CN105195217A - Catalytic cracking catalyst and preparation method and application thereof - Google Patents
Catalytic cracking catalyst and preparation method and application thereof Download PDFInfo
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- CN105195217A CN105195217A CN201410254333.7A CN201410254333A CN105195217A CN 105195217 A CN105195217 A CN 105195217A CN 201410254333 A CN201410254333 A CN 201410254333A CN 105195217 A CN105195217 A CN 105195217A
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Abstract
The invention discloses a catalytic cracking catalyst and a preparation method and application thereof. The catalytic cracking catalyst comprises cracking active components, mesoporous silicon-aluminum materials, clay and binders, wherein the cracking active components comprise, by weight, 70%-90% of Y-type molecular sieves and 10%-30% of MFI structural molecular sieves, and the Y-type molecular sieves comprise first Y-type molecular sieves and second Y-type molecular sieves; the binders are modified aluminum sol containing Cl and Si, Based on the total weight of the modified aluminum sol, the content of Al ranges from 8% to 13% by weight, the content of Cl ranges from 4% to 9% by weight, the weight ratio of Al to Cl is 1.2-2.2 to 1, the content of Si ranges from 0.1% to 1% by weight, and the pH value of the modified aluminum sol ranges from 2.2 to 5.2. The catalytic cracking catalyst has lower coke selectivity and higher catalytic cracking activity in the heavy oil catalytic cracking process, and a higher liquefied gas yield can be achieved.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, the preparation method of described catalytic cracking catalyst and the application of described catalytic cracking catalyst in RFCC.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, occupies very important status in petroleum refining industry.In catalytic cracking process, heavy end (residual oil as vacuum distillate or more heavy constituent) reacts in the presence of a catalyst, be converted into the high value added products such as liquefied gas, gasoline, diesel oil, usually need in this process to use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material, owing to having excellent shape selective catalysis performance and very high cracking reaction activity, is widely used in petroleum refining and processing industry.At present, catalytic cracking catalyst mainly comprises the components such as cracking activity constituent element, clay, binding agent, wherein, Y zeolite has been just the predominant cracking active component of catalytic cracking catalyst since eighties of last century uses the sixties first always, and binding agent is mainly Alumina gel.
US Patent No. P2196016 reports the preparation method of Alumina gel the earliest.At present, the preparation method of Alumina gel (colloidal sol containing chloride and aluminium is called aluminium polychloride often as sewage treatment flocculating agent) has following several: with aluminium chloride with metallic aluminium reacts, with aluminium hydroxide and the hydrochloric acid of fresh preparation and metallic aluminium reacts, use metallic aluminium and hydrochloric acid reaction, be that raw material is prepared through ion-exchange or thermal decomposition with aluminium chloride.
US Patent No. P3464929 is first by the preparation of Alumina gel (referring to colloidal sol containing chloride and aluminium) for catalyst.Owing to having good adhesive property, Alumina gel is the conventional binding agent of current zeolite catalyst particularly high zeolite content catalyst such as catalytic cracking catalyst.But be Cracking catalyst prepared by binding agent with existing colloidal sol containing chloride and aluminium, its matrix-active is on the low side, selective poor.
Chinese patent ZL91108723.0 (CN1029219C) and Chinese patent ZL91108724.9 (CN1029220C) provides the preparation method of the colloidal sol containing chloride and aluminium of modification, and specifically disclose introduce a small amount of phosphate radical in Alumina gel, corrosion and the pollution of hydrogen chloride in catalyst preparation process can be reduced with phosphate radical Substitute For Partial chlorine root, and the adhesive property of Alumina gel can be improved.But hydrocarbon cracking catalyzer prepared by above phosphorus-containing aluminium sol adhesive, its matrix-active is low, and catalytic cracking reaction selectivity of product is poor.
In addition, the coke selectivity comprising the catalytic cracking catalyst of the components such as existing cracking activity constituent element, clay, binding agent is usually higher.
Summary of the invention
The object of the invention is in order to overcome adopt existing catalytic cracking catalyst to carry out RFCC time coke selectivity higher defect, and provide a kind of newly there is lower coke selectivity, higher cracking activity and can obtain the catalytic cracking catalyst of higher yield of liquefied gas, the preparation method of described catalytic cracking catalyst and the application of described catalytic cracking catalyst in RFCC.
The invention provides a kind of catalytic cracking catalyst, described catalytic cracking catalyst contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, with the gross weight of described cracking activity constituent element for benchmark, described cracking activity constituent element contains the Y zeolite of 70-90 % by weight and the MFI structure molecular sieve of 10-30 % by weight, and described Y zeolite contains the first Y zeolite and the second Y zeolite; Described first Y zeolite is rare earth Y type molecular sieve, and in described rare earth Y type molecular sieve with the content of rare earth of oxide basis for 10-25 % by weight, lattice constant is 2.440-2.472nm, and degree of crystallinity is 35-65%, and framework si-al ratio is 2.5-5:1; Described second Y zeolite is the DASY molecular sieve containing rare earth; Described binding agent is the modified aluminium colloidal sol containing Cl and Si, with the gross weight of described modified aluminium colloidal sol for benchmark, in described modified aluminium colloidal sol, Al content is 8-13 % by weight, Cl content 4-9 % by weight, Al/Cl weight ratio is 1.2-2.2:1, Si content is 0.1-1 % by weight, and the pH value of described modified aluminium colloidal sol is 2.2-5.2.
Present invention also offers the preparation method of described catalytic cracking catalyst, the method comprises described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, and then carries out spraying dry, washing, filtration and drying successively.
In addition, present invention also offers the application of described catalytic cracking catalyst in RFCC.
Modified aluminium colloidal sol provided by the invention is chloride and Alumina gel that is silicon, or is the Alumina gel containing aluminium, silicon and phosphorus, and it has good adhesive property, and matrix-active is higher, can be used as the binding agent of zeolite type crystalline aluminosilicate molecular sieve catalyst.The present inventor finds after further investigation, by this specific modified aluminium colloidal sol and specific cracking activity constituent element and mesoporous silica-alumina materials and clay with the use of, the catalytic cracking catalyst obtained is specially adapted to heavy oil catalytic cracking reaction, lower coke selectivity and higher catalytic cracking activity can not only be shown in heavy oil catalytic cracking reaction process, but also higher yield of liquefied gas can be obtained.
A preferred embodiment of the invention, when described mesoporous silica-alumina materials has boehmite crystal phase structure, in described mesoporous silica-alumina materials with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.2) Na
2o (50-86) Al
2o
3(12-50) SiO
2(0.5-10) P
2o
5, and the specific area of described mesoporous silica-alumina materials is 200-600m
2/ g, pore volume is 0.5-1.8cm
3/ g, when average pore size is 8-18nm, more effectively can increase the content of catalytic cracking catalyst mesopore, more be conducive to the macromolecular diffusion of heavy oil and cracking, corresponding catalytic cracking catalyst is used in heavy oil catalytic cracking reaction, lower coke selectivity can be shown.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Catalytic cracking catalyst provided by the invention contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, with the gross weight of described cracking activity constituent element for benchmark, described cracking activity constituent element contains the Y zeolite of 70-90 % by weight and the MFI structure molecular sieve of 10-30 % by weight, and described Y zeolite contains the first Y zeolite and the second Y zeolite; Described first Y zeolite is rare earth Y type molecular sieve, and in described rare earth Y type molecular sieve with the content of rare earth of oxide basis for 10-25 % by weight, lattice constant is 2.440-2.472nm, and degree of crystallinity is 35-65%, and framework si-al ratio is 2.5-5:1; Described second Y zeolite is the DASY molecular sieve containing rare earth; Described binding agent is the modified aluminium colloidal sol containing Cl and Si, with the gross weight of described modified aluminium colloidal sol for benchmark, in described modified aluminium colloidal sol, Al content is 8-13 % by weight (such as 8-12.5 % by weight), Cl content is 4-9 % by weight (such as 4.5-9 % by weight), Al/Cl weight ratio is 1.2-2.2:1 (such as 1.25-2.1 % by weight), Si content is 0.1-1 % by weight (such as 0.2-0.9 % by weight), and the pH value of described modified aluminium colloidal sol is 2.2-5.2 (such as 2.5-5.2).
Also containing water in described modified aluminium colloidal sol, with the gross weight of described modified aluminium colloidal sol for benchmark, the content of water can be 60-80 % by weight usually, and be such as 66-77 % by weight, the water contained in usual modified aluminium colloidal sol is aequum.
Preferably, in described modified aluminium colloidal sol, Al/Si weight ratio is 9.5-100:1, such as, be 9.8-90:1 or 10-80:1 or 10-50:1.
Described modified aluminium colloidal sol can also contain P, and with the gross weight of described modified aluminium colloidal sol for benchmark, in described modified aluminium colloidal sol, P content for being greater than 0 and being no more than 2 % by weight, be preferably 0.3-2 % by weight, and the pH value of described modified aluminium colloidal sol can be able to be 2.5-4.2.Now, in described modified aluminium colloidal sol, Al/P weight ratio is preferably (5-30): (being greater than 0-1) is 5-30:1.
Described modified aluminium colloidal sol can prepare in accordance with the following methods: metallic aluminium, water, solubility silicon-containing compound, optional solubility phosphorus-containing compound and chloride are joined in reactor and react, wherein, described solubility silicon-containing compound and metallic aluminium joined in reactor before chloride, the weight ratio of the aluminium element summation that described metallic aluminium, solubility phosphorus-containing compound and chloride are introduced and the element silicon introduced of solubility silicon-containing compound (namely Al/Si rate of charge) is by weight 10-150:1, such as, be 15-145:1; Preferably, Al/Si rate of charge is by weight 10-100:1, such as, be 15-100:1 or 15-70:1 or 19-60:1; The weight ratio (namely Al/P rate of charge) by weight that summation and the solubility phosphorus-containing compound of the aluminium element that described metallic aluminium, solubility phosphorus-containing compound and chloride are introduced introduce P elements is (5-30): (being greater than 0-1), being preferably 5-30:1, such as, is 8-30:1.
In the present invention, unless stated otherwise, relate to Al concentration or Al content, refer to concentration or the content of aluminium element, the introduction volume (or claiming the inventory of aluminium) of aluminium refers to and the amount of the aluminium element introduced in reactor comprises the amount of the aluminium element of metallic aluminium and aluminum contained compound introducing.Cl concentration or Cl content refer to concentration or the content of chlorine element, and the introduction volume (or claiming the inventory of chlorine) of chlorine refers to the amount of chlorine element in the chlorine-containing compound introduced in reactor.Si concentration or Si content refer to concentration or the content of element silicon, and the introduction volume (or claiming the inventory of silicon) of silicon refers to the amount of element silicon in the solubility silicon-containing compound introduced in reactor.P concentration or P content refer to concentration or the content of P elements, and the introduction volume (or claiming the inventory of phosphorus) of phosphorus refers to the amount of P elements in the solubility phosphorus-containing compound introduced in reactor.
Described solubility silicon-containing compound is can be water-soluble or can react the silicon-containing compound that (such as hydrolysis occurring) generates Si oxide with water, be specifically as follows in waterglass, acidic silicic acid alkoxy silane one or more, it introduces silicon-containing compound by the solution adding described solubility silicon-containing compound itself or solubility silicon-containing compound.
According to a kind of detailed description of the invention of the present invention, introduce described solubility silicon-containing compound by one or more the form added in waterglass, the acidic silicic acid aqueous solution, alkoxy silane and alkoxy silane solution (organic solution of such as alkoxy silane).Wherein, the organic solvent that the organic solvent in the organic solution of described alkoxy silane preferably can be water-soluble, such as, can be selected from methyl alcohol, ethanol, acetone one or more.Wherein, described waterglass can use waterglass solid or SiO
2concentration is the sodium silicate solution of 1-25 % by weight, and modulus of water glass can be 2.0-3.5 is such as 2.6-3.3, can use the waterglass of the above grade of technical grade, such as chemical pure or commercially pure waterglass.SiO in the described acidic silicic acid aqueous solution
2concentration is 1-10 % by weight, and pH value is 1.5-3.0.The chemical formula of described alkoxy silane is Si (OR)
4, wherein, R be carbon number be less than 10 without replace or substituted alkyl (carbon number be less than 10 alkyl or carbon number be less than 10 have substituent alkyl), each other can be identical or different with the R of four in a part.In addition, the solvent that can add in alkoxy silane solution can be such as ethanol, and in described alkoxy silane solution, Si concentration can be 1-10 % by weight.Described alkoxy silane can be more than technical grade, such as, can be that chemical pure or technical grade are pure.Described alkoxy silane can be such as one or more in tetraethoxysilane, tetramethoxy-silicane, a methoxyl group triethoxysilane, dimethoxy diethoxy silane.
In the preparation process of above-mentioned modified aluminium colloidal sol, solubility silicon-containing compound solution can be passed through, pass through chloride solution, by solubility phosphorus-containing compound solution, in reactor, introduce water by adding water such as deionized water or pass through in reactor, to introduce water with the combination of upper type, preferably, add chloride in the water introduced in forward direction reactor with add chloride with the weight ratio of the solubility silicon-containing compound (with Si) introduced in forward direction reactor for 100:0.1-10, be such as 100:1-10 or 100:0.1-5 or 100:0.15-1.4 or 100:0.2-1.3:1.
In the modified aluminium colloidal sol that the present invention obtains, silicon (in element silicon) content is 0.1-1 % by weight, and being preferably 0.2-0.9 % by weight, such as, is 0.3-0.85 % by weight.
In the preparation process of above-mentioned modified aluminium colloidal sol, the addition (in element aluminum) of described metallic aluminium can be the 100-220 % by weight of metallic aluminium consumption in course of reaction, namely adds equivalent or excessive metallic aluminium.Metallic aluminium raw material used can be aluminium ingot, aluminium bits and aluminum shot in one or more, in described metallic aluminium raw material, the content (or purity of metallic aluminium raw material) of aluminium is preferably not less than 95 % by weight, such as, can be 95-99.7 % by weight.Described metallic aluminium can join and join in reactor, after chlorination adds in reactor, muriaticly join in reactor simultaneously or adopt the combination of above-mentioned feed way to be joined in reactor by metallic aluminium in batches adding before chloride adds, preferably, metallic aluminium joined in reactor before chloride adds.
Described muriatic addition should ensure that the weight ratio of Al/Cl in product is 1.2-2.2:1, and therefore, correspondingly, in the preparation process of above-mentioned modified aluminium colloidal sol, Al/Cl rate of charge is by weight 1.2-4:1, such as, be 1.3-3.5:1.Described Al/Cl rate of charge is the weight ratio of aluminium and the chlorine (the chlorine element that described chloride is introduced) introduced in reactor.Described chloride can be aluminium chloride and/or hydrogen chloride.Described chloride can be introduced with the form of its solution, such as, introduces with the form of hydrochloric acid solution or liquor alumini chloridi or the solution containing hydrochloric acid and aluminium chloride.In described chloride solution, the concentration of chlorine is preferably 15-20 % by weight.When described chloride is introduced with the form of hydrochloric acid, be preferably 15-20 % by weight in the concentration of hydrochloric acid of chlorine; Described hydrochloric acid can be technical grade higher level, such as, be chemical pure or technical grade.When described chloride is introduced with the form of liquor alumini chloridi, in muriatic concentration described in the described aqueous chloride solution of Cl element for 15-20 % by weight, its can with crystal aluminum chloride and water formulated, crystal aluminum chloride can be chemical pure or technical grade.During in order to avoid adding a large amount of chloride, reaction speed is too fast and the temperature that induces reaction raises fast, chloride can be added several times or slowly add chloride, such as can make muriatic feed time (being such as 0.5-4 hour) more than 0.5 hour, preferably, the muriatic joining day (or claiming feed time) is 1-4 hour, controlling the temperature added in chloride process is 60-105 DEG C (being such as 80-102 DEG C), wherein, the described muriatic joining day be from be dosed to and terminate the reinforced time used.
Described solubility phosphorus-containing compound is can be water-soluble or be dissolved in the phosphorus-containing compound of hydrochloric acid, phosphorus-containing compound that preferably can be water-soluble.Described solubility phosphorus-containing compound can add in reactor with the form of itself, also can add in reactor with the form of its aqueous solution.Described solubility phosphorus-containing compound can be such as one or more in orthophosphoric acid, aluminium dihydrogen phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate, wherein, described orthophosphoric acid can be more than technical grade, be such as chemical pure or technical pure orthophosphoric acid, preferably orthophosphoric acid being made into concentration is add in described reactor after the solution of 10-85 % by weight.Described aluminium dihydrogen phosphate can be more than technical grade, chemical pure or technical pure, join after being preferably made into phosphate dihydrogen aluminum solution in reactor, in described phosphate dihydrogen aluminum solution, Al concentration can be 2.5-4.5 % by weight, P concentration can be 10-14.5 % by weight.Aluminium element (aluminium element that the chloride comprising metallic aluminium, solubility phosphorus-containing compound and aluminium is introduced) and the weight rate of charge of phosphorus-containing compound (in phosphorus) (namely Al/P rate of charge) are by weight (5-30): (being greater than 0-1), being preferably 5-30:1, such as, can be 8-30:1.Described solubility phosphorus-containing compound can join in reactor before described chloride adds, join with chloride simultaneously and join in reactor in reactor or after chloride adds or take to be joined in reactor by solubility phosphorus-containing compound with the combination of upper type in batches.
In the preparation process of above-mentioned modified aluminium colloidal sol, metallic aluminium, water, solubility silicon-containing compound, optional solubility phosphorus-containing compound and chloride are mixed in the reactor and reacts, cessation reaction when aluminum concentration reaches requirement (such as aluminum concentration reaches 8-13 % by weight) in the modified aluminium colloidal sol be obtained by reacting.In specific operation process, can by unreacted metallic aluminium being separated such as by filtering to stop reacting with product liquid, or stop reaction by cooling, the method for then filtering, such as, temperature is reduced to less than 80 DEG C, be preferably down to the method that less than 70 DEG C (such as 60-70 DEG C) then filter and stop reacting.
In the preparation process of above-mentioned modified aluminium colloidal sol, described chloride is added in reactor after described metallic aluminium and solubility silicon-containing compound add, add in chloride process and namely start chemical reaction occurs, add chloride continue later react a period of time, in gained modified aluminium sol product aluminum concentration reach requirement stop later reaction.The reaction temperature of described reaction (from add temperature between chloride to reaction tailend) can be 60-105 DEG C, be preferably 80-102 DEG C, be more preferably 90-98 DEG C; Reaction time (from add the time that chloride terminates to reaction, also claim total reaction time) usually for 12-72 hour, 16-26 hour can be preferably.According to a kind of detailed description of the invention, the reaction temperature added in chloride process is 60-102 DEG C, the reaction time is 1-4 hour; Add that the reaction temperature after chloride is 80-105 DEG C (such as 90-98 DEG C), the reaction time is 8-71 hour (such as 16-26 hour), then cessation reaction.
As mentioned above, in the preparation process of above-mentioned modified aluminium colloidal sol, the addition sequence of described solubility phosphorus-containing compound does not have particular/special requirement, can before chloride adds, chloride add before, chloride add after, join in reactor with chloride simultaneously, or adopt the combination of above-mentioned any several feed way.Preferably, described solubility phosphorus-containing compound adds the later reaction time and is not shorter than 0.5 hour, such as, be 0.5-72 hour.
A preferred embodiment of the invention, when described modified aluminium colloidal sol is the Alumina gel of silicon and P Modification, described modified aluminium solution prepares according to the method comprised the following steps:
(1) metallic aluminium, water, solubility silicon-containing compound and optional solubility phosphorus-containing compound are mixed in the reactor;
(2) chloride and optional solubility phosphorus-containing compound is added in the reactor;
(3) mixture making step (2) obtain reacts a period of time, then cessation reaction;
Wherein, described solubility phosphorus-containing compound is added at least one step in step (1) and step (2).
Preferably prepare in the embodiment of modified aluminium colloidal sol at this, described solubility phosphorus-containing compound can add in step (1) or step (2), also all can add in step (1) and step (2).Fashionable when adding in step (2), described solubility phosphorus-containing compound can with chloride add simultaneously such as mix after add, also can add after chloride adds.When solubility phosphorus-containing compound adds fashionable after chloride adds, preferably from add chloride and be no more than 4 hours to the time adding solubility phosphorus-containing compound, can be such as 0.5-4 hour, be preferably 1-3.5 hour.
Preferably prepare in the embodiment of modified aluminium colloidal sol at this, before adding chloride, make the temperature of mixture in reactor be not less than 60 DEG C, such as, can be 60-102 DEG C, then add chloride and react.Raise rapidly in order to avoid adding the chloride excessive velocities actuator temperature that induces reaction, the mode that substep can be taked to add or slowly add adds.Normally, the described muriatic speed that adds is as the criterion to make the temperature adding material in chloride post-reactor be no more than 102 DEG C.
In addition, preferably prepare in the embodiment of modified aluminium colloidal sol at this, in step (3), the mixture that step (2) obtains is kept a period of time, material in reactor is reacted.Preferably, mixture step (2) obtained keeps within 8-71 hour, making the material in reactor react at temperature 80-105 DEG C, and namely the reaction temperature of step (3) is 80-105 DEG C, and the reaction time is 8-71 hour; More preferably, the reaction temperature in step (3) is 90-98 DEG C, and the reaction time is 12-25 hour.Reaction is stopped when aluminum concentration in product reaches requirement (in such as gained modified aluminium colloidal sol, the content of aluminium element is 8-13 % by weight).
In the preparation process of above-mentioned modified aluminium colloidal sol, the modified aluminium sol product obtained can also be concentrated, to improve the concentration of wherein aluminium.Such as, if the aluminum concentration of modified aluminium sol product is less than 10 % by weight, the concentration of aluminium in modified aluminium colloidal sol is made to bring up to more than 10 % by weight by concentrated.Described concentrating concentrates by evaporation, and evaporation and concentration condition generally includes: temperature can be 80-105 DEG C, and the time can be 0.5-4 hour.Usually making the aluminum concentration of product be 10-13 % by weight by concentrated, such as, is 10-12 % by weight.
The Alumina gel of silicon or silicon and P Modification can be obtained according to above-mentioned modified aluminium colloidal sol preparation method, the aluminium polychloride micelle of Si modification or silicon and P Modification is formed in this modified aluminium colloidal sol, silicon is evenly distributed in modified aluminium colloidal sol, large silicon oxide particle can not be formed, also can not form silica-alumina gel block, have good adhesive property, matrix-active is higher, can be used as zeolite type crystalline aluminosilicate molecular sieve catalyst binding agent, in particular as SiO
2/ Al
2o
3the binding agent of lower crystalline aluminosilicate molecular sieve catalyst is such as containing the binding agent of the Cracking catalyst of y-type zeolite, prepared catalyst reaction performance is better than colloidal sol containing chloride and aluminium and phosphorated aluminiferous collosol, its adhesive property and matrix-active are better than Alusil catalyst and Ludox catalyst, and better selective.
According to catalytic cracking catalyst provided by the invention, preferably, with the gross weight of described catalytic cracking catalyst for benchmark, described catalytic cracking catalyst contains the binding agent of the cracking activity constituent element of 10-60 % by weight, the mesoporous silica-alumina materials of 1-20 % by weight, the clay of 10-70 % by weight and 10-60 % by weight, is controlled by the content of above-mentioned each component the catalytic cracking catalyst obtained can be made to have better combination property in this preferred scope.
According to catalytic cracking catalyst provided by the invention, preferably, in described rare earth Y type molecular sieve with the content of rare earth of oxide basis for 11-23 % by weight, lattice constant is 2.450-2.470nm, and degree of crystallinity is 40-60%.
Described rare earth Y type molecular sieve can prepare according to existing various method, such as, two can be handed over to roast and prepare in conjunction with deposition of rare-earth process by two.Particularly, described rare earth Y type molecular sieve prepares in accordance with the following methods: the mixed solution of NaY molecular sieve and earth solution or earth solution and ammonium salt is carried out contact pairs, after filtration, washing, after drying, carry out first time calcination process, obtain rare earth sodium Y molecular sieve; Then by rare earth sodium Y molecular sieve making beating and with ammonium salt solution or acid solution contact pairs, mix with earth solution again after filtration, and the pH value of slurries is adjusted to 6-10, filter or do not filter, carry out second time calcination process after drying, obtain described 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 degree of crystallinity is greater than 80%.The mixed solution of NaY molecular sieve and earth solution or earth solution and ammonium salt is being carried out in the process of contact pairs, for 0.06-0.14:1,0.08-0.12:1 can be preferably in the weight ratio of the earth solution of rare earth oxide and NaY molecular sieve butt; Control ph is 3-5; Controlling water sieve weight ratio is 5-30:1, is preferably 8-15:1; The process of described contact pairs is room temperature-100 DEG C, preferably at 70-95 DEG C, process 0.3-3.0 hour, preferred process 0.5-1.5 hour.
In the preparation process of above-mentioned rare earth Y type molecular sieve, described first time calcination process and the condition of the second calcination process identical or different, and independently of one another at 500-650 DEG C, calcination process 0.5-4 hour, preferred 1-3 hour under 0-100% water vapor conditions.Wherein, described first time calcination process and second time calcination process at least one of them carries out under the water vapor conditions of 1-100%, preferably 20-100%, most preferably 100%, steam treatment can impel rare earth ion to move to little cage from molecular sieve supercage.Particularly preferably, described first time calcination process and second time calcination process all carry out under 100% water vapor conditions.
In the preparation process of above-mentioned rare earth Y type molecular sieve, rare earths material in described earth solution can be that the routine of this area is selected, such as, can be rare earth chloride and/or nitric acid rare earth, and can be rare earth chloride or the nitric acid rare earth of Rare Earth Elements Determination composition, wherein common comprise in lanthanum chloride, lanthanum nitrate, cerium chloride, cerous nitrate etc. one or more, also can for the mishmetal containing different rare earth element, such as, rich cerium type and rich lanthanum type mishmetal.
The described DASY molecular sieve containing rare earth refers to the hydro-thermal super stable molecular sieve containing rare earth, wherein, with RE
2o
3the content of rare earth that (rare earth oxide) is counted can be 1.5-3 % by weight.The described DASY molecular sieve containing rare earth can be various commercially available prod, such as, can be the DASY2.0 molecular sieve purchased from Sinopec catalyst asphalt in Shenli Refinery.
Described MFI structure molecular sieve with the anhydrous chemical of the mass ratio range of oxide composition expression formula is: (0-0.3) Na
2o (0.5-5.5) Al
2o
3(1.3-10) P
2o
5(0.7-15) M1
xo
y(0.01-5) M2
mo
n(70-97) SiO
2, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents the number meeting M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents the number meeting M2 oxidation state requisite oxygen.In addition, described MFI structure molecular sieve can be commercially available, and also according to well known to a person skilled in the art that various method prepares, such as, can prepare according to method disclosed in CN1611299A.
According to catalytic cracking catalyst provided by the invention, the kind of described mesoporous silica-alumina materials can be the routine selection of this area, particularly preferably, described mesoporous silica-alumina materials has boehmite crystal phase structure, in described mesoporous silica-alumina materials with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.2) Na
2o (50-86) Al
2o
3(12-50) SiO
2(0.5-10) P
2o
5, and the specific area of described mesoporous silica-alumina materials is 200-600m
2/ g, pore volume is 0.5-1.8cm
3/ g, average pore size is 8-18nm.Adopt this preferred mesoporous silica-alumina materials effectively can increase the content of catalytic cracking catalyst mesopore, be conducive to the macromolecular diffusion of heavy oil and cracking, this catalytic cracking catalyst is specially adapted to RFCC, can show lower coke selectivity and higher catalytic cracking activity in the process of RFCC.
According to catalytic cracking catalyst provided by the invention, more preferably, the specific area of above-mentioned mesoporous silica-alumina materials is 250-550m
2/ g, pore volume is 0.6-1.6cm
3/ g, average pore size is 9-15nm.
In the present invention, described specific area, pore volume and average pore size all adopt nitrogen absorption under low temperature-desorption method to measure, and the instrument adopted is the physical and chemical adsorption instrument ASAP2400 of Micromeritics company of the U.S..
Above-mentioned preferred mesoporous silica-alumina materials can be commercially available, also can according to well known to a person skilled in the art that various method prepares, such as, can prepare in accordance with the following methods: by during aluminium source and alkaline solution are at room temperature to 85 DEG C and plastic, the pH value controlling plastic is 7-11, then according to SiO
2: Al
2o
3the weight ratio of=1:1-7.5 adds silicon source in plastic slurries, ageing 1-5 hour at room temperature to 90 DEG C again, then filter after solid sediment ageing obtained contacts with ammonium salt or acid solution, obtain sodium oxide content lower than 0.3 % by weight solid product, and then described solid product is contacted with phosphorus source, and product of contact is dry; Described phosphorus source is with P
2o
5the weight ratio of the consumption of meter and the butt of described solid product is 0.005-0.1:1.
In the preparation method of above-mentioned mesoporous silica-alumina materials, the step obtained before described solid product all can be carried out with reference to method disclosed in CN1565733A.
Particularly, described aluminium source can for the existing various material that can be converted into aluminium oxide, such as, can be selected from aluminum nitrate, aluminum sulfate and aluminium chloride one or more.
Described alkaline solution can be the existing various material presenting alkalescence, such as, can be selected from ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution one or more.Wherein, the concentration of described alkaline solution can be the routine selection of this area, and therefore not to repeat here.
Described silicon source can for the existing various material that can be converted into silica, such as, can be selected from waterglass, sodium metasilicate, tetraethoxy-silicane and silica one or more.
The present invention is not particularly limited the method contacted with ammonium salt by described solid sediment, such as, can to comprise described solid sediment by its butt: ammonium salt: H
2the weight ratio of O=1:0.1-1:5-30 exchanges at room temperature to 100 DEG C.Wherein, the number of times of described contact can be 1-3 time, and each time of contact can 0.5-1 hour, and the content of sodium oxide molybdena in the solid product obtained specifically should be made to be as the criterion lower than 0.3 % by weight.
In addition, the kind of described ammonium salt can be that the routine of this area is selected, such as, can be selected from ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and carbonic hydroammonium one or more.
The present invention is not particularly limited the method contacted with acid solution by described solid sediment, such as, can to comprise described solid sediment by its butt: acid: H
2the weight ratio of O=1:0.03-0.3:5-30 exchanges at least 0.2 hour at room temperature to 100 DEG C.
In addition, the kind of described acid solution can be that the routine of this area is selected, and is generally inorganic acid, such as, the acid in described acid solution can be selected from sulfuric acid, hydrogen chloride and nitric acid one or more.
According to catalytic cracking catalyst provided by the invention, wherein, contact between described solid product and phosphorus source can be carried out in presence of water, described contact method comprises: by described solid product by its butt: the weight ratio mixing making beating of water=1:5-20, add phosphorus source again and at room temperature to 90 DEG C, react 0.2-5 hour, preferred 0.5-3 hour, again the product of contact obtained being carried out afterwards filtering, washing.In addition, the contact between described solid product with phosphorus source can also for mixing described solid product with phosphorus source and grinding.The product of contact in described solid product and phosphorus source is carried out dry condition generally include: baking temperature can be 100-150 DEG C, and drying time can be 10-20 hour.In addition, optionally, the preparation method of described mesoporous silica-alumina materials can also comprise desciccate is carried out roasting, and it can be 500-700 DEG C that the condition of described roasting generally includes sintering temperature, and roasting time can be 1-4 hour.
The kind in described phosphorus source can be that the routine of this area is selected, such as, can be selected from ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and phosphoric acid one or more.
According to catalytic cracking catalyst provided by the invention, described clay can be the existing various clay that can be used in catalytic cracking catalyst, such as, one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite can be selected from.
The preparation method of catalytic cracking catalyst provided by the invention comprises above-mentioned cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, and then carries out spraying dry, washing, filtration and drying successively.
According to the preparation method of catalytic cracking catalyst provided by the invention, by described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, and follow-up spraying dry, washing, filtration and drying, the implementation method of these operations all can adopt conventional method to implement, their specific implementation method such as has detailed description in CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, introduces in the present invention with for referencial use in the lump here.In addition, usually, after described spraying dry, washing before, the preparation method of described catalytic cracking catalyst also comprises the step of Spray dried products being carried out roasting usually.It can be 500-700 DEG C that the condition of described roasting generally includes sintering temperature, and roasting time can be 1-4 hour.
In addition, present invention also offers the application of above-mentioned catalytic cracking catalyst in RFCC.
Below will be described the present invention by embodiment.
In following preparation example, contrast preparation example, embodiment and comparative example:
Aluminium bits purity used is 99.2 % by weight, and aluminum shot purity is 98.8 % by weight; 1:1 chemical pure hydrochloric acid used is the concentration 36 % by weight chemical pure hydrochloric acid of 1 volume and the mixture of 1 volume water; The chemical pure phosphoric acid of 1:1 used is the concentration 85 % by weight chemical pure phosphoric acid of 1 volume and the mixture of 1 volume water; Rare earth chloride is purchased from Xitu Hi-Tech skill limited company of Baogang, and rare earth element is wherein La and Ce.
Specific area, pore volume and average pore size all adopt nitrogen absorption under low temperature-desorption method to measure, and the instrument adopted is the physical and chemical adsorption instrument ASAP2400 of Micromeritics company of the U.S.; Na in mesoporous silica-alumina materials
2o, Al
2o
3, SiO
2, P
2o
5content with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish);
MFI structure molecular sieve method disclosed in CN1611299A embodiment 1 prepares;
Second Y zeolite is the DASY2.0 molecular sieve purchased from Sinopec catalyst asphalt in Shenli Refinery;
In catalytic cracking catalyst, the content of each component calculates according to inventory.
Preparation example 1
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminium being considered to be worth doing 286 grams (in Al), deionized water 1481 grams and sodium silicate solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 119 grams adds in there-necked flask, is heated to 60 DEG C.Slowly added in there-necked flask by the chemical pure hydrochloric acid 921 milliliters of 1:1, itself and aluminium are considered to be worth doing and reacts, the joining day of hydrochloric acid is 3 hours; After adding hydrochloric acid, react 20 hours at reaction temperature 90-95 DEG C, then product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol SA-1.The aluminium of reaction remnants is considered to be worth doing through being weighed as 36 grams, i.e. aluminium excessive 14.8 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-1: Al content is 9.0 % by weight, Cl content is 6.7 % by weight, Si content is 0.41 % by weight, Al/Cl (weight ratio) for 1.34:1, Al/Si (weight ratio) be 22.0:1, pH value is 3.00.
Preparation example 2
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminium considers 280 grams (in Al), deionized water 1055 grams to be worth doing, sodium silicate solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 115 grams adds in there-necked flask, is heated to 60 DEG C.Slowly added in there-necked flask by 1:1 chemical pure hydrochloric acid 678 milliliters, itself and aluminium are considered to be worth doing and reacts, the joining day of hydrochloric acid is 3 hours; After adding hydrochloric acid, react 19 hours at reaction temperature 90-95 DEG C, then product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol SA-2.The aluminium of reaction remnants is considered to be worth doing through being weighed as 29 grams, i.e. aluminium excessive 11.6 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-2: Al content is 12.20 % by weight, Cl content is 6.5 % by weight, Si content is 0.52 % by weight, Al/Cl (weight ratio) for 1.88:1, Al/Si (weight ratio) be 23.5:1, pH value is 4.00.
Preparation example 3
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminum shot 250 grams (in Al), deionized water 1560 grams, tetraethoxysilane ethanolic solution (containing Si element 3.0 % by weight) 162 grams add in there-necked flask, are heated to 60 DEG C.Slowly added in there-necked flask by the chemical pure hydrochloric acid 524 milliliters of 1:1, itself and aluminum shot are reacted, the joining day of hydrochloric acid is 2 hours; After adding hydrochloric acid, react 68 hours at reaction temperature 93-97 DEG C; Then product is cooled to 60-70 DEG C, filters, obtain modified aluminium colloidal sol SA-3.React the aluminum shot of remnants through being weighed as 48 grams, i.e. aluminium excessive 23.8 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-3: Al content is 8.4 % by weight, Cl content to be 4.3 % by weight, Si content be 0.2 % by weight, Al/Cl (weight ratio) for 1.95:1, Al/Si (weight ratio) be 42.0:1, pH value is 3.8.
Preparation example 4
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminum shot 350 grams (in Al), deionized water 1190 grams and the acidic silicic acid aqueous solution (containing Si element 5.0 % by weight, pH value is 2.0) 356 grams add in there-necked flask, are heated to 60 DEG C.Slowly added in there-necked flask by the chemical pure hydrochloric acid 496 milliliters of 1:1, itself and aluminum shot are reacted, the joining day of hydrochloric acid is 2 hours; After adding hydrochloric acid, react 18 hours at reaction temperature 93-97 DEG C, then product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol SA-4.The aluminum shot of reaction remnants is 176 grams, and namely aluminium is excessive is 101.1 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-4: Al content is 8.0 % by weight, Cl content to be 4.5 % by weight, Si content be 0.82 % by weight, Al/Cl (weight ratio) for 1.78:1, Al/Si (weight ratio) be 9.8:1, pH value is 5.1.
Preparation example 5
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminum shot 350 grams (in Al), deionized water 1510 grams and sodium silicate solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 28 grams add in there-necked flask, are heated to 60 DEG C.Slowly added in there-necked flask by the chemical pure hydrochloric acid 488 milliliters of 1:1, itself and aluminum shot are reacted, the joining day of hydrochloric acid is 2 hours; After adding hydrochloric acid, react 24 hours at reaction temperature 93-97 DEG C, then product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol SA-5.React the aluminum shot of remnants through being weighed as 149 grams, i.e. aluminium excessive 74.1 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-5: Al content is 9.2 % by weight, Cl content is 4.4 % by weight, Si content is 0.12 % by weight, Al/Cl (weight ratio) for 2.09:1, Al/Si (weight ratio) be 76.7:1, pH value is 3.80.
Preparation example 6
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Aluminum shot 250 grams (in Al), deionized water 840 grams and sodium silicate solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 60 grams add in there-necked flask, are heated to 60 DEG C.Slowly added in there-necked flask by the chemical pure hydrochloric acid 829 milliliters of 1:1, itself and aluminum shot are reacted, the joining day of hydrochloric acid is 3 hours; After adding hydrochloric acid, react 17 hours at reaction temperature 95-100 DEG C, then product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol SA-6.The aluminum shot of reaction remnants is through being weighed as 39 grams, and namely aluminium is excessive is 18.5 % by weight.By analysis, result is as follows for modified aluminium colloidal sol SA-6: Al content is 11.1 % by weight, Cl content is 8.6 % by weight, Si content is 0.31 % by weight, Al/Cl (weight ratio) for 1.29:1, Al/Si (weight ratio) be 35.8:1, pH value is 2.9.
Preparation example 7
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Modified aluminium colloidal sol is prepared according to the method for preparation example 2, unlike, replace hydrochloric acid solution with liquor alumini chloridi, Al/Cl rate of charge is constant, and Al/Si rate of charge is constant, the consumption of corresponding minimizing metallic aluminium.By analysis, result is as follows for the modified aluminium colloidal sol SA-7 obtained: Al content is 12.0 % by weight, Cl content is 6.4 % by weight, Si content is 0.51 % by weight, Al/Cl (weight ratio) for 1.88:1, Al/Si (weight ratio) be 23.5:1, pH value is 3.90.
Preparation example 8
This preparation example is for illustration of the preparation method of Si modification Alumina gel provided by the invention.
Modified aluminium colloidal sol is prepared according to the method for preparation example 6, unlike, the hydrochloric acid solution of preparation example 6 is replaced with the mixed solution (ratio of the chlorine that aluminium chloride provides and the chlorine that hydrochloric acid provides is 1:1, and total cl concn is 20 % by weight) of aluminium chloride and hydrochloric acid.By analysis, result is as follows for the modified aluminium colloidal sol SA-8 obtained: be 11.0 % by weight, Cl content containing Al content be 8.5 % by weight, Si content is 0.31 % by weight, Al/Cl (weight ratio) for 1.29:1, Al/Si (weight ratio) be 35.5:1, pH value is 2.90.
Contrast preparation example 1
This contrast preparation example is for illustration of the preparation method of the modified aluminium colloidal sol of reference.
Aluminium bits are used to prepare Alumina gel with hydrochloric acid reaction according to existing method.Aluminium considers 240 grams (in Al) to be worth doing, deionized water 1160 grams puts into there-necked flask, is heated to 60 DEG C.Slowly added in there-necked flask by 1:1 chemical pure hydrochloric acid 640 milliliters, itself and aluminium are considered to be worth doing and reacts, the joining day of hydrochloric acid is 3 hours; After adding hydrochloric acid, react 19 hours at reaction temperature 90-95 DEG C, then product is cooled to 60-70 DEG C, filter, obtain reference modified aluminium colloidal sol DSA-1.By analysis, result is as follows for reference modified aluminium colloidal sol DSA-1: Al content is 12.0 % by weight, Cl content be 6.3 % by weight, Al/Cl (weight ratio) is 1.90:1, and pH value is 3.40.
Preparation example 9
This preparation example is for illustration of the preparation method of silicon provided by the invention and P Modification Alumina gel.
Aluminium is considered 280 grams (in aluminium), deionized water 1480 grams and water glass solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 124 grams to be worth doing and is added in there-necked flask, is heated to 60 DEG C.By the chemical pure hydrochloric acid 921 milliliters of 1:1 and the 2 milliliters of mixing of the chemical pure phosphatase 24 of 1:1, slowly add in there-necked flask, acid is added 3 hours used times, then react 20 hours at reaction temperature 90-95 DEG C, afterwards product is cooled to 60-70 DEG C, filters, obtain modified aluminium colloidal sol PSA-1.The aluminium of reaction remnants is considered to be worth doing through being weighed as 35 grams, i.e. aluminium excessive 14.3 % by weight.Modified aluminium colloidal sol PSA-1 by analysis, result is as follows: Al content is 8.9 % by weight, Cl content is 6.6 % by weight, P content is 0.35 % by weight, Si content is 0.42 % by weight, Al/Cl (weight ratio) for 1.35:1, Al/P (weight ratio) are 25.4:1, Al/Si (weight ratio) is 21.2:1, and pH value is 3.20.
Preparation example 10
This preparation example is for illustration of the preparation method of silicon provided by the invention and P Modification Alumina gel.
Aluminum shot 350 grams (in aluminium), deionized water 1040 grams and the acidic silicic acid aqueous solution (containing Si element 5.0 % by weight, pH value is 2.0) 354 grams add in there-necked flask, are heated to 60 DEG C.By the chemical pure hydrochloric acid 498 milliliters of 1:1 and 1:1 chemical pure phosphatase 11 12 milliliters mixing, slowly add in there-necked flask, acid is added 2 hours used times, then react 18 hours at reaction temperature 93-97 DEG C, afterwards product is cooled to 60-70 DEG C, filters, obtain modified aluminium colloidal sol PSA-2.The aluminum shot of reaction remnants is through being weighed as 177 grams, and namely aluminium is excessive is 102.3 % by weight.Modified silicasol PSA-2 by analysis, result is as follows: Al content is 8.1 % by weight, Cl content is 4.6 % by weight, P content is 1.20 % by weight, Si content is 0.83 % by weight, Al/Cl (weight ratio) for 1.76:1, Al/P (weight ratio) are 6.8:1, Al/Si (weight ratio) is 9.8:1, and pH value is 3.0.
Preparation example 11
This preparation example is for illustration of the preparation method of silicon provided by the invention and P Modification Alumina gel.
Aluminum shot 350 grams (in aluminium), deionized water 1440 grams and sodium silicate solution (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 26 grams add in there-necked flask, are heated to 60 DEG C.By the chemical pure hydrochloric acid 495 milliliters of 1:1 and 1:1 chemical pure phosphatase 11 01 milliliter mixing, slowly add in there-necked flask, acid is added 2 hours used times, then react 24 hours at reaction temperature 93-97 DEG C, afterwards product is cooled to 60-70 DEG C, filters, obtain modified aluminium colloidal sol PSA-3.React the aluminum shot of remnants through being weighed as 148 grams, i.e. aluminium excessive 73.3%.Modified aluminium colloidal sol PSA-3 by analysis, result is as follows: Al content is 9.1 % by weight, Cl content is 4.4 % by weight, P content is 1.04 % by weight, Si content is 0.11 % by weight, Al/Cl (weight ratio) for 2.07:1, Al/P (weight ratio) are 8.8:1, Al/Si (weight ratio) is 82.7:1, and pH value is 2.9.
Preparation example 12
This preparation example is for illustration of the preparation method of silicon provided by the invention and P Modification Alumina gel.
Aluminum shot 350 grams (in aluminium), deionized water 1580 grams, sodium silicate solution are (containing Si element 9.33 % by weight, Na element 4.63 % by weight) 154 grams and aluminium dihydrogen phosphate aqueous solution be (containing Al element 4.5 % by weight, P element 13.4 % by weight) 311 grams put into there-necked flask, be heated to 60 DEG C.1:1 chemical pure hydrochloric acid 731 milliliters is slowly added in there-necked flask, with aluminum shot haptoreaction, hydrochloric acid is added 2 hours used times; Then react 16 hours at reaction temperature 93-98 DEG C, afterwards product is cooled to 60-70 DEG C, filter, obtain modified aluminium colloidal sol.The aluminum shot of reaction remnants is through being weighed as 116 grams, and namely aluminium is excessive is 47.5 % by weight.Modified silicasol by analysis, result is as follows: Al content is 8.2 % by weight, Cl content is 4.8 % by weight, P content is 1.4 % by weight, Si content is 0.48 % by weight, Al/Cl (weight ratio) is 1.71, Al/P (weight ratio) is 5.9, and pH value is 2.50.This modified silicasol sample is taken 500 grams and to be placed on electric furnace heating concentrated 40 minutes, 390 grams, sample of weighing after cooling to obtain, is modified aluminium colloidal sol PSA-4.Modified aluminium colloidal sol PSA-4 by analysis, result is as follows: Al content is 10.50 % by weight, Cl content is 6.2 % by weight, P content is 1.80 % by weight, Si content is 0.62 % by weight, Al/Cl (weight ratio) for 1.69:1, Al/P (weight ratio) are 5.8:1, Al/Si (weight ratio) is 16.9:1, and pH value is 2.5.
Contrast preparation example 2
This contrast preparation example is for illustration of the preparation method of the modified aluminium colloidal sol of reference.
Aluminium and hydrochloric acid reaction is used to prepare P Modification Alumina gel according to the method in CN91108724.9, specific as follows:
Aluminium considers 286 grams (in aluminium) to be worth doing and deionized water 921 grams puts into there-necked flask, is heated to 60 DEG C.By 1:1 chemical pure hydrochloric acid 663 milliliters and 1:1 chemical pure phosphoric acid 68 milliliters mixing, slowly add in there-necked flask, in 3 hours, acid is added, then react 19 hours at reaction temperature 90-95 DEG C, afterwards product is cooled to 60-70 DEG C, filters, obtain modified aluminium colloidal sol DPSA-1.Reaction residual Al is considered to be worth doing through being weighed as 48 grams, i.e. aluminium excessive 20 % by weight.By analysis, result is as follows for modified aluminium colloidal sol DPSA-1: Al content is 12.20 % by weight, Cl content to be 6.4 % by weight, P content be 0.58%, Al/Cl (weight ratio) for 1.91:1, Al/P (weight ratio) be 21.0:1, pH value is 3.6.
Preparation example 13
This preparation example is for illustration of mesoporous silica-alumina materials provided by the invention and preparation method thereof.
Take concentration as 90gAl
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102gAl
2o
3/ L, Crater corrosion are the NaAlO of 2.5
2solution is reaction raw materials, at 85 DEG C and to flow plastic and control plastic pH value be 9.5, collects a certain amount of plastic slurries, under agitation presses SiO
2: Al
2o
3it is 60gSiO that the ratio of=1:6.56 adds concentration
2the sodium silicate of/L, is warming up to 70 DEG C of ageings 2 hours, obtains solid sediment.Use NH
4cl solution presses solid sediment (butt): NH
4cl:H
2the weight ratio of O=1:0.8:15 carries out ion-exchange to remove sodium ion to solid sediment at 60 DEG C, ion-exchange repeats twice, carry out 0.5 hour at every turn, obtain sodium oxide content after filtration lower than the solid product of 0.3 % by weight, and then described solid product is pressed solid product (butt): H
2the weight ratio of O=1:8 mixes with water pulls an oar, and presses P
2o
5: the weight ratio of solid product butt=0.022:1 adds diammonium hydrogen phosphate, then reacts 1 hour at 70 DEG C, to filter after washing at 120 DEG C dry 10 hours, obtains mesoporous silica-alumina materials, be designated as A-1.
Mesoporous silica-alumina materials A-1 has structure of similar to thin diaspore, and adopt X-ray fluorescence method to record, mesoporous silica-alumina materials A-1 with the chemical composition of the mass ratio range of oxide is: 0.11Na
2o84.0Al
2o
312.8SiO
22.1P
2o
5.The specific area of mesoporous silica-alumina materials A-1 is 501m
2/ g, pore volume is 1.51cm
3/ g, average pore size is 12.1nm.
Preparation example 14
This preparation example is for illustration of mesoporous silica-alumina materials provided by the invention and preparation method thereof.
Mesoporous silica-alumina materials is prepared according to the method for preparation example 13, unlike, do not comprise described solid product by solid product (butt): H
2the weight ratio of O=1:8 mixes the step after pulling an oar with water, but directly using sodium oxide content lower than 0.3 % by weight the product that obtains after dry 10 hours at 120 DEG C of solid product as the mesoporous silica-alumina materials of reference, be designated as A-2.
Mesoporous silica-alumina materials A-2 has structure of similar to thin diaspore, and adopt X-ray fluorescence method to record, mesoporous silica-alumina materials A-2 with the chemical composition of the mass ratio range of oxide is: 0.19Na
2o81.9Al
2o
316.7SiO
2.The specific area of mesoporous silica-alumina materials DA-1 is 514m
2/ g, pore volume is 1.45cm
3/ g, average pore size is 11.3nm.
Preparation example 15
This preparation example is for illustration of the preparation method of rare earth Y type molecular sieve provided by the invention.
Get 2.6 kilograms of NaY molecular sieve and 18 kilograms of deionized water mixing making beating, add 1.25 liters of concentration 160gRE
2o
3the re chloride of/L and 0.12 kilogram of chloride solid, be warming up to 80 DEG C after stirring evenly and regulate slurries pH to 3.8 with watery hydrochloric acid, continue exchange 1 hour, after filtration, washing, drying, in 570 DEG C of roastings 2 hours under 50% water vapor conditions, obtain a friendship one and roast rare earth sodium Y molecular sieve Y-C1, in Y-C1, the content of sodium oxide molybdena is 4.9 % by weight, and the content of rare earth oxide is 9.9 % by weight.Then molecular sieve is pressed: NH
4cl:H
2the ratio of O=1:0.15:12 is pulled an oar and exchange 1 hour at 75 DEG C, and after filtering washing, reslurry also adds 0.27 liter of concentration 300gRE
2o
3the re chloride of/L, ensures that concentration of slurry is 400-450g/L, adds waterglass and regulates slurry pH value to 8.0 and continue stirring 10 minutes, in air atmosphere in 570 DEG C of roastings 2 hours after drying, obtain rare earth Y type molecular sieve, be designated as Y-C after stirring evenly.After testing, in rare earth Y type molecular sieve Y-C, the content of sodium oxide molybdena is 1.3 % by weight, and be 13.9 heavy % with the content of rare earth of oxide basis, degree of crystallinity is 48.8%, and lattice constant is 2.465nm, and framework silicon-aluminum atomic ratio is 3.1:1.
Embodiment 1
This embodiment is for illustration of catalytic cracking catalyst provided by the invention and preparation method thereof.
Kaolin and water are pulled an oar, prepare the kaolin slurry that solid content is 40 % by weight, then toward in the modified aluminium colloidal sol SA-1 added respectively in the kaolin slurry of 32 weight portions of butt in 9 weight portions of butt, in the slurries of the mesoporous silica-alumina materials A-2 of 5 weight portions of butt (solid content is 40 % by weight), stir 20 minutes, add wherein more afterwards in the rare earth Y type molecular sieve Y-C of 22 weight portions of butt, in the DASY2.0 molecular sieve of 8 weight portions of butt and in the mixed serum of the MFI structure molecular sieve of 5 weight portions of butt (solid content is 40 % by weight), stir and carry out spraying dry after 30 minutes and make microspherical catalyst.Then by the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C
4)
2sO
4solution washing ((NH
4)
2sO
4: microspherical catalyst: H
2o weight ratio=0.05:1:10) to Na
2o content is less than 0.25 % by weight, finally uses deionized water drip washing, microspherical catalyst: H
2o weight ratio=1:10, dries after filtration, obtains catalytic cracking catalyst C1 at 110 DEG C.With the gross weight of described catalytic cracking catalyst C1 for benchmark, the content of described cracking activity constituent element is 43.2 % by weight, the content of described mesoporous silica-alumina materials is 6.2 % by weight, and the content of described clay is 39.5 % by weight, and the content of described binding agent is 11.1 % by weight.
Embodiment 2-12
Embodiment 2-12 is for illustration of catalytic cracking catalyst provided by the invention and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, modified aluminium colloidal sol SA-1 is substituted with modified aluminium colloidal sol SA-2, SA-3, SA-4, SA-5, SA-6, SA-7, SA-8, PSA-1, PSA-2, PSA-3, PSA-4 respectively, obtains catalytic cracking catalyst C2-C12.
Embodiment 13
This embodiment is for illustration of catalytic cracking catalyst provided by the invention and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, the mesoporous silica-alumina materials A-1 of described mesoporous silica-alumina materials A-2 identical weight part replaces, and obtains catalytic cracking catalyst C13.
Comparative example 1-2
Comparative example 1-2 is for illustration of the catalytic cracking catalyst and preparation method thereof of reference.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, Si modification Alumina gel SA-1 is substituted with modified aluminium colloidal sol DSA-1 and DPSA-1 of identical butt consumption respectively, obtains reference catalytic cracking catalyst DC1-DC2.
Test case
Test case is for illustration of the test of catalytic cracking catalyst performance provided by the invention.
Respectively by the catalytic cracking catalyst C1-C13 of above-mentioned preparation and reference catalytic cracking catalyst DC1-DC2 at 800 DEG C, under the condition of 100% water vapour aging 17 hours, be filled in afterwards in small fixed flowing bed ACE device (purchased from American KTI company), amount of fill is 9g separately.Then, reaction temperature be 520 DEG C, air speed is 10h
-1, agent weight of oil is than carrying out catalytic cracking reaction for the feedstock oil shown in his-and-hers watches 1 under the condition of 6:1.The composition of analytical reactions product, and go out conversion ratio and coke selectivity according to following formulae discovery, result is as shown in table 2:
Coke selectivity=coke/conversion ratio.
Table 1
| Density (20 DEG C)/(kg/m 3) | 916.5 |
| Condensation point/DEG C | 20.53 |
| Carbon residue/% | 4.76 |
| Four composition composition/% | |
| Saturated hydrocarbons | 57.8 |
| Aromatic hydrocarbons | 22.5 |
| Colloid | 16.3 |
| Asphalitine | 3.3 |
| Element composition/% | |
| C | 86.94 |
| H | 12.26 |
| S | 0.17 |
| N | 0.22 |
| Tenor/(μ g/g) | |
| Fe | 2.9 |
| Ni | 8.4 |
| V | 0.5 |
| Na | 2.3 |
| Cu | 0.2 |
Table 2
From the results shown in Table 2, catalytic cracking catalyst provided by the invention can not only show lower coke selectivity and higher catalytic cracking activity in heavy oil catalytic cracking process, but also can obtain higher yield of liquefied gas.As can be seen from contrast with embodiment 13 of embodiment 1, when described mesoporous silica-alumina materials is preferred mesoporous silica-alumina materials, corresponding catalytic cracking catalyst is used in heavy oil catalytic cracking reaction, lower coke selectivity can be shown.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (22)
1. a catalytic cracking catalyst, described catalytic cracking catalyst contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, it is characterized in that, with the gross weight of described cracking activity constituent element for benchmark, described cracking activity constituent element contains the Y zeolite of 70-90 % by weight and the MFI structure molecular sieve of 10-30 % by weight, and described Y zeolite contains the first Y zeolite and the second Y zeolite; Described first Y zeolite is rare earth Y type molecular sieve, and in described rare earth Y type molecular sieve with the content of rare earth of oxide basis for 10-25 % by weight, lattice constant is 2.440-2.472nm, and degree of crystallinity is 35-65%, and framework si-al ratio is 2.5-5:1; Described second Y zeolite is the DASY molecular sieve containing rare earth; Described binding agent is the modified aluminium colloidal sol containing Cl and Si, with the gross weight of described modified aluminium colloidal sol for benchmark, in described modified aluminium colloidal sol, Al content is 8-13 % by weight, Cl content is 4-9 % by weight, Al/Cl weight ratio is 1.2-2.2:1, Si content is 0.1-1 % by weight, and the pH value of described modified aluminium colloidal sol is 2.2-5.2.
2. catalytic cracking catalyst according to claim 1, wherein, in described modified aluminium colloidal sol, Al/Si weight ratio is 9.5-100:1.
3. catalytic cracking catalyst according to claim 1, wherein, described modified aluminium colloidal sol is also containing P, with the gross weight of described modified aluminium colloidal sol for benchmark, in described modified aluminium colloidal sol, P content is for being greater than 0 and being no more than 2 % by weight or for 0.3-2 % by weight, and the pH value of described modified aluminium colloidal sol is 2.5-4.2.
4. catalytic cracking catalyst according to claim 3, wherein, in described modified aluminium colloidal sol, Al/P weight ratio is (5-30): (being greater than 0-1).
5. according to the catalytic cracking catalyst in claim 1-4 described in any one, wherein, described modified aluminium colloidal sol prepares in accordance with the following methods:
Metallic aluminium, water, solubility silicon-containing compound, optional solubility phosphorus-containing compound and chloride are joined in reactor and reacts, wherein, described solubility silicon-containing compound and metallic aluminium joined in reactor before chloride, and Al/Si rate of charge is by weight 10-150:1; Al/P rate of charge is by weight (5-30): (being greater than 0-1).
6. catalytic cracking catalyst according to claim 5, wherein, before adding chloride, the element silicon introduced by described solubility silicon-containing compound in described reactor and the weight ratio of water are 0.1-10:100; Al/Si rate of charge is by weight 10-100:1.
7. catalytic cracking catalyst according to claim 5, wherein, described solubility silicon-containing compound is introduced by one or more the form added in waterglass solid, sodium silicate solution, the acidic silicic acid aqueous solution, alkoxy silane and alkoxy silane solution.
8. catalytic cracking catalyst according to claim 5, wherein, the addition of described metallic aluminium is the 100-220 % by weight of metallic aluminium consumption.
9. catalytic cracking catalyst according to claim 5, wherein, Al/Cl rate of charge is by weight 1.2-4:1.
10. catalytic cracking catalyst according to claim 5, wherein, described chloride adds with the form of its aqueous solution, in muriatic concentration described in the described aqueous chloride solution of Cl element for 15-20 % by weight.
11. catalytic cracking catalysts according to claim 5, wherein, described solubility phosphorus-containing compound is one or more in orthophosphoric acid, aluminium dihydrogen phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate.
12. catalytic cracking catalysts according to claim 5, wherein, the reaction temperature of described reaction is 60-105 DEG C.
13. catalytic cracking catalysts according to claim 12, wherein, the reaction temperature of described reaction is 80-105 DEG C, and the reaction time is 12-72 hour; Preferably, described reaction temperature is 90-98 DEG C, and the reaction time is 16-26 hour.
14. according to the catalytic cracking catalyst in claim 5-13 described in any one, and wherein, described modified aluminium colloidal sol prepares in accordance with the following methods:
(1) metallic aluminium, water, solubility silicon-containing compound and optional solubility phosphorus-containing compound are mixed in the reactor;
(2) chloride and optional solubility phosphorus-containing compound is added in the reactor;
(3) mixture making step (2) obtain reacts, then cessation reaction;
Wherein, described solubility phosphorus-containing compound is added at least one step in step (1) and step (2).
15. according to the catalytic cracking catalyst in claim 3-13 described in any one, and wherein, the described muriatic joining day, more than 0.5 hour, is preferably 1-4 hour.
16. catalytic cracking catalysts according to claim 1, wherein, with the gross weight of described catalytic cracking catalyst for benchmark, the content of described cracking activity constituent element is 10-60 % by weight, the content of described mesoporous silica-alumina materials is 1-20 % by weight, the content of described clay is 10-70 % by weight, and the content of described binding agent is 10-60 % by weight.
17. catalytic cracking catalysts according to claim 1 or 16, wherein, described mesoporous silica-alumina materials has boehmite crystal phase structure, in described mesoporous silica-alumina materials with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.2) Na
2o (50-86) Al
2o
3(12-50) SiO
2(0.5-10) P
2o
5, and the specific area of described mesoporous silica-alumina materials is 200-600m
2/ g, pore volume is 0.5-1.8cm
3/ g, average pore size is 8-18nm.
18. catalytic cracking catalysts according to claim 17, wherein, the specific area of described mesoporous silica-alumina materials is 250-550m
2/ g, pore volume is 0.6-1.6cm
3/ g, average pore size is 9-15nm.
19. according to the catalytic cracking catalyst in claim 1-4 described in any one, and wherein, with the gross weight of described Y zeolite for benchmark, the content of described first Y zeolite is 70-99 % by weight, and the content of described second Y zeolite is 1-30 % by weight.
20. according to the catalytic cracking catalyst in claim 1-4 described in any one, and wherein, described MFI structure molecular sieve with the anhydrous chemical of the mass ratio range of oxide composition expression formula is: (0-0.3) Na
2o (0.5-5.5) Al
2o
3(1.3-10) P
2o
5(0.7-15) M1
xo
y(0.01-5) M2
mo
n(70-97) SiO
2, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents the number meeting M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents the number meeting M2 oxidation state requisite oxygen.
The preparation method of the catalytic cracking catalyst in 21. claim 1-20 described in any one, the method comprises described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, and then carries out spraying dry, washing, filtration and drying successively.
The application of catalytic cracking catalyst in 22. claim 1-20 described in any one in RFCC.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109833857A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel for olefin catalysis |
| CN109833860A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier |
| CN113318718A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Carbon tetraene cracking propylene production increasing catalyst containing dichlorodimethylsilane modified rod-shaped mesoporous material and preparation method and application thereof |
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| CN103657712A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109833857A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel for olefin catalysis |
| CN109833860A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier |
| CN109833857B (en) * | 2017-11-28 | 2022-01-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel for olefin catalysis |
| CN109833860B (en) * | 2017-11-28 | 2022-01-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier |
| CN113318718A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Carbon tetraene cracking propylene production increasing catalyst containing dichlorodimethylsilane modified rod-shaped mesoporous material and preparation method and application thereof |
| CN113318718B (en) * | 2020-02-28 | 2023-05-09 | 中国石油化工股份有限公司 | Propylene catalyst for increasing yield by cracking carbon tetraolefin containing dichloro dimethyl silane modified rod-like mesoporous material, and preparation method and application thereof |
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