O mass contents are desirably no more than 0.4%, using in total synthesis method synthetic catalyst predecessor microballoon Na₂O mass contents are desirably no more than 0.7%, when catalyst precursors microballoon meets Na₂O mass contents It is required that, catalyst precursors microballoon can just mix without any treatment with containing III B element sediment, Prepare catalyst of the invention.

For the catalyst precursors microballoon that semisynthesis synthesize, when catalyst precursors microballoon is low sodium Content catalyst precursors microballoon, i.e. Na₂O mass contents are not more than 0.4%, and catalyst precursors are micro- Ball can just mix without any treatment with containing III B element sediment, prepare catalyst of the invention； When catalyst precursors microballoon is sodium content catalyst precursors microballoon high, i.e. Na₂O mass contents are more than 0.4%, catalyst precursors microballoon is needed by treatment, and the mode of its treatment has two kinds：Mode one, Drop sodium treatment is carried out to catalyst precursors microballoon in step (1), the technology is people in the art Well known to member, common washing, ion exchange are drop sodium most common method；Mode two, in step (3) gained is mixed containing III B element sediment with catalyst precursors microballoon, prepares and contain III B element Drop sodium treatment is carried out after the catalytic cracking catalyst of sediment.

The preparation method of catalytic cracking catalyst disclosed in this invention, for urging that total synthesis method synthesizes Agent predecessor microballoon, its Na₂O mass contents are not more than 0.7%.When sodium content is higher than the numerical value When, it is necessary to by the relatively low sodium of method of ion exchange in step (1), the technology is people in the art Member well known to, the most frequently used means have washing, ammonium ion exchange, CN03156915.3, The method is disclosed in CN1334318, CN200810102244.5.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described III B element choosing One or more from scandium, yttrium, lanthanide series rare-earth elements.Described lanthanide rare include lanthanum, cerium, One or more in praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, example Such as can be the mixture of various rare earth elements, or high-purity single rare earth, it is conventional for lanthanum rich rare earth, Cerium-rich rare earth, pure lanthanum or pure cerium.Compound containing III B element is selected from III water-soluble or sour B element Halide, nitrate, sulfate, oxide, the compound of hydroxide in one or more. III B element and the weight ratio of catalyst butt counted with oxide are 0.002~0.06:1.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described precipitating reagent refers to In chemical precipitation reaction, can be chemically reacted with III B races metal ion in system, and make Its product slightly soluble or insoluble material in system.Therefore the species and addition of precipitating reagent are this area Well known to technical staff, using the teaching of the invention it is possible to provide or produce hydroxide ion (OH^-), carbanion (CO₃ ^2- ), bicarbonate ion (HCO₃ ^-), phosphate anion (PO₄ ^3-), phosphoric acid hydrogen radical ion (HPO₄ ^2-), dihydrogen phosphate ions (H₂PO₄ ^-), oxalate denominationby (C₂O₄ ^2-) compound Can be as precipitating reagent of the invention, its addition meets material mol ratio in precipitation reaction i.e. Can.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described precipitating reagent is preferred Oxalic acid, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, ammoniacal liquor, phosphoric acid, diammonium hydrogen phosphate, One or more in ammonium dihydrogen phosphate, ammonium phosphate, urea.Described ammoniacal liquor addition regards molecule screening the pulp Depending on the pH value of liquid, molecular sieve pulp pH value is set to be maintained in the range of 6.5~9.0；Oxalic acid, oxalic acid Ammonium, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid Ammonium, urea addition depending on the addition of III B element compound, make above-mentioned precipitating reagent：III B units The weight ratio of the compound (oxide meter) of element is 0.3~5.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described organic complexing agent Selected from formic acid, acetic acid, adipic acid, citric acid, tartaric acid, benzoic acid, ethylenediamine tetra-acetic acid, bigcatkin willow It is sour and it is above-mentioned acid salt and acetylacetone,2,4-pentanedione, diethanol amine, triethanolamine in one or more, Optimization citric acid, ammonium citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate, EDTA (ethylenediamine tetraacetics Acetic acid) in one or more.Described organic complexing agent is with the mol ratio of metal ion 0.3~10:1.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described dispersant is this Well known to art personnel, be one kind in intramolecular while having two kinds of phase reflexives of lipophile and hydrophily The interfacial agent of matter, homogeneous can disperse to be poorly soluble in liquid containing III B element sediment solid Grain, while the sedimentation and cohesion of solid particle can be also prevented, the material needed for forming stable suspension, its Main Function is to reduce the interfacial tension between liquid-liquid and solid-liquid, and surfactant also can be used as dispersant； And dispersant will not form precipitation with III B races Action of Metal Ions.Described dispersant is selected from carbon number For 2~8 monohydric alcohol or dihydroxylic alcohols, polyethylene glycol, cellulose derivative, polyacrylamide and its spread out One or more in biological, guar gum.The mol ratio of described dispersant and metal ion for 0.2~ 16:1。

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described cellulose derives Thing is typically sodium cellulose glycolate, methyl hydroxyethylcellulose, hydroxypropyl methyl cellulose.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described carbon number is 2~8 monohydric alcohol or dihydroxylic alcohols is well known to chemical art, for example：Carbon number is 2 Monohydric alcohol or polyalcohol be ethanol, ethylene glycol, carbon number be 3 monohydric alcohol or dihydroxylic alcohols be isopropyl Alcohol, normal propyl alcohol, the propyl alcohol of 1,3- bis-, the propyl alcohol of 1,2- bis-.Preferably carbon number of the invention is 2~5 Monohydric alcohol or dihydroxylic alcohols；More preferably in ethanol, ethylene glycol, isopropanol, butanol, methyl anyl alcohol one Plant or various.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, wherein described use half Synthetic method synthetic catalyst predecessor microballoon, is to split the catalysis comprising molecular sieve, matrix, binding agent Change catalyst components and be mixed to form mixed serum, be spray-dried, form catalyst precursors microballoon.Adopt With the component and content in semisynthesis synthetic catalyst predecessor microballoon by those skilled in the art public affairs Know.Molecular sieve is selected from Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, ZSM molecular sieve, titanium One or more in si molecular sieves；Wherein Y type molecular sieve, selected from USY, REUSY, REHY、HY、NH₄Y, REY, phosphorous Y molecular sieve.Described molecular sieve sodium oxide content is not high In 2 (weight) %.Reduce molecular sieve sodium oxide content technology known to those skilled in the art, allusion quotation Type is to exchange drop sodium through Ammonium Salt Ionic to process, and described ammonium salt is selected from ammonium sulfate, ammonium hydrogen sulfate, nitric acid One or more in ammonium, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium salt is mainly used in exchanging molecular sieve On sodium, make that there is surface acidity by the molecular sieve after exchange.Described matrix be catalyst in remove Component outside molecules of active components sieve, binding agent, common are clay, aluminum oxide, silica, oxygen Change the inorganic oxides such as aluminium-silica, amorphous silicon aluminium, titanium oxide, zirconium oxide；Clay is selected from higher Ridge soil, halloysite, montmorillonite, diatomite, sepiolite, galapectite, hydrotalcite, bentonite, One or more in acidifying or alkali soluble kaolin/galapectite；Inorganic oxide outside described clay It is the one kind or many in aluminum oxide, silica, amorphous silicon aluminium, titanium oxide, zirconium oxide or its mixture Kind.The aluminum oxide be selected from various forms aluminum oxide and/or hydrated alumina, such as gama-alumina, η-aluminum oxide, θ-aluminum oxide, a diaspore (Boehmite), gibbsite (Gibbsite), Bayer One or more in stone (Bayreite), but can acid it is molten, acid it is molten after have binding agent act on the thin water of plan Except aluminium stone.Described binding agent be selected from Ludox, Alumina gel, modified silicasol, modified Alumina gel, One or more in amorphous silicon alumina gel, boehmite, preferably boehmite and/or aluminium is molten Glue.With catalyst quality be 100% calculate, comprising 10~55% molecular sieve in terms of butt, Binding agent of 15~85% matrix, 5~30% in terms of butt in terms of oxide.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, described use is semi-synthetic Method synthetic catalyst predecessor microballoon, catalyst precursors microballoon can also be comprising in the periodic table of elements II A, V A, VI A, I B, II B, IV B, V B, VII B, the component of VIII compounds of group, such as magnesium, The components such as calcium, zinc, manganese, phosphorus, its content is 0.5~25% (in terms of oxide), concrete content model Enclose related from different elements.

Preparation method containing rare earth catalyst Cracking catalyst disclosed in this invention, by the control element cycle The addition of III B element compound and control precipitating reagent in table, organic complexing agent and/or dispersant Addition, addition sequence, reach the purpose of the distribution of III B element in regulation catalyst.Can basis Catalyst activity, stability and preventing from heavy metal pollution are actually needed, regulation in the form of an ion and with The ratio of III B element that independent phase form is present, as long as III B element in terms of oxide is done with catalyst The weight ratio of base is 0.002~0.06:1 in the scope.

Production of cracking catalyst containing rare earth catalyst disclosed in this invention, by selecting organic complexing agent And/or dispersant, it is that III B element deposition provides suitable reaction ring on a catalyst in the periodic table of elements Border, advantageously forms the ultra micron of III B element in the periodic table of elements, reduce by III B element sediment Granularity, increases outer surface and the degree of scatter of sediment, by III B element in the periodic table of elements more uniformly Deposition on a catalyst, in the periodic table of elements III B element with it is independent mutually or independent phase/exchange ion it is mixed Close phase formation to exist, i.e. III B element is with independent phase or the mixing phase formation of independent phase/exchange ion It is present in catalyst.Catalyst prepared by the present invention is more beneficial for making polluted heavy metals with a pollution huge sum of money Category passivator (III B element sediment) is contacted in time, effectively, it is to avoid catalyst microspheres passivator point Cloth is uneven, microballoon does not locally arrange passivator, so as to reach the mesh of more effectively trap heavy metals , while not only there is excellent preventing from heavy metal pollution performance using catalyst prepared by the present invention, also have There are excellent activity, stability.

Catalyst prepared by the present invention is applied to RFCC, is particularly suited for heavy metal content of vanadium RFCC high.The heavy oil such as reduced crude, decompression residuum, vacuum gas oil (VGO), normal pressure One or more in gas oil, deasphalted oil and coker gas oil.

Specific embodiment

The present invention is illustrated with embodiment further below, but the present invention is not limited in these examples.

(1) analysis test method used in embodiment

1. granularity：Analyzed using laser particle analyzer method.

2. the determination of activity of catalyst：In the CSA-B type catalyst evaluation devices of Huayang company production Carry out.Catalyst is advance after aging 6h or 17h under 800 DEG C, 100% water vapor conditions, using big Port light diesel fuel carries out determination of activity, 460 DEG C of reaction temperature, reaction time 70s, catalyst dress for raw material Amount 5.0g, oil ratio 3.2.

(2) raw materials used specification in embodiment

1.NaY molecular sieves, REUSY molecular sieves (rare earth ion exchanged molecular sieve, RE₂O₃Content 4.02%, Na₂O content 1.24%), NH₄Y molecular sieve (Na₂O content 1.68%, once by one Secondary hydrothermal calcine), ZSM-5 molecular sieve (Na₂O content 0.10%), kaolin (igloss 14.6%), diatomite (igloss 15.4%), Alumina gel (salic 19.4 heavy %) intends thin water Aluminium stone (igloss 31.8%), ammoniacal liquor (concentration 18%), nitric acid rare earth (RE₂O₃230.5g/L)： It is industrial goods, picks up from Catalyst Factory of Lanzhou Petrochemical Company.

2. ammonium sulfate, ammonium chloride, citric acid, ammonium citrate, ethylene glycol, ethanol, dimethyl hydroxyethyl are fine Dimension element, ammonium oxalate, ethylenediamine tetra-acetic acid, urea, lanthanum nitrate：It is chemical reagent.

3. hydrochloric acid：Concentration 36%, chemical reagent.

Embodiment 1

2g citric acids, 2.48mL nitric acid rare earths and 75mL deionized waters are mixed, forms uniform molten Liquid, adds 2g ammonium oxalate, stirs 15 minutes, forms the sediment slurries CD-1 containing rare earth.

Embodiment 2

2g ethanol, 2.48mL nitric acid rare earths and 75mL deionized waters are mixed, forms uniform molten Liquid, adds 2g ammonium oxalate, stirs 15 minutes, forms the sediment slurries CD-2 containing rare earth.

Comparative example 1

2.48mL nitric acid rare earths and 75mL deionized waters are mixed, uniform solution is formed, added 2g ammonium oxalate, stirs 15 minutes, forms the sediment slurries DCD-1 containing rare earth

Respectively to prepared using embodiment 1,2 and comparative example 1 the sediment slurries CD-1 containing rare earth, CD-2, DCD-1 test the granularity of rare-earth precipitation, are as a result listed in table 1.

The granularity of the rare-earth precipitation of table 1

The result of table 1 shows, compared with the sediment D CD-1 containing rare earth prepared using comparative example 1, Sediment CD-1, CD-2 granularity containing rare earth prepared using embodiment 1,2 is diminished, and illustrates this hair Bright organic complexing agent, dispersant can effectively reduce rare earth and precipitating reagent react formed sediment Grain size.

Embodiment 3

(1) rare earth ion exchanged molecular sieve is prepared：A () adds 1000g NaY molecular sieves (butt) In 7L deionized waters, under stirring, 300g ammonium chlorides, 165mL nitric acid rare earths are added, use hydrochloric acid Regulation 3.82,80 DEG C of slurry pH value at stir 1h, afterwards filter, washing, filter cake in roaster Hydrothermal calcine, 600 DEG C of sintering temperature, roasting time 2 hours are carried out under 100% water vapour atmosphere. B () is by the molecular sieve obtained by step (a), ammonium sulfate and water according to molecular sieve (butt)：Ammonium salt： Water=1：0.3：5 weight forms slurries than mixing, 1 is stirred under the conditions of 75 DEG C, pH=3.5 small When, filtering afterwards, wash, filter cake carries out hydro-thermal roasting in roaster under 100% water vapour atmosphere Burn, 620 DEG C of sintering temperature, roasting time 2 hours obtains rare earth ion exchanged molecular sieve Z-1.

By in 800g (butt) rare earth ion exchanged molecular sieve Z-1 addition 1.2L deionized waters, pass through Sanded treatment, obtains molecular sieve pulp Z-1J.By 619g Alumina gels, 1246g kaolin, 1.3L water Mixing mashing, adds molecular sieve pulp Z-1J afterwards, continues to stir 30min, is spray dried to after homogeneous Type, roasting, the microballoon after roasting is mixed with deionized water, ammonium chloride, wherein the microballoon after roasting： Water：The weight ratio of ammonium chloride is 1：6：0.003, stirred 30 minutes at 80 DEG C of temperature, filtering, Dry, prepare the catalyst precursors microballoon of semisynthesis synthesis.

(2) 16g citric acids, 4g ethylene glycol, 52mL nitric acid rare earths and 0.8L deionized waters are mixed Close, form uniform solution, add 40g ammonium oxalate, stir 15 minutes, form heavy containing rare earth Starch slurries.

(3) the catalyst precursors microballoon and step for preparing 3L deionized waters, step (1) (2) the sediment slurries mixing for being formed, stirs 20 minutes at 20 DEG C of temperature, filtering, dries, Obtain catalyst C-1 of the present invention.

Comparative example 2

(1) rare earth ion exchanged molecular sieve is prepared：A () adds 1000g NaY molecular sieves (butt) In 7L deionized waters, under stirring, 300g ammonium chlorides, 165mL nitric acid rare earths are added, use hydrochloric acid Regulation 3.82,80 DEG C of slurry pH value at stir 1h, afterwards filter, washing, filter cake in roaster Hydrothermal calcine, 600 DEG C of sintering temperature, roasting time 2 hours are carried out under 100% water vapour atmosphere. B () is by the molecular sieve obtained by step (a), ammonium sulfate and water according to molecular sieve (butt)：Ammonium salt： Water=1：0.3：5 weight forms slurries than mixing, 1 is stirred under the conditions of 75 DEG C, pH=3.5 small When, filtering afterwards, wash, filter cake carries out hydro-thermal roasting in roaster under 100% water vapour atmosphere Burn, 620 DEG C of sintering temperature, roasting time 2 hours obtains rare earth ion exchanged molecular sieve DZ- 1。

By in 800g (butt) rare earth ion exchanged molecular sieve DZ-1 addition 1.2L deionized waters, pass through Sanded treatment is crossed, molecular sieve pulp DZ-1J is obtained.By 619g Alumina gels, 1246g kaolin, 1.3L Water mixing mashing, adds molecular sieve pulp DZ-1J afterwards, continues to stir 30min, is sprayed after homogeneous dry Dry shaping, roasting, the microballoon after roasting is mixed with deionized water, ammonium chloride, wherein micro- after roasting Ball：Water：The weight ratio of ammonium chloride is 1：6：0.003, stirred 30 minutes at 80 DEG C of temperature, mistake Filter, dry, prepare the catalyst precursors microballoon of semisynthesis synthesis.

(2) catalyst precursors microballoon prepared by step (1) is mixed with 3.8L deionized waters, Stirred 20 minutes at 20 DEG C of temperature, filter, dry, obtain comparative catalyst DC-1.

Comparative example 3

(1) rare earth ion exchanged molecular sieve is prepared：A () adds 1000g NaY molecular sieves (butt) In 7L deionized waters, under stirring, 300g ammonium chlorides, 217mL nitric acid rare earths are added, use hydrochloric acid 1h is stirred at 3.82,80 DEG C of slurry pH value of regulation, 40g ammonium oxalate is added, stirred 15 minutes, Filter afterwards, wash, filter cake carries out hydrothermal calcine in roaster under 100% water vapour atmosphere, roast Burn 600 DEG C of temperature, roasting time 2 hours.B () is by the molecular sieve obtained by step (a), ammonium sulfate And water is according to molecular sieve (butt)：Ammonium salt：Water=1：0.3：5 weight forms slurry than mixing Liquid, stirs 1 hour under the conditions of 75 DEG C, pH=3.5, filters afterwards, washs, and filter cake is in roaster In carry out hydrothermal calcine under 100% water vapour atmosphere, 620 DEG C of sintering temperature, roasting time 2 is small When, that is, obtain rare earth ion exchanged molecular sieve DZ-2.

By in 800g (butt) rare earth ion exchanged molecular sieve DZ-2 addition 1.2L deionized waters, pass through Sanded treatment is crossed, molecular sieve pulp DZ-2J is obtained.By 619g Alumina gels, 1246g kaolin, 1.3L Water mixing mashing, adds molecular sieve pulp DZ-2J afterwards, continues to stir 30min, is sprayed after homogeneous dry Dry shaping, roasting, the microballoon after roasting is mixed with deionized water, ammonium chloride, wherein micro- after roasting Ball：Water：The weight ratio of ammonium chloride is 1：6：0.003, stirred 30 minutes at 80 DEG C of temperature, mistake Filter, dry, prepare the catalyst precursors microballoon of semisynthesis synthesis.

(2) catalyst precursors microballoon prepared by step (1) is mixed with 3.8L deionized waters, Stirred 20 minutes at 20 DEG C of temperature, filter, dry, obtain comparative catalyst DC-2.

Comparative example 4

(1) 52mL nitric acid rare earths and 0.8L deionized waters are mixed, forms uniform solution, then add Enter 40g ammonium oxalate, stir 15 minutes, form the sediment slurries containing rare earth.

(2) rare earth ion exchanged molecular sieve is prepared：A () adds 1000g NaY molecular sieves (butt) In 7L deionized waters, under stirring, 300g ammonium chlorides, 165mL nitric acid rare earths are added, use hydrochloric acid Regulation 3.82,80 DEG C of slurry pH value at stir 1h, afterwards filter, washing, filter cake in roaster Hydrothermal calcine, 600 DEG C of sintering temperature, roasting time 2 hours are carried out under 100% water vapour atmosphere. B () is by the molecular sieve obtained by step (a), ammonium sulfate and water according to molecular sieve (butt)：Ammonium salt： Water=1：0.3：5 weight forms slurries than mixing, 1 is stirred under the conditions of 75 DEG C, pH=3.5 small When, filtering afterwards, wash, filter cake carries out hydro-thermal roasting in roaster under 100% water vapour atmosphere Burn, 620 DEG C of sintering temperature, roasting time 2 hours obtains rare earth ion exchanged molecular sieve DZ- 3。

By in 800g (butt) rare earth ion exchanged molecular sieve DZ-3 addition 1.2L deionized waters, pass through Sanded treatment is crossed, molecular sieve pulp DZ-3J is obtained.By 619g Alumina gels, 1246g kaolin, 1.3L Water mixing mashing, the sediment slurries for adding molecular sieve pulp DZ-3J, step (1) to be formed afterwards, Continue to stir 30min, spray drying forming after homogeneous, roasting, by microballoon and deionization after roasting Water, ammonium chloride mixing, wherein the microballoon after roasting：Water：The weight ratio of ammonium chloride is 1：6： 0.003, stirred 30 minutes at 80 DEG C of temperature, filtering, dry, prepare semisynthesis synthesis Catalyst precursors microballoon.

(3) catalyst precursors microballoon prepared by step (2) is mixed with 3.8L deionized waters, Stirred 20 minutes at 20 DEG C of temperature, filter, dry, obtain comparative catalyst DC-3.

Embodiment 4

(1) by 588g (butt meter) REUSY molecular sieves, 12g (butt meter) ZSM-5 molecules Sieve, water are according to molecular sieve (butt)：Water=1：2 weight forms molecular sieve pulp Z- than mixing 2J.619g Alumina gels, 1513g diatomite, 1.6L water are mixed into mashing, molecule screening the pulp is added afterwards Liquid Z-2J, continue stir 30min, spray drying forming after homogeneous, roasting, by the microballoon after roasting with Deionized water, ammonium chloride mixing, make microballoon：Water：The weight ratio of ammonium chloride is 1：6：0.003, Stirred 20 minutes at 15 DEG C of temperature, filtering prepares the catalyst precursors of semisynthesis synthesis Microballoon.

(2) 82g ethylenediamine tetra-acetic acids, 78mL nitric acid rare earths, shape are added in 0.6L deionized waters Into solution, the pH value for adding ammoniacal liquor regulation mixed serum is 8.8, adds 17g ethanol, room temperature Stirred 30 minutes under (25 DEG C), form the slurries containing rare-earth precipitation thing.

(3) catalyst precursors microballoon, the mixing of 3L deionized waters for obtaining step (1), add The sediment slurries that step (2) is formed, stir 30 minutes under room temperature (25 DEG C), filter, dry, Obtain catalyst C-2 of the present invention.

Comparative example 5

(1) according to the preparation method of rare-earth-containing molecular sieve disclosed in Chinese patent CN99105792.9： By 798g (butt meter) REUSY molecular sieves, 16g (butt meter) ZSM-5 molecular sieve, water according to Molecular sieve (butt)：Water=1：3 weight is beaten than mixing, forms molecular sieve pulp, adds 110g ethylenediamine tetra-acetic acids, are 8.8 with the pH value of ammoniacal liquor Molecular regulator screening the pulp liquid, add 23g second Alcohol, stirs 30 minutes under room temperature (25 DEG C).Filtering, washing, filter cake is in 200 DEG C of dryings.Obtain Contrast molecular sieve DZ-4.

By in 600g (butt) molecular sieves DZ-4 addition 1.2L deionized waters, molecular sieve pulp is obtained DZ-4J.619g Alumina gels, 1513g diatomite, 1.6L water are mixed into mashing, molecular sieve is added afterwards Slurries DZ-4J, continue stir 30min, spray drying forming after homogeneous, roasting, by roasting after it is micro- Ball mixes with deionized water, ammonium chloride, makes microballoon：Water：The weight ratio of ammonium chloride is 1：6： 0.003, to be stirred 20 minutes at 15 DEG C of temperature, filtering prepares the catalysis of semisynthesis synthesis Agent predecessor microballoon.

(2) catalyst precursors microballoon, the mixing of 3.6L deionized waters, room for obtaining step (1) Stirred 30 minutes under warm (25 DEG C), filter, dry, obtain comparative catalyst DC-4.

Embodiment 5

(1) by 600g (butt) NH₄Y molecular sieve is added in 1.2L deionized waters, at sand milling Reason, obtains molecular sieve pulp Z-3J.1054g kaolin, 587g boehmites, 1.4L water are mixed Mashing is closed, 60mL hydrochloric acid is added, stirred 1 hour, be subsequently adding molecular sieve pulp Z-3J, stirred 15min, adds 515g Alumina gels, continues to stir 30min plastics, is spray dried to after homogeneous Type, roasting, the microballoon after roasting is mixed with deionized water, ammonium chloride, makes microballoon：Water：Ammonium chloride Weight ratio be 1：5：0.002, to be stirred 30 minutes at 55 DEG C of temperature, filtering prepares half The catalyst precursors microballoon of synthetic method synthesis.

(2) 155g urea, 85g lanthanum nitrates are added in 0.8L deionized waters, stirring is adjusted with ammoniacal liquor Section system pH adds 14g ethylene glycol in the range of 6.5~9.0, continues under room temperature (25 DEG C) Stirring 1.5 hours, forms the slurries containing rare-earth precipitation thing.

(3) catalyst precursors microballoon, the mixing of 2.5L deionized waters for obtaining step (1), add The sediment slurries that step (2) is formed, stir 1.5 hours under room temperature (25 DEG C), filter, do It is dry, obtain catalyst C-3 of the present invention.

Comparative example 6

(1) 85g lanthanum nitrates, stirring, with ammoniacal liquor regulation system pH are added in 0.8L deionized waters Value continues to stir 1.5 hours in the range of 6.5~9.0, under room temperature (25 DEG C), is formed and contains rare-earth precipitation The slurries of thing.

(2) by 600g (butt meter) NH₄Y molecular sieve is added in 1.2L deionized waters, at sand milling Reason, obtains molecular sieve pulp, the sediment slurries for adding step (1) to be formed, under room temperature (25 DEG C) Stirring 15 minutes, obtains molecular sieve pulp DZ-5J.1054g kaolin, 587g are intended into thin water aluminium Stone, the mixing mashing of 1.4L water, add 60mL hydrochloric acid, stir 1 hour, are subsequently adding molecular sieve pulp DZ-5J, stirs 15min, adds 515g Alumina gels, continues to stir 30min plastics, is sprayed after homogeneous Mist drying and moulding, roasting, the microballoon after roasting is mixed with deionized water, ammonium chloride, makes microballoon： Water：The weight ratio of ammonium chloride is 1：5：0.002, stirred 30 minutes at 55 DEG C of temperature, filtering, Prepare the catalyst precursors microballoon of semisynthesis synthesis.

(3) catalyst precursors microballoon, the mixing of 3.3L deionized waters, room temperature for obtaining step (2) Stirred 1.5 hours under (25 DEG C), filter, dry, obtain comparative catalyst DC-5.

Embodiment 6

(1) urged according to in-situ crystallization type disclosed in Chinese patent CN200810102244.5 embodiments 8 The preparation method of fluidized cracking catalysts:

20Kg (butt) kaolin is added water and is made solid content and is 35% slurries, and add sodium pyrophosphate With the auxiliary agent that NaOH amounts to 3%, spray shaping obtains the spraying soil ball of 15Kg.Spraying soil ball point 980 DEG C of roastings must not be calcined soil ball A1 for 2 hours in Muffle furnace, must be roasted within 3.5 hours in 750 DEG C of roastings Earth burning ball B1.Successively by sodium metasilicate (containing 19.84% SiO under stirring₂, 6.98% Na₂O) 750g, the mother liquor from gel method NaY synthesis (using the method for embodiment 3 in US3639099) (8.04%SiO₂, 0.67%Al₂O₃, 4.29%Na₂O=60: 5: 32) 300g, NaOH 11.2g, directed agents are (containing 11.65% SiO₂, 1.32% Al₂O₃, 12.89% Na₂O)96g、 In deionized water 200g, 260gA1,140gB1 input stainless steel reactor, 90 DEG C and perseverance are warmed up to Warm crystallization 20 hours.After crystallization terminates, mother liquor is filtered to remove, washing, dry cake obtain original position Crystallization product.Determined by X-ray diffraction method, in-situ crystallization product is containing 31% y-type zeolite, boiling The silica alumina ratio (mol ratio) of stone is 4.5.500g crystallization products, sulfuric acid are put under being stirred in stainless steel kettle Ammonium and deionized water, ammonium sulfate/crystallization product=0.38 are exchanged under the conditions of pH=3.0~3.5,90 DEG C 1.5 hours, it is filtered to remove filtrate, filter cake deionised water, is dried to obtain a friendship material；One is handed over Material roasting under conditions of 560 DEG C, vapor intake are for 45% obtains a baked material in 2 hours；One baked material is again Exchanged once with rare earth chloride, give-and-take conditions are：Rare earth/mono- baked material=0.05, pH=3.5~4.2, temperature It is 90 DEG C to spend, and the time is 1 hour, and the material after exchange is through filtering, washing, being dried to obtain two friendships Material；Two hand over material roasting under conditions of 670 DEG C, vapor intake are for 100% to obtain within 2 hours two roastings Material；Two baked materials are first swapped with ammonium chloride, ammonium chloride/bis- baked material=0.45, pH=3.8~4.5, Exchange 0.5 hour backward exchange and introduce in solution diammonium hydrogen phosphate, additional proportion be phosphorus/bis- baked material= 0.03, pH=4.0~4.8, exchange 0.5 hour, product is exchanged through filtering, washing, be dried to obtain Na₂O content is that 0.77%, content of rare earth is catalyst precursors that 2.95%, phosphorus content is 2.13% Microballoon YW-1.

(2) 13.8mL nitric acid rare earths, 3.3g ammonium citrates, 0.6g are added in 0.2L deionized waters Methyl hydroxyethylcellulose, stirs 15 minutes at 25 DEG C of temperature, adds 12.8g ammonium oxalate, continues Stirring 15 minutes, forms the slurries containing rare-earth precipitation thing.

(3) by obtained in 400g steps (1) catalyst precursors microballoon YW-1 add 0.8L go from In sub- water, under stirring, the slurries containing rare-earth precipitation thing for adding step (2) to be formed, temperature Stirred 15 minutes at 25 DEG C, filter, wash, dry, obtain catalyst C-4 of the present invention.

Comparative example 7

(1) urged according to in-situ crystallization type disclosed in Chinese patent CN200810102244.5 embodiments 8 The preparation method of fluidized cracking catalysts, is prepared for catalyst precursors microballoon YW-1.

(2) catalyst precursors microballoon YW-1 obtained in 400g steps (1) is added into 1L deionizations In water, stirred 15 minutes at 25 DEG C of temperature, filter, wash, dry, obtain comparative catalyst DC- 6。

In order to investigate the cracking activity and hydrothermal stability of catalyst, by urging for being prepared using embodiment 3~6 Agent C-1~C-4 and comparative catalyst DC-1~the DC-6 prepared using comparative example 2~7, is tested respectively By the activity after 17h steam agings, test result is listed in table 2 to catalyst.

In order to investigate the preventing from heavy metal pollution ability of catalyst, above-mentioned catalyst is used into incipient impregnation Method, impregnates 5000 μ g/g V, 3000 μ g/g Ni (relative to catalyst), through vanadium, nickel contamination respectively Catalyst process 6h under the conditions of 800 DEG C, 100% water vapour, test vanadium, nickel contamination catalyst 6h Activity after steam aging, test result is listed in table 2.

In table 2, the preventing from heavy metal pollution ability of catalyst is characterized with activity preservation rate R1.Definition:Activity Retention rate R1=vanadium, nickel contamination 6h steam agings activity/17h steam agings activity × 100%.

The result of table 2 shows, with the comparative catalyst DC-1~DC-6 phases prepared using comparative example 2~7 Than, catalyst C-1~C-4 prepared by the embodiment of the present invention 3~6, its activity preservation rate R1 is improved, Illustrate that modified molecular sieve catalyst of the present invention has stronger anti-vanadium, nickel contamination ability. The activity and preventing from heavy metal performance of the catalyst of table 2

Compared with the catalyst DC-1 prepared using comparative example 2, with prepared by the embodiment of the present invention 3 urging Agent C-1, its 17h are active apparently higher than comparative catalyst DC-1,2 percentage point high；With the present invention Catalyst C-1 prepared by embodiment 3, the activity after its vanadium, nickel contamination catalyst 6h steam agings Apparently higher than 7 percentage points of comparative catalyst (DC-1), activity preservation rate R1 improves 11 percentages Point, illustrates that catalyst of the present invention containing precipitating rare earth has activity stability and anti-vanadium, nickel contamination higher Ability.Compared with the catalyst DC-2 prepared using comparative example 3, prepared with the embodiment of the present invention 3 Catalyst C-1, its 17h activity are suitable with comparative catalyst DC-2, but its vanadium, nickel contamination catalyst Apparently higher than 3 percentage points of comparative catalyst (DC-2), activity retains activity after 6h steam agings Rate R1 improves 6 percentage points, illustrates that the present invention prepares precipitation using organic complexing agent and dispersant dilute The catalyst of soil has anti-vanadium higher, nickel contamination ability.With the catalyst prepared using comparative example 4 DC-3 is compared, and with catalyst C-1 prepared by the embodiment of the present invention 3, its 17h activity is urged higher than contrast 1 percentage point of agent；Activity after its vanadium, nickel contamination catalyst 6h steam agings is apparently higher than right Than 4 percentage points of catalyst (DC-3), activity preservation rate R1 improves 7 percentage points, illustrates this hair Bright use organic complexing agent and dispersant prepare precipitating rare earth catalyst have activity stability higher and Anti-vanadium, nickel contamination ability.

Compared with the catalyst DC-4 prepared using comparative example 5, with prepared by the embodiment of the present invention 4 urging Agent C-2, its 17h activity are apparently higher than 4 percentage points of comparative catalyst；Its vanadium, nickel contamination catalysis Activity after agent 6h steam agings is apparently higher than 12 percentage points of comparative catalyst (DC-4), activity Retention rate R1 improves 16 percentage points, illustrates that catalyst of the present invention containing precipitating rare earth has higher Activity stability and anti-vanadium, nickel contamination ability.

Compared with the catalyst DC-5 prepared using comparative example 6, with prepared by the embodiment of the present invention 5 urging Agent C-3, the activity after its vanadium, nickel contamination catalyst 6h steam agings is catalyzed apparently higher than contrast 6 percentage points of agent (DC-5), activity preservation rate R1 improves 10 percentage points, illustrates that the present invention contains The catalyst of precipitating rare earth has anti-vanadium higher, nickel contamination ability.

Compared with the catalyst DC-6 prepared using comparative example 7, with prepared by the embodiment of the present invention 6 urging Agent C-4, its 17h activity are high 3 percentage points with comparative catalyst DC-6；Its vanadium, nickel contamination are urged Activity after agent 6h steam agings is higher than 9 percentage points of comparative catalyst (DC-6), and activity retains Rate R1 improves 9 percentage points, illustrates the catalyst containing precipitating rare earth of present invention preparation with higher Activity stability and anti-vanadium, nickel contamination ability.

Certainly, the present invention can also have other various embodiments, without departing substantially from spiritual and its essence of the invention In the case of, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention, But these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.

Claims (16)

1. a kind of preparation method containing rare earth catalyst Cracking catalyst, it is characterised in that the preparation method Including：

(1) semi-synthetic or total synthesis method synthetic catalyst predecessor microballoon is used；

(2) in the compound containing the B metal ions of the periodic table of elements III being dissolved in into water or acid, formed Solution, with (a) organic complexing agent and/or dispersant, (b) precipitant mix, 5~100 DEG C of temperature Under, stir at least 10 minutes, formed and contain III B element sediment, described organic complexing agent and III B The mol ratio of metal ion is 0.3~10:1, the dispersant is with the mol ratio of III B metal ions 0.2~16:1；

(3) gained is mixed containing III B element sediment with catalyst precursors microballoon, in temperature Stirred at 5~100 DEG C at least 10 minutes, filter, dry, prepared the catalysis containing III B element sediment and split Change catalyst；Wherein, III B element in terms of oxide is with the weight ratio of catalyst butt 0.002~0.06:1.

2. preparation method according to claim 1, it is characterised in that described organic complexing agent It is 0.5~6 with the mol ratio of III B metal ions:1, preferably 1.0~4:1.

3. preparation method according to claim 1, it is characterised in that the dispersant and III B The mol ratio of metal ion is 1~11:1, preferably 2~7:1.

4. preparation method according to claim 1, it is characterised in that organic complexing agent and III B The mol ratio of metal ion is 0.5~6:1；The dispersant is 1~11 with the mol ratio of metal ion:1.

5. preparation method according to claim 1, it is characterised in that described in terms of oxide III B element is 0.004~0.03 with the weight ratio of catalyst butt:1, preferably 0.006~0.015:1.

6. the preparation method according to Claims 1 to 5 any claim, it is characterised in that step Suddenly the compound containing the periodic table of elements III B metal ions is dissolved in water or acid described in (2), shape Into solution, it following is passed through with (a) organic complexing agent and/or dispersant, (b) precipitant mix One mode is realized：Mode 1, will contain the B metal ion solutions of the periodic table of elements III and organic complexing agent and/or After dispersant is uniform, precipitating reagent is added, stirred at least 10 minutes, form heavy containing III B element Starch；Mode 2, by precipitating reagent and organic complexing agent and/or dispersant it is uniform after, add and contain The solution of the compound of the B metal ions of the periodic table of elements III, stirs at least 10 minutes, is formed and contains III B Element sediment；Mode 3, precipitating reagent is molten with the compound containing the B metal ions of the periodic table of elements III After liquid mixing, organic complexing agent and/or dispersant are added, stirred at least 10 minutes, formed and contain III B Element sediment；Mode 4, will contain the B metal ion solutions of the periodic table of elements III and organic complexing agent and/or Dispersant, precipitating reagent add mixing simultaneously, stir at least 10 minutes, are formed containing III B element precipitation Thing.

7. the preparation method according to Claims 1 to 5 any claim, it is characterised in that institute Catalyst precursors microballoon is stated, using Na in semisynthesis synthetic catalyst predecessor microballoon₂O mass Content is not more than 0.4%, using Na in total synthesis method synthetic catalyst predecessor microballoon₂O mass contains Amount is not more than 0.7%.

8. the preparation method according to Claims 1 to 5 any claim, it is characterised in that institute State using Na in semisynthesis synthetic catalyst predecessor microballoon₂O mass contents are more than 0.4%, urge Agent predecessor microballoon is selected from the mode of one of the following by drop sodium treatment, the mode of its treatment：Mode 1, drop sodium treatment is carried out to catalyst precursors microballoon in step (1)；Mode 2, in step (3) gained is mixed containing III B element sediment with catalyst precursors microballoon, prepares and contain III B element Drop sodium treatment is carried out after the catalytic cracking catalyst of sediment.

9. the preparation method according to Claims 1 to 5 any claim, it is characterised in that right In the catalyst precursors microballoon of total synthesis method synthesis, its Na₂O mass contents are more than 0.7%, To catalyst precursors microballoon by drop sodium treatment in step (1).

10. the preparation method according to Claims 1 to 5 any claim, it is characterised in that The precipitating reagent is for that can provide or produce hydroxide ion, carbanion, bicarbonate ion, phosphorus Acid ion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, the compound of oxalate denominationby.

11. preparation methods according to claim 10, it is characterised in that the precipitating reagent is selected from Oxalic acid, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, ammoniacal liquor, phosphoric acid, diammonium hydrogen phosphate, One or more in ammonium dihydrogen phosphate, ammonium phosphate, urea.

12. preparation methods according to claim 11, it is characterised in that after the ammoniacal liquor is added Molecular sieve pulp pH value 6.5~9.0；Oxalic acid, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, Phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, the addition of urea meet precipitating reagent and with oxygen The weight ratio of the compound of III B element of compound meter is 0.3~5.

13. preparation method according to Claims 1 to 5 any claim, it is characterised in that The organic complexing agent is selected from formic acid, acetic acid, adipic acid, citric acid, tartaric acid, benzoic acid, second two In the salt and acetylacetone,2,4-pentanedione, diethanol amine, triethanolamine of amine tetraacethyl, salicylic acid and above-mentioned acid One or more.

14. preparation method according to Claims 1 to 5 any claim, it is characterised in that Described dispersant is selected from the monohydric alcohol or dihydroxylic alcohols, polyethylene glycol, cellulose that carbon number is 2~8 One or more in derivative, polyacrylamide and its derivative, guar gum.

15. preparation methods according to claim 14, it is characterised in that the cellulose derives Thing is sodium cellulose glycolate, methyl hydroxyethylcellulose, hydroxypropyl methyl cellulose；Described carbon is former Subnumber be 2~8 monohydric alcohol or dihydroxylic alcohols be ethanol, ethylene glycol, carbon number be 3 monohydric alcohol or Dihydroxylic alcohols is isopropanol, normal propyl alcohol, the propyl alcohol of 1,3- bis-, the propyl alcohol of 1,2- bis-.

16. preparation method according to Claims 1 to 5 any claim, it is characterised in that III described B element is selected from one or more in scandium, yttrium, lanthanide series rare-earth elements.