CN102173436B - 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 especially a kind of high-specific surface area and have abundant
The preparation method of the high activity 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 very important effect to its activity and selectivity in catalytic process, and manage to improve its sour density and acid strength is the direction that the researcher 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, namely prepare so-called hyperastable Y-type RE molecular sieve, a kind of preparation method of rare earth superstable Y-type molecular sieve is disclosed such as CN1053808A, comprise and adopt the mixed chlorinated rare earth aqueous solution that the NaY molecular sieve is carried out ion-exchange, then 500～600 ℃ of lower double roastings obtained hyperastable Y-type RE molecular sieve in 1～3 hour in the circulating water vapor atmosphere, its structural deterioration 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 not, and the preparation method of double roasting both complicated loaded down with trivial details cost is also very high.
Also be that NaY is then carried out steam treatment with rare earth ion exchanged first 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 steam 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, structural deterioration makes the low and active not high enough defective of specific 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 heavy damage the structural intergrity of molecular sieve cause the low and active deficiency of low, the sour density of molecular sieve specific area.
CN1121903C, CN1162327C, CN1230496C, CN1051029C, CN1281493C, CN101081369A etc. all adopt SiCl
4The high silicon Y that vapor phase method is processed 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 significantly descends 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, namely use phosphorus and rare earth to the preparation method of Y molecular sieve modification, the structure cell of molecular sieve does not significantly shrink in preparation process, Olefins falls preferably though have, the acid strength 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 adopting steam roasting, cause framework dealumination to reduce sour density, the specific 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 the catalytic process such as catalytic cracking owing to there is the poor reason of hydrothermal stability that is difficult to overcome in small crystal grain molecular sieve.
Such as CN1733362A, CN1733363A a kind of preparation method of rare earth Y type molecular sieve is disclosed with the present invention comparatively approaches, the 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 alkaline 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 % steam, 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 technique of secondary that it adopts exchange is prepared has also improved the utilization rate of rare earth, but prepared molecular sieve specific 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 technical method, prepare rare-earth Y molecular sieve by adding the precipitating reagent precipitating rare earth and having introduced simultaneously aluminium ion, adding the precipitating reagent precipitating rare earth there is no substantial different from aforementioned prior art with ammonia precipitation process, the aluminium ion of introducing can not form framework of molecular sieve aluminium, can not improve the acidity of molecular sieve, so the method there be the defective identical with aforementioned prior art.
The method that adopts simplification technique to prepare rare-earth Y molecular sieve also has report, a kind of method that adopts circulation one to hand over the standby rare earth Y type molecular sieve of a roasting is disclosed such as CN1069553C, the method comprises carries out rare earth ion exchanged one time with the NaY molecular sieve, then the filter cake that filtration is obtained is at 450～600 ℃, roasting is 1～4 hour under the condition of 100 heavy % steam atmospheres, then 10～40 heavy % circulations of roasting afterproduct are returned and continued top described operation in the next group rare earth exchanged slurries, remaining as the REY zeolite product for the preparation of catalyst, carry out so continuously, although simplified technique, but cause product quality and structural stability significantly to descend, 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 such as CN100389173C, CN1246079C, so that the sodium ion in the molecular sieve is difficult for is exchanged, the gained rare-earth Y molecular sieve acid obviously not enough, hydrothermal stability is very poor, can not in the real processes such as catalytic cracking, use.
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 such as CN1363517A, is the sodium chabazite that goes out rich aluminium by adjusting synthetic rate of charge crystallization.CN101096274A and CN101096275A then disclose a kind of synthetic method of rich aluminium Beta zeolite, in the presence of hydrolytic reagent, synthesize first a sial cogelled, perhaps prepare silicon and aluminum source with dipping silicon source, acidic aluminum source, synthesize rich aluminium Beta zeolite as silicon, aluminium source after roasting and the pulverizing.Then prepare the rich aluminium Beta zeolite of nano-scale in CN101274764A and CN101353168A with similar approach or in the presence of fluorine ion, these methods that prepare rich aluminum molecular screen all realize in a Hydrothermal Synthesis process.There is no rich aluminium Y molecular sieve preparation method's report in the prior art, early stage X-type molecular sieve, described such as USP2882244, although also belong to the molecular sieve of the very high faujasite 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 intermediate water process for thermosynthesizing 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 lower calcination activation 3-6 of 0.085mmHg hours preparation Cu (I) Y molecular sieves, the preparation condition main purpose that it adopts is vacuum dehydration, because vacuum is had relatively high expectations, in actual production, relatively be difficult to realize.In molecular sieve modified preparation process, adopt the vacuum baking method when reducing roasting molecular sieve self adsorbed water when high temperature to the removing of framework of molecular sieve aluminium, migration, obtain the very complete and sour density of structure and enrich, particularly
The technology of the high surface 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 activity 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, 60～110 ℃ of lower intermediate water thermal synthesis 0.5～4 hour, obtain the NaY molecular sieve of rich surface aluminium, after regulating the pH value to 7 of slurries～10 through the rare earth ion hydrothermal exchange, with ammoniacal liquor and carrying out deposited lanthanide oxide, 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 area 〉=600 meters squared per gram.
The NaY molecular sieve that adopts 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 reactant mixture of the present invention for example mixes silicon source, aluminium source by the molar ratio that calculates Na wherein for conventionally known to one of skill in the art under stirring condition
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid.The silicon source of described preparation colloid is selected from waterglass, Ludox, silica gel; The aluminium source of described preparation colloid is selected from sodium aluminate, aluminum sulfate, aluminium chloride, aluminium hydroxide, aluminium oxide.After NaY type molecular sieve and identical weight colloid mixed, 85～100 ℃ of lower intermediate water thermal synthesis 1～2 hour, can in the stainless steel crystallizing kettle, carry out by method well-known to those skilled in the art under the preferred condition.Fixedly the mixed proportion between colloid and the molecular sieve can adopt several different methods, ratio such as the aluminium oxide in the fixing colloid and the aluminium oxide in the molecular sieve is constant, perhaps fixedly the ratio of silica is constant in silica 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 during for convenient preparation, simultaneously experimental result shows and also can make molecular sieve that similar alkaline rich aluminium thermal and hydric environment is arranged when the intermediate water thermal synthesis, makes that aluminate forms rich aluminium surface layer structure on the molecular sieve surface in the solution.But the present invention adopts the method fix both weight not limit uses the method that adopts fixing a certain component, and the method for fixing both alumina rations such as employing is perhaps fixed the method for both proportion of silica.
Also comprise the step of the rich aluminium NaY of gained molecular sieve being carried out rare earth ion exchanged, rare earth deposition among the preparation method of rare earth Y type molecular sieve provided by the present invention.The rare earth ion hydrothermal exchange adopts and to contain in lanthanum, cerium, praseodymium, the neodymium ion one or more at interior chloride or the aqueous solution of nitrate, perhaps from the chloride 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.Operating procedure 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 0.1～1,60～100 ℃ of lower stirrings 0.1～4 hour; Preferred condition is solvent and solute weight ratio 10～20, rare-earth salts: molecular sieve weight ratio 0.2～0.8,80～95 ℃ of lower stirrings 0.5～2 hour.
The rare earth deposition is to carry out deposited lanthanide oxide with the pH value to 7 of ammoniacal liquor adjusting slurries～10, the operating procedure condition of deposition is well known to those skilled in the art, namely in slurries, add ammoniacal liquor under the stirring condition, the concentration of ammoniacal liquor is unrestricted, make the pH value of slurries be increased to 7～10, rare earth chloride or nitric acid rare earth in the slurries are deposited on the molecular sieve after the acid-base neutralization reaction, the gained filter cake finally is deposited on the molecular sieve with the rare earth oxide form through calcination steps the time after filtering, and gained rare earth Y type molecular sieve product is with RE
2O
3Be 12～18 heavy % under the content of rare earth preferable case on the molecular sieve of meter.It is in order not introduce metal ion making things convenient for the ammonium salt washing exchange in the subsequent technique that the present invention adopts ammoniacal liquor to regulate pH value, but does not therefore limit and regulate the pH value with other alkaline matters.
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 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 ammonium carbonate, is with ammonium salt aqueous solution molecular sieve to be exchanged to Na under the optimum condition
2The heavy % in O content≤1.0, operating procedure 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 0.1～1,60～100 ℃ of lower stirrings 0.1～4 hour; Preferred condition is solvent and solute weight ratio 10～20, ammonium salt: molecular sieve weight ratio 0.2～0.8,80～95 ℃ of lower stirrings 0.5～2 hour, remove by filter filtrate, and 100～120 ℃ of dryings of gained filter cake namely 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 crystal 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 crystal structure that obtains is very complete and have very abundant
The acid site, BET specific 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 Kaolinite Preparation of Catalyst, fluidized catalytic cracking catalyst for example needing especially to be suitable for the active component of highly active mink cell focus and poor oil catalytic cracking catalyst.Owing to its high catalytic activity and selective, transformation efficiency and the product distribution that has improved reaction have effectively been improved when adopting the prepared rare-earth Y molecular sieve of the present invention in the catalytic cracking process of hydro carbons, to use.
The specific embodiment
The present invention is further illustrated for the following examples, 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 Rigaku D/max2500 type XRD diffractometer 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 300 ℃ of lower mensuration of pyridine adsorption infra-red sepectrometry.
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 ℃ straight distillation light diesel oil, 460 ℃ of reaction temperatures, weight space velocity are 16 hours
-1, oil ratio 3.2.The catalyst of be used for estimating all needs in advance through aging 4 hours or 17 hours of 800 ℃, 100% steam.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: catalyst loading amount 90 grams, reaction raw materials are the heavy % decompression residuum of the 80 defeated VGO+20 of heavy % pipe, 500 ℃ of reaction temperatures, weight space velocity 20～30 hours
-1, oil ratio 6.0.The catalyst that is used for estimating all needs in advance through 800 ℃, the processing in aging 4 hours of 100 heavy % steam.
Other detects referring to (" oil and oil product 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 aluminum sulfate (Shandong Aluminum Plant, Al
2O
390 grams per liters, proportion 1.25 grams per liters) under stirring 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 (aluminium oxide 23.9 heavy %), under 90 ℃, stirred 1 hour in the presence of 5 premium on currency with 94 gram chemical pure solid lanthanum chlorides (Beijing chemical reagent company commodity) after filtration, the washing, carry out the rare earth exchanged reaction.Use afterwards concentrated ammonia liquor (Beijing chemical reagent company commodity) that pH is adjusted to 8～9 rear stirring filtrations after 15 minutes, 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 lower roastings 2 hours, 90 ℃ of lower making beating washings of ammonium chloride solution with 5 liter of 1 heavy % exchange 1 hour, filtration obtains the rare earth Y type molecular sieve filter cake, BET specific 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 235 milliliters in water under stirring condition, mix, 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 (aluminium oxide 23.5 heavy %), filter, wash chloride (industrial goods rear and 150 gram solid lanthanum rich mischmetals, the Baotou Rare Earth Factory is produced, 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, under 95 ℃, stirred 2 hours, carry out the rare earth exchanged reaction.Use afterwards concentrated ammonia liquor (the same) that pH is adjusted to 9～10 rear stirring filtrations after 15 minutes, 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 lower roastings 1.5 hours; Then washed 2 hours with 90 ℃ of lower making beating of ammonium sulfate of 6 liter of 10 % by weight, filter and obtain the rare earth Y type molecular sieve filter cake, BET specific area 629 meters squared per gram are with RE
2O
3It is 16 % by 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 Ludox
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 stirring 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 (aluminium oxide 23.8 heavy %), filter, wash chloride (industrial goods rear and 100 gram solid cerium-rich mischmetals, the Baotou Rare Earth Factory is produced, wherein CeO
250 heavy %, La
2O
321 heavy %, Pr
2O
314 heavy %, Nd
2O
313 heavy %) in the presence of 6 premium on currency, under 90 ℃, stirred 2 hours, carry out the rare earth exchanged reaction.Use afterwards concentrated ammonia liquor (the same) that pH is adjusted to 7～8 rear stirring filtrations after 15 minutes, 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 lower roastings 2.5 hours, then washed 2 hours with 90 ℃ of lower making beating of ammonium nitrate solution of 6 liter of 10 % by weight, filtration obtains the rare earth Y type molecular sieve filter cake, BET specific area 625 meters squared per gram are with RE
2O
3It is 14.2 % by 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 resulting rich aluminium NaY molecular sieve 500 grams, under 90 ℃, stirred 2 hours 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.Concentrated ammonia liquor (the same) is adjusted to 9～10 rear stirring filtrations after 15 minutes, washing, crushed after being dried with pH 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 lower roastings 1 hour; Then washed 2 hours with 90 ℃ of lower making beating of ammonium nitrate solution of 6 liter of 10 % by weight, filter and obtain the rare earth Y type molecular sieve filter cake, BET specific area 621 meters squared per gram are with RE
2O
3It is 16.4 % by 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 resulting rich aluminium NaY molecular sieve 500 grams, under 90 ℃, stirred 2 hours 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 rear stirring filtrations after 15 minutes, 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 0.02MPa and 580 ℃ of lower roastings 2 hours; Then washed 1 hour with 90 ℃ of lower making beating of sal volatile of 5 liter of 10 % by weight, filter and obtain the rare earth Y type molecular sieve filter cake, BET specific area 625 meters squared per gram are with RE
2O
3It is 16.3 % by 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
This Comparative Examples is used for the preparation method of the close rare earth Y type molecular sieve of explanation prior art, prepares rare earth Y type molecular sieve according to the method for CN1733362A embodiment 1.BET specific area 497 meters squared per gram are with RE
2O
3It is 16.2 % by 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 the explanation 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 area 480 meters squared per gram are with RE
2O
3It is 15.8 % by 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 for the preparation method that the rare earth Y type molecular sieve that a roasting simplifies is handed in explanation available technology adopting circulation one, prepares rare earth Y type molecular sieve according to the method for CN1069553C embodiment 1.BET specific area 450 meters squared per gram are with RE
2O
3It is 13.6 % by 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 for the explanation 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 area 590 meters squared per gram are with RE
2O
3It is 13.8 % by 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 for explanation and adopts the cracking reaction after the hydrothermal aging of rare earth Y type molecular sieve provided by the invention is processed active.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 large 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 % steam, wore out 4 hours and 17 hours respectively, the results are shown in Table 1 can find out, 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 for the product distribution situation that the catalyst for heavy oil catalytic cracking that employing rare-earth Y molecular sieve provided by the invention is prepared into is described.
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 large remarkable company of kaolin, the stone that raw materials used employing China Kaolin Co., Ltd produces produces, the 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 product distribution situation of the catalyst of table 2, two kinds of prepared one-tenth of rare-earth Y molecular sieve:
| Project | Comparative Examples 1 catalyst | Embodiment 1 catalyst |
| Dry gas | 1.8 | 1.6 |
| Liquefied gas | 8.0 | 7.9 |
| Gasoline | 54.0 | 56.9 |
| Light diesel fuel | 18.5 | 17.8 |
| Heavy oil | 8.3 | 7.2 |
| Coke | 9.4 | 8.6 |
| Conversion ratio | 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, 60～110 ℃ of lower intermediate water thermal synthesis 0.5～4 hour, obtain the NaY molecular sieve of rich surface aluminium, after regulating the pH value to 7 of slurries～10 through the rare earth ion hydrothermal exchange, with ammoniacal liquor and carrying out deposited lanthanide oxide, 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 rare earth Y type molecular sieve of 10～20 heavy %, BET specific 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 rear 85～100 ℃ of lower intermediate water thermal synthesis 1～2 hour.
3. the preparation method of rare-earth Y molecular sieve according to claim 1, the silicon source that it is characterized by described preparation colloid is selected from waterglass, Ludox, silica gel.
4. the preparation method of rare-earth Y molecular sieve according to claim 1, the aluminium source that it is characterized by described preparation colloid is selected from sodium aluminate, aluminum sulfate, aluminium chloride, aluminium hydroxide, aluminium 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 interior chloride 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 ammonium carbonate.
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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| CN104211083B (en) * | 2013-06-05 | 2016-06-08 | 中国石油天然气股份有限公司 | The preparation method of a kind of composite modified Y molecular sieve |
| CN106984292A (en) * | 2017-04-11 | 2017-07-28 | 中国地质科学院郑州矿产综合利用研究所 | Molecular sieve vacuum activation method |
| CN110540214B (en) * | 2018-05-28 | 2021-02-09 | 中国石油化工股份有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| TWI831784B (en) | 2018-05-28 | 2024-02-11 | 大陸商中國石油化工科技開發有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110871102B (en) * | 2018-08-29 | 2022-06-24 | 中国石油化工股份有限公司 | Preparation method of micro-mesoporous composite material containing Y-type molecular sieve |
| CN111085246B (en) * | 2018-10-23 | 2022-08-09 | 中国石油化工股份有限公司 | Composite catalytic material and preparation method thereof |
| CN111617798A (en) * | 2019-02-28 | 2020-09-04 | 中国石油化工股份有限公司 | Preparation method of rare earth modified composite material |
| CN111620350B (en) * | 2019-02-28 | 2024-04-02 | 中国石油化工股份有限公司 | Micro-mesoporous composite material and preparation method thereof |
| CN111617796A (en) * | 2019-02-28 | 2020-09-04 | 中国石油化工股份有限公司 | Modified composite material and preparation method thereof |
| CN111617797A (en) * | 2019-02-28 | 2020-09-04 | 中国石油化工股份有限公司 | Preparation method of rare earth type composite catalytic material |
| CN111744528B (en) * | 2019-03-27 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method of multi-metal modified composite material |
| CN111744530A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Composite material containing phosphorus and rare earth |
| CN111744531B (en) * | 2019-03-27 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method of hierarchical porous material |
| CN111744529A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Method for modifying composite catalytic material by rare earth |
| CN111747425B (en) * | 2019-03-27 | 2023-05-05 | 中国石油化工股份有限公司 | Porous catalytic material containing mesopores and micropores |
| CN111744535A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Catalytic material jointly modified by rare earth and phosphorus and preparation method thereof |
| CN111744533A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of rare earth type hierarchical pore material |
| CN111747424B (en) * | 2019-03-27 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of rare earth and phosphorus-containing porous material |
| CN111744532A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Method for modifying porous material by multiple elements |
| CN113694880B (en) * | 2021-09-10 | 2023-10-10 | 润和催化剂股份有限公司 | Rare earth-containing Li-LSX zeolite and preparation method and application thereof |
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| CN100344374C (en) * | 2004-08-13 | 2007-10-24 | 中国石油化工股份有限公司 | Rare earth Y molecular screen and process for preparing the same |
| CN101433857B (en) * | 2007-11-15 | 2011-05-11 | 石大卓越科技股份有限公司 | Method for preparing rare-earth ultra-steady Y molecular sieve |
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