CN103657700B - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents
A kind of catalytic cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of catalytic cracking catalyst and preparation method thereof, this catalytic cracking catalyst contains cracking activity constituent element, clay and binding agent, wherein, described cracking activity constituent element contains a kind of rare earth Y type molecular sieve, the content of rare earth of described rare earth Y type molecular sieve is calculated as 10～25 weight % with rare earth oxide, lattice constant is 2.440～2.472nm, degree of crystallinity is 35～65%, framework silicon-aluminum atomic ratio is 2.5～5.0, in this molecular sieve X-ray diffraction spectrogram in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at 2 peaks, θ=11.8 ± 0.1 ° and molecular sieve in the product value of the rare earth weight percentage of rare earth oxide more than 50；The preparation method of described catalyst includes preparing and includes the mixed serum of cracking activity constituent element, binding agent and clay, spray drying, washing and dry step.Compared with prior art, institute of the present invention Y-shaped molecular sieve containing rare earth structural stability and activity stability are better, and the heat of catalyst and hydrothermal stability are better, can reduce molecular sieve consumption in the catalyst, reduce Catalyst Production cost.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst containing rare earth modified Y type molecular sieve and preparation thereof.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, occupies very important status in petroleum refining industry.In catalytic cracking process, the residual oil of heavy end such as vacuum distillate or more heavy constituent reacts in the presence of a catalyst, it is converted into the high value added products such as liquefied gas, gasoline, diesel oil, typically requires in this process and use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material, owing to having excellent shape selective catalysis performance and significantly high cracking reaction activity, is widely used in petroleum refining and processing industry.Wherein Y type molecular sieve since the sixties uses first, has just been always up the chief active constituent element of catalytic cracking catalyst from last century.Especially through rare earth modified Y type molecular sieve, the improvement of acidic zeolite and structural stability there is remarkable effect.
In recent years, owing to rare earth price rapidly goes up, considerably increase the production cost of rare-earth modified molecular-sieve, cause no small pressure to manufacturing enterprise.In order to effectively utilize rare earth resources, reduce the molecular sieve production cost of molecular sieve production cost, particularly high rare-earth content, the rare earth utilization rate in modifying process must be improved, reduce rare earth to run off, also to ensure the cracking performance of molecular sieve simultaneously, improve the activity stability of molecular sieve as far as possible.
Current rare earth Y type molecular sieve is used widely in catalytic cracking catalyst as active component, in olefine lowering catalyst, such as it is generally adopted two friendships two roasts technique, i.e. twice liquid phase rare earth ion exchanged and twice high-temperature roasting, molecular sieve Rare-Earth Content reaches 16-22 weight %, there is higher hydrogen transfer activity, Olefin decrease effect is obvious, but there is coke yield height, the problem affecting octane number and diesel yield ".
A kind of olefine lowering catalyst and preparation method thereof disclosed in CN1317547A, this catalyst mainly contains the PREY molecular sieve that content of rare earth is 12-20 weight %, the degree of crystallinity REY molecular sieve more than 50% and content of rare earth to be 2-12 weight %, phosphorus content be 0.2-3 weight %, the phosphorus of lattice constant 2.445-2.465nm and rare earth are composite modified, compared with conventional catalyst, this catalyst Olefin decrease effect substantially and can ensure product slates and octane number.
A kind of hyperastable Y-type RE molecular sieve disclosed in CN1506161A, same employing two friendship two roasting techniques, namely after obtaining a friendship one roasting rare earth sodium Y, substep reacts with rare earth and phosphorus containg substances again, and carry out second time roasting, obtain the composite modified Y molecular sieve of content of rare earth 8-25 weight %, phosphorus content 0.1-3.0 weight %, degree of crystallinity 30-55%, lattice constant 2.455-2.477nm, this molecular sieve has the significant effect reducing gasoline olefin, coke yield is moderate, diesel yield is high, and the utilization rate of modifying element is high.
Molecular sieve prepared by two friendship two roasting techniques is adopted also to have some other feature, molecular sieve such as the improved coking behavior disclosed in CN101537366A and preparation method thereof, two friendships two are still adopted to roast technique, this molecular sieve phosphorus content 0.05-5.0%, content of rare earth is few, it is only 0.05-4.0%, lattice constant 2.430-2.440nm, degree of crystallinity 35-55%.
A kind of modcfied faujasite and the hydrocarbon cracking catalyzer containing this zeolite disclosed in CN1436727A, adopt a friendship one roasting technique, namely NaY first carries out an exchange reaction with phosphorus compound and ammonium compounds, adding earth solution subsequently and continue reaction, obtain then through filtration, washing and hydrothermal calcine, this preparation process flow process is short, by the catalyst activity good stability of this molecular sieve, gasoline yield is high, and coke yield is low, has stronger heavy oil cracking ability and preventing from heavy metal pollution ability.
A kind of high silicon rare earth Y type zeolite disclosed in CN1382631A, gas-phase reaction by rare earth Y type zeolite Yu Silicon chloride., obtain a kind of intracrystalline content of rare earth 4-15 weight %, lattice constant 2.450-2.458nm, collapse temperature 1000-1056 DEG C, silica alumina ratio 8.3-8.8, the sodium oxide content rare earth Y type zeolite less than 1.0 weight %, this zeolite has good heavy oil cracking activity and selectivity, can improve yield of light oil, improve quality of gasoline, and there is good coke selectivity.
A kind of modified Y molecular sieve disclosed in CN101823726A, adopt a friendship one roasting technique, namely NaY first carries out an exchange reaction with earth solution, adding phosphorus compound subsequently and continue reaction, obtain then through filtration, washing and hydrothermal calcine, its content of rare earth is about 11-23 weight %, rare earth is predominantly located in sodalite cage, molecular sieve stability improves, and adjustable change acidic zeolite simultaneously, the catalyst containing this molecular sieve has the advantages that heavy oil conversion performance is strong, coke selectivity is good.
A kind of rare-earth Y molecular sieve and preparation method thereof disclosed in CN100344374C, content of rare earth is calculated as 12-22 weight % with rare earth oxide, and rare earth ion is entirely located in the little cage of molecular sieve, in its 27AlMASNMR spectrogram, be that 0ppm goes out not have peak to occur in chemical shift.Described preparation method is to adopt a friendship one roasting technique, with alkaline solution adjustment pH value of solution to 8-11 after handing over one, it is filtered again, washes, dries and roasting, or separate molecular sieve filter cake after handing over one, collect filtrate, filtrate adds alkaline solution and regulates pH value of solution to 8-11, then making beating that the rare earth hydrate filter cake obtained and molecular sieve filter cake are added water, filter, wash, dry and roasting.This technique makes rare earth ion precipitation unnecessary in solution avoid rare earth run off and can ensure that rare earth ion is entirely located in the little cage of molecular sieve.CN1322928C discloses a kind of catalyst being active component with this molecular sieve, it is possible to catalytic cracking gasoline olefine content is greatly lowered, and has the heavy oil conversion performance of excellence simultaneously.
In prior art, two friendships two no matter are adopted to roast the rare-earth Y molecular sieve that technique or one hands over a roasting technique to obtain, content of rare earth in its product is always lower than the total rare earth (TRE) amount put into, such as CN1053808A, CN1069553C, several rare-earth Y molecular sieves disclosed in CN1026225C all have this feature, even if there being more rare earth ion to be positioned in little cage, but inevitably have part rare earth ion and be still in supercage, rare earth ion in supercage can by under backwash in follow-up washing process, cause rare earth to run off, cause the reduction of rare earth utilization rate.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalytic cracking catalyst and preparation method thereof, and this catalyst has higher active and better heat and hydrothermal stability, can reduce molecular sieve consumption in the catalyst.
Catalytic cracking catalyst provided by the invention contains cracking activity constituent element, clay and binding agent, and wherein, described cracking activity constituent element contains a kind of rare earth Y type molecular sieve, and the content of rare earth of this rare earth Y type molecular sieve is with rare earth oxide (RE2O3) it is calculated as 10-25 weight %, lattice constant is 2.440-2.472nm, degree of crystallinity is 35-65%, framework silicon-aluminum atomic ratio is 2.5-5.0, in this molecular sieve X-ray diffraction spectrogram in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at 2 peaks, θ=11.8 ± 0.1 ° and molecular sieve in the product value of the rare earth weight percentage of rare earth oxide more than 50.
Preferably, with the weight of catalyst for benchmark, described catalytic cracking catalyst contains 10-60 weight % cracking activity constituent element, 20-70 weight % clay and 10-50 weight % binding agent.
Described rare earth Y type molecular sieve is to hand over two roastings through two, obtains in conjunction with deposition of rare-earth process.More specifically, obtain through following preparation process: NaY molecular sieve is carried out contacting process with earth solution or earth solution with the mixed solution of ammonium salt, through filtering, washing, after drying, carry out first time calcination process, obtain rare earth sodium Y molecular sieve；Then rare earth sodium Y molecular sieve pulled an oar and contact process with ammonium salt solution or acid solution, mixing with earth solution again after filtration, and the pH value regulating serosity is 6-10, filter or do not filter, drying, carrying out second time calcination process, obtain described rare earth Y type molecular sieve.
In above-mentioned rare earth Y type molecular sieve preparation process, the sial atomic ratio of raw material NaY molecular sieve be preferably greater than 2.5 and degree of crystallinity more than 80%.In the described process that NaY molecular sieve and earth solution or rare earth carry out contacting process with the mixed solution of ammonium salt, earth solution with rare earth oxide count with the part by weight of NaY molecular sieve butt be 0.06-0.14, preferred 0.08-0.12, adjustment pH is 3.0-5.0, controlling water sieve weight ratio at 5-30, preferred 8-15, the process that described contact processes is to carry out 0.3-3.0 hour, preferred 0.5-1.5 hour room temperature-100 DEG C, at preferred 70-95 DEG C.
In above-mentioned preparation process, described first time calcination process, is at 500-650 DEG C, under 0-100% water vapor conditions calcination process 0.5-4.0 hour, preferred 1.0-3.0 hour.Wherein first time calcination process is preferred embodiment carry out under 100% water vapor conditions.
In above-mentioned preparation process, described by the making beating of rare earth sodium Y molecular sieve and contact the process processed with ammonium salt solution be process 0.3-3.0 hour, preferred 0.5-1.5 hour room temperature-100 DEG C, at preferred 60-80 DEG C, its middle rare earth sodium Y molecular sieve, by molecular sieve butt, is 1:(0.05-0.5 with the part by weight of ammonium salt and water): (5-30), preferred 1:(0.1-0.4): (8-15).Described by the making beating of rare earth sodium Y molecular sieve and contact the process processed with acid solution be process 0.3-2.0 hour, preferred 0.5-1.0 hour room temperature-100 DEG C, at preferred 60-80 DEG C, its middle rare earth sodium Y molecular sieve is by molecular sieve butt, with acid and H2The part by weight of O is 1:(003-0.2): (5-30), preferred 1:(0.05-0.1): (8-15).The described ammonium salt mixture of any one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate.Described acid can be mineral acid or organic acid, and mineral acid can be selected from one or more the mixture in sulphuric acid, hydrochloric acid or nitric acid, and organic acid can be selected from one or more the mixture in oxalic acid, acetic acid, citric acid or tartaric acid.
In above-mentioned preparation process, by adding akaline liquid, to regulate slurry pH value be 6-10, preferable ph be 7-9, makes rare earth ion all precipitate formation rare-earth hydroxide, i.e. the process of deposition of rare-earth.Described akaline liquid can be selected from one or more the mixture in ammonia, waterglass, sodium metaaluminate or sodium hydroxide.
In above-mentioned preparation process, described second time calcination process, be 500-650 DEG C, process 0.5-4 hour, preferred 1-3 hour under 0-100% water vapor conditions.Wherein second time calcination process is preferred embodiment carry out under 100% water vapor conditions.
In above-mentioned preparation process, rare earths material is well known to those skilled in the art, rare earth chloride or nitric acid rare earth can be selected from, can be rare earth chloride or the nitric acid rare earth of Rare Earth Elements Determination composition, wherein common include lanthanum chloride, Lanthanum (III) nitrate, cerium chloride or cerous nitrate etc., can also be the mischmetal of different rare earth element ratio, such as rich cerium type or rich lanthanum type mischmetal.
In above-mentioned preparation process, it is once carry out under the water vapor conditions of 1-100%, more preferably 20-100%, most preferably 100% that the double roasting that preferred embodiment is wherein described has at least in processing, steam treatment promotes rare earth ion to migrate from molecular sieve supercage to little cage, therefore, it is most preferred that embodiment be that double roasting described in preparation process processes be all carry out under the water vapor conditions of 100%.
The preparation method that present invention also offers a kind of described catalytic cracking catalyst, the method includes, by the mixing making beating of cracking activity constituent element, clay and binding agent, being then sequentially carried out spray drying, washing, filtration and dry step.
The active component that catalytic cracking catalyst provided by the invention contains includes a kind of rare earth Y type molecular sieve, it passes through a liquid phase rare earth ion exchanged and a solid phase ion transition process, adopt the mode of deposition of rare-earth, then through calcination process, rare earth ion is migrated from supercage to little cage, rare earth does not run off, molecular sieve structure good stability is (particularly through 800 DEG C, after 100% steam burin-in process 17 hours, crystallization of molecular sieves reservation degree is high), activity stability better (light oil micro-reactor MA value), this preparation process can modulation content of rare earth flexibly, accurately control, simple to operate, and rare earth utilization rate is high, up to more than 98%, save rare earth resources, reduce production cost.Catalytic cracking catalyst provided by the invention, has higher heat and hydrothermal stability.When content of rare earth quite or slightly lower, than prior art catalyst, there is higher cracking activity, molecular sieve content remains to when relatively low obtain the active and good product slates of higher catalysis in the catalyst, therefore reduces the production cost of catalyst.
Detailed description of the invention
According to catalytic cracking catalyst provided by the invention, described cracking activity constituent element contains the first Y type molecular sieve, described first Y type molecular sieve is rare earth Y type molecular sieve, its content of rare earth is calculated as 10-25 weight % with rare earth oxide, lattice constant is 2.440-2.472nm, degree of crystallinity is 35-65%, framework silicon-aluminum atomic ratio is 2.5-5.0, in this molecular sieve X-ray diffraction spectrogram in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at 2 peaks, θ=11.8 ± 0.1 ° and molecular sieve in the product value of the rare earth weight percentage of rare earth oxide more than 50；In embodiments of the invention, this product value is further preferably greater than 55.
According to catalytic cracking catalyst provided by the invention, in described cracking activity constituent element except containing the first described Y type molecular sieve, it is also possible to containing/or without other Y type molecular sieve.Other Y type molecular sieve described is preferably the DASY molecular sieve (the hydro-thermal super-stable Y molecular sieves containing rare earth, the present invention is called the second Y type molecular sieve) containing rare earth, with RE2O3(rare earth oxide) is counted, and the described DASY molecular sieve Rare-Earth Content containing rare earth is 1.5-3.0 weight %, and the described DASY molecular sieve containing rare earth can be various commercially available prod, for instance the DASY2.0 molecular sieve of middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery.With the butt weight of described active component for benchmark, counting the content of described second Y type molecular sieve for 0-50 weight % with butt can be such as 0-30 weight %, 0-20 weight %, and the content of described first Y type molecular sieve is 50-100 weight % can be such as 70-100% weight or 80-100 weight %.Preferably, when containing other Y type molecular sieve, with the butt weight of catalyst for benchmark, the content of the rare earth Y type molecular sieve (the first Y type molecular sieve) described in described catalytic cracking catalyst is 10-60%, for instance can be 20-40 weight %；The content of other Y type molecular sieve is less than 35 weight %, for instance the content of other Y type molecular sieve can be 0.5-30 weight %, 0-10 weight % or 0-5 weight %.
In the present invention, described clay can be clay conventional in catalytic cracking catalyst, for instance can be one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, meerschaum, attapulgite, brucite and bentonite.
In the present invention, described binding agent can be conventional use of various binding agents in catalytic cracking catalyst, for instance can be one or more in Ludox, Alumina gel and boehmite, it is preferred to the double aluminium binder of Alumina gel and boehmite.
In preferred situation, catalytic cracking catalyst provided by the invention, with the butt weight of described catalytic cracking catalyst for benchmark, the content that described cracking activity constituent element is counted with butt is for 10-50 weight %, the content that described clay is counted with butt is for 20-60 weight %, and the content that described binding agent is counted with butt is for 10-40 weight %.More preferably, with the butt weight of described catalytic cracking catalyst for benchmark, the content that described cracking activity constituent element is counted with butt is for 20-40 weight %, and the content that described clay is counted with butt is for 20-45 weight %, and described binding agent such as can for 25-35 weight % for 20-40 weight % with the content that butt is counted.
The preparation method of catalytic cracking catalyst provided by the invention, it is preferable that comprise the following steps:
(1) carry out contacting process with the mixed solution of ammonium salt with earth solution or earth solution by NaY molecular sieve, through filtering, washing, after drying, carry out first time calcination process, obtain rare earth sodium Y molecular sieve；Then rare earth sodium Y molecular sieve pulled an oar and contact process with ammonium salt solution or acid solution, mix with earth solution again after filtration, and the pH value regulating serosity is 6-10, filter or do not filter, drying, carry out second time calcination process, obtain rare earth Y type molecular sieve provided by the invention (the first Y type molecular sieve)；
(2) by the mixing making beating of cracking activity constituent element, clay and binding agent, then it is sequentially carried out spray drying, washing, filtration and dries, wherein, described cracking activity constituent element includes the described Y type molecular sieve (the first Y type molecular sieve) containing rare earth, containing or without other Y type molecular sieves.
In above-mentioned preparation process, in step (1), the sial atomic ratio of raw material NaY molecular sieve be preferably greater than 2.5 and degree of crystallinity more than 80%.In the described process that NaY molecular sieve and earth solution or earth solution carry out contacting process with the mixed solution of ammonium salt, earth solution with rare earth oxide count with the part by weight of NaY molecular sieve butt be 0.06-0.14, preferred 0.08-0.12, adjustment pH is 3.0-5.0, controlling water sieve weight ratio at 5-30, preferred 8-15, the process that described contact processes is to carry out 0.3-3.0 hour, preferred 0.5-1.5 hour room temperature-100 DEG C, at preferred 70-95 DEG C.
In above-mentioned preparation process, the first time calcination process described in step (1), is at 500-650 DEG C, under 0-100% water vapor conditions calcination process 0.5-4.0 hour, preferred 1.0-3.0 hour.Wherein first time calcination process is preferred embodiment carry out under 100% water vapor conditions.
In above-mentioned preparation process, described in step (1) by the making beating of rare earth sodium Y molecular sieve and contact the process processed with ammonium salt solution and be room temperature-100 DEG C, process 0.3-3.0 hour, preferred 0.5-1.5 hour at preferred 60-80 DEG C, its middle rare earth sodium Y molecular sieve, by molecular sieve butt, is 1:(0.05-0.5 with the part by weight of ammonium salt and water): (5-30), preferred 1:(0.1-0.4): (8-15).Described by the making beating of rare earth sodium Y molecular sieve and contact the process processed with acid solution be process 0.3-2.0 hour, preferred 0.5-1.0 hour room temperature-100 DEG C, at preferred 60-80 DEG C, its middle rare earth sodium Y molecular sieve is by molecular sieve butt, with acid and H2The part by weight of O is 1:(0.03-0.2): (5-30), preferred 1:(0.05-0.1): (8-15).The described ammonium salt mixture of any one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate.Described acid can be mineral acid or organic acid, mineral acid can be selected from one or more the mixture in sulphuric acid, hydrochloric acid (its proportioning is in HCl) or nitric acid, and organic acid can be selected from one or more the mixture in oxalic acid, acetic acid, citric acid or tartaric acid.
In above-mentioned preparation process, in step (1), by adding akaline liquid, to regulate slurry pH value be 6-10, preferable ph be 7-9, makes rare earth ion all precipitate formation rare-earth hydroxide, i.e. the process of deposition of rare-earth.Described akaline liquid can be selected from one or more the mixture in ammonia, waterglass, sodium metaaluminate or sodium hydroxide solution.
In above-mentioned preparation process, in step (1), described second time calcination process, be 500-650 DEG C, process 0.5-4 hour, preferred 1-3 hour under 0-100% water vapor conditions.Wherein second time calcination process is preferred embodiment carry out under 100% water vapor conditions.
In above-mentioned preparation process, rare earths material is well known to those skilled in the art, rare earth chloride or nitric acid rare earth can be selected from, can be rare earth chloride or the nitric acid rare earth of Rare Earth Elements Determination composition, wherein common include lanthanum chloride, Lanthanum (III) nitrate, cerium chloride or cerous nitrate etc., can also be the mischmetal of different rare earth element ratio, such as rich cerium type or rich lanthanum type mischmetal.
In above-mentioned preparation process, it is once carry out under the water vapor conditions of 1-100%, more preferably 20-100%, most preferably 100% that the double roasting that preferred embodiment is wherein described has at least in processing, steam treatment promotes rare earth ion to migrate from molecular sieve supercage to little cage, therefore, further preferred embodiment is the double roasting process described in preparation process is all carry out under the water vapor conditions of 100%.
Preparation method according to catalytic cracking catalyst provided by the invention, by the mixing making beating of described cracking activity constituent element, clay and binding agent, and follow-up spray drying, washing, filtration and dry, the implementation of these operations all can adopt the method for routine to implement, their specific implementation method such as has detailed description in patent application CN1916166A, CN1362472A, CN1727442A, CN1132898C, CN1727445A and CN1098130A, introduces in the present invention by reference here in the lump.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the second Y type molecular sieve is DASY2.0 molecular sieve, rare earth oxide content 2 weight %, sial atomic molar ratio 4.1, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce；
Alumina gel is produced by middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery, the Al of Alumina gel2O3Content is 21.5 weight %；
Kaolin is purchased from Suzhou China Kaolin Co., Ltd；
Boehmite is purchased from Shandong Aluminum Plant；
In each embodiment and comparative example, the chemical composition of molecular sieve x-ray fluorescence method measures (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui surely waits and compiles, Science Press, and nineteen ninety publishes).The thing phase of molecular sieve and crystallinity data adopt X-ray diffraction method to measure, and the framework silicon-aluminum atomic ratio of molecular sieve adopts NMR method to measure.
Embodiment 1
(1) preparation of rare earth Y type molecular sieve
Take 2.6 kilograms of NaY molecular sieve (middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery, igloss 22.5 weight %, silica alumina ratio 2.7, degree of crystallinity 88%, lower with) and 15 kilograms of deionized waters mixing pull an oar, add 1.0 liters of concentration 160gRE2O3The re chloride of/L and 0.24 kilogram of chloride solid, it is warming up to 70 DEG C after stirring evenly and regulates serosity pH to 4.0 with dilute hydrochloric acid, continue exchange 1.5 hours, filter, washing, dried, in 550 DEG C of roastings 2 hours under 100% water vapor conditions, obtaining a friendship one, to roast the chemical composition of rare earth sodium Y molecular sieve Y-A1, Y-A1 be sodium oxide 5.1 weight %, rare earth oxide 7.8 weight %.Then molecular sieve is pressed: NH4Cl:H2The ratio of O=1:0.2:10 is pulled an oar and exchanges 1 hour in 70 DEG C, and after filtering washing, reslurry also adds 0.27 liter of concentration 300gRE2O3The re chloride of/L, ensure concentration of slurry 400-450g/L, add ammonia after stirring evenly and regulate serosity pH to 7.5 and continue stirring 10 minutes, after drying in 600 DEG C of roastings 2 hours under 100% steam, obtain rare earth Y type molecular sieve finished product of the present invention, be designated as Y-A.
Sodium oxide 1.5 weight % in Y-A, rare earth oxide 11.8 weight %, degree of crystallinity 50.3%, lattice constant 2.458nm, framework silicon-aluminum atomic ratio 3.5.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 89.7.
(2) preparation of catalytic cracking catalyst
The boehmite of 18 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 40 parts by weight kaolin clay in butt, Alumina gel in 9 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-A serosity of 33 weight portions in butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C1.
Embodiment 2
The boehmite of 22 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 34 parts by weight kaolin clay in butt, Alumina gel in 11 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-A of 31 weight portions in butt and the DASY2.0 molecular sieve mixed serum of 2 weight portions in butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C2.
Embodiment 3
(1) preparation of rare earth Y type molecular sieve
Take 2.6 kilograms of NaY molecular sieve and 18 kilograms of deionized water mixing making beating, add 1.25 liters of concentration 160gRE2O3The re chloride of/L and 0.12 kilogram of chloride solid, it is warming up to 80 DEG C after stirring evenly and regulates serosity pH to 3.8 with dilute hydrochloric acid, continue exchange 1 hour, filter, washing, dried, in 570 DEG C of roastings 2 hours under 50% water vapor conditions, obtaining a friendship one, to roast the chemical composition of rare earth sodium Y molecular sieve Y-C1, Y-C1 be sodium oxide 4.9 weight %, rare earth oxide 9.9 weight %.Then molecular sieve is pressed: NH4Cl:H2The ratio of O=1:0.15:12 is pulled an oar and exchanges 1 hour in 75 DEG C, and after filtering washing, reslurry also adds 0.27 liter of concentration 300gRE2O3The re chloride of/L, ensure concentration of slurry 400-450g/L, add waterglass after stirring evenly and regulate serosity pH to 8.0 and continue stirring 10 minutes, after drying in air atmosphere in 570 DEG C of roastings 2 hours, obtain rare earth Y type molecular sieve finished product of the present invention, be designated as Y-C.
Sodium oxide 1.3 weight % in Y-C, rare earth oxide 13.9 weight %, degree of crystallinity 48.8%, lattice constant 2.465nm, framework silicon-aluminum atomic ratio 3.1.The intensity I at its peak, 2 θ=11.8 ± 0.1 °1Intensity I with 2 peaks, θ=12.3 ± 0.1 °2Ratio (I1/I2) with the product value of rare earth weight percentage counted with rare earth oxide in molecular sieve for 55.6.
(2) preparation of catalytic cracking catalyst
The boehmite of 18 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 39 parts by weight kaolin clay in butt, Alumina gel in 11 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-C of 30 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve in 2 weight portions of butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C3.
Embodiment 4
(1) preparation of rare earth Y type molecular sieve
Take 2.6 kilograms of NaY molecular sieve and 18 kilograms of deionized water mixing making beating, add 1.25 liters of concentration 160gRE2O3The re chloride of/L and 0.12 kilogram of chloride solid, it is warming up to 80 DEG C after stirring evenly and regulates serosity pH to 3.8 with dilute hydrochloric acid, continue exchange 1 hour, filter, washing, dried, in air atmosphere in 600 DEG C of roastings 1.5 hours, obtaining a friendship one, to roast the chemical composition of rare earth sodium Y molecular sieve Y-D1, Y-D1 be sodium oxide 4.9 weight %, rare earth oxide 9.9 weight %；Then molecular sieve is pressed: NH4Cl:H2The ratio of O=1:0.15:12 is pulled an oar and exchanges 1 hour in 75 DEG C, and after filtering washing, reslurry also adds 0.4 liter of concentration 300gRE2O3The re chloride of/L, ensure concentration of slurry 400-450g/L, add waterglass after stirring evenly and regulate serosity pH to 8.0 and continue stirring 10 minutes, after drying in 570 DEG C of roastings 3 hours under 100% steam, obtain rare earth Y type molecular sieve finished product of the present invention, be designated as Y-D.
Sodium oxide 1.3 weight % in Y-D, rare earth oxide 15.9 weight %, degree of crystallinity 46.9%, lattice constant 2.466nm, framework silicon-aluminum atomic ratio 3.0.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 57.2.
(2) preparation of catalytic cracking catalyst
The boehmite of 22 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 37 parts by weight kaolin clay in butt, Alumina gel in 10 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-D of 28 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve in 3 weight portions of butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C4.
Embodiment 5
(1) preparation of rare earth Y type molecular sieve
Take 2.6 kilograms of NaY molecular sieve and 20 kilograms of deionized water mixing making beating, add 1.5 liters of concentration 160gRE2O3The re chloride of/L, it is warming up to 75 DEG C after stirring evenly and regulates serosity pH to 3.5 with dilute hydrochloric acid, continue exchange 1 hour, filter, washing, dried, in 600 DEG C of roastings 2 hours under 100% water vapor conditions, obtaining a friendship one, to roast the chemical composition of rare earth sodium Y molecular sieve Y-E1, Y-E1 be sodium oxide 4.8 weight %, rare earth oxide 11.9 weight %；Then molecular sieve is pressed: NH4Cl:H2The ratio of O=1:0.3:10 is pulled an oar and exchanges 1 hour in 70 DEG C, and after filtering washing, reslurry also adds 0.4 liter of concentration 300gRE2O3The re chloride of/L, it is ensured that concentration of slurry 400-450g/L, adds ammonia and regulates serosity pH to 7.9 and continue stirring 10 minutes after stirring evenly, filter washing, after drying in 600 DEG C of roastings 2 hours under 80% steam, obtain rare earth Y type molecular sieve finished product of the present invention, be designated as Y-E.
Sodium oxide 1.3 weight % in Y-E, rare earth oxide 17.9 weight %, degree of crystallinity 45.2%, lattice constant 2.467nm, framework silicon-aluminum atomic ratio 3.2.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 62.6.
(2) preparation of catalytic cracking catalyst
The boehmite of 19 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 42 parts by weight kaolin clay in butt, Alumina gel in 9 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-E of 25 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve in 5 weight portions of butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C5.
Embodiment 6
(1) preparation of rare earth Y type molecular sieve
Take 2.6 kilograms of NaY molecular sieve and 20 kilograms of deionized water mixing making beating, add 1.5 liters of concentration 160gLa2O3The lanthanum chloride solution of/L, it is warming up to 75 DEG C after stirring evenly and regulates serosity pH to 3.5 with dilute hydrochloric acid, continue exchange 1 hour, filter, washing, dried, in air atmosphere in 620 DEG C of roastings 2 hours, obtaining a friendship one, to roast the chemical composition of rare earth sodium Y molecular sieve Y-F1, Y-F1 be sodium oxide 4.8 weight %, lanthana 11.9 weight %；Then molecular sieve is pressed: oxalic acid: H2The ratio of O=1:0.08:12 is pulled an oar and exchanges 1 hour in 65 DEG C, and after filtering washing, reslurry also adds 0.67 liter of concentration 300gLa2O3The lanthanum chloride solution of/L, ensure concentration of slurry 400-450g/L, add ammonia after stirring evenly and regulate serosity pH to 8.2 and continue stirring 10 minutes, after drying in 620 DEG C of roastings 3 hours under 100% steam, obtain rare earth Y type molecular sieve finished product of the present invention, be designated as Y-F.
Sodium oxide 1.5 weight % in Y-F, lanthana 21.9 weight %, degree of crystallinity 41.7%, lattice constant 2.470nm, framework silicon-aluminum atomic ratio 3.1.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 70.1.
(2) preparation of catalytic cracking catalyst
The boehmite of 19 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 43 parts by weight kaolin clay in butt, Alumina gel in 10 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve Y-F of 23 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve in 5 weight portions of butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst C6.
Comparative example 1
(1) preparation of rare earth Y type molecular sieve
This comparative example is rare-earth Y molecular sieve prepared by method described in CN1053808A.
By NaY molecular sieve and re chloride (160gRE2O3/ L) and deionized water mixing, regulate serosity pH to 3.5 and exchange 1 hour in 90 DEG C, filtering, wash, filter cake is put in pipe type calciner and pass into steam when being warming up to 200 DEG C, be continuously heating to 550 DEG C of roastings 2 hours, by gained molecular sieve and (NH4)2SO4And H2O pulls an oar in the ratio of 1:0.2:40 and exchanges 15 minutes in 60 DEG C, and filtration drying obtains comparative sample, is designated as DB-1.
The chemical composition of DB-1 is sodium oxide 1.3 weight %, rare earth oxide 12.1 weight %, degree of crystallinity 56.7%, lattice constant 2.468nm, framework si-al ratio 4.2.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 33.9.
(2) preparation of catalytic cracking catalyst
The boehmite of 18 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 40 parts by weight kaolin clay in butt, Alumina gel in 9 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve DB-1 serosity of 33 weight portions in butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst DC-1.
Comparative example 2
(1) preparation of rare earth Y type molecular sieve
This comparative example conventionally two hands over two roasting methods to prepare rare-earth Y molecular sieve.
By NaY molecular sieve and re chloride (160gRE2O3/ L) and deionized water mix by a certain percentage, exchange 1 hour at 90 DEG C, filter, washing, dried, roasting 2 hours under 520 DEG C of air atmospheres, by gained molecular sieve again with re chloride and H2O pulls an oar in proportion and exchanges 1 hour in 90 DEG C, and filtration drying again carries out calcination process and obtains comparative sample, is designated as DB-2.
The chemical composition of DB-2 is sodium oxide 1.9 weight %, rare earth oxide 18.2 weight %, degree of crystallinity 43.6%, lattice constant 2.469nm, framework si-al ratio 2.7.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 16.4.
(2) preparation of catalytic cracking catalyst
The boehmite of 22 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 37 parts by weight kaolin clay in butt, Alumina gel in 10 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve DB-2 of 28 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve of 3 weight portions afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst DC-2.
Comparative example 3
(1) preparation of rare earth Y type molecular sieve
This comparative example is rare-earth Y molecular sieve prepared by method described in CN100344374C.
NaY molecular sieve is mixed with deionized water and is warming up to 90 DEG C, add ammonium sulfate and with salt acid for adjusting pH to 3.5-4.0, after exchanging 1 hour, filter cake adds water making beating and is proportionally added into re chloride, salt acid for adjusting pH, to 3.5-5.5, stirs 1 hour under room temperature, adds ammonia and stirs 5 minutes, after washing and drying, when weight space velocity 0.1-1Lower 540 DEG C of roastings of steam 1.5 hours；Molecular sieve after roasting is washed 10 minutes with 60 DEG C of ammonium chloride solutions, dries and obtain comparative sample, be designated as DB-3.
The chemical composition of DB-3 is sodium oxide 0.2 weight %, rare earth oxide 20.6 weight %, degree of crystallinity 50.7%, lattice constant 2.472nm, framework si-al ratio 3.7.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 26.8.
(2) preparation of catalytic cracking catalyst
The boehmite of 19 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 42 parts by weight kaolin clay in butt, Alumina gel in 9 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve DB-3 of 25 weight portions in butt and the mixed serum of the DASY2.0 molecular sieve of 5 weight portions afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2OWeight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst DC-3.
Comparative example 4
(1) preparation of rare earth Y type molecular sieve
This comparative example is rare-earth Y molecular sieve prepared by method described in CN100344374C.
NaY molecular sieve is mixed with deionized water making beating, adds the re chloride of metering, after stirring 5 minutes at 60 DEG C with salt acid for adjusting pH between 3.5-5.5, after continuing stirring 1 hour, add ammonia and stir filtration in 5 minutes, after washing and drying, when weight space velocity 0.2-1Lower 600 DEG C of roastings of steam 1.5 hours；Molecular sieve after roasting is washed 10 minutes with 90 DEG C of ammonium chloride solutions, dries and obtain comparative sample, be designated as DB-4.
The chemical composition of DB-4 is sodium oxide 0.8 weight %, rare earth oxide 11.8 weight %, degree of crystallinity 56.5%, lattice constant 2.465nm, framework si-al ratio 3.3.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 40.1.
(2) preparation of catalytic cracking catalyst
The boehmite of 18 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 38 parts by weight kaolin clay in butt, Alumina gel in 9 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve DB-4 serosity of 35 weight portions in butt afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Washing ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst DC-4.
Comparative example 5
(1) preparation of rare earth Y type molecular sieve
This comparative example is rare-earth Y molecular sieve prepared by method described in CN100344374C.
NaY molecular sieve is mixed with deionized water making beating, adds the re chloride of metering, after stirring 5 minutes at 60 DEG C with salt acid for adjusting pH between 3.5-5.5, after continuing stirring 1 hour, add ammonia to stir 5 minutes and filter, after washing and drying, 550 DEG C of roastings 1.5 hours；Molecular sieve after roasting is washed 10 minutes with 60 DEG C of ammonium chloride solutions, dries and obtain comparative sample, be designated as DB-5.
The chemical composition of DB-5 is sodium oxide 1.0 weight %, rare earth oxide 15.7 weight %, degree of crystallinity 52.9%, lattice constant 2.467nm, framework si-al ratio 3.6.The product value of the rare earth weight percentage counted with rare earth oxide in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at its peak, 2 θ=11.8 ± 0.1 ° and molecular sieve is for 30.9.
(2) preparation of catalytic cracking catalyst
The boehmite of 22 weight portions in butt is mixed with deionized water making beating, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, the acid aluminum ratio weight ratio of the boehmite counted with butt (the described 36 weight % hydrochloric acid with) is for 0.20, it is warming up to 65 DEG C of acidifyings 1 hour, it is separately added into the serosity of 35 parts by weight kaolin clay in butt, Alumina gel in 10 weight portions of butt, stir 20 minutes, it is added thereto to the rare earth Y type molecular sieve DB-5 of 30 weight portions in butt and the mixed serum of the DASY molecular sieve of 3 weight portions afterwards again, stirring obtains the serosity of solid content 30 weight % for 30 minutes, spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4 washs ((NH4)2SO4: microspherical catalyst: H2O weight ratio=0.05:1:10) to Na2O content, less than 0.25 weight %, finally uses deionized water drip washing, microspherical catalyst: H2O weight ratio=1:10, dries at 110 DEG C after filtration, obtains catalytic cracking catalyst DC-5.
Embodiment 7
The present embodiment summarizes the rare earth availability data of the rare earth Y type molecular sieve in embodiment 1-6 and comparative example 1-5.
The rare earth utilization rate of molecular sieve is listed in table 1
Table 1
| Sieve sample | Theoretical RE2O3Inventory/% | RE in product2O3Content/% | Rare earth utilization rate/% |
| Y-A | 12.0 | 11.8 | 98.3 |
| Y-B | 12.0 | 11.9 | 99.2 |
| Y-C | 14.0 | 13.9 | 99.3 |
| Y-D | 16.0 | 15.9 | 99.4 |
| Y-E | 18.0 | 17.9 | 99.4 |
| Y-F | 22.0 | 21.9 | 99.5 |
| DB-1 | 14.0 | 12.1 | 86.4 |
| DB-2 | 24.0 | 18.2 | 75.8 |
| DB-3 | 23.0 | 20.6 | 89.6 |
| DB-4 | 13.0 | 11.8 | 90.7 |
| DB-5 | 17.5 | 15.7 | 89.7 |
From table 1, the rare earth utilization rate of the molecular sieve that embodiment provides is all more than 98%, and comparative example middle rare earth utilization rate is relatively low, and the rare earth utilization rate of comparative example 2 only about 75%, the utilization rate of other comparative examples is slightly higher, but basic below 90%.Adopt the two of the present invention to hand over the technique of two roastings and deposition of rare-earth to be effectively increased rare earth utilization rate, decrease the waste of rare earth resources.
Embodiment 8
The present embodiment is in order to illustrate that rare earth Y type molecular sieve in embodiment 1-6 and comparative example 1-5 is through 800 DEG C, physicochemical data after burin-in process 17 hours under 100% water vapor conditions.
By the molecular sieve in above-described embodiment and comparative example and ammonium chloride solution hybrid switching, by Na therein2O content is washed till 0.3 weight below %, after filtration drying, 800 DEG C, burin-in process 17 hours under 100% water vapor conditions, carries out materialization sign and measures light oil microactivity MA.Light oil micro-reactor appreciation condition: molecular sieve loading amount 2g, raw oil is huge port straight distillation light diesel oil, oil inlet quantity 1.56g, reaction temperature 460 DEG C.
The physico-chemical property characterization result of molecular sieve is in Table 2.
Table 2
| Sieve sample | RE2O3Content/% | Structure cell/nm | Crystallization reservation degree/% | MA |
| Y-A | 11.7 | 2.436 | 45.4 | 63 |
| Y-B | 11.8 | 2.436 | 45.9 | 63 |
| Y-C | 13.8 | 2.438 | 46.0 | 65 |
| Y-D | 15.9 | 2.439 | 46.3 | 67 |
| Y-E | 17.9 | 2.441 | 47.8 | 70 |
| Y-F | 21.8 | 2.445 | 46.0 | 72 |
| DB-1 | 11.8 | 2.433 | 27.1 | 56 |
| DB-2 | 17.1 | 2.438 | 35.0 | 65 |
| DB-3 | 19.5 | 2.441 | 39.6 | 68 |
| DB-4 | 11.8 | 2.433 | 34.9 | 56 |
| DB-5 | 14.9 | 2.436 | 38.4 | 63 |
From table 2, molecular sieve through ammonium described in embodiment hands over content of rare earth after washing sodium to be substantially free of change, illustrate that rare earth ion is primarily targeted in the little cage of molecular sieve, will not be got off by anticommuting, it is in the rare earth ion in little cage and molecular sieve structure is had significant Stabilization, crystallization reservation degree is more than more than 45%, and light oil activity is higher than the contrast sample that content of rare earth is suitable.
Embodiment 9
The present embodiment is in order to illustrate the Catalytic Cracking Performance of the catalyst of embodiment 1-6 and comparative example 1-5.
Respectively by catalytic cracking catalyst C1-C6 and the DC1-DC5 of above-mentioned preparation, 800 DEG C, 100% water vapour when aging 12 hours, be filled in afterwards in small fixed flowing bed ACE device (purchased from American KTI company), amount of fill is each 9g.Then, reaction temperature be 510 DEG C, weight (hourly) space velocity (WHSV) be 12h-1, oil ratio (weight) be 6 when, the fcc raw material oil shown in table 3 is injected in the fixed fluidized bed ACE device being filled with described catalytic cracking catalyst C1-C6 and DC1-DC5 carry out catalytic cracking reaction respectively.The composition of analytical reactions product, and calculate conversion ratio according to below equation, the catalytic cracking reaction results of property of catalyst is as shown in table 4 below:
Table 3
| Density (20 DEG C)/(kg/m3) | 922.1 |
| Condensation point/DEG C | 33 |
| Carbon residue/weight % | 3.66 |
| Four component composition/weight % | |
| Saturated hydrocarbons | 53.3 |
| Aromatic hydrocarbons | 31.5 |
| Colloid | 14.5 |
| Asphalitine | 0.7 |
| Elementary composition/weight % | |
| C | 86.51 |
| H | 12.72 |
| S | 0.35 |
| N | 0.18 |
| Tenor/(μ g/g) | |
| Fe | 6.9 |
| Ni | 10.7 |
| V | 6.5 |
| Na | 0.1 |
| Ca | 1.7 |
Table 4
From table 4, when the content of rare earth of rare earth Y type molecular sieve used is suitable, catalytic cracking catalyst of the present invention shows higher activity in residual oil cracking process, and cracking reaction conversion ratio significantly improves (visible by the comparison of embodiment 1 and comparative example 1)；When content of rare earth in rare earth Y type molecular sieve used is relatively low, catalyst provided by the invention remains to obtain higher conversion ratio (referring to embodiment 4 and comparative example 2, embodiment 5 and comparative example 3)；Suitable at the content of rare earth of rare earth Y type molecular sieve used, catalytic cracking catalyst provided by the invention is in the less situation of consumption of molecular sieve, remain to obtain and existing catalyst quite or higher conversion ratio (referring to embodiment 1 and comparative example 4, embodiment 4 and comparative example 5), therefore the activity stability of the present invention not only catalyst is good, and can reduce the production cost of catalyst.
Claims (8)
1. a catalytic cracking catalyst, containing cracking activity constituent element, clay and binding agent, wherein, described cracking activity constituent element contains rare earth Y type molecular sieve, it is characterized in that, the content of rare earth of described rare earth Y type molecular sieve is calculated as 10-25 weight % with rare earth oxide, lattice constant is 2.440-2.472nm, degree of crystallinity is 35-65%, framework silicon-aluminum atomic ratio is 2.5-5.0, in this molecular sieve X-ray diffraction spectrogram in the ratio (I1/I2) of the intensity I 2 at intensity I 1 and 2 peak, θ=12.3 ± 0.1 ° at 2 peaks, θ=11.8 ± 0.1 ° and molecular sieve in the product value of the rare earth weight percentage of rare earth oxide more than 50.
2. the catalytic cracking catalyst described in claim 1, it is characterised in that described catalytic cracking catalyst contains 10-60 weight % cracking activity constituent element, 20-70 weight % clay and 10-50 weight % binding agent.
3. the catalytic cracking catalyst described in claim 1, it is characterised in that the content of rare earth of described rare earth Y type molecular sieve is calculated as 11-23 weight % with rare earth oxide, and lattice constant is 2.450-2.470nm, and degree of crystallinity is 40-60%.
4. the catalytic cracking catalyst described in claim 1, it is characterised in that described rare earth Y type molecular sieve through 800 DEG C, crystallization reservation degree after 100% steam burin-in process 17 hours is more than 45%.
5. according to the catalytic cracking catalyst of claim 1, it is characterised in that described rare earth Y type molecular sieve is to hand over two roast and obtain in conjunction with deposition of rare-earth process through two.
6. the catalytic cracking catalyst described in claim 5, it is characterised in that described two hand over two to roast and in conjunction with the rare earth utilization rate of deposition of rare-earth process more than 98%.
7. the catalytic cracking catalyst described in claim 1, it is characterised in that the intensity I at 2 peaks, θ=11.8 ± 0.1 ° in described molecular sieve X-ray diffraction spectrogram1Intensity I with 2 peaks, θ=12.3 ± 0.1 °2Ratio (I1/I2) with molecular sieve in the product value of the rare earth weight percentage of rare earth oxide more than 55.
8. the preparation method of the arbitrary described catalytic cracking catalyst of claim 1-7, the method includes: the rare earth Y type molecular sieve that preparation is described；Preparation includes the serosity of described rare earth Y type molecular sieve, clay and binding agent；By prepared serosity spray drying；The preparation method of described rare earth Y type molecular sieve includes: carry out contacting process with the mixed solution of ammonium salt with earth solution or rare earth by NaY molecular sieve, through filtering, washing, after drying, carries out first time calcination process, obtains rare earth sodium Y molecular sieve；Then rare earth sodium Y molecular sieve pulled an oar and contact process with ammonium salt solution or acid solution, mixing with earth solution again after filtration, and the pH value regulating serosity is 6-10, filter or do not filter, drying, carrying out second time calcination process, obtain described rare earth Y type molecular sieve.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210341407.1A CN103657700B (en) | 2012-09-14 | 2012-09-14 | A kind of catalytic cracking catalyst and preparation method thereof |
| SG11201501897RA SG11201501897RA (en) | 2012-09-14 | 2013-06-27 | A catalytic cracking catalyst having a rare earth-containing y zeolite and a preparation process thereof |
| JP2015531422A JP6301336B2 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst having rare earth-containing Y-type zeolite and method for producing the same |
| KR1020157009020A KR102109395B1 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| EP13837046.5A EP2896456B1 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| PCT/CN2013/000767 WO2014040365A1 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| AU2013314978A AU2013314978B2 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst of rare earth-containing Y-type molecular sieve and preparation method therefor |
| US13/929,078 US9656255B2 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst having a rare earth-containing Y zeolite and a preparation process thereof |
| RU2015113601A RU2628071C2 (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst containing ree-containing zeolite, and how to obtain it |
| TW102123169A TWI568495B (en) | 2012-09-14 | 2013-06-27 | Catalytic cracking catalyst with rare earth Y type molecular sieve and preparation method thereof |
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| CN106925335B (en) * | 2015-12-29 | 2019-12-10 | 中国石油天然气股份有限公司 | Heavy metal resistant catalytic cracking catalyst and preparation method thereof |
| CN108262056A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst with adjustable pore volume and preparation method thereof |
| CN113318777A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing rare earth Y-type molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250428A (en) * | 2008-04-07 | 2008-08-27 | 华东理工大学 | In-situ crystallization cracking catalyst and preparation method thereof |
| CN101767028A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Preparation method of fluid catalytic cracking catalyst |
| CN102009985A (en) * | 2010-12-21 | 2011-04-13 | 南京工业大学 | MCM-22 zeolite molecular sieve with framework containing rare earth heteroatoms and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250428A (en) * | 2008-04-07 | 2008-08-27 | 华东理工大学 | In-situ crystallization cracking catalyst and preparation method thereof |
| CN101767028A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Preparation method of fluid catalytic cracking catalyst |
| CN102009985A (en) * | 2010-12-21 | 2011-04-13 | 南京工业大学 | MCM-22 zeolite molecular sieve with framework containing rare earth heteroatoms and preparation method thereof |
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