CN105148985B - A kind of catalytic cracking catalyst and its preparation method and application - Google Patents

Abstract

The invention discloses a kind of catalytic cracking catalysts and its preparation method and application.The catalytic cracking catalyst contains cracking activity constituent element, clay and binding agent, wherein, the cracking activity constituent element contains the 3rd Y type molecular sieve of the first Y type molecular sieve of 35 70 weight %, the second Y type molecular sieve of 20 60 weight % and 2 20 weight %；The binding agent is the modification Aluminum sol containing Cl and Si, and on the basis of the total weight of the modified Aluminum sol, Al content is that 8 13 weight %, Cl contents are that 49 weight %, Al/Cl weight ratios are 1.2 2.2：1, Si content is 0.1 1 weight %, and the pH value of the modified Aluminum sol is 2.2 5.2.The catalytic cracking catalyst not only has relatively low coke selectivity and higher catalytic cracking activity during heavy oil catalytic cracking, but also can obtain higher diesel yield.

Description

A kind of catalytic cracking catalyst and its preparation method and application

Technical field

The present invention relates to a kind of catalytic cracking catalyst, the preparation method of the catalytic cracking catalyst and the catalysis Application of the Cracking catalyst in heavy oil catalytic cracking.

Background technology

Catalytic cracking (FCC) is important crude oil secondary processing process, and very important status is occupied in petroleum refining industry. In catalytic cracking process, heavy end (such as vacuum distillate or the residual oil of more heavy constituent) occurs instead in the presence of a catalyst Should, the high value added products such as liquefied gas, gasoline, diesel oil are converted into, usually require to live using with high cracking in this process The catalysis material of property.Micro-pore zeolite catalysis material due to excellent shape selective catalysis performance and very high cracking reaction activity, It is widely used in petroleum refining and processing industry.At present, catalytic cracking catalyst mainly includes cracking activity constituent element, glues The components such as soil, binding agent, wherein, Y type molecular sieve has been always just that catalytic cracking is urged since the last century 60's for the first time use The predominant cracking active component of agent, and binding agent is mainly Aluminum sol.

United States Patent (USP) USP2196016 reports the preparation method of Aluminum sol earliest.At present, Aluminum sol (colloidal sol containing chloride and aluminium, Be frequently termed as aluminium polychloride as sewage treatment flocculating agent) preparation method have it is following several：It is anti-with metallic aluminium with aluminium chloride It answers, reacts with freshly prepared aluminium hydroxide and hydrochloric acid and metal reactive aluminum, with metallic aluminium and hydrochloric acid, passed through by raw material of aluminium chloride It is prepared by ion exchange or thermal decomposition.

Aluminum sol (referring to colloidal sol containing chloride and aluminium) is used for the preparation of catalyst by United States Patent (USP) USP3464929 for the first time.Due to having Good adhesive property, Aluminum sol are that such as catalytic cracking of current zeolite catalyst particularly high zeolite content catalyst is catalyzed The common binding agent of agent.However, it is Cracking catalyst prepared by binding agent with existing colloidal sol containing chloride and aluminium, matrix-active is inclined Low, selectivity is poor.

Chinese patent ZL91108723.0 (CN1029219C) and Chinese patent ZL91108724.9 (CN1029220C) are carried The preparation method of modified colloidal sol containing chloride and aluminium has been supplied, and has specifically disclosed and a small amount of phosphate radical is introduced in Aluminum sol, with phosphoric acid Root, which substitutes part chlorine root, can reduce the corrosion and pollution of hydrogen chloride in catalyst preparation process, and can improve the bonding of Aluminum sol Performance.However, hydrocarbon cracking catalyzer prepared by Yi Shang phosphorus-containing aluminium sol adhesive, matrix-active is low, catalytic cracking reaction Selectivity of product is poor.

In addition, the coke choosing of the catalytic cracking catalyst including components such as existing cracking activity constituent element, clay, binding agents Selecting property is usually higher.

The content of the invention

The purpose of the invention is to overcome using coke during existing catalytic cracking catalyst progress heavy oil catalytic cracking The defects of selectivity is higher, and providing a kind of new have relatively low coke selectivity, compared with high cracking activity and can obtain The catalytic cracking catalyst of higher diesel yield, the preparation method of the catalytic cracking catalyst and the catalytic cracking are urged Application of the agent in heavy oil catalytic cracking.

The present invention provides a kind of catalytic cracking catalyst, the catalytic cracking catalyst contains cracking activity constituent element, is situated between Hole silica-alumina material, clay and binding agent, wherein, on the basis of the total weight of the cracking activity constituent element, the cracking activity group The 3rd of first Y type molecular sieve of the member containing 35-70 weight %, the second Y type molecular sieve of 20-60 weight % and 2-20 weight % Y type molecular sieve；First Y type molecular sieve is rare earth Y type molecular sieve, and in the rare earth Y type molecular sieve in terms of oxide Content of rare earth is 10-25 weight %, lattice constant 2.440-2.472nm, crystallinity 35-65%, and framework si-al ratio is 2.5-5：1；Second Y type molecular sieve is the super-stable Y molecular sieves containing magnesium；3rd Y type molecular sieve is containing rare earth DASY molecular sieves；The binding agent is the modification Aluminum sol containing Cl and Si, on the basis of the total weight of the modified Aluminum sol, Al content is that 8-13 weight %, Cl content 4-9 weight %, Al/Cl weight ratio is 1.2-2.2 in the modified Aluminum sol：1, Si Content is 0.1-1 weight %, and the pH value of the modified Aluminum sol is 2.2-5.2.

The present invention also provides the preparation method of the catalytic cracking catalyst, this method is included the cracking activity group First, optional mesoporous silica-alumina materials, clay and binding agent is mixed with beating, be then spray-dried, washed successively again, being filtered and It is dry.

In addition, the application the present invention also provides the catalytic cracking catalyst in heavy oil catalytic cracking.

Modified Aluminum sol provided by the invention is chloride and silicon Aluminum sol or is the Aluminum sol containing aluminium, silicon and phosphorus, With good adhesive property, matrix-active is higher, can be used as the binding agent of zeolite type crystalline aluminosilicate molecular sieve catalyst.This The inventor of invention has found after further investigation, using this specific modified Aluminum sol as binding agent and with specific cracking Active component and optional mesoporous silica-alumina materials and clay are used cooperatively, and obtained catalytic cracking catalyst is especially suitable for weight Oily catalytic cracking reaction can not only show relatively low coke selectivity and higher during heavy oil catalytic cracking reaction Catalytic cracking activity, but also higher diesel yield can be obtained.

A preferred embodiment of the invention, when the catalytic cracking catalyst also contains mesoporous silica-alumina materials, And the mesoporous silica-alumina materials have boehmite crystal phase structure, with the weight ratio meter of oxide in the mesoporous silica-alumina materials Anhydrous chemical expression be：(0-0.2)Na₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, and it is described The specific surface area of mesoporous silica-alumina materials is 200-600m²/ g, pore volume 0.5-1.8cm³/ g, can when average pore size is 8-18nm More effectively increase the content of catalytic cracking catalyst mesoporous, be more advantageous to the diffusion and cracking of heavy oil macromolecular, it will be corresponding Catalytic cracking catalyst is used to that in heavy oil catalytic cracking reaction lower coke selectivity can be shown.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Specific embodiment

The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

Catalytic cracking catalyst provided by the invention contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, Wherein, on the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains the first Y of 35-70 weight % 3rd Y type molecular sieve of type molecular sieve, the second Y type molecular sieve of 20-60 weight % and 2-20 weight %；State the first Y type molecules It sieves for rare earth Y type molecular sieve, and using the content of rare earth that oxide is counted as 10-25 weight %, structure cell in the rare earth Y type molecular sieve Constant is 2.440-2.472nm, crystallinity 35-65%, framework si-al ratio 2.5-5：1；Second Y type molecular sieve be containing The super-stable Y molecular sieves of magnesium；3rd Y type molecular sieve is the DASY molecular sieves containing rare earth；The binding agent be containing Cl and The modification Aluminum sol of Si, on the basis of the total weight of the modified Aluminum sol, Al content is 8-13 weights in the modified Aluminum sol % (such as 8-12.5 weight %) is measured, Cl contents are 4-9 weight % (such as 4.5-9 weight %), and Al/Cl weight ratios are 1.2- 2.2：1 (such as 1.25-2.1 weight %), Si contents are 0.1-1 weight % (such as 0.2-0.9 weight %), and the modified aluminium The pH value of colloidal sol is 2.2-5.2 (such as 2.5-5.2).

Also contain water in the modified Aluminum sol, on the basis of the total weight of the modified Aluminum sol, the content of water is usual It can be 60-80 weight %, be, for example, 66-77 weight %, the water contained in usually modified Aluminum sol is aequum.

Preferably, Al/Si weight ratios are 9.5-100 in the modified Aluminum sol：1, it is, for example, 9.8-90：1 or 10-80：1 Or 10-50：1.

The modified Aluminum sol can also contain P, and on the basis of the total weight of the modified Aluminum sol, the modified aluminium P content can be more than 0 and no more than 2 weight %, preferably 0.3-2 weight %, and the pH of the modified Aluminum sol in colloidal sol Value can be 2.5-4.2.At this point, Al/P weight ratios are preferably (5-30) in the modified Aluminum sol：(being more than 0-1), it is preferably 5-30：1.

The modified Aluminum sol can be prepared in accordance with the following methods：By metallic aluminium, water, soluble silicon-containing compound, Optional soluble phosphorus-containing compound and chloride is added in reactor and is reacted, wherein, the solubility silicide-comprising It closes object and metallic aluminium is added to before chloride in reactor, the metallic aluminium, soluble phosphorus-containing compound and chloride (Al/Si's weight ratio for the element silicon that the aluminium element summation of introducing is introduced with soluble silicon-containing compound i.e. by weight feeds intake Than) it is 10-150：1, it is, for example, 15-145：1；Preferably, Al/Si rate of charges by weight are 10-100：1, it is, for example, 15- 100：1 or 15-70：1 or 19-60：1；The aluminium element that the metallic aluminium, soluble phosphorus-containing compound and chloride introduce it is total It is (5-30) with the weight ratio (Al/P rate of charges i.e. by weight) with soluble phosphorus-containing compound introducing P elements：(it is more than 0-1), it is preferably 5-30：1, it is, for example, 8-30：1.

In the present invention, unless stated otherwise, it is related to Al concentration or Al content, refers to the concentration or content of aluminium element, aluminium Introduction volume (or inventory of aluminium) refer to be introduced into the amount of the aluminium element in reactor, draw including metallic aluminium and aluminum contained compound The amount of the aluminium element entered.Cl concentration or Cl contents refer to the concentration or content of chlorine element, the introduction volume of chlorine (or chlorine feeds intake Amount) refer to be introduced into the amount of chlorine element in chlorine-containing compound in reactor.Si concentration or Si contents refer to element silicon concentration or Content, the introduction volume (or inventory of silicon) of silicon refer to be introduced into element silicon in the soluble silicon-containing compound in reactor Amount.P concentration or P content refer to the concentration or content of P elements, and the introduction volume (or inventory of phosphorus) of phosphorus refers to introduce reaction The amount of P elements in soluble phosphorus-containing compound in device.

The solubility silicon-containing compound is given birth to for that can be dissolved in water or can react (such as hydrolysis occurs) with water Into the silicon-containing compound of Si oxide, the one or more being specifically as follows in waterglass, acidic silicic acid alkoxy silane can By adding in the soluble silicon-containing compound in itself or the solution of soluble silicon-containing compound introduces silicon-containing compound.

A kind of specific embodiment according to the present invention, by adding in waterglass, acidic silicic acid aqueous solution, alkoxy silane The solubility is introduced with one or more forms in alkoxy silane solution (such as organic solution of alkoxy silane) Silicon-containing compound.Wherein, the organic solvent in the organic solution of the alkoxy silane is preferably capable being dissolved in the organic molten of water Agent, for example, can be selected from the one or more in methanol, ethyl alcohol, acetone.Wherein, the waterglass can be consolidated using waterglass Body or SiO₂Concentration is the sodium silicate solution of 1-25 weight %, and modulus of water glass can be that 2.0-3.5 is, for example, 2.6-3.3, The waterglass of technical grade ratings above, such as chemical pure or commercially pure waterglass can be used.The acidic silicic acid aqueous solution Middle SiO₂Concentration is 1-10 weight %, pH value 1.5-3.0.The chemical formula of the alkoxy silane is Si (OR)₄, wherein, R is Unsubstituted or substitution alkyl (alkyl of carbon number alkyl less than 10 or carbon number substituted base less than 10) of the carbon number less than 10, together Four R in one molecule each other can be identical or different.It for example can be with furthermore, it is possible to add in solvent in alkoxy silane solution For ethyl alcohol, Si concentration can be 1-10 weight % in the alkoxy silane solution.The alkoxy silane can be technical grade More than, such as can be that chemical pure or technical grade is pure.The alkoxy silane for example can be tetraethoxysilane, tetramethoxy One or more in silane, a methoxyl group triethoxysilane, dimethoxy diethoxy silane.

In the preparation process of above-mentioned modified Aluminum sol, can by soluble silicon-containing compound solution, pass through chloride Solution introduces water into reactor by soluble phosphorus-containing compound solution, by adding in water such as deionized water or passes through Water is introduced into reactor with the combination of upper type, it is preferable that add in chloride with the water introduced in forward direction reactor and addition Chloride is using the weight ratio of soluble silicon-containing compound (being counted using Si elements) introduced in forward direction reactor as 100：0.1-10, example Such as it is 100：1-10 or 100：0.1-5 or 100：0.15-1.4 or 100:0.2-1.3:1.

Silicon (counts) content as 0.1-1 weight % using element silicon in the modification Aluminum sol that the present invention obtains, and is preferably 0.2-0.9 Weight % is, for example, 0.3-0.85 weight %.

In the preparation process of above-mentioned modified Aluminum sol, the addition (in terms of element aluminum) of the metallic aluminium can be reaction The 100-220 weight % of metallic aluminium consumption in the process add the metallic aluminium of equivalent or excess.Metal aluminum feedstock used can be with It is the one or more in aluminium ingot, aluminium skimmings and aluminum shot, the content (or purity of metal aluminum feedstock) of aluminium in the metal aluminum feedstock Preferably not less than 95 weight %, such as can be 95-99.7 weight %.The metallic aluminium can add in before chloride addition It is added in reactor or adopts into reactor, while being added to after chlorination adds in reactor, adding in chloride Metallic aluminium is added portionwise in reactor with the combination of above-mentioned feed way, it is preferable that metallic aluminium is before chloride addition It is added in reactor.

The addition of the chloride should ensure that Al/Cl weight ratios are 1.2-2.2 in product：1, therefore, correspondingly, upper In the preparation process for stating modified Aluminum sol, Al/Cl rate of charges by weight are 1.2-4：1, it is, for example, 1.3-3.5：1.It is described Al/Cl rate of charges are the weight ratio of the aluminium and chlorine (chlorine element that the chloride introduces) introduced in reactor.The chloride Can be aluminium chloride and/or hydrogen chloride.The chloride can be introduced in the form of its solution, for example, with hydrochloric acid solution or chlorine The form for changing aluminum solutions or the solution containing hydrochloric acid and aluminium chloride introduces.The concentration of chlorine is preferably 15- in the chloride solution 20 weight %.When the chloride is introduced in the form of hydrochloric acid, the concentration of hydrochloric acid in terms of chlorine is preferably 15-20 weight %；Institute State hydrochloric acid can be technical grade with higher level, be, for example, chemical pure or technical grade.When the chloride is in the form of liquor alumini chloridi During introducing, using the concentration of chloride described in the aqueous chloride solution that Cl elements are counted as 15-20 weight %, knot can be used Brilliant aluminium chloride is formulated with water, and crystal aluminum chloride can be chemical pure or technical grade.During in order to avoid adding in a large amount of chlorides Reaction speed is too fast and reaction temperature is caused quickly to raise, can add in chloride several times or is slowly added to chloride, example Can such as make the feed time of chloride when 0.5 is small more than (when being, for example, 0.5-4 small), it is preferable that during the addition of chloride Between (or feed time) for 1-4 it is small when, control and adds in the temperature in chloride process as 60-105 DEG C of (for example, 80-102 DEG C), wherein, the addition time of the chloride is from charging is started to the time terminated used in charging.

The solubility phosphorus-containing compound is preferably capable being dissolved in for that can be dissolved in water or be dissolved in the phosphorus-containing compound of hydrochloric acid The phosphorus-containing compound of water.The solubility phosphorus-containing compound can be to add in the form of itself in reactor, can also be with it The form of aqueous solution is added in reactor.The solubility phosphorus-containing compound for example can be orthophosphoric acid, aluminium dihydrogen phosphate, phosphoric acid One or more of ammonium dihydrogen and diammonium hydrogen phosphate, wherein, the orthophosphoric acid can be more than technical grade, be, for example, that chemistry is pure Or technical pure orthophosphoric acid, it is added in after orthophosphoric acid preferably is made into the solution that concentration is 10-85 weight % in the reactor.It is described Aluminium dihydrogen phosphate can be more than technical grade, and chemical pure or technical pure is added to after being preferably made into phosphate dihydrogen aluminum solution In reactor, Al concentration can be that 2.5-4.5 weight %, P concentration can be 10-14.5 weights in the phosphate dihydrogen aluminum solution Measure %.Aluminium element (aluminium element that the chloride including metallic aluminium, soluble phosphorus-containing compound and aluminium introduces) and phosphorus-containing compound The weight rate of charge (Al/P rate of charges i.e. by weight) of (in terms of phosphorus) is (5-30)：(being more than 0-1) is preferably 5-30：1, Such as can be 8-30：1.It is described solubility phosphorus-containing compound can the chloride addition before be added in reactor, It is added to simultaneously with chloride in reactor or is added in reactor or is taken with top after chloride adds in Soluble phosphorus-containing compound is added portionwise in reactor for the combination of formula.

In the preparation process of above-mentioned modified Aluminum sol, by metallic aluminium, water, soluble silicon-containing compound, optional solvable Property phosphorus-containing compound and chloride mix reacted in the reactor, and aluminum concentration reaches in modified Aluminum sol obtained by the reaction It is required that reaction is terminated when (such as aluminum concentration reaches 8-13 weight %).It, can be by will be unreacted in specific operation process Metallic aluminium is separated for example with product liquid by filtering to stop reacting or be stopped by cooling and then the method filtered Reaction, for example, temperature is reduced to less than 80 DEG C, the method that is preferably dropped to less than 70 DEG C (such as 60-70 DEG C) and then filters is stopped Only react.

In the preparation process of above-mentioned modified Aluminum sol, the chloride is in the metallic aluminium and soluble silicon-containing compound It adds in and adds in afterwards into reactor, add in chloride process and chemical reaction takes place, add continuation after chloride For a period of time, aluminum concentration stops reacting after reaching requirement in gained modified aluminium sol product for reaction.The reaction temperature of the reaction Degree can be 60-105 DEG C (from the temperature being initially added into during chloride terminates to reaction), be preferably 80-102 DEG C, more preferably For 90-98 DEG C；Reaction time (from time of the chloride to reaction end, also referred to as total reaction time is initially added into) is typically When 12-72 is small, when being preferably 16-26 small.According to a kind of specific embodiment, the reaction temperature added in chloride process is 60-102 DEG C, the reaction time for 1-4 it is small when；The reaction temperature after chloride is added as 80-105 DEG C (such as 90-98 DEG C), reaction Time for 8-71 it is small when small (such as 16-26), then terminate reaction.

As described above, in the preparation process of above-mentioned modified Aluminum sol, the addition sequence of the solubility phosphorus-containing compound There is no particular/special requirement, can chloride addition before, chloride add before, chloride add after, with chloride simultaneously It is added to the combination in reactor or using above-mentioned arbitrary several feed way.Preferably, the soluble phosphorus-containing compound adds The complete later reaction time be shorter than 0.5 it is small when, be, for example, 0.5-72 it is small when.

A preferred embodiment of the invention, when the modified Aluminum sol is the Aluminum sol of silicon and P Modification, The modified aluminum solutions are prepared according to method comprising the following steps：

(1) metallic aluminium, water, soluble silicon-containing compound and optional soluble phosphorus-containing compound are mixed in the reactor It closes；

(2) chloride and optional soluble phosphorus-containing compound are added in the reactor；

(3) make mixture reaction a period of time that step (2) obtains, then terminate reaction；

Wherein, the soluble phosphorus-containing compound is added at least one step in step (1) and step (2).

In the embodiment for preferably preparing modified Aluminum sol, the solubility phosphorus-containing compound can be in step (1) or in step (2) add in, can also be added in step (1) and step (2).It is described when being added in step (2) Soluble phosphorus-containing compound can simultaneously be added in chloride for example mix after add in, can also chloride add after plus Enter.When soluble phosphorus-containing compound after chloride adds when adding in, preferably from chloride is initially added into adding solubility The time of phosphorus-containing compound be no more than 4 it is small when, such as can be 0.5-4 it is small when, be preferably 1-3.5 it is small when.

In the embodiment for preferably preparing modified Aluminum sol, add in before chloride, make mixture in reactor Temperature not less than 60 DEG C, such as can be 60-102 DEG C, then add in chloride and reacted.In order to avoid adding in chloride Excessive velocities cause temperature of reactor to raise rapidly, and the mode that substep is added in or is slowly added to can be taken to add in.Normally, it is described The addition speed of chloride is so that the temperature for adding in material in chloride post-reactor is no more than subject to 102 DEG C.

In addition, in the embodiment for preferably preparing modified Aluminum sol, mixed in step (3) by what step (2) obtained It closes object and is kept for a period of time, reacted material in reactor.Preferably, mixture step (2) obtained is in temperature 80- It keeps being reacted the material in reactor when 8-71 is small at 105 DEG C, i.e., the reaction temperature of step (3) is 80-105 DEG C, instead When being 8-71 small between seasonable；It is highly preferred that the reaction temperature in step (3) is 90-98 DEG C, when the reaction time is 12-25 small.When Stop when aluminum concentration reaches requirement (such as the content of aluminium element is 8-13 weight % in the modified Aluminum sol of gained) in reaction product Reaction.

In the preparation process of above-mentioned modified Aluminum sol, obtained modified aluminium sol product can also be concentrated, with Improve the concentration of wherein aluminium.For example, if the aluminum concentration of modified aluminium sol product is less than 10 weight %, can modification be made by concentration The concentration of aluminium is increased to more than 10 weight % in Aluminum sol.The concentration can be concentrated by evaporation, and evaporation and concentration condition is led to Often include：Temperature can be 80-105 DEG C, when the time can be 0.5-4 small.Usually by concentration the aluminum concentration of product is made to be 10- 13 weight % are, for example, 10-12 weight %.

The Aluminum sol of silicon or silicon and P Modification, the modification Aluminum sol can be made according to above-mentioned modified Aluminum sol preparation method Middle formation Si modification or the aluminium polychloride micelle of silicon and P Modification, silicon are evenly distributed in modified Aluminum sol, will not be formed big Silicon oxide particle, silica-alumina gel block will not be formed, have good adhesive property, matrix-active is higher, can be used as zeolite Type crystalline aluminosilicate molecular sieve catalyst binding agent, particularly as SiO₂/Al₂O₃It is urged than relatively low crystalline aluminosilicate molecular sieve The binding agent of the binding agent of the agent such as Cracking catalyst containing y-type zeolite, prepared catalyst reaction performance is better than chloride Aluminum sol and phosphorated aluminiferous collosol, adhesive property and matrix-active are better than Alusil catalyst and Ludox catalyst, and select Property is preferable.

The catalytic cracking catalyst provided according to the present invention, it is preferable that using the total weight of the catalytic cracking catalyst as Benchmark, the catalytic cracking catalyst contain the cracking activity constituent element of 10-60 weight %, the clay and 10-60 of 10-60 weight % The catalytic cracking that the content control of above-mentioned each component enables in the preferred scope is catalyzed by the binding agent of weight % Agent has better comprehensive performance.

The catalytic cracking catalyst provided according to the present invention, it is preferable that in the rare earth Y type molecular sieve in terms of oxide Content of rare earth is 11-23 weight %, lattice constant 2.450-2.470nm, crystallinity 40-60%.

The rare earth Y type molecular sieve can be prepared according to existing various methods, such as can hand over two roastings by two And be prepared with reference to deposition of rare-earth process.Specifically, the rare earth Y type molecular sieve is prepared in accordance with the following methods：It will NaY molecular sieve carries out contact processing with earth solution or the mixed solution of earth solution and ammonium salt, after filtered, washing, drying, First time calcination process is carried out, obtains rare earth sodium Y molecular sieve；Then by rare earth sodium Y molecular sieve be beaten and with ammonium salt solution or acid Solution contact is handled, and is mixed again with earth solution after filtering, and the pH value of slurries is adjusted to 6-10, is filtered or is not filtered, does Second of calcination process is carried out after dry, obtains the rare earth Y type molecular sieve.

In the preparation process of above-mentioned rare earth Y type molecular sieve, the sial atomic ratio of raw material NaY molecular sieve is preferably greater than 2.5 And crystallinity is more than 80%.NaY molecular sieve and earth solution or the mixed solution of earth solution and ammonium salt are being subjected to contact position During reason, the weight ratio of earth solution and NaY molecular sieve butt in terms of rare earth oxide can be 0.06-0.14：1, Preferably 0.08-0.12：1；Control ph is 3-5；It is 5-30 to control water sieve weight ratio：1, it is preferably 8-15：1；The contact The process of processing be in -100 DEG C of room temperature, preferably at 70-95 DEG C handle 0.3-3.0 it is small when, preferred process 0.5-1.5 it is small when.

In the preparation process of above-mentioned rare earth Y type molecular sieve, the item of the first time calcination process and the second calcination process Part is identical or different, and when calcination process 0.5-4 is small under 500-650 DEG C, 0-100% water vapor conditions independently, it is excellent When selecting 1-3 small.Wherein, at least one in the first time calcination process and second of calcination process in 1-100%, preferably It is carried out under 20-100%, most preferably 100% water vapor conditions, steam treatment can promote rare earth ion from molecular sieve supercage It is migrated into small cage.It is particularly preferred that the first time calcination process and second of calcination process are in 100% water vapor conditions Lower progress.

In the preparation process of above-mentioned rare earth Y type molecular sieve, the rare earths material in the earth solution can be this field Conventional selection, for example, can be rare earth chloride and/or nitric acid rare earth, and can be Rare Earth Elements Determination composition chlorination Rare earth or nitric acid rare earth, wherein the common one or more included in lanthanum chloride, lanthanum nitrate, cerium chloride, cerous nitrate etc., also may be used The mischmetal containing different rare earth elements is thought, for example, rich cerium type and rich lanthanum type mischmetal.

The catalytic cracking catalyst provided according to the present invention, second Y type molecular sieve are the superstable gamma-type molecule containing magnesium Sieve.It is preferably 0.5-25 weights using the content of magnesium that magnesia is counted as 0.1-25 weight % in the super-stable Y molecular sieves containing magnesium Measure %.The super-stable Y molecular sieves containing magnesium can be prepared according to the various methods of this field routine, such as can be according to Following two methods are prepared：(1) by dissolve or after abundant wet-milling magnesium compound (such as selected from magnesia, magnesium chloride, At least one of magnesium sulfate and magnesium nitrate) it is dispersed in super-stable Y molecular sieves (USY molecular sieve) slurries, add or be not added with Ammonium hydroxide, dry after mixing and roasting；(2) it is the super-stable Y molecular sieves (USY molecular sieve) after abundant wet-milling are homodisperse In the solution of magnesium compound (such as selected from least one of magnesium chloride, magnesium sulfate and magnesium nitrate), it is equal to add in ammonium hydroxide mixing It is filtered, washs, dries and roasts successively after even.The above-mentioned preparation method of the super-stable Y molecular sieves containing magnesium it is specific Implementation process is for example referred to CN1297018A, particularly embodiment 1-5 therein.

The catalytic cracking catalyst provided according to the present invention, the 3rd Y type molecular sieve are the DASY molecular sieves containing rare earth. The DASY molecular sieves containing rare earth refer to the hydro-thermal super stable molecular sieve containing rare earth, wherein, with RE₂O₃(rare earth oxide) meter Content of rare earth can be 1.5-3 weight %.The DASY molecular sieves containing rare earth can be various commercial product, for example, can be with To be purchased from the DASY2.0 molecular sieves of Sinopec catalyst asphalt in Shenli Refinery.

The catalytic cracking catalyst provided according to the present invention, it is preferable that the catalytic cracking catalyst also contains mesoporous silicon Aluminum material, and on the basis of the total weight of the catalytic cracking catalyst, the content of the mesoporous silica-alumina materials is 1-20 weights % is measured, the catalytic cracking catalyst so enabled to is used to that in heavy oil catalytic cracking reaction lower coke can be shown Selectivity.

The catalytic cracking catalyst provided according to the present invention, the species of the mesoporous silica-alumina materials can be the normal of this field Rule selection, particularly preferably, the mesoporous silica-alumina materials have boehmite crystal phase structure, in the mesoporous silica-alumina materials with The anhydrous chemical expression of the weight ratio meter of oxide is：(0-0.2)Na₂O·(50-86)Al₂O₃·(12-50)SiO₂· (0.5-10)P₂O₅, and the specific surface area of the mesoporous silica-alumina materials is 200-600m²/ g, pore volume 0.5-1.8cm³/ g, it is average Aperture is 8-18nm.The content of catalytic cracking catalyst mesoporous can be effectively increased using this preferred mesoporous silica-alumina materials, Be conducive to the diffusion and cracking of heavy oil macromolecular, which urges especially suitable for heavy oil catalytic cracking in heavy oil Lower coke selectivity and higher catalytic cracking activity can be shown during changing cracking.

The catalytic cracking catalyst provided according to the present invention, it is highly preferred that the specific surface area of above-mentioned mesoporous silica-alumina materials is 250-550m²/ g, pore volume 0.6-1.6cm³/ g, average pore size 9-15nm.

In the present invention, the specific surface area, pore volume and average pore size are surveyed using nitrogen absorption under low temperature-desorption method Fixed, used instrument is the physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S..

Above-mentioned preferred mesoporous silica-alumina materials can be commercially available, can also according to well known to a person skilled in the art Various methods are prepared, for example, can be prepared in accordance with the following methods：By silicon source and alkaline solution in room temperature at 85 DEG C Plastic is neutralized, the pH value of plastic is controlled as 7-11, according still further to SiO₂：Al₂O₃=1：The weight ratio of 1-7.5 adds into plastic slurries Enter silicon source, then obtained solid sediment and ammonium salt or acid solution then will be aged to when ageing 1-5 is small at 90 DEG C in room temperature It is filtered after contact, obtains the solid product that sodium oxide content is less than 0.3 weight %, then again connect the solid product with phosphorus source It touches, and product of contact is dried；Phosphorus source is with P₂O₅The dosage of meter and the weight ratio of the butt of the solid product are 0.005- 0.1：1.

In the preparation method of above-mentioned mesoporous silica-alumina materials, obtain the solid product before the step of be referred to Method disclosed in CN1565733A carries out.

Specifically, source of aluminium can be the existing various substances that can be converted into aluminium oxide, for example, nitre can be selected from One or more in sour aluminium, aluminum sulfate and aluminium chloride.

The alkaline solution can be the existing various substances that alkalescence is presented, for example, ammonium hydroxide, sodium hydroxide can be selected from One or more in solution, potassium hydroxide solution and sodium aluminate solution.Wherein, the concentration of the alkaline solution can be this The conventional selection in field, therefore not to repeat here.

The silicon source can be the existing various substances that can be converted into silica, for example, waterglass, silicon can be selected from One or more in sour sodium, tetraethoxy-silicane and silica.

The present invention is not particularly limited the method for contacting the solid sediment with ammonium salt, for example, can include The solid sediment is pressed into its butt：Ammonium salt：H₂O=1：0.1-1：The weight ratio of 5-30 is in room temperature to being handed at 100 DEG C It changes.Wherein, the number of the contact can be 1-3 times, each time of contact can with 0.5-1 it is small when, should specifically make to obtain Solid product in sodium oxide molybdena content less than subject to 0.3 weight %.

In addition, the species of the ammonium salt can be this field conventional selection, for example, can be selected from ammonium chloride, ammonium sulfate, One or more in ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.

The present invention is not particularly limited the method for contacting the solid sediment with acid solution, for example, can be with Including the solid sediment is pressed its butt：Acid：H₂O=1：0.03-0.3：The weight ratio of 5-30 is in room temperature to handing at 100 DEG C Shift to few 0.2 it is small when.

In addition, the species of the acid solution can be the conventional selection of this field, it is usually inorganic acid, for example, described Acid in acid solution can be selected from the one or more in sulfuric acid, hydrogen chloride and nitric acid.

The catalytic cracking catalyst provided according to the present invention, wherein, contact between the solid product and phosphorus source can be with It carries out in presence of water, the contact method includes：The solid product is pressed into its butt：Water=1：The weight ratio of 5-20 is mixed Close mashing, add phosphorus source and in room temperature to react at 90 DEG C 0.2-5 it is small when, preferably 0.5-3 is small when, connect again by what is obtained afterwards Tactile product is filtered, washes.In addition, contact between the solid product and phosphorus source can also be by the solid product with Phosphorus source is mixed and ground.The condition that the product of contact of the solid product and phosphorus source is dried is generally included：Drying temperature It can be 100-150 DEG C, when drying time can be 10-20 small.Further, optionally, the preparation side of the mesoporous silica-alumina materials Method can also include roasting desciccate, and it can be 500-700 DEG C that the condition of the roasting, which generally includes calcination temperature, When roasting time can be 1-4 small.

The species of phosphorus source can be this field conventional selection, for example, can be selected from ammonium phosphate, diammonium hydrogen phosphate, One or more in ammonium dihydrogen phosphate and phosphoric acid.

The catalytic cracking catalyst provided according to the present invention, the clay can be it is existing it is various can be used in catalysis split Change the clay in catalyst, for example, kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite, tired can be selected from Hold in the palm one or more of soil, sepiolite, attapulgite, hydrotalcite and bentonite.

The preparation method of catalytic cracking catalyst provided by the invention is included above-mentioned cracking activity constituent element, optional mesoporous Silica-alumina material, clay and binding agent are mixed with beating, and are then spray-dried, washed, filtered and dried successively again.

The preparation method of the catalytic cracking catalyst provided according to the present invention contains the cracking activity constituent element, selectivity Some mesoporous silica-alumina materials, clay and binding agent are mixed with beating and subsequent spray drying, washing, filtering and drying, these The implementation of process can be used conventional method and implement, their specific implementation method for example CN1916166A, There is detailed description in CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, here It is introduced into together in the present invention by reference.Typically also, after the spray drying, before washing, the catalytic cracking The preparation method of catalyst also typically includes the step of being roasted Spray dried products.The condition of the roasting generally includes Calcination temperature can be 500-700 DEG C, when roasting time can be 1-4 small.

In addition, the application the present invention also provides above-mentioned catalytic cracking catalyst in heavy oil catalytic cracking.

The present invention will be described in detail by way of examples below.

In following preparation example, comparison preparation example, embodiment and comparative example：

Aluminium skimmings purity used is 99.2 weight %, and aluminum shot purity is 98.8 weight %；Used 1:1 chemical pure hydrochloric acid is 1 body Long-pending 36 weight % chemistry pure hydrochloric acid of concentration and the mixture of 1 volume of water；Used 1:The pure phosphoric acid of 1 chemistry is the concentration of 1 volume The mixture of 85 weight % chemistry pure phosphoric acids and 1 volume of water；Rare earth chloride is purchased from Xitu Hi-Tech skill limited company of Baogang, In rare earth element be La and Ce.

Specific surface area, pore volume and average pore size are measured using nitrogen absorption under low temperature-desorption method, and used instrument is The physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S.；Na in mesoporous silica-alumina materials₂O、Al₂O₃、SiO₂、 P₂O₅Content measured with x-ray fluorescence method (referring to《Petrochemical Engineering Analysis method (RIPP experimental methods)》, Yang Cui surely compile by grade, section Publishing house is learned, nineteen ninety publishes)；

Second Y type molecular sieve is prepared according to the method disclosed in CN1297018A embodiments 1；

3rd Y type molecular sieve is the DASY2.0 molecular sieves purchased from Sinopec catalyst asphalt in Shenli Refinery；

The content of each component is calculated according to inventory in catalytic cracking catalyst.

Preparation example 1

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

By aluminium skimmings 286 grams (in terms of Al), 1481 grams of deionized water and sodium silicate solution (9.33 weight % of element containing Si, 4.63 weight % of Na elements) 119 grams add in there-necked flask, be heated to 60 DEG C.By 1:1 921 milliliters of chemical pure hydrochloric acid slowly adds Enter in there-necked flask, it is made to be reacted with aluminium skimmings, when the addition time of hydrochloric acid is 3 small；After adding hydrochloric acid, in 90-95 DEG C of reaction temperature When lower reaction 20 is small, product is then cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-1.The remaining aluminium skimmings warp of reaction It is weighed as 36 grams, the i.e. excessive 14.8 weight % of aluminium.Modified Aluminum sol SA-1 is as a result as follows through analysis：Al content is 9.0 weights % is measured, Cl contents are that 6.7 weight %, Si contents are that 0.41 weight %, Al/Cl (weight ratio) is 1.34:1, Al/Si (weight ratio) For 22.0:1, pH value 3.00.

Preparation example 2

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Aluminium skimmings 280 grams (in terms of Al), 1055 grams of deionized water, sodium silicate solution (element containing Si 9.33 weight %, Na member 4.63 weight % of element) 115 grams add in there-necked flask, be heated to 60 DEG C.By 1:1 chemical 678 milliliters of pure hydrochloric acid is slowly added to three mouthfuls In bottle, it is made to be reacted with aluminium skimmings, when the addition time of hydrochloric acid is 3 small；After adding hydrochloric acid, reacted at 90-95 DEG C of reaction temperature 19 it is small when, product is then cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-2.The aluminium skimmings for reacting remaining are weighed to be 29 grams, the i.e. excessive 11.6 weight % of aluminium.Modified Aluminum sol SA-2 is as a result as follows through analysis：Al content is 12.20 weight %, Cl Content is that 6.5 weight %, Si contents are that 0.52 weight %, Al/Cl (weight ratio) is 1.88:1, Al/Si (weight ratio) is 23.5: 1, pH value 4.00.

Preparation example 3

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Aluminum shot 250 grams (in terms of Al), 1560 grams of deionized water, tetraethoxysilane ethanol solution (3.0 weight of element containing Si Measure %) 162 grams add in there-necked flask, be heated to 60 DEG C.By 1:1 524 milliliters of chemical pure hydrochloric acid is slowly added in there-necked flask, is made It is reacted with aluminum shot, when the addition time of hydrochloric acid is 2 small；After adding hydrochloric acid, when reaction 68 is small at 93-97 DEG C of reaction temperature； Then product is cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-3.The weighed aluminum shot for reacting remaining is 48 grams, i.e., The excessive 23.8 weight % of aluminium.Modified Aluminum sol SA-3 is as a result as follows through analysis：Al content is that 8.4 weight %, Cl contents are 4.3 Weight %, Si content are that 0.2 weight %, Al/Cl (weight ratio) is 1.95:1, Al/Si (weight ratio) is 42.0:1, pH value is 3.8。

Preparation example 4

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Aluminum shot 350 grams (in terms of Al), 1190 grams of deionized water and acidic silicic acid aqueous solution (element containing Si 5.0 weight %, pH It is worth and is added in for 2.0) 356 grams in there-necked flask, is heated to 60 DEG C.By 1:1 496 milliliters of chemical pure hydrochloric acid is slowly added to there-necked flask In, it is made to be reacted with aluminum shot, when the addition time of hydrochloric acid is 2 small；After adding hydrochloric acid, 18 are reacted at 93-97 DEG C of reaction temperature Hour, product is then cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-4.The remaining aluminum shot of reaction is 176 grams, i.e., Aluminium is excessively 101.1 weight %.Modified Aluminum sol SA-4 is as a result as follows through analysis：Al content is that 8.0 weight %, Cl contents are 4.5 weight %, Si contents are that 0.82 weight %, Al/Cl (weight ratio) is 1.78:1, Al/Si (weight ratio) is 9.8:1, pH value For 5.1.

Preparation example 5

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Aluminum shot 350 grams (in terms of Al), 1510 grams of deionized water and sodium silicate solution (9.33 weight % of element containing Si, 4.63 weight % of Na elements) 28 grams add in there-necked flask, be heated to 60 DEG C.By 1:1 488 milliliters of chemical pure hydrochloric acid is slowly added to In there-necked flask, it is made to be reacted with aluminum shot, when the addition time of hydrochloric acid is 2 small；After adding hydrochloric acid, at 93-97 DEG C of reaction temperature React 24 it is small when, product is then cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-5.The aluminum shot of remnants is reacted through claiming Weight is 149 grams, i.e. the excessive 74.1 weight % of aluminium.Modified Aluminum sol SA-5 is as a result as follows through analysis：Al content is 9.2 weight %, Cl contents are that 4.4 weight %, Si contents are that 0.12 weight %, Al/Cl (weight ratio) is 2.09:1, Al/Si (weight ratio) be 76.7:1, pH value 3.80.

Preparation example 6

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Aluminum shot 250 grams (in terms of Al), 840 grams of deionized water and sodium silicate solution (element containing Si 9.33 weight %, Na member 4.63 weight % of element) 60 grams add in there-necked flask, be heated to 60 DEG C.By 1:1 829 milliliters of chemical pure hydrochloric acid is slowly added to three mouthfuls In bottle, it is made to be reacted with aluminum shot, when the addition time of hydrochloric acid is 3 small；After adding hydrochloric acid, reacted at 95-100 DEG C of reaction temperature 17 it is small when, reaction product is then cooled to 60-70 DEG C, filtering obtains modified Aluminum sol SA-6.The aluminum shot of remnants is reacted through claiming Weight is 39 grams, i.e., aluminium is excessively 18.5 weight %.Modified Aluminum sol SA-6 is as a result as follows through analysis：Al content is 11.1 weights % is measured, Cl contents are that 8.6 weight %, Si contents are that 0.31 weight %, Al/Cl (weight ratio) is 1.29:1, Al/Si (weight ratio) For 35.8:1, pH value 2.9.

Preparation example 7

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Method according to preparation example 2 prepares modified Aluminum sol, unlike, replace hydrochloric acid solution, Al/ with liquor alumini chloridi Cl rate of charges are constant, and Al/Si rate of charges are constant, the corresponding dosage for reducing metallic aluminium.Obtained modification Aluminum sol SA-7 through analysis, As a result it is as follows：Al content is that 12.0 weight %, Cl contents are that 6.4 weight %, Si contents are 0.51 weight %, Al/Cl (weight Than) it is 1.88:1, Al/Si (weight ratio) is 23.5:1, pH value 3.90.

Preparation example 8

The preparation example is used for the preparation method for illustrating Si modification Aluminum sol provided by the invention.

Method according to preparation example 6 prepares modified Aluminum sol, unlike, with aluminium chloride and the mixed solution (chlorine of hydrochloric acid The ratio for changing the chlorine that the chlorine of aluminium offer and hydrochloric acid provide is 1:1, total cl concn is by 20 weight %) replace the hydrochloric acid solution of preparation example 6. Obtained modification Aluminum sol SA-8 is as a result as follows through analysis：It is that 11.0 weight %, Cl contents are 8.5 weight % containing Al content, Si contents are that 0.31 weight %, Al/Cl (weight ratio) is 1.29:1, Al/Si (weight ratio) is 35.5:1, pH value 2.90.

Compare preparation example 1

The comparison preparation example is used for the preparation method for illustrating the modification Aluminum sol of reference.

According to existing method Aluminum sol is prepared using aluminium skimmings and hydrochloric acid reaction.Aluminium skimmings 240 grams of (in terms of Al), deionized waters 1160 grams are put into there-necked flask, are heated to 60 DEG C.By 1:1 chemical 640 milliliters of pure hydrochloric acid is slowly added in there-necked flask, makes itself and aluminium Bits reaction, when the addition time of hydrochloric acid is 3 small；After adding hydrochloric acid, when reaction 19 is small at 90-95 DEG C of reaction temperature, then will Product is cooled to 60-70 DEG C, and filtering obtains reference and is modified Aluminum sol DSA-1.Reference is modified Aluminum sol DSA-1 through analyzing, as a result It is as follows：Al content is that 12.0 weight %, Cl contents are that 6.3 weight %, Al/Cl (weight ratio) are 1.90:1, pH value 3.40.

Preparation example 9

The preparation example is used for the preparation method for illustrating silicon and P Modification Aluminum sol provided by the invention.

Aluminium skimmings 280 grams (in terms of aluminium), 1480 grams of deionized water and water glass solution (element containing Si 9.33 weight %, Na member 4.63 weight % of element) 124 grams add in there-necked flask, be heated to 60 DEG C.By 1:921 milliliters of 1 chemical pure hydrochloric acid and 1:1 chemistry The 2 milliliters of mixing of pure phosphatase 24, are slowly added in there-necked flask, by acid add the used time 3 it is small when, then at 90-95 DEG C of reaction temperature React 20 it is small when, product is cooled to 60-70 DEG C afterwards, filtering obtains modified Aluminum sol PSA-1.The remaining aluminium skimmings warp of reaction It is weighed as 35 grams, the i.e. excessive 14.3 weight % of aluminium.Modified Aluminum sol PSA-1 is as a result as follows through analysis：Al content is 8.9 weights % is measured, Cl contents are 6.6 weight %, and P content is that 0.35 weight %, Si content is that 0.42 weight %, Al/Cl (weight ratio) is 1.35:1, Al/P (weight ratio) is 25.4:1, Al/Si (weight ratio) is 21.2:1, pH value 3.20.

Preparation example 10

The preparation example is used for the preparation method for illustrating silicon and P Modification Aluminum sol provided by the invention.

Aluminum shot 350 grams (in terms of aluminium), 1040 grams of deionized water and acidic silicic acid aqueous solution (element containing Si 5.0 weight %, pH It is worth and is added in for 2.0) 354 grams in there-necked flask, is heated to 60 DEG C.By 1:498 milliliters of 1 chemical pure hydrochloric acid and 1:1 chemical pure phosphoric acid 112 milliliters of mixing, are slowly added in there-necked flask, by acid add the used time 2 it is small when, then react 18 at 93-97 DEG C of reaction temperature Hour, product is cooled to 60-70 DEG C afterwards, filtering obtains modified Aluminum sol PSA-2.The aluminum shot for reacting remaining is weighed to be 177 grams, i.e. aluminium is excessively 102.3 weight %.Modified silicasol PSA-2 is as a result as follows through analysis：Al content is 8.1 weight %, Cl contents are 4.6 weight %, and P content is that 1.20 weight %, Si contents are that 0.83 weight %, Al/Cl (weight ratio) is 1.76:1, Al/P (weight ratio) is 6.8:1, Al/Si (weight ratio) is 9.8:1, pH value 3.0.

Preparation example 11

The preparation example is used for the preparation method for illustrating silicon and P Modification Aluminum sol provided by the invention.

Aluminum shot 350 grams (in terms of aluminium), 1440 grams of deionized water and sodium silicate solution (element containing Si 9.33 weight %, Na 4.63 weight % of element) 26 grams add in there-necked flask, be heated to 60 DEG C.By 1:495 milliliters of 1 chemical pure hydrochloric acid and 1:1 chemistry The mixing of 101 milliliters of pure phosphoric acid, is slowly added in there-necked flask, by acid add the used time 2 it is small when, then at 93-97 DEG C of reaction temperature React 24 it is small when, product is cooled to 60-70 DEG C afterwards, filtering obtains modified Aluminum sol PSA-3.The remaining aluminum shot warp of reaction It is weighed as 148 grams, i.e. aluminium excessive 73.3%.Modified Aluminum sol PSA-3 is as a result as follows through analysis：Al content is 9.1 weight %, Cl contents are 4.4 weight %, and P content is that 1.04 weight %, Si contents are that 0.11 weight %, Al/Cl (weight ratio) is 2.07:1, Al/P (weight ratio) is 8.8：1, Al/Si (weight ratio) is 82.7:1, pH value 2.9.

Preparation example 12

The preparation example is used for the preparation method for illustrating silicon and P Modification Aluminum sol provided by the invention.

Aluminum shot 350 grams (in terms of aluminium), 1580 grams of deionized water, sodium silicate solution (element containing Si 9.33 weight %, Na member 4.63 weight % of element) 154 grams and 311 grams of aluminium dihydrogen phosphate aqueous solution (element containing Al 4.5 weight %, 13.4 weight % of P element) It is put into there-necked flask, is heated to 60 DEG C.By 1:1 chemical 731 milliliters of pure hydrochloric acid is slowly added in there-necked flask, is contacted with aluminum shot instead Should, by hydrochloric acid add the used time 2 it is small when；Then when reaction 16 is small at 93-98 DEG C of reaction temperature, product is cooled to 60- afterwards 70 DEG C, filtering obtains modified Aluminum sol.The weighed aluminum shot for reacting remaining is 116 grams, i.e., aluminium is excessively 47.5 weight %.Change Property Ludox through analysis, it is as a result as follows：Al content be 8.2 weight %, Cl contents be 4.8 weight %, P content be 1.4 weight %, Si contents are that 0.48 weight %, Al/Cl (weight ratio) is that 1.71, Al/P (weight ratio) is 5.9, pH value 2.50.This is modified Ludox sample weighs 500 grams and is placed on heating concentration 40 minutes, 390 grams of sample of weighing after cooling to obtain on electric furnace, is modified aluminium Colloidal sol PSA-4.Modified Aluminum sol PSA-4 is as a result as follows through analysis：Al content is that 10.50 weight %, Cl contents are 6.2 weights % is measured, P content is that 1.80 weight %, Si contents are that 0.62 weight %, Al/Cl (weight ratio) is 1.69:1, Al/P (weight ratio) For 5.8:1, Al/Si (weight ratio) is 16.9:1, pH value 2.5.

Compare preparation example 2

The comparison preparation example is used for the preparation method for illustrating the modification Aluminum sol of reference.

P Modification Aluminum sol is prepared using aluminium and hydrochloric acid reaction according to the method in CN91108724.9, it is specific as follows：

921 grams of aluminium skimmings 286 grams (in terms of aluminium) and deionized water are put into there-necked flask, are heated to 60 DEG C.By 1:The 1 pure salt of chemistry 663 milliliters and 1 of acid:1 chemical 68 milliliters of mixing of pure phosphoric acid, are slowly added in there-necked flask, interior when 3 is small to add acid, Ran Hou When reaction 19 is small at 90-95 DEG C of reaction temperature, product is cooled to 60-70 DEG C afterwards, filtering obtains modified Aluminum sol DPSA- 1.The weighed remaining aluminium skimmings of reaction are 48 grams, i.e. the excessive 20 weight % of aluminium.Modified Aluminum sol DPSA-1 is as a result as follows through analysis： Al content is that 12.20 weight %, Cl contents are 6.4 weight %, and P content 0.58%, Al/Cl (weight ratio) is 1.91:1, Al/ P (weight ratio) is 21.0:1, pH value 3.6.

Preparation example 13

The preparation example is used to illustrate mesoporous silica-alumina materials provided by the invention and preparation method thereof.

Using concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, the NaAlO that Crater corrosion is 2.5₂ Solution is reaction raw materials, cocurrent plastic and plastic pH value is controlled to collect a certain amount of plastic slurries, stirring for 9.5 at 85 DEG C SiO is pressed down₂:Al₂O₃=1:It is 60gSiO that 6.56 ratio, which adds in concentration,₂The sodium silicate of/L, be warming up to 70 DEG C ageing 2 it is small when, Obtain solid sediment.Use NH₄Cl solution presses solid sediment (butt):NH₄Cl:H₂O=1:0.8:15 weight ratio is at 60 DEG C Under to solid sediment carry out ion exchange to remove sodium ion, ion exchange repeats twice, every time carry out 0.5 it is small when, The solid product that sodium oxide content is less than 0.3 weight % is obtained after filtering, it is then again that the solid product is (dry by solid product Base):H₂O=1:8 weight ratio is mixed with beating with water, and by P₂O₅:Solid product butt=0.022:1 weight ratio adds in phosphorus Sour hydrogen diammonium, when reaction 1 is small at 70 DEG C, filtering washing obtains mesoporous silica-alumina materials when drying 10 is small at 120 DEG C, It is denoted as A-1.

Mesoporous silica-alumina materials A-1 has structure of similar to thin diaspore, is measured using X-ray fluorescence method, mesoporous silicon aluminium Expect A-1 using the chemical composition of the weight ratio meter of oxide as：0.11Na₂O·84.0Al₂O₃·12.8SiO₂·2.1P₂O₅.It is mesoporous The specific surface area of silica-alumina material A-1 is 501m²/ g, pore volume 1.51cm³/ g, average pore size 12.1nm.

Preparation example 14

The preparation example is used to illustrate mesoporous silica-alumina materials provided by the invention and preparation method thereof.

Method according to preparation example 13 prepares mesoporous silica-alumina materials, unlike, do not include the solid product by solid Body product (butt):H₂O=1:8 weight ratio be mixed with beating with water after the step of, but directly sodium oxide content is less than The solid product of 0.3 weight % at 120 DEG C it is dry 10 it is small when after the mesoporous silica-alumina materials of obtained product as reference, be denoted as A-2。

Mesoporous silica-alumina materials A-2 has structure of similar to thin diaspore, is measured using X-ray fluorescence method, mesoporous silicon aluminium Expect A-2 using the chemical composition of the weight ratio meter of oxide as：0.19Na₂O·81.9Al₂O₃·16.7SiO₂.Mesoporous silica-alumina materials The specific surface area of DA-1 is 514m²/ g, pore volume 1.45cm³/ g, average pore size 11.3nm.

Preparation example 15

The preparation example is used for the preparation method for illustrating rare earth Y type molecular sieve provided by the invention.

2.6 kilograms of NaY molecular sieves and 18 kilograms of deionized waters is taken to be mixed with beating, add in 1.25 liters of concentration 160gRE₂O₃/ L's Re chloride and 0.12 kilogram of chloride solid are warming up to 80 DEG C and adjust slurries pH to 3.8 with dilute hydrochloric acid after stirring evenly, after It is continuous exchange 1 it is small when, filtering, washing, it is dry after, under 50% water vapor conditions when 570 DEG C of roastings 2 are small, obtain a friendship one and roast The content of sodium oxide molybdena is 4.9 weight % in rare earth sodium Y molecular sieve Y-C1, Y-C1, and the content of rare earth oxide is 9.9 weight %.So Molecular sieve is pressed afterwards:NH₄Cl:H₂O=1:0.15:When 12 ratio is beaten and exchange 1 is small at 75 DEG C, after filtering washing, beat again It starches and adds in 0.27 liter of concentration 300gRE₂O₃The re chloride of/L, guarantee concentration of slurry are 400-450g/L, are added after stirring evenly Enter waterglass to adjust slurry pH value to 8.0 and continue stirring 10 minutes, after drying in air atmosphere when 570 DEG C of roastings 2 are small, Rare earth Y type molecular sieve is obtained, is denoted as Y-C.After testing, the content of sodium oxide molybdena is 1.3 weight % in rare earth Y type molecular sieve Y-C, with The content of rare earth of oxide meter be 13.9 heavy %, crystallinity 48.8%, lattice constant 2.465nm, framework silicon-aluminum atomic ratio For 3.1:1.

Embodiment 1

The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.

Kaolin and water are beaten, prepare the kaolin slurry that solid content is 40 weight %, then toward 29 in terms of butt The modification Aluminum sol SA-1 of 10 parts by weight in terms of butt is added in the kaolin slurry of parts by weight, is stirred 20 minutes, Zhi Houzai The 2nd Y types point of the rare earth Y type molecular sieve Y-C of 17 parts by weight in terms of butt and 15 parts by weight in terms of butt are added in thereto The mixed serum (solid content is as 40 weight %) of son sieve and the 3rd Y type molecular sieve of 5 parts by weight counted using butt, 30 points of stirring Spray drying is carried out after clock, microspherical catalyst is made.Then the microspherical catalyst is roasted at 500 DEG C 1 it is small when, then at 60 DEG C It is lower to use (NH₄)₂SO₄Solution washs ((NH₄)₂SO₄:Microspherical catalyst:H₂O weight ratio=0.05:1:10) to Na₂O content is less than 0.25 weight %, is finally eluted, microspherical catalyst with deionized water:H₂O weight ratio=1:10, it filters and is dried after at 110 DEG C, Obtain catalytic cracking catalyst C1.On the basis of the total weight of the catalytic cracking catalyst C1, the cracking activity constituent element Content is 48.7 weight %, and the content of the clay is 38.1 weight %, and the content of the binding agent is 13.2 weight %.

Embodiment 2-12

Embodiment 2-12 is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.

Method according to embodiment 1 prepares catalytic cracking catalyst, unlike, will modified Aluminum sol SA-1 respectively with changing Property Aluminum sol SA-2, SA-3, SA-4, SA-5, SA-6, SA-7, SA-8, PSA-1, PSA-2, PSA-3, PSA-4 substitute, urged Fluidized cracking catalysts C2-C12.

Embodiment 13

The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.

Method according to embodiment 1 prepares catalytic cracking catalyst, unlike, this method further includes Jie of 9 parts by weight Hole silica-alumina material A-1 is added in together with the modification Aluminum sol SA-1 of 10 parts by weight in kaolin slurry, and the kaolinite in terms of butt The dosage of soil paste liquid is 20 parts by weight, obtains catalytic cracking catalyst C13.With the total weight of the catalytic cracking catalyst C13 On the basis of, the content of the cracking activity constituent element is 48.7 weight %, and the content of the mesoporous silica-alumina materials is 11.8 weight %, The content of the clay is 26.3 weight %, and the content of the binding agent is 13.2 weight %.

Embodiment 14

The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.

Method according to embodiment 13 prepares catalytic cracking catalyst, unlike, the mesoporous silica-alumina materials A-1 phases Mesoporous silica-alumina materials A-2 with parts by weight is replaced, and obtains catalytic cracking catalyst C14.

Comparative example 1-2

Comparative example 1-2 is used to illustrate catalytic cracking catalyst of reference and preparation method thereof.

Method according to embodiment 1 prepares catalytic cracking catalyst, unlike, Si modification Aluminum sol SA-1 is used respectively Modification the Aluminum sol DSA-1 and DPSA-1 of identical butt dosage are substituted, and obtain reference catalytic cracking catalyst DC1-DC2.

Test case

Test case is used for the test for illustrating catalytic cracking catalyst performance provided by the invention.

The catalytic cracking catalyst C1-C14 of above-mentioned preparation and reference catalytic cracking catalyst DC1-DC2 are existed respectively 800 DEG C, when aging 17 is small under conditions of 100% water vapour, be filled in small fixed flowing bed ACE devices afterwards (purchased from the U.S. KTI companies) in, amount of fill is each 9g.Then, reaction temperature be 505 DEG C, air speed 12h^-1, agent weight of oil ratio be 5:1 Under conditions of to shown in table 1 feedstock oil carry out catalytic cracking reaction.The composition of reaction product is analyzed, and according to the following formula meter Conversion ratio and coke selectivity are calculated, the results are shown in Table 2：

Coke selectivity=coke/conversion ratio.

Table 1

Density (20 DEG C)/(kg/m3)	917.1
		Condensation point/DEG C	20
Carbon residue/%	1.91
		Four component compositions/%
Saturated hydrocarbons	59.6
		Aromatic hydrocarbons	27.3
Colloid	13.1
		Asphalitine	＜ 0.1
Element composition/%
		C	85.96
H	12.37
		S	1.0
N	0.35
		Tenor/(μ g/g)
Fe	12.3
		Ni	4.7
Al	4.9
		Na	0.9
Ca	8.3

Table 2

From the results shown in Table 2, catalytic cracking catalyst provided by the invention in heavy oil catalytic cracking process not Relatively low coke selectivity and higher catalytic cracking activity can be only shown, but also higher diesel oil can be obtained and received Rate.It can be seen that from the comparison of embodiment 1 and embodiment 13 and embodiment 14 when the catalytic cracking catalyst is also containing preferred Mesoporous silica-alumina materials when, corresponding catalytic cracking catalyst is lower for that can show in heavy oil catalytic cracking reaction Coke selectivity.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that the specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (23)

1. a kind of catalytic cracking catalyst, the catalytic cracking catalyst contains cracking activity constituent element, clay and binding agent, special Sign is, on the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains the first of 35-70 weight % 3rd Y type molecular sieve of Y type molecular sieve, the second Y type molecular sieve of 20-60 weight % and 2-20 weight %；The first Y types point Son sieve is rare earth Y type molecular sieve, and using the content of rare earth that oxide is counted as 10-25 weight % in the rare earth Y type molecular sieve, it is brilliant Born of the same parents' constant is 2.440-2.472nm, crystallinity 35-65%, framework si-al ratio 2.5-5：1；Second Y type molecular sieve is Super-stable Y molecular sieves containing magnesium；3rd Y type molecular sieve is the DASY molecular sieves containing rare earth；The binding agent is to contain Cl With the modification Aluminum sol of Si, on the basis of the total weight of the modified Aluminum sol, Al content is 8-13 in the modified Aluminum sol Weight %, Cl content are that 4-9 weight %, Al/Cl weight ratio are 1.2-2.2：1, Si content is 0.1-1 weight %, and described is changed Property Aluminum sol pH value be 2.2-5.2；

Wherein, the modified Aluminum sol is prepared in accordance with the following methods：

Metallic aluminium, water, soluble silicon-containing compound, optional soluble phosphorus-containing compound and chloride are added to reactor In reacted, wherein, it is described solubility silicon-containing compound and metallic aluminium be added to before chloride in reactor, with weight The Al/Si rate of charges of meter are 10-150：1；Al/P rate of charges by weight are (5-30)：(being more than 0-1).

2. catalytic cracking catalyst according to claim 1, wherein, Al/Si weight ratios are in the modified Aluminum sol 9.5-100：1.

3. catalytic cracking catalyst according to claim 1, wherein, the modified Aluminum sol also contains P, with the modification On the basis of the total weight of Aluminum sol, P content is and the modified aluminium more than 0 and no more than 2 weight % in the modified Aluminum sol The pH value of colloidal sol is 2.5-4.2.

4. catalytic cracking catalyst according to claim 3, wherein, P content is 0.3-2 weights in the modified Aluminum sol Measure %.

5. the catalytic cracking catalyst according to claim 3 or 4, wherein, Al/P weight ratios are in the modified Aluminum sol (5-30)：(being more than 0-1).

6. catalytic cracking catalyst according to claim 1, wherein, it adds in before chloride, passes through in the reactor The element silicon and the weight ratio of water that the solubility silicon-containing compound introduces are 0.1-10：100；Al/Si by weight feeds intake Than for 10-100：1.

7. catalytic cracking catalyst according to claim 1, wherein, by add in waterglass solid, sodium silicate solution, One or more forms in acidic silicic acid aqueous solution and alkoxy silane introduce the soluble silicon-containing compound.

8. catalytic cracking catalyst according to claim 1, wherein, the addition of the metallic aluminium is metallic aluminium consumption 100-220 weight %.

9. catalytic cracking catalyst according to claim 1, wherein, Al/Cl rate of charges by weight are 1.2-4：1.

10. catalytic cracking catalyst according to claim 1, wherein, the chloride is added in the form of its aqueous solution, Using the concentration of chloride described in the aqueous chloride solution that Cl elements are counted as 15-20 weight %.

11. catalytic cracking catalyst according to claim 1, wherein, the solubility phosphorus-containing compound is orthophosphoric acid, phosphorus One or more in acid dihydride aluminium, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

12. catalytic cracking catalyst according to claim 1, wherein, the reaction temperature of the reaction is 60-105 DEG C.

13. catalytic cracking catalyst according to claim 12, wherein, the reaction temperature of the reaction is 80-105 DEG C, When reaction time is 12-72 small.

14. catalytic cracking catalyst according to claim 13, wherein, the reaction temperature is 90-98 DEG C, the reaction time For 16-26 it is small when.

15. catalytic cracking catalyst according to claim 1, wherein, the modified Aluminum sol is prepared in accordance with the following methods It obtains：

(1) metallic aluminium, water, soluble silicon-containing compound and optional soluble phosphorus-containing compound are mixed in the reactor；

(2) chloride and optional soluble phosphorus-containing compound are added in the reactor；

(3) reacted the mixture that step (2) obtains, then terminate reaction；

Wherein, the soluble phosphorus-containing compound is added at least one step in step (1) and step (2).

16. the catalytic cracking catalyst according to claim 1 or 15, wherein, the addition time of the chloride is small 0.5 When more than.

17. catalytic cracking catalyst according to claim 16, wherein, when the addition time of the chloride is 1-4 small.

18. catalytic cracking catalyst according to claim 1, wherein, using the total weight of the catalytic cracking catalyst as Benchmark, the content of the cracking activity constituent element are 10-60 weight %, and the content of the clay is 10-60 weight %, the bonding The content of agent is 10-60 weight %.

19. the catalytic cracking catalyst according to claim 1 or 18, wherein, the catalytic cracking catalyst is also containing Jie Hole silica-alumina material, and on the basis of the total weight of the catalytic cracking catalyst, the content of the mesoporous silica-alumina materials is 1-20 Weight %.

20. catalytic cracking catalyst according to claim 19, wherein, the mesoporous silica-alumina materials have boehmite Crystal phase structure, in the mesoporous silica-alumina materials using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.2)Na₂O· (50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, and the specific surface area of the mesoporous silica-alumina materials is 200- 600m²/ g, pore volume 0.5-1.8cm³/ g, average pore size 8-18nm.

21. catalytic cracking catalyst according to claim 20, wherein, the specific surface area of the mesoporous silica-alumina materials is 250-550m²/ g, pore volume 0.6-1.6cm³/ g, average pore size 9-15nm.

22. the preparation method of the catalytic cracking catalyst in claim 1-21 described in any one, this method is included by described in Cracking activity constituent element, optional mesoporous silica-alumina materials, clay and binding agent are mixed with beating, be then spray-dried successively again, Washing, filtering and drying.

23. application of the catalytic cracking catalyst in claim 1-21 described in any one in heavy oil catalytic cracking.