CN1733362A - Rare earth Y molecular screen and process for preparing the same - Google Patents
Rare earth Y molecular screen and process for preparing the same Download PDFInfo
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Abstract
This invention discloses a rare earth Y molecular sieve and preparation; wherein, the rare earth content is 12~22 w.t% considering the quantity of rare earth oxide in molecular sieve, all rare earth ion is in molecular sieve small cage; there is no peak at 0ppm in 27Al M AS NMR spectrogram. The step to obtain molecular sieve comprises: exchanging NaY molecular sieve liquid with ammonium salt or not, taking ion exchange with rare earth chloride by weight ratio of NaY dry basis:RECl3=1:0.17~0.35 at temperature 5~100Deg; pH=2.5~7.5, water: NaY=3~50; adjusting pH value to 8~11 with alkaline solution; mixing, filtering, cleaning, drying; baking for more than 0.1h with 0~100% vapor at temperature 200~950Deg; then, dealing with the molecular sieve according to weight ratio molecular sieve dry basis: ammonium salt :water=1:0~1:2~50 at temperature 60~100Deg; finally, cleaning, filtering, drying and obtaining the product.
Description
Technical field
The invention relates to a kind of Y molecular sieve and preparation method thereof, further say so about a kind of rare Y molecular sieve and preparation method thereof of going up.
Background technology
The quality of gasoline that environmental regulation is produced the FCC process has proposed the requirement of increasingly stringent, is≤20 volume % as world's fuel oil standard content of olefin in gasoline II class standard, and the III class standard is≤10 volume %.
In order to reduce the FCC content of olefin in gasoline, the strategy that extensively adopts is that to adopt the Y zeolite that contains rare earth with high hydrogen transfer activity be active component at present.As the said catalyst of CN1317547A is to be active component with REY and PREY, and they all adopt two to hand over the preparation technologies of two roastings, cause the molecular sieve cost higher
I.Bresinska, K.J.Balkus, Jr. wait people [J.Phys.Chem.98 (1994) 12989～12994] to study to feed intake in the exchange of NaY and rare earth-iron-boron liquid phase the relation of rare earth and molecular sieve mol ratio and rare earth exchanged degree, discovery exchanges product middle rare earth/NaY mole and always is lower than the rare earth that feeds intake/NaY mol ratio.
The REY of a roasting is handed in CN1053808A preparation one, and its rare earth oxide that feeds intake/NaY mass ratio is 0.20, and rare earth oxide among the product REY/REY mass ratio is 0.14.
CN1069553C is equipped with REY through two friendships, two roastings, and its rare earth oxide that always feeds intake/NaY mass ratio is 0.23, and rare earth oxide among the product REY/REY mass ratio is 0.15.CN1069553C has proposed one and has handed over a wet method that bakes and will partly exchange the product of roasting circulation to prepare REY, at the rare earth oxide that feeds intake/NaY mass ratio is 0.20, and internal circulating load is that rare earth oxide among the product REY/REY mass ratio can reach 0.158 under 25% the situation.Tradition one hands over the REY molecular sieve of a roasting technology preparation to have quite a few rare earth ion to be in the Y zeolite supercage.CN1069553C and CN1026225C adopt one to hand over the method for a wet roasting, the rare earth ion after the exchange is positioned in the little cage more, but still has the part rare earth ion to be in the supercage.
The method rare earth utilization rate of industrial preparation REY molecular sieve is not too high at present, and rare earth ion liquid phase exchange back also has quite a few rare earth ion to stay in the exchange liquid, drains with filtrate after filtering.Even the preparation middle rare earth is excessive a lot, with the traditional REHY molecular sieve of handing over a roasting method to prepare of present employing, maximum oxidation content of rare earth generally is lower than 14m%; And its rare earth oxide content of REY that adopts part to exchange the method preparation of product of roasting circulation is not higher than 16m% yet.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have the rare-earth Y molecular sieve of special performance and its preparation method is provided.
Rare-earth Y molecular sieve provided by the invention, the content of rare earth that it is characterized in that this molecular sieve is counted 12～22 heavy % with rare earth oxide, be preferably 13～20 heavy %, more preferably 14～18 weigh %, rare earth ion all is positioned at the little cage of molecular sieve, be embodied in molecular sieve after the ammonium exchange, content of rare earth does not reduce, this molecular sieve
27In the AlMAS NMR spectrogram, be that the 0ppm place does not have the peak to occur in chemical shift.
Sodium oxide content is 0.1～1.0 heavy % in the said rare-earth Y molecular sieve.
Rare-earth Y molecular sieve provided by the invention, content of rare earth does not reduce after the ammonium exchange.Y zeolite has three kinds of cages, i.e. supercage, sodalite cage and hexagonal prism cage, and wherein supercage window diameter is 7.4 , and sodalite cage and hexagonal prism cage window diameter are 2.2 , sodalite cage and hexagonal prism generally are called little cage.In the process of ammonium exchange, the rare earth ion that is in the supercage can be changed in the solution by the ammonium ion reciprocal cross in the solution, and runs off in filtration subsequently, causes the reduction of ammonium exchange back molecular sieve content of rare earth.Rare-earth Y molecular sieve provided by the invention, there is not rare earth ion to exist in the supercage, its rare earth ion all is positioned at little cage, the rare earth ion that is arranged in little cage can not exchange with the ammonium ion of solution, and rare-earth Y molecular sieve therefore provided by the invention can not reduce through ammonium exchange back molecular sieve content of rare earth.
There is not non-framework aluminum in rare-earth Y molecular sieve provided by the invention, shows it
27In the Al MAS NMR spectrum, be that the 0ppm place does not have the peak to occur in chemical shift, and XRD spectra show that the characteristic diffraction peak that does not have free rare earth oxide exists.
The present invention also provides the preparation method of above-mentioned rare-earth Y molecular sieve, it is characterized in that with the NaY molecular sieve pulp with or with ammonium salt exchange after, with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, use alkaline solution regulator solution pH to 8～11 then, stirring, filtration, washing, drying, again at 200～950 ℃, roasting is more than 0.1 hour under 0～100% steam, the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, obtains the finished product molecular sieve through washing, filtration, drying.
The present invention also provides another preparation method, it is characterized in that with the NaY molecular sieve pulp with or not with ammonium salt exchange, again with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, isolated molecule sieving cake, collect filtrate, in filtrate, add alkaline solution, regulator solution pH 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, drying is again at 200～950 ℃, roasting is more than 0.1 hour under 0～100% steam, the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, through washing, filter, drying obtains the finished product molecular sieve.
Among the said preparation method, said rare earth chloride consists of single rare earth chloride or compound rare-earth.Preferred lanthanum chloride of said single rare earth chloride or cerium chloride.
Said alkaline solution is selected from one or more mixture of ammoniacal liquor, waterglass, sodium metaaluminate, magnesium hydroxide or NaOH, wherein is preferably ammoniacal liquor or waterglass.
Among the preparation method provided by the invention, the silica of said NaY molecular sieve raw material and the mol ratio of aluminium oxide are preferably greater than 4.9.
Rare-earth Y molecular sieve provided by the invention is after an ionic liquid phase exchange process, and the rare earth of deposition carries out one time the solid phase ion exchange process again in roasting process subsequently, i.e. the exchange process of liquid-solid combination obtains.The preparation method who is provided is that solution and the Y zeolite that will contain rare earth ion carry out the ionic liquid phase exchange earlier, regulating exchange liquid pH value with alkaline matter then makes rare earth ion unnecessary in the solution be precipitated as rare earth hydrate, its effect is to avoid rare earth to run off, the rare earth ion of precipitation is moved in the molecular sieve sodalite cage, and sodium ion is moved to the molecular sieve outside.Compare with the method for preparing rare-earth Y molecular sieve of prior art, preparation method provided by the invention is roasting process for once, and molecular sieve middle rare earth content is accurately adjustable at 12～22 heavy %, and the rare earth utilization rate reaches 100%, and rare earth ion all is positioned at the molecular sieve cage.
Description of drawings
Fig. 1 is the CDY-1 sieve sample of embodiment 1 preparation
27Al MAS NMR spectrogram.
Fig. 2 is the XRD spectra of the CDY-1 sieve sample of embodiment 1 preparation.
Fig. 3 is the DB-1 sieve sample of Comparative Examples 1 preparation
27Al MAS NMR spectrogram.
Fig. 4 is the DB-3 sieve sample of Comparative Examples 3 preparation
27Al MAS NMR spectrogram.
The specific embodiment
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In an embodiment,
27The assay method of Al MAS NMR spectrogram is: adopt Varian 300M NMR spectrometer with superconducting magnet, solid double resonance probe, 6mmZrO
2Rotor, magic angle rotating speed is 5KHz.
27The resonant frequency that Al detects nuclear is 78.162MHz, 0.02 second sampling time, pulsewidth 1.6 microseconds, 0.6 second circulation delay time.Data acquisition 4k point, accumulative frequency 800 times, probe temperature are room temperature.
In an embodiment, the assay method of XRD spectra is: Siemens D5005 type X-ray diffractometer, and experiment condition: the Cu target, the Ka radiation, tube voltage 30Kv, tube current 40mA, filter plate are Ni, 5 °≤2 θ≤50 °, 2 °/min of sweep speed.
Embodiment 1
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, adds 5.3 kilograms of solid lanthanum chlorides again, and 90 ℃ were stirred 2 hours down, added 1.5 kilograms of sodium aluminate solutions and 1.2 kilograms of ammoniacal liquor, stirred filtration after 5 minutes, and washing, the laggard roaster of pneumatic conveying drying, when weight space velocity 0.5
-1Following 550 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-1A, in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 60 ℃ ammonium chloride solution washing 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-1.
It is 15.9 heavy % that fluorescence method records CDY-1A lanthana content, and sodium oxide molybdena is 4.5 heavy %; CDY-1 lanthana content is 16.2 heavy %, and sodium oxide content is 0.6 heavy %, its
27Al MAS NMR spectrum is seen Fig. 1, in Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.Fig. 2 is the XRD spectra of CDY-1, and Fig. 2 shows that CDY-1 does not have the diffraction maximum of free rare earth oxide to exist.
With CDY-1 once more with after the ammonium chloride solution exchange, the lanthana content that fluorescence method records wherein is 16.3 heavy %, the molecular sieve content of rare earth slightly increases, illustrate that rare earth ion is in little cage, rare earth ion in the little cage in the ammonium chloride exchange process can not with ammonium ion exchange, thereby total amount of rare earth is constant before and after the exchange, but the ammonium exchange can further reduce sodium oxide content in the molecular sieve, thereby causes molecular sieve middle rare earth content to increase.
Embodiment 2
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system PH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, (rare earth oxide concentration is 312 grams per liters to wherein adding 10.4 liters of re chlorides again, down together), stir under the room temperature after 5 minutes with between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour, add 2.2 kg water glass solutions and 1.3 kilograms of ammoniacal liquor, stir after 5 minutes and filter, and washing, the laggard roaster of pneumatic conveying drying, 550 ℃ of roastings 1.5 hours obtain molecular sieve and are designated as CDY-2A after the cooling, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was in 60 ℃ of ammonium chloride solutions washings 10 minutes, drying obtains finished product, and molecular sieve is numbered CDY-2.
It is 21.1 heavy % that fluorescence method records CDY-2A rare earth oxide content, and sodium oxide molybdena is 3.9 heavy %; Rare earth oxide content is 21.6 heavy % among the CDY-2, and sodium oxide content is 0.3 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 21.6 heavy % with CDY-2, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 3
Get 46.6 kilograms NaY molecular sieve pulp (Shandong catalyst plant, NaY concentration is 30.0 heavy %, the NaY silica alumina ratio is 5.1) and 80 kilograms of deionized waters join in the reactor, again to wherein adding 5.3 liters of re chlorides, 60 ℃ are stirred down after 5 minutes with between hydrochloric acid regulation system PH to 3.5～5.5, continue to stir after 1 hour, add 1.6 kilograms of ammoniacal liquor, stir after 5 minutes and to filter, and washing, the laggard roaster of pneumatic conveying drying, when weight space velocity 0.2
-1Following 600 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-3A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 90 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-3.
It is 11.9 heavy % that fluorescence method records CDY-3A rare earth oxide content, and sodium oxide molybdena is 4.8 heavy %; Rare earth oxide content is 12.1 heavy % among the CDY-3, and sodium oxide content is 0.7 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
With after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 12.2 heavy % with CDY-3, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 4
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 110 kilograms of deionized waters join in the reactor, be warmed up to 90 ℃, again to the ammonium sulfate that wherein adds 3.5 kilograms, stir and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～4.0, continue to stir after 1 hour, filter, the molecular sieve filter cake adds the making beating of 90 kg water, add 10.4 liters of re chlorides again, stir under the room temperature and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour, add 1.6 kilograms of ammoniacal liquor, stir after 5 minutes and filter, and washing, the laggard roaster of pneumatic conveying drying is when weight space velocity 0.1
-1Following 540 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-4A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 60 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-4.
It is 21.2 heavy % that fluorescence method records CDY-4A rare earth oxide content, and sodium oxide molybdena is 3.9 heavy %; Rare earth oxide content is 21.6 heavy % among the CDY-4, and sodium oxide content is 0.2 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the oxidation rare earth content that fluorescence method records wherein is 21.6 heavy % with CDY-4, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 110 kilograms of deionized waters join in the reactor, add 10.4 liters of re chlorides again, stir under the room temperature and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour and filter.Collect filtrate, add 1.5 kg of hydrogen sodium oxide molybdenas in the filtrate and make the rare earth ion in the filtrate be converted into the rare earth hydrate precipitation, filter, wash, again rare earth hydrate filter cake and the molecular sieve filter cake that obtains added the making beating of 80 kg water, filtration, the laggard roaster of pneumatic conveying drying are when weight space velocity 0.1
-1Following 540 ℃ of roastings of water vapour 2.5 hours, obtain molecular sieve after the cooling and be designated as CDY-5A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 80 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-5.
It is 21.0 heavy % that fluorescence method records CDY-5A rare earth oxide content, and sodium oxide molybdena is 3.7 heavy %; Rare earth oxide content is 21.4 heavy % among the CDY-5, and sodium oxide content is 0.3 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 21.4 heavy % with CDY-5, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 6
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, add 5.3 kilograms of solid lanthanum chlorides again, 90 ℃ were stirred 2 hours down, added 1.5 kilograms of sodium aluminate solutions and 1.2 kilograms of ammoniacal liquor, stirred after 5 minutes and filtered, and directly advance roaster after the washing, pneumatic conveying drying, 650 ℃ of roastings are 1.5 hours under dry air, obtain molecular sieve after the cooling and are designated as CDY-6A, again with 10 times deionized water washing 10 minutes, drying obtains the finished product molecular sieve, is numbered CDY-6.
It is 15.9 heavy % that fluorescence method records CDY-6A lanthana content, and sodium oxide molybdena is 4.6 heavy %; Lanthana content is 16.2 heavy % among the CDY-6, and sodium oxide content is 0.7 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
With CDY-6 once more with after the ammonium chloride solution exchange, the lanthana content that fluorescence method records wherein is 16.3 heavy %, the molecular sieve content of rare earth slightly increases, illustrate that rare earth ion is in little cage, rare earth ion in the little cage in the ammonium chloride exchange process can not with ammonium ion exchange, thereby total amount of rare earth is constant before and after the exchange, but the ammonium exchange can further reduce the molecular sieve sodium oxide content, thereby causes molecular sieve middle rare earth content to increase.
Comparative Examples 1
This Comparative Examples is to hand over the REY of a roasting according to one of the described method preparation of CN1053808A.
Press NaY butt: RECl
3: the weight ratio of water=1: 0.3: 15 is mixed making beating with NaY with rare earth chloride, regulate pH to 3.5, is warmed up to 90 ℃ and stirs 1 hour, filters, washing, and with the filter cake tube furnace of packing into, beginning to feed weight space velocity when being warming up to 200 ℃ is 1.0 o'clock
-1Steam, continue to be warmed up to 550 ℃, this temperature roasting 2 hours, cooling obtains molecular sieve and is numbered DB-1, and again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was washed 10 minutes with 60 ℃ of ammonium chloride solutions, drying obtains molecular sieve and is designated as DB-1w.
It is 14.0 heavy % that fluorescence method records among the DB-1 rare earth oxide content, and sodium oxide content is 3.9 heavy %, its
27Al MAS NMR spectrogram is seen Fig. 3, as can be seen, is that the 0ppm place has the peak to occur in chemical shift among Fig. 3.
It is 13.5 heavy % that fluorescence method records among the DB-1w rare earth oxide content, and sodium oxide content is 0.9 heavy %, and this contrast molecular sieve content of rare earth after ammonium chloride washed reduces, and illustrates that the part rare earth ion is positioned at supercage in the molecular sieve.
Comparative Examples 2
This Comparative Examples is to hand over the REY of a roasting according to the preparation of method described in the CN1069553C one.
Press NaY butt: RECl
3: the weight ratio of water=1: 0.3: 15 is mixed making beating with NaY with rare earth chloride, regulate pH to 3.5, being warmed up to 90 ℃ stirred 0.5 hour, to wherein adding the REY-1 that accounts for NaY butt weight 25%, continue to stir 0.5 hour, filter, washing, with the filter cake tube furnace of packing into, beginning to feed weight space velocity when being warming up to 200 ℃ is 1.0 o'clock
-1Steam, continue to be warmed up to 550 ℃, this temperature roasting 2 hours, cooling obtains contrasting sample DB-2, again with ammonium chloride solution in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was in 60 ℃ of washings 10 minutes, and drying obtains finished product molecular sieve contrast sample, numbering DB-2w.
It is 15.4 heavy % that fluorescence method records among the DB-2 rare earth oxide content, and sodium oxide content is 3.5 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 3, is that the 0ppm place has the peak to occur in chemical shift.
It is 14.7 heavy % that fluorescence method records among the DB-2w rare earth oxide content, sodium oxide content is 0.9 heavy %, the molecular sieve content of rare earth reduces after the ammonium chloride exchange, illustrate that the REY molecular sieve that prior art provides all has the part rare earth ion to be positioned at supercage, this part rare earth ion is run off by the ammonium ion anticommuting in ammonium chloride washing process.
Comparative Examples 3
The preparation process of the REY of two roastings is handed in this Comparative Examples explanation conventional two.
Press RECl
3: the weight ratio of molecular sieve butt=0.22,90 ℃ of exchange roastings after 1 hour, 520 ℃ of control roaster bed of material temperature; Press RECl once more
3: the weight ratio of molecular sieve butt=0.12,90 ℃ of exchange roastings once more after 1 hour, obtain finished product molecular sieve contrast sample, be numbered DB-3, again in molecular sieve: ammonium chloride: the ratio of water=0.1: 1: 10 was with 60 ℃ of ammonium chloride solutions washings 10 minutes, drying obtains finished product molecular sieve contrast sample, is numbered DB-3w.
It is 20.0 heavy % that fluorescence method records among the DB-3 rare earth oxide content, and sodium oxide content is 2.11 heavy %, its
27Al MAS NMR spectrogram is seen Fig. 4, as can be seen from Figure 4, is that the 0ppm place has the peak to occur in chemical shift.
It is 18.5 heavy % that fluorescence method records among the DB-3w rare earth oxide content, rare earth oxide content reduces, the declaratives rare earth ion is positioned at supercage, and this part rare earth ion is run off by the ammonium ion anticommuting in the ammonium chloride exchange process and causes the molecular sieve content of rare earth to reduce.
Claims (10)
1, a kind of rare-earth Y molecular sieve is characterized in that the content of rare earth of this molecular sieve is counted 12～22 heavy % with rare earth oxide, and rare earth ion all is positioned at the little cage of molecular sieve, its
27In the Al MAS NMR spectrogram, be that the 0ppm place does not have the peak to occur in chemical shift.
2, according to the molecular sieve of claim 1, its rare earth oxide content is 13～20 heavy %.
3, according to the molecular sieve of claim 2, its rare earth oxide content is 14～18 heavy %.
4, according to the molecular sieve of one of claim 1～3, its sodium oxide content is 0.1～1.0 heavy %.
5, the preparation method of claim 1 rare-earth Y molecular sieve, it is characterized in that with the NaY molecular sieve pulp with or not with ammonium salt exchange, again with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, use alkaline solution regulator solution pH to 8～11 then, stirring, filtration, washing, drying, roasting is more than 0.1 hour under 200～950 ℃, 0～100% steam again, and the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, through washing, filtration, drying.
6, the preparation method of claim 1 rare-earth Y molecular sieve, it is characterized in that with the NaY molecular sieve pulp with or not with ammonium salt exchange, again with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, isolated molecule sieving cake, collect filtrate, in filtrate, add alkaline solution, regulator solution pH 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, drying is in 200～950 ℃, roasting is more than 0.1 hour under 0～100% steam, the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, through washing, filter, dry.
7,, it is characterized in that said rare earth chloride consists of single rare earth chloride or compound rare-earth according to the preparation method of claim 5 or 6.
8, according to the preparation method of claim 7, said single rare earth chloride is lanthanum chloride or cerium chloride.
9, according to the preparation method of claim 5 or 6, said alkaline solution is selected from one or more mixture of ammoniacal liquor, waterglass, sodium metaaluminate, magnesium hydroxide or NaOH.
10, according to the preparation method of claim 9, said alkaline solution is ammoniacal liquor or waterglass.
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| CN1005385B (en) * | 1986-12-06 | 1989-10-11 | 中国石油化工总公司石油化工科学研究院 | Y-type molecular sieve cracking catalyst containing rare earths oxidate |
| CN1020280C (en) * | 1989-11-30 | 1993-04-14 | 中国石油化工总公司石油化工科学研究院 | Catalytic cracking promoter with high octane number |
| CN1026225C (en) * | 1991-02-28 | 1994-10-19 | 中国石油化工总公司石油化工科学研究院 | Preparation method for rare earth Y molecular sieve |
| US5302567A (en) * | 1991-11-04 | 1994-04-12 | W. R. Grace & Co.-Conn. | Zeolite octane additive |
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