CN1301801A - Catalytic cracking catalyst containing phosphorus and zeolite and its preparing method - Google Patents

Abstract

A catalytic cracking catalyst contains zeolite, clay and adhesive as well as an homogeneously dispersed additive containing phosphorus and aluminium. It contains zeolite 25-70 wt%, clay 5-55 wt% and adhesive 5-50 wt%, and the additive contains phosphorus and aluminum in the amount of 0.5-20 wt% of the solid additive. The additive is obtained through the reaction between phosphoric acid solution and the oxide and/or hydroxide of aluminium, and has a specific weight of 1.2-1.7 g/cu cm. The catalyst has very high wearing strength.

Description

Catalytic cracking catalyst of a kind of phosphorous and zeolite and preparation method thereof

The invention relates to a kind of catalytic cracking of hydrocarbon that is used for, contain catalytic cracking catalyst of zeolite and preparation method thereof, more particularly, is catalytic cracking catalyst about a kind of phosphorous and zeolite that is used for catalytic cracking of hydrocarbon and preparation method thereof.

In recent years, catalytically cracked stock is becoming heavy and is becoming bad, and detrimental impurity such as vanadium, nickel, basic metal, alkaline-earth metal, alkali nitrogen increase in the stock oil, and slag-mixing amount also improves constantly, this makes the more difficult cracking of catalytically cracked material, and the coke that generates on the catalyzer is more and inactivation is faster.For this reason, need the exploitation activity higher, heavy oil conversion performance is stronger, and the preventing from heavy metal ability is stronger, the better catalytic cracking catalyst of coke selectivity.Achieve the above object, improve the molecular sieve content in the catalytic cracking catalyst, perhaps improve the pore volume of catalytic cracking catalyst, the catalyzer of preparation macroporous structure is a kind of solution route.In addition, the development of catalytic cracking novel technique as short contact or ultrashort duration of contact and reduce the development of olefin catalytic cracking technology, also requires the polymer sieve content that matches with it and/or the catalyzer of macroporous structure.

Add phosphorus and can improve activity of such catalysts in catalytic cracking catalyst, to the selectivity of lightweight oil and the ability of preventing from heavy metal pollution, prior art is existing a lot of to the report of this respect.The adding mode of phosphorus roughly is divided into following several.

1. with clay composition and/or zeolite component in the phosphorus modification catalytic cracking catalyst.

US4,454,241 disclose a kind of catalyzer, and this catalyzer contains a kind of crystal silicon-aluminate zeolite by the clay preparation, the residue that a kind of described clay generates and the phosphorus of significant quantity.Described Preparation of catalysts method comprises that (1) carry out ion-exchange with a kind of by the zeolite of clay preparation and residue and a kind of non-alkalimetal ion that is generated by described clay, with the alkali metal content in the zeolite that reduces alkali metal containing, (2) zeolite and the residue after the roasting ion-exchange, (3) zeolite that obtains is contacted time enough with residue with a kind of medium, make zeolite and residue contain the phosphorus of significant quantity, described medium contains a kind of a kind of negatively charged ion that is selected from phosphoric acid hydrogen radical ion, dihydrogen phosphate ions and composition thereof.This catalyzer has advantages of high catalytic activity.

US4,465,780 disclose a kind of and US4, the similar catalyzer of 454,241 described catalyzer, different just except that with zeolite and residue with described negatively charged ion contacts, also itself and a kind of ammonium salt are exchanged.

US5,110,776 disclose a kind of preparation method who contains the catalytic cracking catalyst of zeolite, and this method comprises that (1) handle a kind of zeolite with the phosphorous aqueous solution, with this zeolite of modification, forms a kind of aqueous mixture; (2) aqueous mixture that will contain phosphorus-modified zeolite directly mixes with a kind of matrix precursor, forms a kind of slurries; And, form catalyzer (3) with the slurries spraying drying.The catalyzer of this method preparation has abrasive wear resistance preferably.

US4,839,319 disclose a kind of catalyzer, this catalyzer contains a kind of nonzeolite inorganic oxide matrix and a kind of overstable gamma zeolite, described zeolite has passed through pre-treatment, pretreated method is that described zeolite is contacted the sufficiently long time with a kind of phosphorus compound, makes the described zeolite-loaded phosphorus of going up significant quantity, and described phosphorus compound is selected from phosphoric acid, phosphorous acid, phosphoric acid salt, phosphite and their mixture.Compare with phosphorated catalyzer not, this catalyzer has lower coke and gas-selectively.

2. use the solution containing phosphate washing catalyst, in catalyzer, introduce phosphorus.

CN1,062,750A discloses a kind of hyperastable Y-type RE zeolite catalyst that is used for cracking hydrocarbon, this catalyzer is made up of with the mixture of ZSM-5 zeolite, the clay of the heavy % of 0-95, the high-temperature inorganic oxide of the heavy % of 0-85 and the phosphorus of 0.1-1 weight % the hyperastable Y-type RE zeolite of the heavy % of 1-40 or its, wherein, the content of rare earth in the hyperastable Y-type RE zeolite is the heavy % of 0.5-6.This Preparation of catalysts method comprises that the precursor with zeolite slurry, clay and/or high-temperature inorganic oxide is mixed in proportion, spray drying forming behind the homogeneous, carry out one or many ion-exchange aftertreatment with the P contained compound aqueous solution then, filter and drying.This catalyzer has higher hydrothermal stability, abrasive wear resistance and activity.

3. in catalyst preparation process, add phosphorus aluminium colloidal sol.

CN1,076,714A discloses a kind of phosphorated hydrocarbon cracking catalyzer, and this catalyzer is by the zeolite of the heavy % of 0-50, and the phosphorus aluminium colloidal sol (in aluminum oxide) of the heavy % of 8-34 and the clay of surplus are formed.This Preparation of catalysts method comprises that (1) is mixed into uniform slurries with clay and the phosphorated aluminiferous collosol that adds water, pH greater than 3.0 situation under, add an amount of zeolite slurry, the solid content that makes slurries is the heavy % of 30-42, spraying drying behind homogeneous; (2) with pH less than 3.1, Na ₂O content is heated to 30-80 ℃ less than the decationized Y sieve water of 5ppm, with the solvent and solute weight ratio is 10-60: the product that 1 consumption washing (1) obtains, the pulp time is 10-60 minute, filter, (3) with temperature being 30-80 ℃ ammoniacal liquor, is 10-60 with the solvent and solute weight ratio: the product that 1 consumption washing (2) obtains, and the pulp time is 10-60 minute, filter drying then.This catalyzer has good activity, hydrothermal stability, lower gas and coke selectivity, higher gasoline yield and abrasive wear resistance.

4. with phosphoric acid and aluminium colloidal sol or silicon sol reaction, preparation catalyzer or support of the catalyst.

US5,139,989 disclose a kind of catalyzer, and this catalyzer contains the solid solution of a kind of phosphorus, silicon, aluminum oxide, and this solid solution contains the aluminum oxide of the heavy % of 5-60, the silicon oxide of the heavy % of 10-90 and the Vanadium Pentoxide in FLAKES of the heavy % of 5-40.The preparation method of this solid solution comprises aluminium colloidal sol, silicon sol and phosphorus compound is mixed that form gel, spraying drying perhaps is dispersed in gel in the high temperature oil bath then, forms the solid solution of phosphorus, aluminium, Si oxide.This solid solution can be used as hydrocarbon conversion catalyst or support of the catalyst.

5. with the binding agent of phosphorus aluminium colloidal sol as catalyzer.

CN1,070,384A discloses a kind of method for preparing phosphorated aluminiferous collosol, this method is included under the continuous stirring, at aluminum concentration is the heavy % of 6-13, and aluminium/chlorine weight ratio is 1.2-1.8: add phosphide in 1 the aluminium colloidal sol, the add-on of phosphide is the heavy % (in P) of 0.5-4, at 80-100 ℃ with the colloidal sol depolymerization that forms 0.5-4 hour, up to the basicly stable postcooling of viscosity.But when aluminum concentration evaporation concentration during, when the pH of colloidal sol adds metallic aluminium less than 3 the time, to improve the pH value of colloidal sol less than 10 heavy %.The phosphorated aluminiferous collosol of this method preparation can be used as the binding agent of zeolite catalyst.

CN1,070,385A discloses a kind of preparation method of phosphorated aluminiferous collosol, this method comprises metallic aluminium and water or phosphide solution is heated to more than 60 ℃, then, adds the mixing solutions or the chloride soln of muriate and phosphorus compound in 1-4 hour, temperature 80-105 ℃ of reaction 12-72 hour, cooling, filtration obtain phosphorated aluminiferous collosol, and the phosphorated aluminiferous collosol of this method preparation can be used as the binding agent of zeolite catalyst.

US4,407,730 disclose a kind of support of the catalyst, and this support of the catalyst is made up of magnesium oxide-aluminum oxide-aluminum phosphate substrate after 10 hours basically through 500 ℃ of roastings, and the mean pore size of this carrier is the 10-300 dust, specific surface 100-350 rice ²/ gram, pore volume 0.3-1.5 milliliter/gram, wherein content of magnesia is 0.5 to less than 10 moles of % or 25-75 mole %, and alumina content is 2-90 mole %, and aluminum phosphate content is 3-95 mole %.The preparation method of this support of the catalyst is, the phosphoric acid solution of aluminum nitrate aqueous solution and magnesium nitrate and 85% is mixed, and adds solution of ammonium hydroxide again, precipitates under the condition of pH=9, filters, and is dry and in about 10 hours of 500 ℃ of roastings.This support of the catalyst has higher gasoline selective with the catalytic cracking catalyst of making after zeolite mixes, and can be used as the catalyzer of the high metal content raw material of cracking.

US4,919,787 disclose the passivating method of metal in a kind of hydrocarbon raw material, and this method is included under the passivation condition, and hydrocarbon raw material is contacted with a kind of passivator of significant quantity, and this passivator is a kind of porous precipitation, contains rare earth oxide-aluminum oxide-aluminum phosphate.The preparation method of this passivator comprises with the neutralization of a kind of alkaline solution and is dissolved in rare earth metal and aluminium in the phosphoric acid, dehydration then.This passivator can place before the catalyst cracker and use, and the part and the catalytic cracking catalyst that also can be used as catalyzer are mixed together use, as makes a kind of coating or catalyst junction lumps together use.

US4,873,211 disclose a kind of composition, and said composition can be used as the cracking catalyst component, and said composition contains zeolite and a kind of substrate material, and described zeolite is embedded in the described matrix, and described matrix is made up of aluminum phosphate basically.Essentially no aluminum oxide of this aluminum phosphate substrate and magnesium oxide.This matrix is that precipitation contains the solution of aluminium and phosphoric acid, hydrogen phosphate or phosphate radical under suitable pH value, washing, dry and prepare.Said composition demonstrates hydrothermal stability preferably.

6. with the binding agent of aluminum phosphate as catalyzer.

US5,286,369 disclose a kind of catalyst cracking method of hydrocarbon raw material, this method is included under the catalytic cracking process condition and a kind of catalyzer exists down, a kind of hydrocarbon raw material is reacted, described catalyzer contains a kind of a kind of zeolite and a kind of crystalline aluminophosphate binding agent that is selected from overstable gamma zeolite, ZSM-5 zeolite, Beta zeolite, SAPO zeolite, ALPO zeolite, and the specific surface of described crystalline aluminophosphate binding agent is less than 20 meters ²/ gram, pore volume is less than 0.1 milliliter/gram.A kind of preferred manufacturing procedure of this catalyzer comprises a kind of aluminum salt solution, is preferably a kind of Al of containing (NO ₃) ₃9H ₂The heavy %'s of aluminum nitrate solution and phosphoric acid solution, particularly phosphoric acid 20-86 of the heavy % of O 29-61, pH value is 0.5-0.9 and aluminium with the mol ratio of phosphorus is that the phosphoric acid solution of 0.4-1.4 mixes, and obtains a kind of aluminum phosphate solution.The aluminum phosphate solution that obtains is mixed with the slurries of zeolite (as the Beta zeolite) and clay (preferred kaolin), obtaining a kind of solid content is the spray-dryable slurries of the heavy % of 20-45, in butt, these slurries contain the aluminum phosphate of the heavy % of 8-25, the zeolite of the heavy % of 10-40 and the clay of the heavy % of 35-82.200-400 ℃ of spraying drying, in drying process, aluminum phosphate solution is transformed into a kind of binding agent with slurries.

WO99/02260 discloses a kind of catalyst composition, and said composition contains a kind of granular acidic molecular sieve and a kind of substrate material, and described substrate material contains amorphous phosphoric acid aluminium, and wherein, the aluminium of aluminum phosphate and the atomic ratio of phosphorus are greater than 1 to 1.5.The preparation method of described aluminum phosphate adopts sedimentary method.This catalyzer has higher activity.

Though disclosed catalyzer has advantages of high catalytic activity and/or to the selectivity of lightweight oil and/or the ability of preventing from heavy metal pollution in the above-mentioned prior art, some also has certain abrasion resistance, but the common shortcoming that they exist is, zeolite content in catalytic cracking catalyst surpasses 35 heavy %, when particularly weighing % above 40, perhaps, when the pore volume of catalytic cracking catalyst during greater than 0.35 milliliter/gram, the abrasive wear resistance of catalyzer can not satisfy the requirement that increases catalyzer mesolite content and increase catalyst pore volume with remarkable variation.Therefore, how to prepare and have more polymer sieve content or macropore volume more, and the catalytic cracking catalyst with high abrasion resistance strength has become a problem that urgency is to be solved.

Purpose of the present invention promptly provides higher phosphorous and zeolite catalysis cracking catalyst of a kind of abrasive wear resistance and preparation method thereof.

As previously mentioned, used phosphorus aluminium colloidal sol (or aluminum phosphate solution) adopts phosphorus compound and aluminium colloidal sol in the prior art, and silicon sol reacts under the condition of controlling pH＞3 and prepares (as CN1070384A and CN1070385A); Perhaps, under the condition of pH=9, precipitate the phosphoric acid solution of aluminum nitrate and magnesium nitrate and prepare (as US4,407,730) with solution of ammonium hydroxide; Perhaps, prepare (US4,919,787) with the solution of alkali solution precipitate phosphoric acid and rare earth ion; Perhaps, contain the solution of aluminum ion and phosphate radical, hydrogen phosphate with alkali solution precipitate and prepare (as US4,873,211); Perhaps, be selected from the ammonium salt of the ammonium salt of phosphoric acid, inferior ortho-phosphoric acid ammonium salt and diphosphanetetroic acid and the phosphorus compound of phosphoric acid directly joins (US5,472,922) in the slurries that contain silicon chlorides, clay and zeolite with a kind of; Perhaps, be that the aluminum phosphate solution of 0-1 directly joins (US5,286,369) in the slurries that contain zeolite and inorganic oxide with pH.The present inventor finds, when adopting the method for preparing catalyzer, though can increase the abrasive wear resistance of catalyzer to a certain extent,, when higher or catalyst pore volume was big when molecular sieve content in the catalyzer, its abrasive wear resistance was still not enough.Though, mechanism wherein it be unclear that, but, have been found that when higher or catalyst pore volume is big when molecular sieve content in the catalyzer, when adopting existing phosphorus aluminium colloidal sol to prepare catalyzer, breaking in various degree taken place in granules of catalyst, particularly after high-temperature vapor is aging, and worse off.By inference, owing to contain too much chlorine, ammonium, nitrate radical plasma in the above-mentioned phosphorus aluminium colloidal sol, these ions have certain stable combining with the component that wherein plays cohesive action probably, make the component that wherein plays cohesive action be in a kind of inactive state.In catalyst preparation process, still be in this inactive state, thereby, on the one hand, this stable combination has reduced the bond effect of the component of a cohesive action, on the other hand, in the spray-drying process of catalyzer, particularly in the water vapour weathering process, with adhesion component the chlorine of stable bond is arranged, ammonium, it is unstable that nitrate radical becomes, generate hydrogenchloride respectively, ammonia, nitrogen, gases such as oxygen, the generation of these gases make inner generate " bubble " in a large number of granules of catalyst, and these bubbles can be gone out from catalyzer inside when temperature raises, caused the damage of shape of catalyst, cause breaking of granules of catalyst under the serious situation, thereby reduced the cohesive action of various binding agents, the abrasion resistance of catalyzer is reduced greatly.

In order to overcome above-mentioned shortcoming, the present inventor has invented higher phosphorous and zeolite catalysis cracking catalyst of a kind of abrasive wear resistance and preparation method thereof.

Catalyzer provided by the invention contains zeolite, clay and binding agent, wherein, this catalyzer also contains a kind of additive that is evenly dispersed in the phosphorous and aluminium in the catalyzer, with the total catalyst weight is benchmark, the content of zeolite is the heavy % of 25-70, and the content of clay is the heavy % of 5-55, and the content of binding agent is the heavy % of 5-50, in additive solids content, phosphorous and content of additive aluminium is the heavy % of 0.5-20.Described oxide compound and/or oxyhydroxide phosphorous and that additive aluminium is phosphoric acid solution and aluminium react the reaction product that obtains, and its proportion is the 1.2-1.7 grams per milliliter, and the atomic ratio of phosphorus and aluminium is greater than 1 to 12,

Method for preparing catalyst provided by the invention comprises zeolite, clay, binding agent and/or its precursor and deionized water mix making beating, spraying drying then, wherein, also added a kind of additive, described additive is that the oxide compound and/or the oxyhydroxide of phosphoric acid solution and aluminium reacts the reaction product that obtains, its proportion is the 1.2-1.7 grams per milliliter, the mol ratio of phosphorus and aluminium is greater than 1 to 12, with the total catalyst weight is benchmark, described zeolite, clay, it is the heavy % of 25-70 that the add-on of binding agent and/or its precursor and additive makes the content of the catalyzer mesolite that obtains, the content of clay is the heavy % of 5-55, the content of binding agent is the heavy % of 5-50, in additive solids content, content of additive is the heavy % of 0.5-20.

According to catalyzer provided by the invention, the content of described zeolite is preferably the heavy % of 35-65, and the content of clay is preferably the heavy % of 5-40, and the content of binding agent is preferably the heavy % of 8-45, and phosphorous and content of additive aluminium is preferably the heavy % of 1-12.

According to catalyzer provided by the invention, described additive solids content refers to the additive solids content that described additive obtains under catalytic cracking catalyst spraying drying condition.General spray-dired temperature is 500-600 ℃.

The mol ratio of phosphorus and aluminium is greater than 1 to 12 in the additive of described phosphorous and aluminium, is preferably 2 to 10, and the proportion of described additive is the 1.2-1.7 grams per milliliter, is preferably the 1.3-1.5 grams per milliliter.

Described additive is the reaction product that obtains after the oxide compound of phosphoric acid solution and aluminium and/or the oxyhydroxide reaction.The oxide compound of described phosphoric acid solution and aluminium and/or the reaction of oxyhydroxide comprise: in room temperature to 100 ℃, be preferably under 70-95 ℃ the temperature phosphoric acid solution is contacted with the oxide compound and/or the oxyhydroxide of aluminium.It is greater than 1 to 12 that the oxide compound of the concentration of phosphoric acid solution and consumption and aluminium and/or the consumption of oxyhydroxide should make the phosphorus of the additive that obtains and the mol ratio of aluminium, is preferably 2 to 10, and proportion is the 1.2-1.7 grams per milliliter, is preferably the 1.3-1.5 grams per milliliter.Duration of contact, the change with temperature changed, and when temperature was low, duration of contact was longer, and when temperature was higher, duration of contact was shorter.Should make at least described duration of contact does not have alumina granules to exist in the mixture, under above-mentioned preferred temperature, be generally duration of contact 1-6 hour.

According to catalyzer provided by the invention, can also contain in magnesium, rare earth, titanium, zirconium, the tin one or more in the additive of described phosphorous and aluminium.Wherein, a kind of atomic ratio in phosphorus and these elements is 1-20, is preferably 2-12.The additive that contains above-mentioned element is the reaction product that obtains after the oxide compound of the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or one or more reactions in the oxyhydroxide.The oxide compound of the oxide compound of described phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or one or more the reaction in the oxyhydroxide comprise: in room temperature to 100 ℃, be preferably under 70-95 ℃ the temperature, the oxide compound of the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or in the oxyhydroxide one or more are contacted.The oxide compound of the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or one or more the consumption in the oxyhydroxide should make the atomic ratio of the phosphorus of the additive that obtains and aluminium for greater than 1-12, are preferably 2-10; A kind of mol ratio in phosphorus and magnesium, rare earth, titanium, zirconium, the tin is 1-20, is preferably 2-12.Described additive proportion is the 1.2-1.7 grams per milliliter, is preferably the 1.3-1.5 grams per milliliter.The oxide compound of the oxide compound of described phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or the contacting of one or more in the oxyhydroxide can proceed step by step,, react and add the oxide compound of magnesium, rare earth, titanium, zirconium, tin and/or in the oxyhydroxide one or more after finishing again phosphoric acid and aluminum oxide or aluminium hydroxide reaction as earlier.The oxide compound of the oxide compound of described phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or one or more the reaction in the oxyhydroxide also can be carried out simultaneously, carry out contact reacts when being about to the oxide compound of the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, tin and/or in the oxyhydroxide one or more.Each goes on foot the catalytic time and changes with the change of temperature, and when temperature was low, the contact reacts time was longer, and when temperature was higher, the contact reacts time was shorter.The contact reacts time in each step should make does not at least have the particulate state oxide compound to exist in the mixture, under above-mentioned preferred temperature, the contact reacts time in each step was generally 1-6 hour.

Wherein, described rare earth can be one or more in lanthanum, cerium, spectrum, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium, is preferably lanthanum, cerium or mainly contains the mixed rare-earth elements of lanthanum and cerium.

According to catalyzer provided by the invention, described zeolite can be existing various macropores and in the mesopore zeolite one or more as the catalytic cracking catalyst active ingredient.Under the preferable case, this zeolite is selected from one or more in faujusite, ZSM series zeolite, Beta zeolite, the mordenite.More under the preferable case, described zeolite is selected from one or more in X type zeolite, y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, mordenite, the ZSM-5 zeolite.Described sealumination modified Y zeolite is preferably used the sealumination modified Y zeolite of the method preparation of silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing, and the described sealumination modified Y zeolite of the method preparation of silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing of using can be referring to CN1127161A.

Described clay can be selected from one or more in the clay that is commonly used for the catalytic cracking catalyst component, as in kaolin, halloysite, polynite, diatomite, the wilkinite one or more.Under the preferable case, described clay is selected from kaolin, halloysite or their mixture.

Described binding agent is selected from binder component commonly used, as in silicon sol, aluminium colloidal sol, silicon-aluminum sol, pseudo-boehmite, the water glass one or more.

In order to prepare the catalyzer of macropore volume, catalyzer provided by the invention can also contain the gel that a kind of water glass and Tai-Ace S 150 are mixed with, and this gel is in catalyst preparation process, and drying becomes a kind of component of catalyzer.Compare with the catalyzer that does not contain this component, contain the catalyzer of this component, when molecular sieve content is identical or close, have bigger pore volume.

According to Preparation of catalysts method provided by the invention, the solid content of the additive of described zeolite, clay, binding agent and/or its precursor, phosphorous and aluminium and the slurries of deionized water is conventional scope, promptly conveniently carry out spraying drying for being advisable, generally speaking, described solid content is the heavy % of 10-45, is preferably the heavy % of 15-30.

According to Preparation of catalysts method provided by the invention, the pH value of described slurries is conventional pH value scope, as the scope of 2-5.When the pH of described slurries value greater than 5 the time, usually adding a spot of hydrochloric acid, to regulate the pH of slurries be 2-5.Though its mechanism it be unclear that,, the chlorine that exists in the hydrochloric acid of Jia Ruing and the prior art phosphorus aluminium colloidal sol is different here, can not influence the abrasion resistance of catalyzer.

According to Preparation of catalysts method provided by the invention, described spraying drying is carried out under normal condition, and as being 500-600 ℃ in temperature in, temperature out is to carry out under 200-350 ℃ the condition.

According to Preparation of catalysts method provided by the invention, described additive can add by the arbitrary steps before spraying drying.For example, zeolite, clay, binding agent and/or its precursor (also adding small amount of hydrochloric acid sometimes) and deionized water and described additive can be mixed together evenly, be prepared into described slurries.Can be earlier with one or more and deionized water making beating of zeolite, clay, binding agent and/or its precursor, add described additive again, then, add the pH value that hydrochloric acid is regulated slurries again.Can be earlier with one or more and deionized water making beating of zeolite, clay, binding agent and/or its precursor, add hydrochloric acid again, then, add described additive again.Also can add zeolite, clay, binding agent and/or its precursor and hydrochloric acid more earlier with additive and deionized water making beating.

Catalyzer provided by the invention has following advantage:

1. catalyzer provided by the invention has higher abrasion resistance.

For example, according to catalyzer provided by the invention, when zeolite content reached nearly 60 heavy % and/or pore volume greater than 0.35 milliliter/gram, its wear-resistant index was still less than 3% o'clock-1.

Again for example, from stereoscan photograph as can be seen, contain zeolite up to 50 heavy %, pore volume is that the fresh dose of uniform particles of catalyzer provided by the invention of 0.38-0.46 milliliter/gram is complete, after 800 ℃ of 100% water vapour wore out 17 hours, still keep good form, and the method for employing prior art, when zeolite content reached 50 weight %, its fresh dose of coating of particles was very poor, after aging 17 hours, its shape is just poorer (referring to accompanying drawing 1-8) through 800 ℃ of 100% water vapour

This is explanation simultaneously also, catalyzer provided by the invention has overcome the zeolite content of prior art in catalytic cracking catalyst and has surpassed 35 heavy %, when particularly weighing % above 40, perhaps, when the pore volume of catalytic cracking catalyst during greater than 0.35 milliliter/gram, the abrasive wear resistance of catalyzer is with the shortcoming of remarkable variation.

2. in magnesium, rare earth, titanium, zirconium, the tin one or more can also be contained in the described additive in the catalyzer provided by the invention,, these materials can be required to add according to difference catalytic cracking catalyst according to catalyzer provided by the invention.As when the needs catalyzer has the preventing from heavy metal pollution ability, should add components such as rare earth, titanium, magnesium.When catalyzer need have the ability of high-yield diesel oil, should add the magnesium component.When catalyzer need have stronger isomerization ability, should add components such as zirconium, titanium, when catalyzer need have the ability of desulfurization, nitrogen, components such as rare earth, tin should be added, when catalyzer need have the alkene of falling ability, components such as rare earth, zirconium, magnesium should be added.The adding of each component is simple and easy to do, is more suitable for large-scale industrial production.

3. in addition, Preparation of catalysts method provided by the invention is except adding described additive, and is all identical with existing commercial run, and on the one hand, this method of industrial employing can change flow process, just can produce better catalyzer.On the other hand, the pH of the slurries of preparation catalyzer is in the scope of 2-5, therefore, can use the zeolite molecular sieve of any kind according to different needs to catalyzer, and US5, the pH of 286,369 disclosed methods is too low, only is fit to super steady Y, the such supersiliceous zeolite of Beta zeolite.

Fig. 1 is fresh dose a stereoscan photograph of catalyzer provided by the invention;

Fig. 2 is the stereoscan photograph of the aging agent of catalyzer provided by the invention;

Fig. 3 is fresh dose a stereoscan photograph of reference catalyst;

Fig. 4 is fresh dose a stereoscan photograph of reference catalyst;

Fig. 5 is fresh dose a stereoscan photograph of reference catalyst;

Fig. 6 is fresh dose a stereoscan photograph of reference catalyst;

Fig. 7 is fresh dose a stereoscan photograph of reference catalyst;

Fig. 8 is fresh dose a stereoscan photograph of reference catalyst.

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

Example 1

The preparation of additive of the present invention.

Taking by weighing concentration is the phosphoric acid (chemical pure of 85 heavy %, Beijing chemical industry two factories) 525 grams mix with 1500 gram deionized waters, under the ebullient situation, add 88 gram hydrated aluminum oxides (salic 65 heavy %), reacted 4 hours 90 ℃ temperature with under stirring, obtain additive of the present invention, be designated as PAA.The atomic ratio of the proportion of PAA and phosphorus and aluminium is listed in the table 1.Described atomic ratio is got by calculating.

Example 2

The preparation of additive of the present invention.

Taking by weighing concentration is the phosphoric acid (chemical pure of 85 heavy %, Beijing chemical industry two factories) 3920 grams mix with 11760 gram deionized waters, reacted 4 hours 90 ℃ temperature with under stirring adding 761 gram hydrated aluminum oxides (salic 65 heavy %) and 833 gram rare-earth hydroxides (solid content is 50 heavy %) under the ebullient situation, obtain additive of the present invention, be designated as PAB.The atomic ratio of the atomic ratio of the proportion of PAB, phosphorus and aluminium and phosphorus and rare earth element is listed in the table 1.

Wherein, be benchmark with butt weight, in the oxyhydroxide of described rare earth, contain La ₂O ₃20 heavy %, CeO ₂60 heavy %, other rare earth oxides 20 heavy %.With RE ₂O ₃Meter, molecular-weight average is about 341.

Example 3-6

The preparation of additive of the present invention.

Method by example 2 prepares additive, and the different just consumptions of hydrated aluminum oxide is respectively 1026 grams, 889.2 grams, 447.2 grams, 588 grams, respectively with 142.9 gram magnesium oxide (MgO), 492 gram zirconium white (ZrO ₂), 396 gram titanium oxide (TiO ₂), 573.8 gram stannic oxide (SnO ₂) replace the rare-earth hydroxide mixture, obtain additive PAC, PAD, PAE and PAF.The atomic ratio of the atomic ratio of the proportion of PAC, PAD, PAE and PAF, phosphorus and aluminium and phosphorus and magnesium, zirconium, titanium, tin is listed in the table 1.

Table 1

Example number	The precursor numbering	Proportion, grams per milliliter	Phosphorus and al atomic ratio	Phosphorus and other atoms of elements ratios
					????1	????PAA	????1.32	????4.1	????-
????2	????PAB	????1.50	????3.5	????P∶RE????9.5
					????3	????PAC	????1.40	????2.6	????P∶Mg????9.7
????4	????PAD	????1.50	????3.0	????P∶Zr????8.6
					????5	????PAE	????1.38	????6.0	????P∶Ti????6.9
????6	????PAF	????1.48	????4.5	????P∶Sn????8.9

Example 7-10

The preparation of additive of the present invention.

Taking by weighing concentration is the phosphoric acid (chemical pure of 85 heavy %, Beijing chemical industry two factories) 6200 grams mix with 21500 gram deionized waters, under the boiling situation, add 2410.9 grams, 712.7 grams, 1108.6 grams and 623.6 gram hydrated aluminum oxides (salic 55 heavy %) and 1546.6 grams, 1354.7 grams, 1658.2 grams and 1256.6 gram examples, 2 described rare-earth hydroxides respectively, reacted 3 hours, 6 hours, 4 hours and 5 hours 90 ℃ temperature with under stirring, add magnesium oxide (MgO), the zirconium white (ZrO of 432.6 grams, 669.6 grams, 731.1 grams and 1028.3 grams more respectively ₂), titanium oxide (TiO ₂), stannic oxide (SnO ₂), reacted 1 hour, 2 hours, 2 hours and 4 hours 90 ℃ temperature with under stirring, obtain additive precursor PABC of the present invention, PABD, PABE and PABF.The atom of the atomic ratio of the proportion of PABC, PABD, PABE and PABF, phosphorus and aluminium, phosphorus and the rare earth element when atomic ratio of phosphorus and magnesium, zirconium, titanium, tin is listed in the table 2.Each atomic ratio gets by calculating.

Wherein, the solid content of magnesium oxide (MgO) is 98 heavy %, chemical pure, and chemical industry two factories in Beijing produce.

Zirconium white (ZrO ₂) solid content be 99 heavy %, chemical pure, chemical reagent six factories in Beijing produce.

Titanium oxide (TiO ₂) solid content be 98 heavy %, analytical pure, chemical industry two factories in Beijing produce.

Stannic oxide (SnO ₂) solid content be 99.8 heavy %, analytical pure, dicyclo chemical reagent work in Beijing produces.

Table 2

Example number	The precursor numbering	Proportion, grams per milliliter	Phosphorus and al atomic ratio	The atomic ratio of phosphorus and rare earth element	Phosphorus and other atoms of elements ratios
						????7	????PABC	????1.48	????2.1	????8.2	??P∶Mg????5.1
????8	????PABD	????1.32	????7.0	????9.2	??P∶Zr??10.0
						????9	????PABE	????1.50	????4.5	????7.5	??P∶Ti????5.9
????10	????PABF	????1.42	????8.0	????10.0	??P∶Sn????7.9

Example 11

Preparation of catalysts provided by the invention.

(solid content is 85 heavy % with kaolin, Suzhou kaolin company product) 3.6 kilograms and 12.5 kilograms of deionized waters making beating, mix, add 6.13 kilograms of aluminium colloidal sols (salic 21.5 heavy %, produce), add 4.6 kilograms of additive PAA (solid content is 23.8 heavy %), the pH value of slurries is 3.6, (lattice constant is 24.46 dusts to add the type-Y high silicon zeolite that the method with silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing prepares, solid content is 95 heavy %) 5.8 kilograms, behind the homogeneous, 550 ℃ of temperature ins, temperature out is a spray drying forming under 250 ℃ of conditions, obtains catalyzer C1 provided by the invention.The stereoscan photograph that the amplification that catalyzer C1 is fresh dose is 800 times as shown in Figure 1, through the stereoscan photograph of 1000 times of the amplification of 800 ℃ of 100% water vapour after aging 17 hours as shown in Figure 2, stereoscan photograph obtains on LEO 435VP type scanning electron microscope.The pore volume that the composition of each component and water droplet method are measured among the catalyzer C1 is listed in the table 3.Each component concentration is got by calculating.

Wherein, be by the method for CN1127161A example 4 and the preparation of each raw material consumption with the type-Y high silicon zeolite of the method for silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing preparation.

Comparative Examples 1 (DB1)

The preparation of reference catalyst.

Method by example 11 prepares catalyzer, and the different aluminium colloidal sols identical with the butt weight of additive precursor of just using replace additive PAA, obtain reference catalyst B1.The stereoscan photograph that the amplification that reference catalyst B1 is fresh dose is 800 times as shown in Figure 3, through the stereoscan photograph of 1000 times of the amplifications of the aging agent of 800 ℃ of 100% water vapour after aging 17 hours as shown in Figure 4.The pore volume that the composition of B1 and water droplet method are measured is listed in the table 3.

Comparative Examples 2 (DB2)

The preparation of reference catalyst.

Method by example 11 prepares catalyzer, and different is aluminum phosphate (chemical pure, chemical industry two factories in Beijing produce) the solution replacement additive PAA of 45 heavy % with 2.4 kilograms of concentration just, obtains reference catalyst B2.The stereoscan photograph that the amplification that reference catalyst B2 is fresh dose is 1000 times as shown in Figure 5, the stereoscan photograph that the amplification of the aging agent that obtains after aging 17 hours through 800 ℃ of 100% water vapour is 510 times is as shown in Figure 6.The pore volume that the composition of B2 and water droplet method are measured is listed in the table 3.

Comparative Examples 3 (DB3)

The preparation of reference catalyst.

Method by example 11 prepares catalyzer, and is different just with 1.11 kilograms aluminum phosphate solid replacement additive PAA, obtains reference catalyst B3.The pore volume that the composition of B3 and water droplet method are measured is listed in the table 3.

Comparative Examples 4 (DB4)

The preparation of reference catalyst.

Method by example 11 prepares catalyzer, and different just presses US5 with 3.1 kilograms, and the aluminum phosphate solution of 286,369 disclosed methods preparation replaces additive PAA, obtains reference catalyst B4.The stereoscan photograph that the amplification that reference catalyst B4 is fresh dose is 900 times as shown in Figure 7.The pore volume that the composition of B4 and water droplet method are measured is listed in the table 3.

Wherein, press US5, the concrete preparation method that 286,369 disclosed methods prepare aluminum phosphate solution is to contain Al (NO with 11 kilograms ₃) ₃9H ₂The phosphoric acid solution of the aluminum nitrate solution of O 40 heavy % and 3.37 kilograms of phosphoric acid 85 heavy %, the aluminium by 0.4 mixes with phosphorus mol ratio (phosphorus is 2.5 with the atomic ratio of aluminium), obtains described aluminum phosphate solution (solid content is 36 heavy %).

Comparative Examples 5 (DB5)

The preparation of reference catalyst.

Method by Comparative Examples 4 prepares reference catalyst, when different is the preparation aluminum phosphate solution, the consumption of the phosphoric acid solution of phosphoric acid 85 heavy % is 5.4 kilograms, aluminium and phosphorus mol ratio are 0.25, the solid content of the aluminum phosphate solution that obtains is 40 heavy %, during the preparation catalyzer, the consumption of aluminum phosphate solution is 2.75 kilograms, obtains reference catalyst B5.The stereoscan photograph that the amplification that reference catalyst B5 is fresh dose is 300 times as shown in Figure 8.The pore volume that the composition of B5 and water droplet method are measured is listed in the table 3.

Comparative Examples 6 (DB6)

The preparation of reference catalyst.

Method by example 11 prepares catalyzer, and different is with 6.75 kilograms of Comparative Examples, the 4 described US5 that press, and 286,369 disclosed methods prepare aluminum phosphate solution and replace additive PAA and aluminium colloidal sol, obtain reference catalyst B6.The pore volume that the composition of B6 and water droplet method are measured is listed in the table 3.

Table 3

Example number	The catalyzer numbering	Zeolite content, heavy %	Clay content, heavy %	Binder content, heavy %	Additive and content thereof (butt), heavy %	Pore volume, grams per milliliter
							????11	????C1	????50	????28	????12	????PAA,10	????0.46
???DBl	????B1	????50	????28	????22	????-	????0.19
							??DB2	????B2	????50	????28	????12	Aluminum phosphate, 10	????0.35
??DB3	????B3	????50	????28	????12	Aluminum phosphate, 10	????0.40
							??DB4	????B4	????50	????28	????12	Aluminum phosphate, 10	????0.35
??DB5	????B5	????50	????28	????12	Aluminum phosphate, 10	????0.47
							??DB6	????B6	????50	????28	????-	Aluminum phosphate, 22	????-

Example 12-20

Preparation of catalysts provided by the invention.

Method by example 11 prepares catalyzer, different just replaces additive PAA with additive PAB, PAC, PAD, PAE, PAF, PABC, PABD, PABE and PABF respectively, the butt consumption of additive PAB, PAC, PAD, PAE, PAF, PABC, PABD, PABE and PABF is identical with PAA, obtains catalyzer C2-C10 provided by the invention.The pore volume that the composition of each catalyzer and water droplet method are measured is listed in the table 4.

Table 4

Example number	The catalyzer numbering	Zeolite and amount thereof, heavy %	Clay content, heavy %	Binding agent and content thereof (butt), heavy %	Additive and content thereof, heavy %	Pore volume, grams per milliliter
							????12	????C2	????50	????28	????12	?PAB,10	?0.38
????13	????C3	????50	????28	????12	?PAC,10	?0.38
							????14	????C4	????50	????28	????12	?PAD,10	?0.40
????15	????C5	????50	????28	????12	?PAE,10	?0.35
							????16	????C6	????50	????28	????12	?PAF,10	?0.38
????17	????C7	????50	????28	????12	?PABC,10	?0.35
							????18	????C8	????50	????28	????12	?PABD,10	?0.4l
????19	????C9	????50	????28	????12	?PABE,10	?0.29
							????20	????C10	????50	????28	????12	?PABF,10,	?0.37

Example 21-22

Preparation of catalysts provided by the invention.

With 6.7 kilograms of hyperastable Y-type RE zeolites (REUSY, solid content are 67 heavy %, and lattice constant is 24.50 dusts, and the Zhou village catalyst plant is produced, and content of rare earth is 1.5 heavy %, wherein, La ₂O ₃Content is 0.3 heavy %, CeO ₂Content is 0.9 heavy %, and other rare earth oxide content are 0.3 heavy %) or 5.7 kilograms of rare earth hydrogen Y zeolite (REHY, solid content are 70 heavy %, and lattice constant is 24.60 dusts, and the Zhou village catalyst plant is produced, and rare earth oxide content is 6 heavy %, wherein, and La ₂O ₃Content is 1.2 heavy %, CeO ₂Content is 3.6 heavy %, other rare earth oxide content are 1.2 heavy %) mix with 2 kilograms of additive PAC (solid content is 24.6 heavy %), 3.9 kilograms of kaolin (specification is with example 11), 7.87 kilograms of aluminium colloidal sols (specification is with example 11) and 9.95 kilograms of deionized waters respectively, the pH value of slurries is respectively 3.5 and 3.2,550 ℃ of inlet temperatures, spraying drying under the condition that temperature out is 250 ℃ obtains catalyzer C11 provided by the invention and C12.The pore volume that the composition of C11 and C12 and water droplet method are measured is listed in the table 5.

Comparative Examples 7 (DB7)

The preparation of reference catalyst.

Method by example 2l prepares catalyzer, different just with 1.05 kilograms of concentration be 45 heavy % aluminum phosphate (with Comparative Examples 2) solution and 0.078 kilogram magnesium nitrate (containing magnesium nitrate 95 heavy %) replacement additive PAC, obtain reference catalyst B7.The pore volume that the composition of B7 and water droplet method are measured is listed in the table 5.

Table 5

Example number	The catalyzer numbering	Zeolite content, heavy %	Clay content, heavy %	Binder content, heavy %	Additive (butt) and content thereof, heavy %	Pore volume, grams per milliliter
							????21	????Cll	????45.0	????33.1	????17.0	?PAC,4.9	?0.19
????22	????C12	????42.1	????34.8	????17.9	?PAC,5.2	?0.18
							??DB7	????B6	????45.0	????33.1	????17.0	Aluminum phosphate+magnesium oxide, 4.9	?0.22

Example 23

Preparation of catalysts provided by the invention.

With 16 kilograms of deionized waters and 4.75 kilograms of kaolin (solid content 84.5 heavy %, Suzhou kaolin company produces) mix and pull an oar, under agitation add additive PAE (solid content is 24.3 heavy %) l kilogram, add aluminium colloidal sol (specification is with example 11) 16 kilograms, adding hydrochloric acid is controlled at 3.2 with the pH of solution, (solid content is 85.7 heavy % for 8 kilograms in RFUSY zeolite (specification is with example 21) and ZSM-5 zeolite, silica alumina ratio is 20, chemical plant, Nanjing product) 0.9 kilogram, after mixing, spraying drying obtains catalyzer C13 provided by the invention.The pore volume that the composition of catalyzer C13 and water droplet method are measured is listed in the table 6.

Example 24

Preparation of catalysts provided by the invention.

With 15 kilograms of deionized waters and 5 kilograms of kaolin (solid content 84 heavy %, Suzhou kaolin company produces) mix and pull an oar, under agitation add 16 kilograms of aluminium colloidal sols (specification is with example 11), after stirring, add again 3.5 premium on currency glass (concentration be 216 the gram silicon oxide/liter, the Zhou village catalyst plant is produced), add additive precursor PAE2.88 kilogram (solid content is 24.3 heavy %), the pH value of slurries is 3.6, add REUSY zeolite (specification is with example 21) 15 kilograms, mix, spray drying forming obtains catalyzer C14 provided by the invention.The pore volume that the composition of catalyzer C14 and water droplet method are measured is listed in the table 6.

Example 25

Preparation of catalysts provided by the invention.

With 18.93 kilograms of deionized waters and 2.6 kilograms of kaolin (solid content 75 heavy %, Suzhou kaolin company produces) mix and pull an oar, add 3 kilograms of additive precursor PAB (solid content is 25.7 heavy %), after mixing, add pseudo-boehmite (salic 35.3 heavy %, Shandong Aluminum Plant's product) 5.4 kilogram, adding concentration is the hydrochloric acid of 33 heavy %, and the pH that regulates slurries is 3.2, stirs, be warming up to 60 ℃, aging 1 hour, be cooled to room temperature, (alumina content is 21.5 heavy % to add 8.5 kilograms of aluminium colloidal sols, the Zhou village catalyst plant is produced), the pH of last slurries is 3.5.(silica alumina ratio is 6 to add 7.5 kilograms of high-silicon Y-Zeolites (specification is with example 11), the overstable gamma zeolite that the method with silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing prepares, lattice constant is 24.48 dusts, solid content is 65.5 heavy %, the Zhou village catalyst plant is produced) 2.8 kilograms and the industrial trade mark be that (a kind of silica alumina ratio is 15 ZSM-5 type zeolite for the zeolite of ZRP-4, solid content is 94.5 heavy %, Zhou village catalyst plant product) 1.3 kilogram, mix the back 550 ℃ of inlet temperatures, spraying drying under the condition that temperature out is 250 ℃ obtains catalyzer C15 provided by the invention.The pore volume that the composition of catalyzer C15 and water droplet method are measured is listed in the table 6.

Comparative Examples 8 (DB8)

The preparation of reference catalyst.

Method by example 25 prepares catalyzer, and different is, (solid content is 50 heavy %, and this rare earth chloride is behind roasting formation oxide compound, and it consists of La with the rare earth chloride of 1.49 kilograms aluminum phosphate solutions (solid content is 45 heavy %) and 0.2 kilogram ₂O ₃20 heavy %, CeO ₂60 heavy %, other rare earth oxides 20 heavy %, produce in the chemical plant, packet header) and replace additive precursor PAB, obtain reference catalyst B8.The pore volume that the composition of B8 and water droplet method are measured is listed in the table 6.

Example 26-28

Preparation of catalysts provided by the invention.

Method by example 25 prepares catalyzer, different is that (silica alumina ratio is 20 with 1.336 kilograms of HZSM-5, solid content is 92 heavy %, produces in the chemical plant, Nanjing) replace ZRP, (silica alumina ratio is 30 perhaps to use 1.293 kilograms of Beta zeolites, solid content is 95 heavy %, Fushun No.3 Petroleum Factory produces) replace ZRP or (lattice constant is 24.60 dusts, and solid content is 78 heavy %, and rare earth oxide content is 8 weight % with 8.2 kilograms of rare earth hydrogen Y zeolite, wherein, La ₂O ₃Content is 1.6 heavy %, CeO ₂Be 4.8 heavy %, other rare earth oxide content are 1.6 heavy %, the Zhou village catalyst plant is produced) replace high-silicon Y-Zeolite, obtain catalyzer C16 provided by the invention, C17 and C18 respectively, the pore volume that the composition of catalyzer C16, C17 and C18 and water droplet method are measured is listed in the table 6.

Table 6

Example number	The catalyzer numbering	Zeolite content, heavy %	Clay content, heavy %	Binder content, heavy %	Additive and content thereof (butt), heavy %	Pore volume, grams per milliliter
							????23	????C13	????44.4	????29.0	????24.9	?PAE,1.8	?0.35
????24	????C14	????52.5	????21.9	????21.9	?PAE,3.6	?0.40
							????25	????C15	????59.5	????12.3	????23.4	?PAB,4.8	?0.46
???DB8	????B8	????59.5	????12.3	????23.4	Aluminum phosphate+rare earth oxide, 4.8	?0.38
							????26	????C16	????59.5	????12.3	????23.4	?PAB5,4.8	?0.40
????27	????C17	????59.5	????12.3	????23.4	?PAB3,4.8	?0.42
							????28	????C18	????59.5	????12.3	????23.4	?PAB,4.8	?0.38

Example 29

Preparation of catalysts provided by the invention.

With 16 liters of concentration be 215 gram silicon oxide/liter water glass with 6.8 liters, concentration be 70 restrain aluminum oxide/liter alum liquor mix, at 60 ℃ of aging l hours, be prepared into gel, filter, and with deionized water wash 2 times, the consumption of deionized water is 60 liters at every turn.Get 12 kilograms of filter cakes (solid content is 10 heavy %) and mix making beating with 16 kilograms of deionized waters, (solid content is 75 heavy % under agitation to add l kilogram kaolin, Suzhou kaolin company produces), additive PAB2.1 kilogram, stir, add pseudo-boehmite (salic 33 heavy %, Shandong Aluminum Plant's product) 5.7 kilogram, stir, be warming up to 65 ℃ and wore out 1 hour, be cooled to room temperature, the pH of slurries is 3, add overstable gamma zeolite (USY, the heavy % of solid content 65, lattice constant is 24.50 dusts, the Zhou village catalyst plant is produced) 5 kilograms, behind the homogeneous 550 ℃ of inlet temperatures, spray drying forming under the condition that temperature out is 260 ℃ obtains catalyzer C19 provided by the invention, and the pore volume that the composition of C19 and water droplet method are measured is listed in the table 7.

Example 30

Preparation of catalysts provided by the invention.

The filter cake (solid content is 10 heavy %) of getting 29 preparations of 12 kilograms of examples mixes making beating with 20 kilograms of deionized waters, (solid content is 75 heavy % under agitation to add 3.2 kilograms of kaolin, Suzhou kaolin company produces), additive PAB2.5 kilogram, stir, add aluminium colloidal sol (salic 21.5 heavy %, product) 13.4 kilogram, the pH of slurries is 3.2, add overstable gamma zeolite (USY, solid content 85 heavy %, lattice constant is 24.50 dusts, and the Zhou village catalyst plant is produced) 4.1 kilograms and the industrial trade mark be 1.4 kilograms in the molecular sieve (solid content is 94.4 heavy %, and the Zhou village catalyst plant is produced) of ZRP-4, behind the homogeneous 550 ℃ of inlet temperatures, spray drying forming under the condition that temperature out is 250 ℃ obtains catalyzer C20 provided by the invention, and the pore volume that the composition of C20 and water droplet method are measured is listed in the table 7.

Comparative Examples 9 (DB9)

The preparation of reference catalyst.

Method by example 30 prepares catalyzer, different just, re chloride (with Comparative Examples 8) the replacement additive PAB with 1.24 kilograms aluminum phosphate solutions (solid content is 45 heavy %) and 0.17 kilogram obtains reference catalyst B9.The composition of B9 and and the pore volume measured of water droplet method list in the table 7.

Table 7

Example number	The catalyzer numbering	Zeolite content, heavy %	Clay content, heavy %	Binder content, heavy %	Additive and content thereof (butt), heavy %	Pore volume, grams per milliliter
							????29	????C19	????42.7	????9.8	????40.4	?PAB,7.1	0.42
????30	????C20	????40.3	????20.1	????34.3	?PAB,5.3	0.46
							???DB9	????B9	????40.3	????20.1	????34.3	Aluminum phosphate+rare earth oxide, 5.3	0.40

Example 31

Following example illustrates the abrasion resistance of catalyzer provided by the invention.

Adopt the RIPP29-90 method to measure the abrasion index of the catalyzer C1 of example 11 preparations, test method is referring to " petrochemical complex analytical procedure (RIPP test method) ", Science Press, 73-75,1990.The results are shown in Table 8.

Comparative Examples 10-15

The abrasion resistance of following Comparative Examples explanation reference catalyst.

The method of pressing example 31 is measured the abrasion index of reference catalyst B1-B6, and the results are shown in Table 8.

Table 8

Example number	The catalyzer numbering	Abrasion index is during % -1
			????31	????C1	????1.2
Comparative Examples 10	????B1	????5
			Comparative Examples 11	????B2	????＞6
Comparative Examples 12	????B3	????＞9
			Comparative Examples 13	????B4	????＞9
Comparative Examples 14	????B5	????＞＞10
			Comparative Examples 15	????B6	????＞＞10

Example 32-40

Following example illustrates the abrasion resistance of catalyzer provided by the invention.

The method of pressing example 3l is measured the abrasion index of catalyzer C2-C10, and the results are shown in Table 9.

Table 9

Example number	The catalyzer numbering	Abrasion index is during % -1
			????32	????C2	?????0.8
????33	????C3	?????1.5
			????34	????C4	?????0.5
????35	????C5	?????1.7
			????36	????C6	?????0.2
????37	????C7	?????1.7
			????38	????C8	?????2.7
????39	????C9	?????2.6
			????40	????C10	?????1.5

Example 41-42

Following example illustrates the abrasion resistance of catalyzer provided by the invention.

The method of pressing example 31 is measured the abrasion index of C11-C12.The results are shown in Table 10.

Comparative Examples 16

The abrasion resistance of following Comparative Examples explanation reference catalyst.

The method of pressing example 31 is measured the abrasion index of reference catalyst B7.The results are shown in Table 10.

Table 10

Example number	The catalyzer numbering	Abrasion index is during % -1
			????41	????C11	?????0.5
????42	????C12	?????0.2
			Comparative Examples 16	????B7	????5

Example 43-48

Following example illustrates the abrasion resistance of catalyzer provided by the invention.

The method of pressing example 31 is measured the abrasion index of catalyzer C13-C18.The results are shown in Table 11.

Comparative Examples 17

The abrasion resistance of following example explanation reference catalyst.

The method of pressing example 31 is measured the abrasion index of reference catalyst B8.The results are shown in Table 11.

Table 11

Example number	The catalyzer numbering	Abrasion index is during % -1
			????43	????C13	?????1.4
????44	????C14	?????2.6
			????45	????C15	?????2.8
Comparative Examples 17	????B8	?????6
			????46	????C16	?????2.8
????47	????C17	????2.7
			????48	????C18	?????26

The result of table 8-11 shows, on the one hand, is forming under the identical or proximate situation, and the abrasion resistance of catalyzer provided by the invention is higher than existing catalyzer far away.On the other hand, according to the catalyzer that invention provides, when zeolite content weighed % up to 59.5, its abrasion index is the highest had only at 2.8% o'clock ^-1Catalyzer provided by the invention is adopted in this explanation, can use higher zeolite content.

Example 49-50

Following example illustrates the abrasion resistance of catalyzer provided by the invention.

The method of pressing example 31 is measured the abrasion index of catalyzer C19-C20.The results are shown in Table 12.

Comparative Examples 18

The abrasion resistance of following Comparative Examples explanation reference catalyst.

The method of pressing example 31 is measured the abrasion index of catalyst B 9.The results are shown in Table 12.

Table 12

Example number	The catalyzer numbering	Abrasion index is during % -1
			????49	????C19	?????2.8
????50	????C20	?????2.6
			Comparative Examples 18	????B9	?????9.8

The result of table 12 shows according to the catalyzer that invention provides, when pore volume is big, to have low abrasion index equally.Catalyzer provided by the invention is adopted in this explanation, can improve the pore volume of catalyzer.

Example 51

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

Catalyzer C1 was worn out 4 hours with 100% water vapour down at 800 ℃, and at the catalytic performance of estimating the catalyzer after wearing out on the heavy oil microreactor, the catalyzer loading amount is 4 grams, and raw materials used oil is vacuum gas oil, and the raw material oil properties is listed in the table 13.Reaction conditions is 520 ℃ of temperature of reaction, and weight hourly space velocity is 16 hours ^-1, agent weight of oil ratio is 3.Evaluation result is listed in the table 14.

Wherein, the heavy % in transformation efficiency=(gas content+gasoline content+coke content+loss)/inlet amount * 100;

Coke selectivity=coke yield/transformation efficiency;

Gasoline selective=gasoline yield/transformation efficiency;

Light oil yield=gasoline yield+diesel yield;

Each components contents adopts gas chromatographic analysis in the reaction product.

Comparative Examples 19-21

The catalytic performance of following Comparative Examples explanation reference catalyst.

Press method aging reference catalyst B1, B2 and the B4 of example 51, and estimate reference catalyst B1, B2 after aging and the catalytic performance of B4, evaluation result is listed in the table 14.

Table 13

The stock oil title	Vacuum gas oil
		Proportion, gram per centimeter 2Viscosity, mm 2/s	?????0.8652
????50℃	?????14.58
		????100℃	?????4.37
Carbon residue, heavy % boiling range, ℃	?????0.04
		Initial boiling point	?????227
????5％	?????274
		????10％	?????289
????20％	?????322
		????30％	?????347
????40％	?????373
		????50％	?????389
????60％	?????401
		????70％	?????417
????80％	?????431
		????90％	?????446
????95％	?????458
		Do	?????478

Table 14

Example number		????51	Comparative Examples 19	Comparative Examples 20	Comparative Examples 21
						Catalyzer		??C1	????B1	????B2	????B4
Product distributes and weighs %	Gas	????14.2	????15.8	????16.2	????15.9
						Coke	????1.7	????2.1	????2.1	????1.8
	Gasoline	????64.5	????60.9	????59.2	????57.9
						Diesel oil	????15.7	????16.9	????17.4	????14.8
	＞330 ℃ of fractions	????3.9	????4.3	????5.1	????9.6
						Propylene	????4.1	????4.4	????4.5	????4.1
	Butylene	????3.1	????3.7	????3.9	????5.6
						Transformation efficiency, heavy %		????80.4	????78.8	????77.5	????75.6
Yield of light oil, heavy %		??80.4	??77.87	??76.6	??72.7
						Coke selectivity		????2.1	????2.7	????2.7	????2.5
Gasoline selective		????80.2	????78.3	????76.4	????79.6

Real wasteful 452

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

Catalyzer C20 was worn out 17 hours with 100% water vapour down at 800 ℃, and at the catalytic performance of estimating the catalyzer after wearing out on the heavy oil microreactor, the catalyzer loading amount is 4 grams, and raw materials used oil is vacuum gas oil shown in the table 13.Reaction conditions is 520 ℃ of temperature of reaction, and weight hourly space velocity is 16 hours-1, and agent weight of oil ratio is 5.Evaluation result is listed in the table 15.

Comparative Examples 22

The catalytic performance of following Comparative Examples explanation reference catalyst.

Press the aging reference catalyst B9 of method of example 52, and estimate the catalytic performance of the reference catalyst B9 after wearing out, evaluation result is listed in the table 15.

Table 15

Example number		????51	Comparative Examples 22
				Catalyzer		????C20	????B9
Product distributes and weighs %	Gas	????8.0	????9.2
				Coke	????1.9	????2.1
	Gasoline	????55.6	????51.1
				Diesel oil	????21.1	????21.9
	＞330 ℃ of fractions	????13.4	????15.9
				Propylene	????2.3	????2.4
	Butylene	????2.5	????3.1
				Transformation efficiency, heavy %		????65.5	????62.4
Yield of light oil, heavy %		????76.7	????73.0
				Coke selectivity		????2.9	????3.4
Gasoline selective		????84.9	????81.9

Example 53-54

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

Catalyzer C9 and C7 are carried out nickel and pollution of vanadium with Mitchell (mitchell) method (Ind.Eng. Chem., Prod.Res.Dev., 17,209,1980).Promptly 550 ℃ with catalyzer roasting 2 hours, with naphthenic acid vanadium and nickel naphthenate solution impregnation catalyst, in 100 ℃ of oven dry, 600 ℃ of roastings 5 hours.The catalyzer that soaks vanadium and nickel after the roasting is containing in 100% water vapour atmosphere aging 4 hours in 800 ℃, pollutes the lotus scale to improve.

Estimating vanadium in the different pollutions, nickel and the catalyzer after wearing out on the heavy oil microreactor respectively.Reaction raw materials is the listed vacuum gas oil of table 13, and reaction conditions is 520 ℃ of temperature of reaction, weight hourly space velocity 16 hours ^-1, agent weight of oil ratio is 5.Vanadium, nickel content (pollution level) and evaluation result are listed in the table 16 in the catalyzer.

Table 16

Example number		????53	????54
				Catalyzer		????C9	????C7
Content of vanadium, ppm		????3000	????3000
				Nickel content, ppm		????1000	????1000
Product distributes and weighs %	Gas	????13.1	????13.2
				Coke	????2.7	????2.7
	Gasoline	????54.3	????54.1
				Diesel oil	????20.4	????20.8
	＞330 ℃ of fractions	????9.5	????9.2
				Propylene	????3.3	????3.2
	Butylene	????5.1	????4.6
				Transformation efficiency, heavy %		????70.1	????70.0
Yield of light oil, heavy %		????74.7	????74.9
				Coke selectivity		????3.9	????3.9
Gasoline selective		????77.4	????77.2

The result of table 16 shows, contains the catalyzer that contains the additive of components such as rare earth, magnesium, titanium of the present invention and not only has high abrasion resistance and high heavy oil conversion performance, and have very high preventing from heavy metal pollution ability.

Claims (26)

1. phosphorous and catalytic cracking catalyst zeolite contains zeolite, clay and binding agent, it is characterized in that, with the total catalyst weight is benchmark, this catalyzer also contains a kind of additive that is evenly dispersed in the phosphorous and aluminium in the catalyzer, is benchmark with the total catalyst weight, and the content of zeolite is the heavy % of 25-70, the content of clay is the heavy % of 5-55, the content of binding agent is the heavy % of 5-50, and in additive solids content, phosphorous and content of additive aluminium is the heavy % of 0.5-20; Described oxide compound and/or oxyhydroxide phosphorous and that additive aluminium is phosphoric acid solution and aluminium react the reaction product that obtains, and its proportion is the 1.2-1.7 grams per milliliter, and the atomic ratio of phosphorus and aluminium is greater than 1 to 12.

2. catalyzer according to claim 1 is characterized in that, the content of described zeolite is the heavy % of 35-65, and the content of clay is the heavy % of 5-40, and the content of binding agent is the heavy % of 8-45, and phosphorous and content of additive aluminium is the heavy % of 1-12.

3. catalyzer according to claim 1 is characterized in that, the atomic ratio of phosphorus and aluminium is 2 to 10 in the additive of described phosphorous and aluminium, and the proportion of described additive is the 1.3-1.5 grams per milliliter.

4. catalyzer according to claim 1, it is characterized in that, the oxide compound of described phosphoric acid solution and aluminium and/or the reaction of oxyhydroxide comprise phosphoric acid solution are contacted with the oxide compound and/or the oxyhydroxide of aluminium, the contact temperature is a room temperature to 100 ℃, it is 1.2-1.7 that the oxide compound of the concentration of phosphoric acid solution and consumption and aluminium and/or the consumption of oxyhydroxide make the proportion of the additive that obtains, and the atomic ratio of phosphorus and aluminium is greater than 1 to 12.

5. catalyzer according to claim 4, it is characterized in that, described phosphoric acid solution is 70-95 ℃ with the oxide compound of aluminium and/or the temperature that contacts of oxyhydroxide, be 1-6 hour duration of contact, it is 1.3-1.5 that the oxide compound of the concentration of phosphoric acid solution and consumption and aluminium and/or the consumption of oxyhydroxide make the proportion of the additive that obtains, and the atomic ratio of phosphorus and aluminium is greater than 2 to 10.

6. catalyzer according to claim 1 is characterized in that, also contains in magnesium, rare earth, titanium, zirconium, the tin one or more in the additive of described phosphorous and aluminium, and wherein, a kind of atomic ratio in phosphorus and these elements is 1-20.

7. catalyzer according to claim 6 is characterized in that, described atomic ratio is 2-12.

8. catalyzer according to claim 6, it is characterized in that, the described magnesium that contains, rare earth, titanium, zirconium, the preparation method of the additive of one or more in the tin and phosphorus and aluminium comprises the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, the oxide compound of tin and/or one or more contacts in the oxyhydroxide, the temperature of contact is a room temperature to 100 ℃, the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, it is the 1.2-1.7 grams per milliliter that the consumption of one or more in tin-oxide and/or the oxyhydroxide makes the proportion of the additive that obtains, the mol ratio of phosphorus and aluminium is greater than 1 to 12 in the additive, phosphorus and magnesium, rare earth, titanium, zirconium, a kind of atomic ratio in the tin is 1-20.

9. catalyzer according to claim 8, it is characterized in that, the oxide compound of described phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, bore, the oxide compound of tin and/or one or more the contact temperature in the oxyhydroxide are 70-95 ℃, be 1-6 hour duration of contact, the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, it is the 1.3-1.5 grams per milliliter that the consumption of one or more in tin-oxide and/or the oxyhydroxide makes the proportion of the additive that obtains, the mol ratio of phosphorus and aluminium is 2 to 10 in the additive, phosphorus and magnesium, rare earth, titanium, zirconium, a kind of atomic ratio in the tin is 2-12.

10. catalyzer according to claim 1 is characterized in that, described zeolite is one or more in macropore and the mesopore zeolite.

11. catalyzer according to claim 10 is characterized in that, described zeolite is selected from one or more in faujusite, ZSM series zeolite, Beta zeolite, the mordenite.

12. catalyzer according to claim 11 is characterized in that, described zeolite is selected from one or more in X type zeolite, y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, mordenite, the ZSM-5 zeolite.

13. catalyzer according to claim 12 is characterized in that, described sealumination modified Y zeolite refers to the sealumination modified Y zeolite with the preparation of silicon tetrachloride gas phase aluminium-eliminating and silicon-replenishing method.

14. catalyzer according to claim 1 is characterized in that, described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, the wilkinite.

15. catalyzer according to claim 14 is characterized in that, described clay is selected from kaolin, halloysite or their mixture.

16. catalyzer according to claim 1 is characterized in that, described binding agent is selected from one or more in silicon sol, aluminium colloidal sol, silicon-aluminum sol, pseudo-boehmite and the water glass.

17. claim 1 Preparation of catalysts method comprises zeolite, clay, binding agent and/or its precursor and deionized water mix making beating, spraying drying then, it is characterized in that, also added a kind of additive, described additive is that the oxide compound and/or the oxyhydroxide of phosphoric acid solution and aluminium reacts the reaction product that obtains, its proportion is the 1.2-1.7 grams per milliliter, the atomic ratio of phosphorus and aluminium is greater than 1 to 12, with the total catalyst weight is benchmark, described zeolite, clay, it is the heavy % of 25-70 that the add-on of binding agent and/or its precursor and additive makes the content of the catalyzer mesolite that obtains, the content of clay is the heavy % of 5-55, the content of binding agent is the heavy % of 5-40, in additive solids content, content of additive is the heavy % of 0.5-20.

18. method according to claim 17 is characterized in that, the arbitrary steps of described additive before spraying drying adds.

19. method according to claim 17 is characterized in that, described phosphorous and content of additive aluminium is the heavy % of 1-12.

20. method according to claim 17 is characterized in that, the mol ratio of phosphorus and aluminium is 2 to 10 in the additive of described phosphorous and aluminium, and the proportion of described precursor is the 1.3-1.5 grams per milliliter.

21. method according to claim 17, it is characterized in that, the oxide compound of described phosphoric acid solution and aluminium and/or the reaction of oxyhydroxide comprise phosphoric acid solution are contacted with the oxide compound and/or the oxyhydroxide of aluminium, the contact temperature is a room temperature to 100 ℃, it is 1.2-1.7 that the oxide compound of the concentration of phosphoric acid solution and consumption and aluminium and/or the consumption of oxyhydroxide make the proportion of the additive that obtains, and the atomic ratio of phosphorus and aluminium is greater than 1 to 12.

22. method according to claim 21, it is characterized in that, described contact temperature is 70-95 ℃, be 1-6 hour duration of contact, it is 1.3-1.5 that the oxide compound of the concentration of phosphoric acid solution and consumption and aluminium and/or the consumption of oxyhydroxide make the proportion of the additive that obtains, and the atomic ratio of phosphorus and aluminium is 2 to 10.

23. method according to claim 17 is characterized in that, also contains in magnesium, rare earth, titanium, zirconium, the tin one or more in the additive of described phosphorous and aluminium, wherein, a kind of atomic ratio in phosphorus and these elements is 1-20.

24. method according to claim 23 is characterized in that, described atomic ratio is 2-12.

25. method according to claim 23, it is characterized in that, contain magnesium, rare earth, titanium, zirconium, the preparation method of the additive of one or more in the tin and phosphorus and aluminium comprises the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, one or more contacts in tin-oxide and/or the oxyhydroxide, the temperature of contact is a room temperature to 100 ℃, the oxide compound of phosphoric acid solution and aluminium and/or oxyhydroxide and magnesium, rare earth, titanium, zirconium, it is the 1.2-1.7 grams per milliliter that the consumption of one or more in tin-oxide and/or the oxyhydroxide makes the proportion of the additive that obtains, the mol ratio of phosphorus and aluminium is greater than 1 to 12 in the additive, phosphorus and magnesium, rare earth, titanium, zirconium, a kind of atomic ratio in the tin is 1-20.

26. method according to claim 25, the temperature that it is characterized in that described contact is 70-95 ℃, and be 1-6 hour duration of contact.

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