CN104528756B - A kind of Al-ITQ-13 zeolite containing rare earth and synthetic method thereof - Google Patents
A kind of Al-ITQ-13 zeolite containing rare earth and synthetic method thereof Download PDFInfo
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The present invention provides a kind of Al-ITQ-13 zeolite containing rare earth and synthetic method thereof, RE in the described Al-ITQ-13 zeolite containing rare earth2O3/SiO2(mol ratio)=0.0005��0.1, SiO2/Al2O3(mol ratio)=10��2000; Described method comprises and rare earth source, germanium oxide, silicon source and water being uniformly mixed, and adjust ph adds R (OH) after stirring2, obtain A; Distilled water adds aluminium source and fluorine source, obtains B; A and B is mixed, and adds crystal seed, stir and form gel mixture, after crystallization, obtain described zeolite. Products obtained therefrom good hydrothermal stability, catalytic cracking shows higher catalytic activity, better product slates and olefine selective; The advantages such as described method repeatability is good, content of rare earth is adjustable, aluminium easily enters framework of molecular sieve, the utilization ratio height in aluminium source, silica alumina ratio is adjustable.
Description
Technical field
The present invention provides a kind of Al-ITQ-13 zeolite containing rare earth and synthetic method thereof.
Background technology
ITQ-13 molecular sieve (USP6471941) is the novel microporous material of a kind of three-dimensional orthogonal connected pore channel structure with 9 Yuans rings and 10 Yuans rings of Mobil company invention in 2002, its 9 Yuans ring ducts are parallel to a axle, for straight hole road, openings of sizes is 0.40nm �� 0.49nm; Other two covers, 10 membered ring channels, are respectively the straight hole road (0.47nm �� 0.51nm) being parallel to b axle and are in substantially parallel relationship to the tortuous duct (0.48nm �� 0.57nm) of sinusoidal of c axle. Due to ITQ-13 and ZSM-5 molecular sieve pore passage similar, and average pore size is less, and what can produce uniqueness in catalytic cracking process selects shape effect, especially can significantly improve the selectivity of propylene. In addition, ITQ-13 molecular sieve also demonstrates good catalytic performance in the reactions such as aromizing, isomerization, toluene disproportionation, alkylation, lubricating oil dewaxing, modifying lubricating oil and preparing light olefins from methanol.
Therefore, ITQ-13 zeolite, since it is invented, has caused investigators and has paid close attention to greatly, developed multiple ITQ-13 zeolite and synthetic method thereof. Preparing pure silicon ITQ-13 zeolite method as USP6471941 discloses one, USP20030171634 discloses a kind of method preparing boron silicon ITQ-13 zeolite. CN02810867.1 discloses the two amine dihydroxide of application hexane and makes guiding agent, makes the method preparing the ITQ-13 of pure silicate and borosilicate form in silicon source with tetraethyl orthosilicate. WO096803A1 discloses with TEOS (tetraethoxy) as silicon source, with six alkyl trimethyl two oxyammonias as template, then adds HF, formed altogether gel then by gel 135 DEG C of heat 28 days. By filter, washing, dry and roasting, namely obtain the ITQ-13 molecular sieve of pure silicon. Xu Chenguan (physical chemistry journal, 2009,25 (11): 2275-2278) etc. synthesizes pure silicon ITQ-13 molecular sieve with the use of tetraethoxy as silicon source.The prior art of above-mentioned synthesis ITQ-13 is all adopt tetraethoxy (tetraethorthsilicate.TEOS) as silicon source, in building-up process, require tetraethoxy complete hydrolysis and complete for the ethanol of its hydrolysis volatilization is gone out, meanwhile, the less (H of amount of water required in synthetic system2O/SiO2Mol ratio is generally less than 10), and hydrolytic process unavoidably loses moisture, the colloid therefore formed relatively glues thick, it is not easy to stir evenly, and thus hydrolytic process is not easily held, and causes building-up process repeatability poor.
Patent recited above and document all relate to pure silicon or the synthesis of boron silicon ITQ-13 molecular sieve, and its acidity is very weak, usually used as sorbent material. It is well known that it is general from aluminium as its acidity of acid molecular sieve catalyst. But the synthesis for the ITQ-13 molecular sieve containing aluminium, mainly contain two kinds of methods at present: one is the ITQ-13 molecular sieve of isomorphous substitution method preparation containing aluminium; Another kind is that hydrothermal method directly synthesizes Al-ITQ-13 molecular sieve. In published synthetic method, directly synthesis contains the ITQ-13 molecular sieve of aluminium is very difficult, makes the crystallization rate of ITQ-13 molecular sieve slower because introducing Al in synthesized gel rubber process. CN1512965A discloses the two amine dihydroxide of application hexane and makes guiding agent, the ITQ-13 preparing borosilicate form in silicon source is made with tetraethyl orthosilicate, ITQ-13 containing aluminium can be exchanged by the aluminium of borosilicate material and prepare, namely borosilicate zeolite (B-ITQ-13) is first synthesized, then with Al (NO3)3Solution under high temperature hydro-thermal dynamic condition through the method for liquid-solid isomorphous substitution, B-ITQ-13 is carried out aluminium exchange make, concrete grammar is as follows: get calcined B-ITQ-13 molecular sieve, according to molecular sieve: aluminum nitrate: the mass ratio of water is 1:(10��40): (80��150) mix, react 24��72 hours at 120��150 DEG C, after filtration, washing, dry and roasting, obtain the ITQ-13 zeolite product containing aluminium. The people such as Jiao Yongdong (petroleum journal (refining of petroleum), 2006, (supplementary issue): 184-187) adopt the method for isomorphous substitution to synthesize the ITQ-13 molecular sieve containing aluminium. In the method for isomorphous substitution, process is more loaded down with trivial details, part broken wafers in product, and the large percentage of non-framework aluminum, thermostability is poor.
2006, (the J.Catal.2006 such as R.Castaneda, 238,79��87) a kind of method of direct synthesizing Si-Al ITQ-13 is reported, but silicon source and aluminium source are only limitted to tetraethoxy and aluminum isopropylate (AluminiumIsopropoxide, AlP), and template used is very expensive, meanwhile, the less (H of amount of water required in synthetic system2O/SiO2Mol ratio is generally less than 10), and hydrolytic process unavoidably loses moisture, the colloid therefore formed relatively glues thick, it is not easy to stir evenly, causes building-up process repeatability poor.
The synthetic method that patent discloses a kind of ITQ-13 molecular sieve of CN101530812A, for the synthesis of pure silicon ITQ-13, it is characterised in that take white carbon black as silicon source; For the synthesis of sial ITQ-13, it is characterised in that take white carbon black as silicon source, taking aluminum isopropylate or ANN aluminium nitrate nonahydrate as aluminium source.
The synthetic method that patent discloses a kind of ITQ-13 of preparation molecular sieve of CN103224242A: template is dissolved in deionized water, then promotor, alkali source, germanium dioxide, aluminium source, crystal seed is added, after its dissolving, add silicon source, fluorine source successively, stir and form uniform gel; At temperature 100-220 DEG C, carrying out crystallization under autogenous pressure, crystallization time is 0.5 day-8 days;With cold water quenching, crystallization product fully washs through deionized water and obtains molecular screen primary powder after drying.
Disclosed patent and document all relate to pure silicon ITQ-13 or contain aluminium ITQ-13 molecular sieve and synthesis thereof above. It is well known that in the catalyzed reaction that industry is actual, molecular sieve is the exacting terms such as meet Lingao temperature, hydro-thermal usually, and this can cause, and molecular sieve crystallinity declines, structural collapse and inactivation gradually. Introduce rare earth element can adjust in molecular sieve and become some process based prediction model of molecular sieve so that it is show unique characteristic. The effect of rare earth in molecular sieve is mainly manifested in: the first, and rare earth can strengthen thermostability and the hydrothermal stability of molecular sieve. Molecular sieve often faces the exacting terms such as high temperature, thermal and hydric environment, particularly thermal and hydric environment in actual application and molecular sieve crystallinity decline, the de-of framework aluminum often can be caused to remove, and finally causes molecular sieve structure to subside and inactivation. After rare earth ion enters molecular sieve crystal inside, title complex can be formed with skeleton oxygen, inhibit molecular sieve framework dealumination effect under hydrothermal conditions, enhance thermostability and the hydrothermal stability of framework of molecular sieve structure. 2nd, rare earth can strengthen the activity of molecular sieve. Rare earth ion adds on framework silicon hydroxyl and aluminium hydroxyl electronics to the migration probability in cage by polarization and inducing action in molecular sieve cage, increase the cloud density in molecular sieve cage, making hydroxyl show stronger acidity, B strength of acid increases, and correspondingly improves catalyst activity. 3rd, rare earth can improve the anti-vanadium pollutant performance of catalyzer. In catalytic cracking reaction process, the vanadiumism effect in stock oil makes the destruction of framework of molecular sieve structure, causes its activity decrease. And rare-earth oxidation thing is easy and vanadium reaction produces stable vanadic acid rare earth, the appearance vanadium ability of catalyzer can be significantly improved, play the effect of protection molecular sieve structure, slow down the fall off rate of catalyst activity.
Being introduced by rare earth ion at present in molecular sieve is mainly scattered in zeolite molecular sieve surface or duct by methods such as dipping (US4900428), vapour deposition (US437429, CN8607531, CN1034680A) and ion-exchanges (US4178269, US4152362, CN101722021A, CN103508467A) by rare earth element, and these methods are all a kind of post-modification methods. Owing to the hydrated ion diameter of rare earth is 0.79nm, these pickling processes, vapour deposition process and ion exchange method are relatively applicable to as NaY, HY, USY, SBA-25 and MCM-41 etc. have the molecular sieve of larger aperture. And the pore size formed by 9 rings of ITQ-13 zeolite molecular sieve is 0.40nm �� 0.49nm; The pore size formed by 10 rings is (0.47nm �� 0.51nm) and (0.48nm �� 0.57nm) respectively, aperture is much smaller than the hydrated ion diameter of rare earth, thus very difficult conventional ion-exchange techniques introduces rare earth ion in ITQ-13 molecular sieve, in addition the silica alumina ratio of ITQ-13 molecular sieve is very high, can be used for the cation-bit of ion-exchange little, so rare earth ion exchanged method is not effective ways concerning ITQ-13; Adopt dipping or vapour deposition process only can be scattered in by rare earth element in zeolite molecular sieve surface or duct, duct can be blocked like this, reduce molecular sieve specific surface area and pore volume, there is rare earth element uneven, the active ingredient of the distribution easily shortcoming such as loss in addition, seriously hinder the further raising of rare-earth molecular sieve catalyst hydrothermal stability and catalytic activity. In order to improve these defects, can by the initial reactant in rare earth source and synthesis of molecular sieve in zeolite molecular sieve synthesizes, synthesize under certain hydrothermal condition with certain proportioning, the rare earth containing zeolite in this way synthesized, rare earth generally enters the skeleton structure of molecular sieve, the Rare earth zeolites catalyzer that so just likely obtained dispersity is high. But the normally used alkaline medium of zeolite water thermal synthesis, rare earth ion is very easily hydrolyzed in alkaline medium and generates difficult molten oxyhydroxide, is unfavorable for that rare earth element effectively enters framework of molecular sieve. The approach introducing rare earth element in zeolite molecular sieve for exploring, it is crystal seed that CN1058382A adopts different brilliant guiding method to add rare earth X zeolite in synthesizing five-membered ring structure high-silicon zeolite system, Hydrothermal Synthesis obtains a kind of ZSM-5 zeolite containing rare earth, and this molecular sieve has good hydrothermal stability.CN1209356A also adopts different brilliant guiding method to synthesize beta zeolite containing rare earth, and this zeolite molecular sieve has high resistance to nitrogen ability and high stability. CN103204519A adopts different brilliant guiding method, taking the compound of the xln of rare earth silicon, aluminium, pure water, mineral acid or mineral alkali and directed agents as initial feed synthesizing rare-earth molecular sieve, in the method rare earth ion all or major part directly replace sodium ion, do not enter the skeleton of molecular sieve.
According to mentioned above, ITQ-13 molecular sieve is in aromizing, isomerization, toluene disproportionation, alkylation, lubricating oil dewaxing, modifying lubricating oils etc. also demonstrate good catalytic performance in reacting, demonstrate important industrial application value, and containing rare earth Al-ITQ-13 particularly skeleton will very likely demonstrate the performance more excellent than ITQ-13 containing the Al-ITQ-13 of rare earth, but do not contain any patent and the document report of the Al-ITQ-13 zeolite molecular sieve of rare earth at present, instruction according to prior art is also difficult to effectively synthesis containing the Al-ITQ-13 of rare earth, therefore develop a kind of effective synthesis, containing the method for rare earth, there is realistic meaning very much.
Summary of the invention
It is an object of the invention to provide a kind of containing rare earth Al-ITQ-13 zeolite so that it is there is good hydrothermal stability, the catalytic activity of enhancing, the excellent selectivity to low-carbon alkene.
Another object of the present invention is to provide a kind of direct synthesis can be effectively incorporated into by rare earth element in Al-ITQ-13 skeleton containing the method, particularly the method for rare earth Al-ITQ-13 zeolite; The kind in the silicon source used can be widened, make synthesis ITQ-13 molecular sieve analog no longer be limited to a few class raw material of the minorities such as TEOS; The utilization ratio to aluminium source can be improved.
In order to realize above-mentioned purpose, on the one hand, the present invention provides a kind of Al-ITQ-13 zeolite containing rare earth, wherein, and RE2O3/SiO2(mol ratio)=0.0005��0.1, SiO2/Al2O3(mol ratio)=10��2000, wherein RE represents rare earth element.
On the other hand, present invention also offers the synthetic method of the described Al-ITQ-13 zeolite containing rare earth, the method comprises:
Rare earth source, germanium oxide, silicon source and water being uniformly mixed when temperature 30��90 DEG C, adjust ph is 2.0��6.5, continues stirring after 4��24 hours, adds the two ammonium of dihydroxy-hexane, obtains mixture A; Distilled water adds aluminium source and fluorine source, obtains mixture B; Mixture B is mixed with mixture A, and adds crystal seed, continue to stir formation gel mixture temperature 30��90 DEG C; The mol ratio that wherein control formation gel mixture system always forms is: SiO2/Al2O3=10��2000, GeO2/SiO2=0.001��2.0, R (OH)2/SiO2=0.01��1.0, RE2O3/SiO2=0.0005��0.1, F/SiO2=0.01��1.0, H2O/SiO2=2��50, wherein R (OH)2For the two ammonium of dihydroxy-hexane, RE2O3For rare-earth oxidation thing;
Have in above-mentioned gel mixture is proceeded in the stainless steel cauldron of tetrafluoroethylene and carry out crystallization, temperature is 120��200 DEG C, crystallization time 1��15 day, then by product filtration, washing, drying, 300��600 DEG C of roastings 3��10 hours, obtain the Al-ITQ-13 zeolite containing rare earth.
Of the present invention containing in the synthetic method of the Al-ITQ-13 zeolite of rare earth, on the one hand, in alkaline environment, oxyhydroxide or hydrous oxide precipitation is generated because of hydrolysis in order to effectively reduce rare-earth heteroatoms, rare-earth heteroatoms is conducive to enter framework of molecular sieve, the present invention utilizes germanium to the guide effect containing two tetra-atomic ring secondary structure unit molecular sieve, by germanium oxide, silicon source and the mixing of rare earth source, the pH value adding acid-conditioning solution is 2.0��6.5, preferable ph is 3.0��6.0, wherein said acid includes but not limited to hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, one or more in acetic acid, its coreaction in acidic medium is made to prepare rare earth germanium silicate sol precursor,On the other hand, in order to make aluminium enter framework of molecular sieve, improve the utilization ratio to aluminium source, making the silica alumina ratio of molecular sieve adjustable, fluorine source and the reaction of aluminium source are generated fluorine aluminium complex by the present invention ingeniously in advance, and then by above-mentioned rare earth germanium silicate sol precursor and fluorine aluminium complex hybrid reaction, prepare gel mixture, stir hydrothermal crystallizing after evenly, thus rare earth element and aluminium element are incorporated on the skeleton of ITQ-13 micro porous molecular sieve, obtain the Al-ITQ-13 zeolite molecular sieve containing rare earth; In addition, fluorine also contributes to the two tetra-atomic ring structure and [4 in ITQ-13 skeleton structure of zeolite15262] formation of these two kinds of secondary structure units of cage and stable.
According to the specific embodiment of the present invention, in the synthetic method of the described Al-ITQ-13 zeolite containing rare earth, wherein said rare earth source comprises rare earth compound and/or the Y zeolite containing rare earth. Wherein said rare earth compound be usually selected from rare earth chloride, rare earth nitrate, rare earth sulfate, lanthanon acetate one or more, it is preferable that one or more in lanthanum nitrate, Lanthanum trichloride, cerous nitrate, Cerium II Chloride. The described Y zeolite containing rare earth comprises in the REY zeolite containing rare earth, the REHY zeolite containing rare earth or the REUSY zeolite containing rare earth one or more.
The wherein said REY zeolite containing rare earth by buying the REY product containing rare earth (such as: China's oil Catalyst Factory of Lanzhou Petrochemical Company) of industrial production, maybe can be prepared by following method: by NaY zeolite with re chloride according to zeolite (bright base): RECl3: H2O is: the weight ratio of 1:0.01��1.0:10��100 exchanges 1��2 hour at 90 DEG C, filters, and washing, 120 DEG C of dryings, then 400��600 DEG C of roastings 0.5��4.0 hour, the zeolite after roasting can repeat above-mentioned steps and carry out that second time exchanges, roasting.
The wherein said REHY zeolite containing rare earth by buying the REHY product containing rare earth (such as: China's oil Catalyst Factory of Lanzhou Petrochemical Company) of industrial production, maybe can be prepared by following method: by HY zeolite with re chloride according to zeolite (bright base): RECl3: H2O is: the weight ratio of 1:0.01��1.0:10��100 exchanges 1��2 hour at 90 DEG C, filter, washing, 120 DEG C, then 400��600 DEG C of roastings 0.5��4.0 hour, the zeolite after roasting can repeat above-mentioned steps carry out second time exchange, roasting.
The wherein said REUSY zeolite containing rare earth by buying the REUSY product (such as: China's oil Catalyst Factory of Lanzhou Petrochemical Company) of industrial production, maybe can be prepared by following method: by USY zeolite with re chloride according to zeolite (bright base): RECl3: H2O is: the weight ratio of 1:0.01��1.0:10��100 exchanges 1��2 hour at 90 DEG C. Filtering, washing, 120 DEG C of dryings, then 400��600 DEG C of roastings 0.5��4.0 hour, the zeolite after roasting can repeat above-mentioned steps and carry out that second time exchanges, roasting.
According to the specific embodiment of the present invention, in the present invention in the synthetic method of the described Al-ITQ-13 zeolite containing rare earth, described silicon source has no longer been confined to tetraethoxy, its can be selected from water glass, silicon sol, gross porosity silicon, white carbon black, methyl silicate, tetraethoxy one or more.
According to the specific embodiment of the present invention, in the present invention described containing in the synthetic method of the Al-ITQ-13 zeolite of rare earth, wherein said aluminium source be selected from pseudo-boehmite, aluminum isopropylate, sodium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum oxide one or more.
According to the specific embodiment of the present invention, in the present invention described containing in the synthetic method of the Al-ITQ-13 zeolite of rare earth, fluorine source be selected from hydrofluoric acid, Neutral ammonium fluoride, ammonium bifluoride, Potassium monofluoride one or more.
According to the specific embodiment of the present invention, in the present invention in the synthetic method of the described Al-ITQ-13 zeolite containing rare earth, wherein said crystal seed is one or both mixtures in pure silicon ITQ-13 zeolite, Al-ITQ-13 zeolite. Preferably, described crystal seed add-on accounts for SiO in silicon source2The 0.1��20% of weight.
According to specific embodiment of the invention scheme, the present invention enters the skeleton of Al-ITQ-13 zeolite molecular sieve crystal by X-ray diffraction comparison diagram and infrared spectra and comparison diagram analytical proof rare-earth heteroatoms thereof. When same test, the peak position at the XRD peak position of the described Al-ITQ-13 zeolite containing rare earth peak more corresponding to the XRD of Al-ITQ-13 offsets to low angle. In addition, there is RE-O-Si absorption peak (wherein RE represents rare earth element) in the described infared spectrum containing the Al-ITQ-13 zeolite of rare earth.
The Al-ITQ-13 zeolite containing rare earth of the present invention has good hydrothermal stability compared with Al-ITQ-13 zeolite, in a specific embodiments of the present invention, the hydrogen type molecular sieve sample of the Al-ITQ-13 zeolite containing rare earth of gained is at 800 DEG C, its crystallization reservation degree of 100% steam-treated 4 hours is 90%, and the hydrogen type molecular sieve adopting Al-ITQ-13 zeolite that the same manner prepares under identical condition degree of reservation be only 75%, absolutely proved that the present invention has good hydrothermal stability containing the Al-ITQ-13 zeolite of rare earth. In addition, the Al-ITQ-13 zeolite containing rare earth of the present invention also has the catalytic activity of enhancing, the excellent selectivity etc. to low-carbon alkene, can extensively for various catalytic process, such as catalytic pyrolysis, catalytic cracking, aromizing, isomerization, toluene disproportionation, alkylation, lubricating oil dewaxing, modifying lubricating oil etc. In a specific embodiments of the present invention, the Al-ITQ-13 zeolite containing rare earth of the present invention being applied to catalytic cracking, it shows higher catalytic activity, better product slates and olefine selective, especially propylene selectivity.
In sum, the present invention provides the synthetic method of a kind of Al-ITQ-13 zeolite containing rare earth and contains the Al-ITQ-13 zeolite of rare earth, and it has following useful technique effect:
(1) utilize germanium to the guide effect containing two tetra-atomic ring secondary structure unit molecular sieve, by germanium oxide, silicon source and rare earth source, the pH value adding acid-conditioning solution is 2.0��6.5, its coreaction in acidic medium is made to prepare rare earth germanium silicate sol precursor, then itself and fluorine aluminium complex are reacted, thus rare earth element is incorporated into the upper of ITQ-13 micro porous molecular sieve. Synthesis cost is low, and zeolite product purity height, repeatability are good, and the content of rare earth of prepared rare earth ITQ-13 zeolite molecular sieve is adjustable.
(2) previously prepared fluorine aluminium complex, makes aluminium easily enter molecular sieve, it is to increase to the utilization ratio in aluminium source, and the prepared silica alumina ratio containing the Al-ITQ-13 zeolite molecular sieve of rare earth is adjustable.
(3) the Al-ITQ-13 zeolite molecular sieve containing rare earth prepared by has good hydrothermal stability, by this product application in catalytic cracking, it shows higher catalytic activity, better product slates and better olefine selective, especially propylene selectivity.
Accompanying drawing explanation
Fig. 1 and Fig. 2 is the XRD spectra of product obtained by comparative example 1 and embodiment 1��5;
Fig. 3 is the infrared spectrum of product obtained by comparative example 1 and embodiment 1��3.
Embodiment
In order to the technology feature to the present invention, object and useful effect have understanding clearly, now in conjunction with specific embodiments and accompanying drawing the technical scheme of the present invention is carried out following detailed explanation, it should be appreciated that these examples are only not used in for illustration of the present invention and limit the scope of the invention.
Source raw materials used in embodiment and content are as follows:
Comparative example 1
When temperature 60 DEG C stirs fast by 0.068g (0.65mmol) GeO2It is dissolved in 10ml distilled water, then adds 29.32g silicon sol (nSiO2=134.5mmol, in 27.5wt%), the pH value then adding the hydrochloric acid conditioning solution of the 0.3M of 10.3ml is 3.0, continues to stir 6 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(100mmol) aqueous solution 20mL, makes mixture A;By 0.18g pseudo-boehmite (nAl2O3=1.22mmol) it is dissolved in 5ml distilled water, add 1.63gNH4F (44.1mmol), makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 0.27g is added after stirring, after temperature 60 DEG C continues to stir a kind of uniform gel mixture of formation, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, crystallization temperature 180 DEG C, crystallization is filtered after 2 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain for 4 hours. Product proves through X-ray diffractometer, infrared spectrometer characterization result: its final product is the Al-ITQ-13 zeolite molecular sieve not containing rare earth. Its X-ray diffraction spectrogram (XRD) is shown in Fig. 1 and Fig. 2, and infrared spectrogram is shown in Fig. 3. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record SiO in molecular sieve2/Al2O3(mol ratio)=106.
Embodiment 1
When temperature 60 DEG C stirs fast by 1.0g Lanthanum trichloride (LaCl3��6H2O) it is dissolved in 10ml distilled water, then adds 0.068gGeO2(0.65mmol) with 29.32g silicon sol (nSiO2=134.5mmol, in 27.5wt%), the pH value then adding the hydrochloric acid conditioning solution of the 0.3M of 10.3ml is 3.0, continues to stir 6 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(10mmol) aqueous solution 20mL, makes mixture A; By 0.18g pseudo-boehmite (nAl2O3=1.22mmol) it is dissolved in 5ml distilled water, add 1.63gNH4F (44.1mmol), makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 0.27g is added after stirring, after temperature 60 DEG C continues to stir a kind of uniform gel mixture of formation, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, crystallization temperature 180 DEG C, crystallization is filtered after 2 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain for 4 hours. Product characterizes through X-ray diffractometer (XRD) and infrared spectrometer, and its XRD spectra is shown in Fig. 1 and Fig. 2, and infrared spectra is shown in Fig. 3. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record La in molecular sieve2O3/SiO2(mol ratio)=0.040, SiO2/Al2O3(mol ratio)=107.
Analysis chart 1 and Fig. 2 can find, the spectrum peak of product is consistent with standard spectrogram, and without any assorted crystalline substance, but the 2Theta value (see table 1) that in figure, embodiment 1 compares ratio 1 moves slightly towards low angle direction, this is because the atomic radius of rare earth element is bigger than the atomic radius of aluminium, after rare earth element enters the skeleton of Al-ITQ-13 molecular sieve, cause the electric charge in molecular sieve and coordination environment and not the Silicified breccias in doped molecular sieve have very big-difference, rare earth enters framework of molecular sieve and makes tetrahedral structure produce distortion to a certain degree, unit cell volume increases, 2Theta value is caused to move slightly towards low angle direction. the infrared spectrogram of the present embodiment product is shown in Fig. 3. as can be seen from Figure 3, comparing the infrared spectrum of ratio 1 product, the infrared spectrogram of the product of embodiment 1 is at about 1072cm-1Wave spectrum place produces new charateristic avsorption band, this is attributed to the RE-O-Si key formed after rare earth atom enters framework of molecular sieve, owing to RE-O-Si key can make the asymmetry of framework of molecular sieve structure increase, there is certain defective bit, thus at this place, absorption peak occurs. XRD and infrared result prove synthesized by product be the Al-ITQ-13 zeolite molecular sieve that skeleton contains rare earth.
Table 1
| Comparative example 1 | Embodiment 1 | Comparative example 1 | Embodiment 1 | Comparative example 1 | Embodiment 1 | Comparative example 1 | Embodiment 1 |
| 2Theta/�� | 2Theta/�� | 2Theta/�� | 2Theta/�� | 2Theta/�� | 2Theta/�� | 2Theta/�� | 2Theta/�� |
| 7.06 | 6.84 | 16.08 | 15.88 | 29.41 | 29.19 | 29.41 | 29.19 |
| 8.02 | 7.85 | 16.65 | 16.38 | 31.12 | 30.77 | 31.12 | 30.77 |
| 8.74 | 8.51 | 17.1 | 16.82 | 33.27 | 33.19 | 33.27 | 33.19 |
| 10.69 | 10.50 | 18.91 | 18.62 | 35.25 | 35.05 | 35.25 | 35.05 |
| 11.24 | 11.00 | 20.5 | 20.37 | 37.45 | 37.37 | 37.45 | 37.37 |
| 14.34 | 14.12 | 21.08 | 20.76 | 38.79 | 38.66 | ||
| 15.54 | 15.17 | 21.47 | 21.24 | 29.41 | 29.19 |
Embodiment 2
Get NaY zeolite 100g (dry base) and 1 heavy % lanthanum chloride solution 2000ml that silica alumina ratio is 5.0 (x-ray diffraction method mensuration) and exchange 1 hour at 90 DEG C.Filtering, washing, 120 DEG C of dryings, then 540 DEG C of roastings 4 hours, the zeolite after roasting repeats above-mentioned steps and carries out that second time exchanges, roasting. What obtain consists of La2O319.0%, Na2O1.5%, Al2O318.5%, SiO2The REY zeolite of 61.0%.
Wherein, when temperature 60 DEG C stirs fast by the above-mentioned 0.33gREY zeolite (n containing lanthanum preparedSiO2=3.34mmol, nAl2O3=0.60mmol, nLa2O3=1.01mmol) join in 10ml distilled water, then add 0.068g (0.65mmol) GeO2With 29.32g (nSiO2=134.4mmol, in 27.5wt%) silicon sol, the pH value then adding the hydrochloric acid conditioning solution of the 0.3M of 10.3ml is 3.0, continues to stir 4 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(10mmol) aqueous solution 20mL, makes mixture A; By 0.18g (nAl2O3=1.22mmol) pseudo-boehmite is dissolved in 5ml distilled water, adds 1.63gNH4F (44.1mmol), makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 0.27g is added after stirring, after continuing to stir a kind of uniform gel mixture of formation at temperature 60 DEG C, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, temperature 180 DEG C, crystallization is filtered after 3 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain product in 4 hours, its XRD spectra is shown in Fig. 1 and Fig. 2, and infrared spectra is shown in Fig. 3. It is that skeleton contains lanthanum Al-ITQ-13 zeolite molecular sieve through XRD and infrared proof product. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record La in molecular sieve2O3/SiO2(mol ratio)=0.0013, SiO2/Al2O3(mol ratio)=103.
Embodiment 3
Get HY zeolite 100g (dry base) and 1 heavy % solution of cerium chloride by oxidation 2000ml that silica alumina ratio is 5.8 (x-ray diffraction method mensuration) and exchange 1 hour at 90 DEG C. Filtering, washing, 120 DEG C of dryings, then 540 DEG C of roastings 4 hours, the zeolite after roasting repeats above-mentioned steps and carries out that second time exchanges, roasting. What obtain consists of Ce2O316.0%, Na2O0.5%, Al2O321.5%, SiO2The REHY zeolite of 61.0%.
Wherein, when temperature 40 DEG C stirs fast by above-mentioned for the 5.6g REHY zeolite (n containing cerium preparedSiO2=56.9mmol, nAl2O3=11.8mmol, nCe2O3=2.73mmol) join in 100ml distilled water, then add 0.9g (8.6mmol) GeO2With 73.3g (nSiO2=336.0mmol, in 27.5wt%) water glass, the pH value then adding the sulfuric acid regulation solution of the 0.2M of 56.2ml is 4.0, continues to stir 8 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(50mmol) aqueous solution 100mL, makes mixture A; 0.18g sodium metaaluminate (0.79��1.76mmol) is dissolved in 10ml distilled water, adds 0.29g (7.8mmol) NH4F, makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 0.27g is added after stirring, after continuing to stir a kind of uniform gel mixture of formation at temperature 40 DEG C, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, temperature 180 DEG C, crystallization is filtered after 3 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain product in 4 hours, its XRD spectra is shown in Fig. 1 and Fig. 2, and infrared spectra is shown in Fig. 3. It is the Al-ITQ-13 zeolite molecular sieve that skeleton contains cerium through XRD and infrared proof product. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record Ce in molecular sieve2O3/SiO2(mol ratio)=0.0076, SiO2/Al2O3(mol ratio)=320.
Embodiment 4
Get USY zeolite 100g (dry base) and 1wt% lanthanum chloride solution 2000ml that silica alumina ratio is 8.0 (x-ray diffraction method mensuration) and exchange 1 hour at 90 DEG C. Filtering, washing, 120 DEG C of dryings, then 540 DEG C of roastings 4 hours, the zeolite after roasting repeats above-mentioned steps and carries out that second time exchanges, roasting. What obtain consists of La2O322.0%, Na2O0.3%, Al2O316.0%, SiO2The REUSY zeolite of 63.0%.
Wherein, when temperature 70 DEG C stirs fast by above-mentioned for the 6.6g REUSY zeolite (n containing lanthanum preparedSiO2=69.3mmol, nAl2O3=10.4mmol, nLa2O3=4.46mmol) join in 100ml distilled water, then add 0.9g (8.6mmol) GeO2With 73.3g (nSiO2=336.0mmol, in 27.5wt%) silicon sol, the pH value then adding the sulfuric acid regulation solution of the 0.2M of 56.2ml is 4.0, continues to stir 3 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(50mmol) aqueous solution 100mL, makes mixture A; 1.1g Tai-Ace S 150 (3.22mmol) is dissolved in 10ml distilled water, adds 2.88gNH4F (77.8mmol), makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 1.0g is added after stirring, after continuing to stir a kind of uniform gel mixture of formation at temperature 70 DEG C, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, temperature 170 DEG C, crystallization is filtered after 3 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain product in 4 hours, and its XRD spectra is shown in Fig. 1 and Fig. 2. Prove that product is the Al-ITQ-13 zeolite molecular sieve that skeleton contains lanthanum through XRD. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record La in molecular sieve2O3/SiO2(mol ratio)=0.013, SiO2/Al2O3(mol ratio)=64.
Embodiment 5
When temperature 60 DEG C stirs fast by 1.0g (2.31mmol) nitrification lanthanum (La (NO)3��6H2O) join in 10ml distilled water, then add 0.27g (2.58mmol) GeO2With 249.0g (nSiO2=1141.25mmol, in 27.5wt%) silicon sol, the pH value then adding the hydrochloric acid conditioning solution of the 0.3M of 5.2ml is 4.5, continues to stir 10 hours, then adds the two ammonium R (OH) of 0.5mol/L dihydroxy-hexane in mixture2(25mmol) aqueous solution 50mL, makes mixture A; 0.29g (1.97mmol) pseudo-boehmite is dissolved in 10ml distilled water, adds 1.92gNH4F (51.89mmol), makes mixture B; Mixture B is joined in mixture A, the Al-ITQ-13 zeolite seed crystal of 0.31g is added after stirring, after continuing to stir a kind of uniform gel mixture of formation at temperature 60 DEG C, then have in being proceeded in the stainless steel cauldron of tetrafluoroethylene, temperature 180 DEG C, crystallization is filtered after 3 days, is washed, 120 DEG C of dried overnight, and 540 DEG C of roastings obtain product in 4 hours, and its XRD spectra is shown in Fig. 1 and Fig. 2. Prove that product is the Al-ITQ-13 zeolite molecular sieve that skeleton contains lanthanum through XRD. Induced coupled plasma atomic emission spectrometry (ICP) is adopted to record La in molecular sieve2O3/SiO2(mol ratio)=0.004, SiO2/Al2O3(mol ratio)=592.
Embodiment 6
Obtained for embodiment 1 is warming up to 550 DEG C of roastings containing rare earth Al-ITQ-13 molecular screen primary powder program in retort furnace, after constant temperature 4h thoroughly removes template, by the NH of molecular sieve and 1.0mol/L in beaker4Cl solution mixes taking weightmeasurement ratio as 1: 10 (g/ml), then beaker is placed in 90 DEG C of water-baths and carries out ion-exchange 1h, after filtration, washing;By the NH of filter cake with previous equivalent4Cl solution repeats ion-exchange once, exists without chlorion in filtration, repetitive scrubbing to filtrate, after 110 DEG C of dryings, obtains Hydrogen containing rare earth Al-ITQ-13 molecular sieve at 550 DEG C of roasting 4h. By Hydrogen containing rare earth Al-ITQ-13 sieve sample at 800 DEG C, its crystallization reservation degree of 100% steam-treated 4 hours is 90%, the obtained Al-ITQ-13 of comparative example 1 is carried out ion friendship according to above-mentioned identical condition and step and makes Hydrogen Al-ITQ-13 molecular sieve, by Hydrogen Al-ITQ-13 sieve sample at 800 DEG C, its crystallization reservation degree of 100% steam-treated 4 hours is 75% (see table 2).
Embodiment 7
The Hydrogen of embodiment 6 gained is mixed with USY molecular sieve as additive containing rare earth Al-ITQ-13 molecular sieve, then after the molecular sieve mixed being mixed with a certain amount of water, press the formula of catalyzer again: molecular sieve (dry base) 35wt%, matrix Suzhou kaolin (dry base) 50wt%, Alumina gel (in aluminum oxide) 15wt%, add the kaolin of metering, Alumina gel tackiness agent, stir after evenly with high speed agitator, put into 120 DEG C of baking ovens dry 4 hours, then 540 DEG C of roastings 4 hours are moved in retort furnace, pulverizing is got 40-60 order particle and is processed 17 hours at 800 DEG C of 100% steam aging and obtain catalyst A. 9.00g catalyst A sample is placed in ACE fixed fluidized-bed reactor (production of Kayser company of the U.S.), heavy oil (its character is in table 3) is carried out catalytic cracking reaction. at agent-oil ratio 6, temperature of reaction 500 DEG C, feeding rate 1.2g/min, N2Purge flow rate 30mL/min, under stripping time 10min, reaction evaluating the results are shown in Table 4.
Being mixed with USY molecular sieve as additive by embodiment 6 gained Hydrogen Al-ITQ-13 molecular sieve and prepare catalyst B according to above-mentioned identical proportioning, and carry out heavy-oil catalytic performance evaluation according to above-mentioned identical reaction conditions, reaction evaluating result is also in table 4.
Table 2
Table 3
Table 4
As can be seen from Table 4, compared with catalyst B, the transformation efficiency of catalyst A improves 2.67 percentage points, when not affecting yield of gasoline, liquefied gas yield improves 2.57 percentage points, heavy oil yield reduces 1.66 percentage points, and coke selectivity is suitable, and propylene selectivity increases by 2.92 percentage points. This shows that catalyst A has the selectivity of higher catalytic activity, better product slates and propylene.
Claims (10)
1. containing a synthetic method for the Al-ITQ-13 zeolite of rare earth, the method comprises:
Rare earth source, germanium oxide, silicon source and water being uniformly mixed when temperature 30��90 DEG C, adjust ph is 2.0��6.5, continues stirring after 4��24 hours, adds the two ammonium of dihydroxy-hexane, obtains mixture A; Distilled water adds aluminium source and fluorine source, obtains mixture B; Mixture B is mixed with mixture A, and adds crystal seed, continue to stir formation gel mixture temperature 30��90 DEG C; The mol ratio that wherein control formation gel mixture system always forms is: SiO2/Al2O3=10��2000, GeO2/SiO2=0.001��2.0, R (OH)2/SiO2=0.01��1.0, RE2O3/SiO2=0.0005��0.1, F/SiO2=0.01��1.0, H2O/SiO2=2��50, wherein R (OH)2For the two ammonium of dihydroxy-hexane, RE2O3For rare-earth oxidation thing;
Have in above-mentioned gel mixture is proceeded in the stainless steel cauldron of tetrafluoroethylene and carry out crystallization, temperature is 120��200 DEG C, crystallization time 1��15 day, then by product filtration, washing, drying, 300��600 DEG C of roastings 3��10 hours, obtain the Al-ITQ-13 zeolite containing rare earth.
2. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein, is uniformly mixed rare earth source, germanium oxide, silicon source and water, and the pH value described in adjustment is 3.0��6.0.
3. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein said rare earth source comprises rare earth compound and/or the Y zeolite containing rare earth.
4. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 3, wherein said rare earth compound is selected from rare earth chloride, rare earth nitrate, rare earth sulfate, in lanthanon acetate one or more; The described Y zeolite containing rare earth be selected from the REY zeolite containing rare earth, the REHY zeolite containing rare earth or the REUSY zeolite containing rare earth one or more.
5. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 4, wherein, described rare earth compound be selected from lanthanum nitrate, Lanthanum trichloride, cerous nitrate, Cerium II Chloride one or more.
6. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein said silicon source be selected from water glass, silicon sol, gross porosity silicon, white carbon black, methyl silicate, tetraethoxy one or more.
7. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein said aluminium source be selected from pseudo-boehmite, aluminum isopropylate, sodium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum oxide one or more.
8. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein said fluorine source be selected from hydrofluoric acid, Neutral ammonium fluoride, ammonium bifluoride, Potassium monofluoride one or more.
9. the synthetic method of the Al-ITQ-13 zeolite containing rare earth according to claim 1, wherein said crystal seed is one or both mixtures in pure silicon ITQ-13 zeolite, Al-ITQ-13 zeolite.
10. the synthetic method of Al-ITQ-13 zeolite containing rare earth according to claim 1 or 9, wherein, the add-on of described crystal seed accounts for SiO in silicon source2The 0.1��20% of weight.
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