CN102173436A - Preparation method of rare earth (RE) yttrium (Y) molecular sieve - Google Patents
Preparation method of rare earth (RE) yttrium (Y) molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of a rare earth (RE) yttrium (Y) molecular sieve. The method is characterized by comprising the following steps of: uniformly mixing a sodium yttrium (NaY) molecular sieve and a colloid which is as heavy as the NaY molecular sieve and prepared by a silicon source and an aluminium source in a molar ratio of Na2O to SiO2 of 0.3 to 0.5, a molar ratio of SiO2 to Al2O3 of 5 to 7 and a molar ratio of H2O to Na2O of 40 to 70; carrying out secondary hydrothermal synthesis for 0.5 to 4 hours at the temperature of 60 to 110 DEG C to obtain a superficial aluminium-enriched NaY molecular sieve; carrying out RE ionized water heat exchange, adjusting the pH value of a size to 7 to 10 by using ammonia water, depositing an RE oxide, and carrying out vacuum baking for 0.5 to 4 hours at the temperature of 450 to 750 DEG C and under the system pressure of 0.001 to 0.09 megapascal (MPa); and exchanging with an ammonium salt aqueous solution until the content of the Na2O is less than or equal to 1.0 weight percent to prepare the high superficial area RE Y molecular sieve which has the content of RE of 10 to 20 weight percent based on RE2O3 and BET specific surface area of more than or equal to 600 m<2>/g. The RE Y molecular sieve prepared by the method has a quite complete crystalline structure, a quite rich acid site and quite high catalytic activity and selectivity when used in the process of catalytic cracking of hydrocarbons.
Description
Technical field
The invention relates to a kind of preparation method of rare-earth Y molecular sieve, relate to a kind of high-specific surface area especially and have abundant
The preparation method of the high reactivity rare-earth Y molecular sieve in acid site.
Background technology
Rare earth Y type molecular sieve is a kind of important molecular sieve kind of being used widely, and all is used as the catalytic cracking catalyst active component all the time, and it is improved research also is among constantly carrying out.For this class solid acid catalyst material of molecular sieve,
The acid site plays important effect to its activity and selectivity in catalytic process, and manage to improve its sour density and strength of acid is the direction that the investigator makes great efforts always.
Improvement research to rare-earth Y molecular sieve in the prior art mainly contains following a few class, one class is in order to improve the hydro-thermal structural stability of molecular sieve, mainly be chosen in utilize on the less Y molecular sieve of structure cell rare earth modified, promptly prepare so-called hyperastable Y-type RE molecular sieve, a kind of preparation method of rare earth superstable Y-type molecular sieve is disclosed as CN1053808A, comprise and adopt the mixed chlorinated rare earth aqueous solution that the NaY molecular sieve is carried out ion-exchange, 500～600 ℃ of following double roastings obtained hyperastable Y-type RE molecular sieve in 1～3 hour in the flowing water vapor atmosphere then, its structure deteriorate is serious, specific surface is low and contain a large amount of non-framework aluminums
Acid site density is low, and in use activity is not high, and selectivity of product is also good inadequately, and the both complicated loaded down with trivial details cost of the preparation method of double roasting is also very high.
Also be that NaY is then carried out steam treatment with rare earth ion exchanged earlier among USP 4584287 and the USP 4429053, make structure cell be retracted to 2.420～2.464 nanometers; USP5340957 and USP5206194 then adopt the NaY of silica alumina ratio 6.0 to carry out carrying out hydrothermal treatment consists after the rare earth exchanged; CN1128673C discloses to adopt in a kind of rare-earth Y molecular sieve preparation process and has mended silicon and steam roasting, makes it have the secondary pore of enriching; The method that CN100544822C adopts the synthetic NaY molecular sieve of conversion crystal seed and improves the roasting severity is prepared the rare-earth Y molecular sieve of high stability, and it still belongs to the hyperastable Y-type RE molecular sieve of water vapour method preparation.What these prior arts were prepared contains rare-earth Y molecular sieve owing to reasons such as structure cell contraction and hydrothermal dealuminations, all exists
Acid site density is low, structure deteriorate makes the low and active not high enough defective of specific surface area.
CN1065844A discloses a kind of rare-earth Y molecular sieve preparation method of sour dealuminzation and CN1317359C carries out rare earth modified preparation method with citric acid dealuminzation, CN1202007C after adopting the oxalic acid dealuminzation again, though managed to reduce the non-framework aluminum that produces the Lewis acid site, sour dealuminzation often havoc the structural integrity of molecular sieve cause the low and active deficiency of low, the sour density of molecular sieve specific surface area.
CN1121903C, CN1162327C, CN1230496C, CN1051029C, CN1281493C, CN101081369A etc. all adopt SiCl
4The high silicon Y that vapor phase process is handled carries out the rare-earth Y molecular sieve of the high silicon of rare earth modified acquisition, and molecular sieve structure is complete, good stability, but the molecular sieve structure cell is little, framework aluminum is few, and total acid density descends significantly and causes
Acid site density is low, and activity is still obviously not enough in the use.
CN1200079C, CN1142023C, CN1111136C, CN110955C, CN1332758C, CN100577566C and CN100586856C etc. disclose the preparation method of another kind of phosphorous and rare-earth Y molecular sieve, promptly use phosphorus and rare earth preparation method to the Y molecular sieve modification, the structure cell of molecular sieve does not shrink significantly in preparation process, though have and fall the alkene performance preferably, the strength of acid of molecular sieve but the phosphorus modification has weakened, when being used for heavy oil catalytic cracking process, conversion capability is obviously not enough, owing to generally adopt steam roasting, cause framework dealumination to reduce sour density, the specific surface area of product molecular sieve is often not high yet.
CN1907854A discloses a kind of technology of preparing of fine grain rare earth Y molecular sieve, has limited its practical application in catalytic processs such as catalytic cracking owing to there is the reason of the hydrothermal stability difference that is difficult to overcome in small crystal grain molecular sieve.
With the present invention comparatively approaching a kind of preparation method of rare earth Y type molecular sieve is disclosed as CN1733362A, CN1733363A, this method comprise with the NaY molecular sieve pulp with or not with the ammonium salt exchange, again with rare earth chloride according to NaY butt: RECl
3Be that 1: 0.17～0.35 weight ratio is at 5～100 ℃, carry out ion-exchange under the condition of pH 2.5～7.5, the weight ratio of water and NaY is 3～50, isolated molecule sieving cake, collect filtrate, with basic solution filtrate pH value is adjusted to 8～11, make the rare earth ion in the filtrate be precipitated as rare earth hydrate, again rare earth hydrate filter cake and the molecular sieve filter cake that obtains added the water making beating, filter, washing, dry, in 200～950 ℃, roasting is more than 0.1 hour under 0～100 heavy % water vapour, the molecular sieve of roasting is again by molecular sieve: ammonium salt: water is weight ratio processing under 60～100 ℃ of 1: 0～1: 2～50, through washing, filter, dry.The rare-earth Y molecular sieve that steam roasting technology of its secondary that adopts exchange is prepared has also improved the utilization ratio of rare earth, but prepared molecular sieve specific surface area is not high, be generally less than 500 meters squared per gram, and the hydro-thermal structural stability is also undesirable, and framework of molecular sieve very easily collapses in the harsh thermal and hydric environment in catalytic cracking regenerator.CN101088613A has adopted identical with it in fact technological method, prepare rare-earth Y molecular sieve by adding the precipitation agent precipitating rare earth and having introduced aluminum ion simultaneously, adding the precipitation agent precipitating rare earth there is no substantial different with aforementioned prior art with ammonia precipitation process, the aluminum ion of being introduced can not form framework of molecular sieve aluminium, can not improve the acidity of molecular sieve, so this method there be the defective identical with aforementioned prior art.
Adopt the method for simplifying the prepared rare-earth Y molecular sieve that report is also arranged, a kind of method that adopts circulation one friendship one roasting to be equipped with rare earth Y type molecular sieve is disclosed as CN1069553C, this method comprises carries out rare earth ion exchanged one time with the NaY molecular sieve, the filter cake that filtration is obtained is at 450～600 ℃ then, roasting is 1～4 hour under the condition of 100 heavy % steam atmospheres, then 10～40 heavy % circulations of roasting after product are returned and continued top described operation in the next batch rare earth exchanged slurries, remaining is used to prepare catalyzer as the REY zeolite product, carry out so continuously, though simplified technology, but cause quality product and structural stability to descend significantly, limited its use in practice, the specific surface of product molecular sieve is little, acid density is low.The method for preparing rare-earth Y molecular sieve that also has a class more to simplify, adopt the preparation technology who saves middle calcination steps as CN100389173C, CN1246079C, make the sodium ion in the molecular sieve be difficult for being exchanged, gained rare-earth Y molecular sieve acidity is obviously not enough, hydrothermal stability is very poor, can not use in actual procedurees such as catalytic cracking.
The method for preparing rich aluminum molecular screen also has report in the prior art, discloses a kind of synthetic method of AFI type molecular sieve of rich aluminium as CN1363517A, is by adjusting the sarcolite that synthetic feed ratio crystallization goes out rich aluminium.CN101096274A and CN101096275A then disclose a kind of synthetic method of rich aluminium Beta zeolite, it is cogelled to synthesize a sial in the presence of hydrolytic reagent earlier, perhaps prepare silicon and aluminum source with dipping silicon source, acidic aluminum source, roasting and pulverizing back synthesize rich aluminium Beta zeolite as silicon, aluminium source.Then prepare the rich aluminium Beta zeolite of nano-scale in CN101274764A and CN101353168A with similar approach or in the presence of fluorion, these methods that prepare rich aluminum molecular screen all realize in a hydro-thermal building-up process.There is no rich aluminium Y molecular sieve preparation method's report in the prior art, early stage X type molecular sieve, described as USP2882244, though also belong to the molecular sieve of the very high faujusite structure of aluminium content, but because it does not belong to the category of Y zeolite, and the hydro-thermal structural stability is very poor, can not replace Y molecular sieve and rich aluminium Y molecular sieve to be used in catalytic cracking process; Adopt the secondary hydrothermal synthesis method to prepare rich aluminium Y molecular sieve and carry out rare earth modified method and in prior art, do not have report.
Mention among the CN1011367033A at system pressure and be not higher than 200～250 ℃ of following calcination activation 3-6 of 0.085mmHg hours preparation Cu (I) Y molecular sieves, the preparation condition main purpose that it adopted is vacuum hydro-extraction, because it is vacuum tightness is had relatively high expectations, difficult to realize in actual production.In molecular sieve modified preparation process, adopt the vacuum baking method when reducing roasting molecular sieve self planar water when high temperature to the removing of framework of molecular sieve aluminium, transporting action, very complete sum acid density is abundant, particularly to obtain structure
The technology of the high surface area rare-earth Y molecular sieve that acid site density is abundant is not still reported.
Summary of the invention
The objective of the invention is in order to overcome deficiency of the prior art, a kind of high-specific surface area is provided and has abundant
The preparation method of the high reactivity rare-earth Y molecular sieve in acid site.
High-specific surface area provided by the present invention also has abundant
The preparation method of acid site rare-earth Y molecular sieve comprises: with NaY type molecular sieve and identical weight by silicon source, aluminium source Na in molar ratio
2O/SiO
20.3～0.5, SiO
2/ Al
2O
35～7, H
2O/Na
2The colloid that O 40～70 makes mixes, synthesized 0.5～4 hour 60～110 ℃ of following secondary hydro-thermals, obtain the NaY molecular sieve of surperficial rich aluminium, after deposited lanthanide oxide is carried out in pH value to 7～10 of regulating slurries through the rare earth ion hydrothermal exchange, with ammoniacal liquor, vacuum baking is 0.5～4 hour under 450～750 ℃ and system pressure 0.001～0.09MPa condition, exchanges to Na with ammonium salt aqueous solution again
2The heavy % in O content≤1.0 is prepared into RE
2O
3The content of rare earth of meter is the rare earth Y type molecular sieve of 10～20 heavy %, BET specific surface area 〉=600 meters squared per gram.
The NaY molecular sieve that is adopted among the preparation method of rare-earth Y molecular sieve provided by the present invention can be purchased gained, perhaps prepare gained by existing common method, these methods are well known to those skilled in the art, such as by disclosed method preparation among USP3639099, the USP3671191.
The step that silicon source, aluminium source are prepared a kind of reaction mixture of the present invention for example mixes silicon source, aluminium source Na wherein by calculating good molar ratio for conventionally known to one of skill in the art under agitation condition
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid.Described preparation colloidal silicon source is selected from water glass, silicon sol, silica gel; Described preparation colloidal aluminium source is selected from sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminium hydroxide, aluminum oxide.After NaY type molecular sieve and identical weight colloid mixed, synthetic 1～2 hour of 85～100 ℃ of following secondary hydro-thermals, can in the stainless steel crystallizing kettle, carry out under the preferred condition by method well-known to those skilled in the art.Fixedly the blending ratio between colloid and the molecular sieve can adopt several different methods, ratio as aluminum oxide in the fixing colloid and the aluminum oxide in the molecular sieve is constant, perhaps fixedly the ratio of silicon oxide is constant in silicon oxide and the molecular sieve in the colloid can reach the purpose of determining the two ratio, the present invention adopts the method for fixing the two part by weight, be that the colloid of identical weight and molecular sieve mix mainly be operation when preparing for convenience, simultaneously experimental result shows and also can make molecular sieve when the secondary hydro-thermal is synthetic similar alkaline rich aluminium thermal and hydric environment be arranged, and makes that aluminate forms rich aluminium surface layer structure on the molecular sieve surface in the solution.But the present invention adopts the method for fixing both weight not limit and uses the method that adopts fixing a certain component, such as the method that both alumina rations are fixed in employing, perhaps fixes the method for both proportion of silica.
Also comprise among the preparation method of rare earth Y type molecular sieve provided by the present invention the rich aluminium NaY of gained molecular sieve is carried out rare earth ion exchanged, the sedimentary step of rare earth.The rare earth ion hydrothermal exchange adopts and to contain in lanthanum, cerium, praseodymium, the neodymium ion one or more at the interior muriate or the aqueous solution of nitrate, perhaps from the muriate of the prepared lucium of rare-earth mineral or the aqueous solution of nitrate, described rare-earth salts can be commercially available.Described rare earth ion exchanged can be carried out one or many, preferably adopts once to exchange and deposit to improve preparation efficiency.The operation steps and the hydrothermal condition of exchange are well known to those skilled in the art, and generally adopt solvent and solute weight ratio 5～40, rare-earth salts/molecular sieve weight ratio to stir 0.1～4 hour down for 0.1～1,60～100 ℃; Preferred condition is solvent and solute weight ratio 10～20, rare-earth salts: the molecular sieve weight ratio stirred 0.5～2 hour down for 0.2～0.8,80～95 ℃.
The rare earth deposition is to carry out deposited lanthanide oxide with pH value to 7～10 of ammoniacal liquor adjusting slurries, sedimentary operation steps condition is well known to those skilled in the art, promptly in slurries, add ammoniacal liquor under the agitation condition, the concentration of ammoniacal liquor is unrestricted, make the pH value of slurries be increased to 7～10, rare earth chloride or rare earth nitrate in the slurries are deposited on the molecular sieve after the acid-base neutralisation reaction, filter back gained filter cake and finally be deposited on the molecular sieve with the rare earth oxide form through calcination steps the time, gained rare earth Y type molecular sieve product is with RE
2O
3Under the content of rare earth preferable case on the molecular sieve of meter 12～18 heavy %.It is in order not introduce metal ion to make things convenient for the ammonium salt washing exchange in the subsequent technique, not use other alkaline matters to regulate the pH value but therefore do not limit that the present invention adopts ammoniacal liquor to regulate the pH value.
Vacuum baking described in the preparation method of rare-earth Y molecular sieve provided by the present invention can make the gained rare earth Y type molecular sieve obtain the hydro-thermal structural stability that high specific surface area is become reconciled, and is vacuum baking 1～3 hour under 550～700 ℃ of temperature, the system pressure 0.01～0.05MPa in condition preferably.
Ammonium salt aqueous solution described in the preparation method of rare-earth Y molecular sieve provided by the present invention adopts one or more the aqueous solution that contains in ammonium chloride, ammonium nitrate, ammonium phosphate, ammonium sulfate, ammonium oxalate, the volatile salt, is with ammonium salt aqueous solution molecular sieve to be exchanged to Na under the optimum condition
2The heavy % in O content≤1.0, the operation steps and the hydrothermal condition of exchange are well known to those skilled in the art, and generally adopt solvent and solute weight ratio 5～40, ammonium salt/molecular sieve weight ratio to stir 0.1～4 hour down for 0.1～1,60～100 ℃; Preferred condition is solvent and solute weight ratio 10～20, ammonium salt: the molecular sieve weight ratio stirred 0.5～2 hour down for 0.2～0.8,80～95 ℃, removed by filter filtrate, and 100～120 ℃ of dryings of gained filter cake promptly get rare-earth Y molecular sieve of the present invention after 1～2 hour.
Adopt the preparation method of rare-earth Y molecular sieve provided by the present invention, general rare-earth Y molecular sieve hydrothermal dealumination, the damaged serious and low density defective in acid site of crystalline structure in preparation process have been overcome, the low deficiency of transformation efficiency when having improved rare-earth Y molecular sieve and using in the catalytic cracking process of hydro carbons, the rare earth Y type molecular sieve crystalline structure that is obtained is very complete and have profuse
The acid site, BET specific surface area 〉=600 meters squared per gram, can obtain under the preferred preparation condition 〉=rare-earth Y molecular sieve of 620 meters squared per gram, active component when can be used as the preparation catalyzer, fluidized catalytic cracking catalyst for example needing especially to be suitable for the active component of highly active mink cell focus and poor quality oil catalytic cracking catalyst.Owing to its high catalytic activity and selectivity, improved transformation efficiency effectively and improved the products distribution of reacting when adopting the prepared rare-earth Y molecular sieve of the present invention in the catalytic cracking process of hydro carbons, to use.
Embodiment
The following examples will the present invention is further illustrated, but not thereby limiting the invention.
In each embodiment, BET specific surface and pore volume adopt the GB/T5816-1995 method to measure; Crystallization reservation degree adopts Japanese D/max2500 type XRD diffractometer of science to measure with reference to ASTM D3906 method, and constituent content adopts x-ray fluorescence analyzer to measure according to GB/T12690.5-90.
Acidic zeolite characterizes reference literature (Li Xuanwen, She Liqin, Liu Xingyun, catalysis journal, 4 (1983), 43) and adopts the pyridine adsorption infrared spectroscopy to measure down for 300 ℃.
Little activity test is undertaken by the method for ASTM D-3907, the little anti-appreciation condition of light oil is: it is 420～841 microns particle that catalyst breakage is become particle diameter, and loading amount is 5 grams, and reaction raw materials is that boiling range is 235～337 ℃ a straight distillation light diesel oil, 460 ℃ of temperature of reaction, weight space velocity are 16 hours
-1, agent-oil ratio 3.2.The catalyzer that is used to estimate all needs in advance through aging 4 hours or 17 hours of 800 ℃, 100% water vapour.Be lower than gasoline yield+gas yield+coke yield of 204 ℃ in light oil microactivity MA=(being lower than gasoline output+gas yield+coke output of 204 ℃ in the product)/charging total amount * 100%=product.
Fixed fluidized bed catalytic cracking appreciation condition is: catalyzer loading amount 90 grams, reaction raw materials are the heavy % vacuum residuum of the 80 defeated VGO+20 of heavy % pipe, 500 ℃ of temperature of reaction, weight space velocity 20～30 hours
-1, agent-oil ratio 6.0.The catalyzer that is used to estimate all needs in advance through 800 ℃, the processing in aging 4 hours of 100 heavy % water vapour.
Other detects referring to (" oil and petroleum products test method national standard " China Standard Press published 1989).
Embodiment 1
With 271 ml water glass solutions (Shandong Aluminum Plant, proportion 1.25 grams per milliliters, SiO
2249 grams per liters, modulus 3.2), 111 milliliters of sodium metaaluminates (Shandong Aluminum Plant, Al
2O
3100 grams per liters, Na
2O 150 grams per liters, proportion 1.25 grams per liters) and 58 milliliters of Tai-Ace S 150 (Shandong Aluminum Plant, Al
2O
390 grams per liters, proportion 1.25 grams per liters) under agitation condition, mix, with 550 gram NaY molecular sieve (Catalyst Factory, Nankai Univ productions, silica alumina ratio 5.2, the heavy % of solid content 85) pack into after stirring and under 90 ℃, carried out hydrothermal crystallizing 2 hours in the stainless steel crystallizing kettle, obtain rich aluminium NaY molecular sieve (aluminum oxide 23.9 heavy %), stirred 1 hour under 90 ℃ in the presence of 5 premium on currency with 94 gram chemical pure solid Lanthanum trichlorides (Beijing chemical reagent company commodity) filtration, washing back, carries out the rare earth exchanged reaction.Use strong aqua (Beijing chemical reagent company commodity) that pH is adjusted to 8～9 backs afterwards and stir 15 minutes after-filtration, washing, crushed after being dried, material is packed in the airtight boiler tube, with oil-sealed rotary pump the roasting boiler tube after airtight is vacuumized and to keep system pressure 0.04MPa and 600 ℃ of following roastings 2 hours, 90 ℃ of washing exchanges 1 hour of pulling an oar down of ammonium chloride solution with 5 liter of 1 heavy %, filtration obtains the rare earth Y type molecular sieve filter cake, BET specific surface area 634 meters squared per gram are with La
2O
3It is 14 heavy % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.5 heavy %,
The acid amount is 0.75mmol/g.
Embodiment 2
With 272 ml water glass solutions (Shandong Aluminum Plant, proportion 1.24 grams per milliliters, SiO
2249 grams per liters, modulus 2.5), 28 gram aluminium hydrate powder (Shandong Aluminum Plant, the heavy % of solid content 60) and water under agitation condition, mix for 235 milliliters, pack into after stirring with 600 gram NaY molecular sieves (the same) and under 100 ℃, to carry out hydrothermal crystallizing 1 hour in the stainless steel crystallizing kettle, obtain rich aluminium NaY molecular sieve (aluminum oxide 23.5 heavy %), the muriate that filter, washing back and 150 restrains the solid lanthanum rich mischmetals (industrial goods, rare earth factory in Baotou produces, and wherein each component content is: Ce
2O
313 heavy %, La
2O
379 heavy %, Pr
6O
111.8 heavy %, Nd
2O
33.4 heavy %, Sm
2O
30.4 heavy %, other 2.4 heavy %) in the presence of 6 premium on currency, stirred 2 hours down at 95 ℃, carry out the rare earth exchanged reaction.Use strong aqua (the same) that pH is adjusted to 9～10 backs afterwards and stir 15 minutes after-filtration, washing, crushed after being dried, material is packed in the airtight boiler tube, with oil-sealed rotary pump the roasting boiler tube after airtight is vacuumized and keeps system pressure 0.02MPa and 650 ℃ of following roastings 1.5 hours; With 90 ℃ of washings 2 hours of pulling an oar down of ammoniumsulphate soln of 6 liter of 10 weight %, filter and obtain the rare earth Y type molecular sieve filter cake then, BET specific surface area 629 meters squared per gram are with RE
2O
3It is 16 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.6 heavy %,
The acid amount is 0.78mmol/g.
Embodiment 3
(Hua Hua group in Wenzhou produces, SiO with 260 gram silicon sol
225 heavy %), 192 milliliters of sodium metaaluminates (Shandong Aluminum Plant, Al
2O
3100 grams per liters, Na
2O 159 grams per liters, proportion 1.25 grams per liters) under agitation condition, mix, pack into after stirring with 500 gram NaY molecular sieves (the same) and under 95 ℃, to carry out hydrothermal crystallizing 2 hours in the stainless steel crystallizing kettle, obtain rich aluminium NaY molecular sieve (aluminum oxide 23.8 heavy %), muriate (the industrial goods that filter, washing back and 100 restrain the solid cerium-rich mischmetals, Baotou rare earth factory produces, wherein CeO
250 heavy %, La
2O
321 heavy %, Pr
2O
314 heavy %, Nd
2O
313 heavy %) in the presence of 6 premium on currency, stirred 2 hours down, carry out the rare earth exchanged reaction at 90 ℃.Use strong aqua (the same) that pH is adjusted to 7～8 backs afterwards and stir 15 minutes after-filtration, washing, crushed after being dried, material is packed in the airtight boiler tube, with oil-sealed rotary pump the roasting boiler tube after airtight is vacuumized and to keep system pressure 0.03MPa and 550 ℃ of following roastings 2.5 hours, pull an oar down for 90 ℃ with the ammonium nitrate solution of 6 liter of 10 weight % then and washed 2 hours, filtration obtains the rare earth Y type molecular sieve filter cake, BET specific surface area 625 meters squared per gram are with RE
2O
3It is 14.2 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.7 heavy %,
The acid amount is 0.74mmol/g.
Embodiment 4
With embodiment 1 resultant rich aluminium NaY molecular sieve 500 grams, stirred 2 hours down at 90 ℃ in the presence of 5 premium on currency with 100 gram solid nitric acid lanthanums (Beijing chemical reagent company commodity), carry out the rare earth exchanged reaction.Strong aqua (the same) is adjusted to 9～10 backs with pH and is stirred 15 minutes after-filtration, washing, crushed after being dried afterwards, material is packed in the airtight boiler tube, with oil-sealed rotary pump the roasting boiler tube after airtight is vacuumized and keeps system pressure 0.01MPa and 680 ℃ of following roastings 1 hour; With 90 ℃ of washings 2 hours of pulling an oar down of ammonium nitrate solution of 6 liter of 10 weight %, filter and obtain the rare earth Y type molecular sieve filter cake then, BET specific surface area 621 meters squared per gram are with RE
2O
3It is 16.4 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.4 heavy %,
The acid amount is 0.74mmol/g.
Embodiment 5
With embodiment 2 resultant rich aluminium NaY molecular sieve 500 grams, stirred 2 hours down at 90 ℃ in the presence of 5 premium on currency with 100 gram solid nitric acid ceriums (Beijing chemical reagent company commodity), carry out the rare earth exchanged reaction.With ammoniacal liquor pH is adjusted to 8～9 backs afterwards and stir 15 minutes after-filtration, washing, crushed after being dried, material is packed in the airtight boiler tube, with oil-sealed rotary pump the roasting boiler tube after airtight is vacuumized and keeps system pressure 0.02MPa and 580 ℃ of following roastings 2 hours; With 90 ℃ of washings 1 hour of pulling an oar down of sal volatile of 5 liter of 10 weight %, filter and obtain the rare earth Y type molecular sieve filter cake then, BET specific surface area 625 meters squared per gram are with RE
2O
3It is 16.3 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.5 heavy %,
The acid amount is 0.76mmol/g.
Comparative Examples 1
The preparation method of the rare earth Y type molecular sieve that this Comparative Examples is used for illustrating that prior art is close prepares rare earth Y type molecular sieve according to the method for CN1733362A embodiment 1.BET specific surface area 497 meters squared per gram are with RE
2O
3It is 16.2 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.9 heavy %,
The acid amount is 0.45mmol/g.
Comparative Examples 2
This Comparative Examples be used for illustrating prior art close the preparation method of another rare earth Y type molecular sieve, prepare rare earth Y type molecular sieve according to the method for CN101088613A embodiment 1.BET specific surface area 480 meters squared per gram are with RE
2O
3It is 15.8 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.8 heavy %,
The acid amount is 0.42mmol/g.
Comparative Examples 3
This Comparative Examples is used to illustrate that available technology adopting circulation one hands over the preparation method of the rare earth Y type molecular sieve that a roasting simplifies, and prepares rare earth Y type molecular sieve according to the method for CN1069553C embodiment 1.BET specific surface area 450 meters squared per gram are with RE
2O
3It is 13.6 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 0.7 heavy %,
The acid amount is 0.40mmol/g.
Comparative Examples 4
This Comparative Examples be used to illustrate available technology adopting omit in the middle of the preparation method of simplification rare earth Y type molecular sieve of calcination steps, prepare rare earth Y type molecular sieve according to the method for CN100389173C embodiment 1.BET specific surface area 590 meters squared per gram are with RE
2O
3It is 13.8 weight % that the content of rare earth of meter accounts for molecular sieve butt weight, Na
2O content 1.2 heavy %,
The acid amount is 0.32mmol/g.
Embodiment 6
This embodiment is used to illustrate the cracking reaction activity after the hydrothermal aging that adopts rare earth Y type molecular sieve provided by the invention is handled.Adopt micro-reactor (MAT-II type, Huiersanji Green Chemical Science and Technology Co., Ltd., Beijing makes) that embodiment 1～5 and Comparative Examples 1～4 are estimated.
The micro-activity of table 1, embodiment 1～5 and Comparative Examples 1～4:
Adopt the kaolin of China Kaolin Co., Ltd's product and the aluminium colloidal sol that the big remarkable company of stone produces, with butt weight by molecular sieve: kaolin: after the weight ratio of aluminium colloidal sol=30: 50: 20 mixes, 120 ℃ of dryings are after 2 hours, be broken into the 20-40 order, and under 800 ℃ 100 heavy % water vapour, wore out 4 hours and 17 hours respectively, the results are shown in Table 1 as can be seen, the catalytic activity behind the hydrothermal aging of rare earth Y type molecular sieve provided by the invention is better than the activity of the prepared rare earth Y type molecular sieve of prior art.
Embodiment 7
This embodiment is used to illustrate the products distribution situation that adopts the catalyst for heavy oil catalytic cracking that rare-earth Y molecular sieve provided by the invention is prepared into.
Embodiment 1 and Comparative Examples 1 prepared rare-earth Y molecular sieve are prepared into catalyst for heavy oil catalytic cracking by CN1733363A embodiment 7～14 described methods respectively, the aluminium colloidal sol that the big remarkable company of kaolin, the stone that raw materials used employing China Kaolin Co., Ltd produces produces, the pseudo-boehmite that Shandong Aluminum Plant produces.
In small fixed flowing bed catalytic cracking unit (FFB-200 type, Huiersanji Green Chemical Science and Technology Co., Ltd., Beijing's manufacturing) carries out evaluating and measuring on, the result shows that the prepared rare-earth Y molecular sieve of the present invention is as the catalytic cracking catalyst active component, its transformation efficiency and crackate distribute and all are better than the made catalyst for heavy oil catalytic cracking of the prepared rare-earth Y molecular sieve of prior art, see Table 2.
The products distribution situation of the catalyzer of table 2, two kinds of prepared one-tenth of rare-earth Y molecular sieve:
| Project | Comparative Examples 1 catalyzer | Embodiment 1 catalyzer |
| Dry gas | 1.8 | 1.6 |
| Liquefied gas | 8.0 | 7.9 |
| Gasoline | 54.0 | 56.9 |
| Solar oil | 18.5 | 17.8 |
| Heavy oil | 8.3 | 7.2 |
| Coke | 9.4 | 8.6 |
| Transformation efficiency | 73.2 | 75.0 |
Claims (10)
1. the preparation method of a rare-earth Y molecular sieve, it is characterized by this molecular sieve and be with NaY type molecular sieve and identical weight by silicon source, aluminium source Na in molar ratio
2O/SiO
20.3～0.5, SiO
2/ Al
2O
35～7, H
2O/Na
2The colloid that O 40～70 makes mixes, synthesized 0.5～4 hour 60～110 ℃ of following secondary hydro-thermals, obtain the NaY molecular sieve of surperficial rich aluminium, after deposited lanthanide oxide is carried out in pH value to 7～10 of regulating slurries through the rare earth ion hydrothermal exchange, with ammoniacal liquor, vacuum baking is 0.5～4 hour under 450～750 ℃ and system pressure 0.001～0.09MPa condition, exchanges to Na with ammonium salt aqueous solution again
2The heavy % in O content≤1.0 is prepared into RE
2O
3The content of rare earth of meter is the high surface area rare earth Y type molecular sieve of 10～20 heavy %, BET specific surface area 〉=600 meters squared per gram.
2. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described NaY type molecular sieve and colloid and mixes the back synthetic 1～2 hour of 85～100 ℃ of following secondary hydro-thermals.
3. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described preparation colloidal silicon source and is selected from water glass, silicon sol, silica gel.
4. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described preparation colloidal aluminium source and is selected from sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminium hydroxide, aluminum oxide.
5. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described rare earth ion hydrothermal exchange and adopts and contain in lanthanum, cerium, praseodymium, the neodymium ion one or more at the interior muriate or the aqueous solution of nitrate.
6. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described ammonium salt aqueous solution and adopts one or more the aqueous solution that contains in ammonium chloride, ammonium nitrate, ammonium phosphate, ammonium sulfate, ammonium oxalate, the volatile salt.
7. the preparation method of rare-earth Y molecular sieve according to claim 1 is characterized by described rare earth Y type molecular sieve with RE
2O
3The content of rare earth of meter is 12～18 heavy %.
8. the preparation method of rare-earth Y molecular sieve according to claim 1, the pressure of system is 0.01～0.05MPa when it is characterized by described vacuum baking.
9. the preparation method of rare-earth Y molecular sieve according to claim 1, the temperature when it is characterized by described vacuum baking is 550～700 ℃.
10. the preparation method of rare-earth Y molecular sieve according to claim 1, the time when it is characterized by described vacuum baking is 1～3 hour.
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