CN103787350B - A kind of divalent metal atom modified molecular screen and preparation method thereof - Google Patents
A kind of divalent metal atom modified molecular screen and preparation method thereof Download PDFInfo
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- CN103787350B CN103787350B CN201210434217.4A CN201210434217A CN103787350B CN 103787350 B CN103787350 B CN 103787350B CN 201210434217 A CN201210434217 A CN 201210434217A CN 103787350 B CN103787350 B CN 103787350B
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Abstract
The present invention discloses a kind of divalent metal atom modified molecular screen and preparation method thereof, the preparation of employing two-step method, Hydrogen or sodium type molecular sieve and divalent metal salt are carried out to sufficient ion-exchange by solid ionic exchange process, molecular sieve after exchange is processed with steam, isolated bridge hydroxyl group mutually is only contained on gained divalent metal atom modified molecular screen surface, between B acid site, will can not produce interaction, surface acid intensity is single. The present invention is for catalyst preparation and application field.<!--1-->
Description
Technical field
The present invention relates to a kind of molecular sieve and preparation method thereof, is more specifically a kind of divalent metal atomModified molecular screen and preparation method thereof, belongs to catalyst preparation and application field.
Background technology
Molecular sieve is a kind of of great value catalysis material, at especially soda acid of various petrochemical industry catalysisIn catalysis, there is the important function can not be substituted. Molecular sieve is as a kind of catalysis material, and it is greatlyActivity in partially catalyzed course of reaction comes from dissimilar acid site, its surface, in these acidThe heart can roughly be divided into the L acid site of carrying protogenic B acid site and accept duplet, in addition, different because of surface texture and surrounding environment, the acid strength in various acid sites also there are differences.
For acid Si-Al molecular sieve, its surperficial sial bridge hydroxyl group the most easily provides proton, isMain source, B acid site. Many petrochemical industry catalytic reactions, as reactions such as hydrocarbon catalytic pyrolysis,Its catalytic active center is considered to the B acid site of certain strength. It is good for catalyst is hadReactivity and selective, will carry out modification to molecular sieve conventionally, modifies with effects on surface, make its surface acid center possess suitable intensity and CONCENTRATION DISTRIBUTION. Metallic atom modification is a kind ofImportant surface modification method of modifying, the method can be described as conventionally: pass through ion exchange process, metallic atom replaces the hydrogen atom on bridge hydroxyl group, reduces or eliminates surperficial B acid site to realizeEffect. But this modification comes with some shortcomings conventionally: nearest studies confirm that, molecular sieveThe bridge hydroxyl group on surface, i.e. B acid site, is generally occurring, and the proximity of bridge hydroxyl group makes thatThis produces interaction, and affects thus the intensity in B acid site, meanwhile, and this paired appearanceBridge hydroxyl group also makes exchanged metallic atom be present in molecular sieve with bivalent ions state.Molecular sieve after metal ion exchanged modification, surface B acid site will by non-selectivity disappearRemove or reduce, intensity also can change because of exchange modification. In the time that exchange degree is lower, moleculeTo there is paired bridge hydroxyl group and bivalent metal ion in sieve surface simultaneously; When hydrogen atom is by completeAfter full exchange, the B acid site on surface will disappear completely, and catalyst is by loss of catalytic activity. TheseMicrostructure is all unfavorable for that catalyst has good catalytic effect.
Summary of the invention
The invention discloses a kind of divalent metal atom modified molecular screen and preparation method thereof, aim to provideA kind of divalent metal atom modified molecular screen with unique surface structure and preparation method thereof,On atomic level, only there is isolated ol group in molecular sieve surface, and what close on mutually with it is and twoThe hydroxyl that valency metallic atom is connected, and without the bridge hydroxyl group occurring in pairs, surperficial B acid site distributesEvenly, intensity is single.
The present invention adopts following technical scheme to realize:
Product technology scheme of the present invention is: a kind of divalent metal atom modified molecular screen, it is special to haveSurface hydroxyl distributed architecture, it is characterized by, on atomic level, as the molecule in B acid siteSieve surperficial bridge hydroxyl group adjacent to one another with the hydroxyl being connected on divalent metal atom, in B acidBetween the bridge hydroxyl group of the heart, can not produce interactional space and close on relation, in other words, pointOnly there is isolated ol group in son sieve surface, and without the bridge hydroxyl group occurring in pairs.
The preferred BETA of the type of indication molecular sieve, L, MAZ, MFI, FER, MOR, Y type in the present inventionOne or more in molecular sieve, metallic atom preferably from divalent alkaline-earth metal Be, Mg, Ca,One or more in Sr, Ba.
Preparation method's technical scheme of the present invention is: Hydrogen or sodium type molecular sieve are sieved as parent molecule, to prepare by two-step method, the first step, by Hydrogen or sodium type molecular sieve and divalent metal salt useSolid ionic exchange process is carried out sufficient ion-exchange, second step, and after exchanging, molecular sieve is 10Between 0 DEG C to 200 DEG C, process with steam. Below this technical scheme is carried out furtherlyBright.
The first step, by Hydrogen or sodium type parent molecule sieve and divalent metal salt solid ionic exchange processCarry out sufficient ion-exchange. Solid ionic is exchanged for known technology, and its process is: by HydrogenOr sodium type parent molecule sieve evenly mixes with exchanged metallic compound, in atmosphere, vacuumOr under inert gas shielding, carry out solid-state reaction, some solid-state reactions at high temperature have betterExchange effect, as 300～400 DEG C.
The preferred vacuum environment of solid ionic exchange process relating in the present invention, parent molecule sieves preferred hydrogenOne or more in BETA, the L of type, MAZ, MFI, FER, MOR, Y molecular sieve, are handed overIn the preferred divalent alkaline-earth metal chloride of metal salt compound or divalent alkaline-earth metal nitrate changingOne or more, this solid-state reaction process will obtain the bivalent metal ion exchange of high exchange degreeMolecular sieve, proton or Na on parent molecule sieve skeleton frame+By completely or connectReplaced by divalent metal atom closely completely.
Course of reaction can be expressed as:
In chemical reaction equilibrium equation, M is divalent metal, as: Mg2+、Ca2+Deng; A is oneValency anion, as: NO3 -、Cl-Deng; Z is monovalence framework of molecular sieve structure; A is molecule moleNumber.
Second step enters the molecular sieve after solid ionic exchange between 100 DEG C to 200 DEG C with steamRow is processed. Its processing procedure is: between 100 DEG C to 200 DEG C, by the divalence of first step gainedMetal exchange molecular sieve contacts with the steam under certain pressure, and this pressure can be 100Pa～1kPa, then modified molecular screen sample is carried out to application of vacuum.
Course of reaction can be expressed as:
Because the present invention adopts above-mentioned steps, by first step solid ionic exchange reaction, a divalenceMetallic atom replaces two protons and exchanged to molecular sieve adjacent to one another, the water of second stepIt is that bridge hydroxyl group recovers again that steam treated makes the B acid site of molecular sieve, produces one and two simultaneouslyValency metallic atom is connected hydroxyl directly, and therefore, molecular sieve surface will can not have living space upper mutualThe bridge hydroxyl group appearance closing on, B acid site can not occur in pairs, thereby the divalent metal of gained changesIsolated bridge hydroxyl group is only contained on property molecular sieve surface, between B acid site, will can not produce mutual workWith.
Beneficial effect of the present invention can be by the characterization result of in-situ ft-ir and solid state nmr in additionIllustrate, as accompanying drawing 1, shown in accompanying drawing 2 and accompanying drawing 3.
Prepare the atom modified ZSM-5 molecular sieve of Ca with the step of method described in embodiment 1. Utilization original position is redThe means of external spectrum obtain sample to parent molecule sieve, solid ionic clearing house respectively, and finalProduct characterizes, and infrared spectrum gathers under the vacuum condition of 500 DEG C, the results are shown in accompanying drawing 1.In Fig. 1, curve A is the infrared spectrum of parent molecule sieve, and curve B is that parent molecule sieves through calcium ionInfrared spectrum after solid ionic exchange, curve C is through the exchange of calcium ion solid ionic and steams through waterThe infrared spectrum of sample after gas disposal. Result shows, on parent molecule sieve infrared spectrum, characterizes bridgeFormula hydroxyl is that the characteristic infrared vibration peak in B acid site (is positioned at 3610cm-1Near) solid in processAfter state ion-exchange, disappear, show the H on parent molecule sieve+By complete exchange; Sample after exchangeAfter steam treatment, bridge hydroxyl group vibration peak (is positioned at 3610cm-1Near) reappear, show to have formed after modification the B acid site of new homogeneous.
Prepare the atom modified ZSM-5 molecular sieve of Ca with the step of method described in embodiment 1. Utilization pyridine is inhaledThe means of attached infrared spectrum obtain sample to parent molecule sieve, solid ionic clearing house respectively, andFinal products characterize: sample is carried out under the vacuum condition of 500 DEG C to pretreatment, in room temperatureLower Adsorption of Pyridine, and in 200 DEG C of applications of vacuum, to remove physical absorption pyridine, infrared spectrum existsUnder the vacuum condition of 200 DEG C, gather, the results are shown in accompanying drawing 1. In Fig. 2, curve D is that parent molecule sieve is inhaledThe infrared spectrum of attached pyridine, curve E is that parent molecule sieve is inhaled after the exchange of calcium ion solid ionicThe infrared spectrum of attached pyridine, curve F is through the exchange of calcium ion solid ionic and after steam treatmentThe infrared spectrum of sample Adsorption of Pyridine. Result shows, on parent molecule sieve infrared spectrum, characterizes B acidThe absorption band at center (is positioned at 1540cm-1Near) after solid ionic exchange, disappearing, tableH on bright parent molecule sieve+By complete exchange; Exchange rear sample after steam treatment, B acidThe absorption band at center (is positioned at 1540cm-1Near) reappear, show to have formed newly after modificationThe B acid site of homogeneous.
Prepare the atom modified ZSM-5 molecular sieve of Mg with the step of method described in embodiment 4, use solid coreThe means of magnetic characterize products obtained therefrom, and sample is processed and also encapsulated for 3 hours through 500 DEG C, carries outSolid state nmr1H composes test, the results are shown in accompanying drawing 3. In figure, be positioned at the chemical shift peak table of 3.9ppmLevy molecular sieve surface bridge hydroxyl group, the chemical shift peak that is positioned at 1.6ppm characterizes molecular sieve surfaceSilicon hydroxyl, the chemical shift peak that is positioned at 0.2ppm characterizes molecular sieve surface and is connected with magnesium atomHydroxyl. Above result shows that molecular sieve surface exists bridge hydroxyl group simultaneously and is connected with magnesium atomHydroxyl, two kinds of hydroxyls are spatially adjacent to one another.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the molecular sieve modified front and back of HZSM-5, and infrared spectrum is at the vacuum bar of 500 DEG CUnder part, gather, in Fig. 1, curve A is the infrared spectrum of parent molecule sieve, and curve B is parent moleculeThe infrared spectrum of sieve after the exchange of calcium ion solid ionic, curve C is to hand over through calcium ion solid ionicChange and the infrared spectrum of sample after steam treatment;
Fig. 2 is the infrared spectrum of the molecular sieve modified front and back of HZSM-5 Adsorption of Pyridine, and infrared spectrum is at 200 DEG CVacuum condition under gather, in Fig. 2, curve D is the infrared spectrum of parent molecule sieve Adsorption of Pyridine,Curve E is the infrared spectrum of parent molecule sieve Adsorption of Pyridine after the exchange of calcium ion solid ionic,Curve F be through calcium ion solid ionic exchange and after steam treatment sample Adsorption of Pyridine infraredSpectrogram;
Fig. 3 is the solid state nmr of preparing gained magnesium ion modified zsm-5 zeolite according to the inventive method1HSpectrum, sample is processed and is also encapsulated for 3 hours through 500 DEG C, carries out solid state nmr1H composes test.
Detailed description of the invention
Below, by reference to the accompanying drawings and specific embodiment, the X kind embodiment of invention is further described。
Embodiment 1
By HZSM-5 molecular sieve and CaCl2Be placed in ball mill at room temperature according to Ca/Al than the ratio of 1:1Fully mixed grinding 1 day, the sample after mixed grinding is processed 4 hours under 400 DEG C, vacuum condition; Sample is cooled to 150 DEG C, imports the steam of 1kPa, balance 3 minutes, then application of vacuum2 hours. Obtain divalent metal atom modified molecular screen.
Embodiment 2
By HY molecular sieve and BaCl2Being placed in ball mill according to Ba/Al than the ratio of 0.5:1 at room temperature fillsPoint mixed grinding 1 day, the sample after mixed grinding is processed 4 hours under 400 DEG C, vacuum condition;Sample is cooled to 100 DEG C, imports the steam of 100Pa, balance 3 minutes, then application of vacuum 2Hour. Obtain divalent metal atom modified molecular screen.
Embodiment 3
By HBETA molecular sieve and BeCl2Being placed in oscillating mill according to Be/Al than the ratio of 0.5:1 existsAbundant mixed grinding 1 day under room temperature, the sample after mixed grinding was 400 DEG C of roastings 4 hours; By sampleProduct, 200 DEG C of applications of vacuum 4 hours, import the steam of 100Pa, balance 3 minutes, then vacuumProcess 2 hours. Obtain divalent metal atom modified molecular screen.
Embodiment 4
By HZSM-5 molecular sieve and anhydrous MgCl2Being placed in ball mill according to Mg/Al than the ratio of 0.5:1 existsAbundant mixed grinding 1 day under room temperature, the sample after mixed grinding is located under 300 DEG C, vacuum conditionManage 4 hours; Sample is cooled to 150 DEG C, imports the steam of 1kPa, balance 2 minutes, 150 DEG C of applications of vacuum 2 hours. Obtain divalent metal atom modified molecular screen.
Embodiment 5
By HMOR molecular sieve and SrCl2Be placed in ball mill according to Sr/Al than the ratio of 0.5:1In abundant mixed grinding 1 day at room temperature, the sample after mixed grinding is at 400 DEG C, vacuum conditionLower processing 4 hours; Sample is cooled to 100 DEG C, imports the steam of 100Pa, balance 3 minutes, then application of vacuum 2 hours. Obtain divalent metal atom modified molecular screen.
The foregoing is only better possible embodiments of the present invention, not thereby limit to patent of the present inventionScope, feature of the present invention only relate to B acid site, molecular sieve surface structure, function andModification and modification, but the knot in the other types acid site simultaneously causing according to the present invention's methodStructure produces and changes and will be contained in protection scope of the present invention.
Claims (8)
1. a divalent metal atom modified molecular screen, is characterized in that, on atomic level,As the bridge hydroxyl group and the hydroxyl being connected on divalent metal atom on the molecular sieve surface in B acid siteBase is adjacent to one another, interactional as not producing between the bridge hydroxyl group in B acid siteRelation is closed in space;
Described metallic atom be a kind of in divalent alkaline-earth metal Be, Mg, Ca, Sr, Ba orMultiple.
2. divalent metal atom modified molecular screen as claimed in claim 1, is characterized in that,The type of described molecular sieve is that BETA, L, MAZ, MFI, FER, MOR, Y type divideOne or more in son sieve.
3. a divalent metal atom modified molecular screen preparation method, comprises the following steps:
The first step, by Hydrogen or sodium type molecular sieve and divalent metal salt solid ionic exchange processCarry out sufficient ion-exchange,
Second step, by molecular sieve after exchange between 100 DEG C to 200 DEG C with steam placeReason;
Described metallic atom be a kind of in divalent alkaline-earth metal Be, Mg, Ca, Sr, Ba orMultiple.
4. divalent metal atom modified molecular screen preparation method as claimed in claim 3, itsFeature in, in the first step, described ion-exchange reaction temperature is 300～400 DEG C.
5. divalent metal atom modified molecular screen preparation method as claimed in claim 3, itsBe characterised in that, described inGuState ion-exchange is in vacuum environment.
6. divalent metal atom modified molecular screen preparation method as claimed in claim 3, itsBe characterised in that, in second step, water vapour pressure can be 100Pa～1kPa.
7. divalent metal atom modified molecular screen preparation method as claimed in claim 3, itsBe characterised in that, after second step, then carry out application of vacuum.
8. divalent metal atom modified molecular screen preparation method as claimed in claim 3, itsBe characterised in that, in the first step, BETA, L that described hydrogen type molecular sieve is Hydrogen, MAZ,One or more in MFI, FER, MOR, Y molecular sieve, described slaine is diatomic baseOne or more in earth metal chloride or divalent alkaline-earth metal nitrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100324A (en) * | 1985-04-01 | 1986-08-06 | 中国石油化工总公司抚顺石油化工研究院 | Distillate Hydrodewaxing catalyst and preparation method thereof |
| US5190903A (en) * | 1991-03-31 | 1993-03-02 | Uop | Low acidity Y zeolite |
| CN101723404A (en) * | 2008-10-24 | 2010-06-09 | 北京化工大学 | Method for preparing high-transition metal content molecular sieves |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100324A (en) * | 1985-04-01 | 1986-08-06 | 中国石油化工总公司抚顺石油化工研究院 | Distillate Hydrodewaxing catalyst and preparation method thereof |
| US5190903A (en) * | 1991-03-31 | 1993-03-02 | Uop | Low acidity Y zeolite |
| CN101723404A (en) * | 2008-10-24 | 2010-06-09 | 北京化工大学 | Method for preparing high-transition metal content molecular sieves |
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