CN1151885C - Zeolite molecular sieve containing rare-earth heteroatoms with MOR structure and its synthesis process - Google Patents
Zeolite molecular sieve containing rare-earth heteroatoms with MOR structure and its synthesis process Download PDFInfo
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- CN1151885C CN1151885C CNB001358375A CN00135837A CN1151885C CN 1151885 C CN1151885 C CN 1151885C CN B001358375 A CNB001358375 A CN B001358375A CN 00135837 A CN00135837 A CN 00135837A CN 1151885 C CN1151885 C CN 1151885C
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Abstract
The present invention relates to a zeolite molecular sieve whose skeleton is in the MOR structure containing rare-earth hetero atoms. The zeolite molecular sieve has a characteristic X-ray diffraction pattern disclosed in specification 1, the zeolite molecular sieve has anhydrous chemical components by oxide molar ratio: xRe2O3. yNa2O. Al2O3. zSiO2, wherein x=0.01 to 5.0, y=0.005 to 16.0, and z=5 to 300. The present invention also relates to a hydrothermal synthesis method for zeolite without organic amine template agents. According to the method of the present invention, the zeolite is prepared from industrial water glass as Si and Al source compounds, rare-earth compounds, inorganic alkali and fluoride as raw material through hydrothermal crystallization synthesis at 80 to 250 DEG C. The present invention is suitable for various application fields of mordenites and various oxidation reduction processes to which hetero atom zeolites are applied.
Description
The present invention relates to a kind of MOR structural zeolite molecular sieve and synthetic method thereof that contains rare-earth heteroatoms.In particular, the invention relates to the hydrothermal synthesis method that a kind of skeleton contains the zeolite molecular sieve with MOR structure of rare-earth heteroatoms and do not use organic amine.
Zeolite molecular sieve with MOR structure (by zeolite molecular sieve structure type symbol of International Union for Pure and AppliedChemistry recommendation), as modenite, has good heat-resisting, acidproof and anti-steam performance, petrochemical industry and other industrial process have been widely used in, as be used for gas or liquid mixture as adsorbent, comprise the separation process of acidic components, basic component; Be used for catalytic cracking as catalyst, hydrocarbon isomerization, alkylation, disproportionation and transalkylation are reformed, dewaxing pour point depression, processes such as methyl alcohol amination.
Press SiO
2/ Al
2O
3Mol ratio is divided, and modenite can be divided into low silicon and high silicon two classes.
1948, Barrer sodium carbonate was mineralizer, mixed silicic acid gel and sodium aluminate aqueous solution hydrothermal crystallizing, had synthesized modenite first.According to prior art, the conventional method of not using the template agent, the SiO of synthetic gained modenite
2/ Al
2O
3Mol ratio mostly be 5～10 (US 3,996,337; US 4,503, and 023; US 4,511, and 547; US 4,581, and 216), suitable with natural mordenite zeolite.
Concerning some reactions, high SiO
2/ Al
2O
3The mol ratio modenite has better catalytic performance, and for meeting the demands, the modenite of taking different dealumination process processing silica alumina ratios about 10 usually is with the preparation high silicon mordenite, but the operating process more complicated.
Directly synthetic high SiO
2/ Al
2O
3The mol ratio modenite, (spy opens clear 58-88,118 generally to need to add the agent of organic amine template; EP 80,615; US 4,585, and 640; US 5,219, and 546; CN 1147479).These organic base source difficulties, price is higher, and is toxic, contaminated environment, industrial production is also often had any problem.Non-amine method is synthetic obtains certain progress (CN 1050011A), and we are more with SiO
2/ Al
2O
3Mol ratio is brought up to (CN 1257831A) more than 60.
Contain heteroatomic zeolite molecular sieve, especially contain the excellent oxidation reducing property of heteroatomic 12 yuan of rings such as rare earth, titanium, vanadium, 10 yuan of ring zeolite molecular sieves, attract people extensively to explore and study their synthetic method.With regard to contain the rare earth zeolite molecular sieve synthetic with regard to, generally introduce rare earth element by the method for xenocryst guiding.CN 1058382A has announced a kind of method of not having the synthetic high-Si zeolite containing rare-earth five-membered ring structure of amine, with waterglass, aluminum phosphate and inorganic acid is that raw material and REY or REHY zeolite are crystal seed, hydro-thermal is synthetic have a ZSM-5 zeolite family x-ray diffraction spectra feature contain the rare earth zeolite.CN 1147420A has further improved synthetic method, obtains having the molecular sieve of the phosphorous and rare earth of MFI structure, and this molecular sieve has good hydrothermal stability.CN 1209356A has announced the xenocryst guiding synthetic method of beta zeolite containing rare earth.But the still exoskeletal so far synthetic report of MOR structural zeolite that contains rare earth element.
The purpose of this invention is to provide a kind of MOR structural zeolite molecular sieve that contains rare-earth heteroatoms, to be used for various catalytic processes.
Another object of the present invention is on the basis of our non-amine method synthesizing high-silicon aluminum ratio MOR structural zeolite sieve technology, a kind of no amine synthetic method of above-mentioned zeolite is provided, and can be adjusted to high silica alumina ratio.
Other purpose of the present invention can be learnt from the specification that comprises embodiment.
The present invention is to provide a kind of zeolite molecular sieve that contains rare earth and have the MOR structure, it has feature X-ray diffracting spectrum (XRD) as shown in table 1, and its anhydrous chemical composition (in oxide mol ratio) expression formula is: xRE
2O
3YNa
2OAl
2O
3ZSiO
2Wherein, x=0.01～5.0, y=0.005～16.0, z=5～300.This zeolite is to be raw material with waterglass cheap and easy to get, aluminium salt or aluminate, inorganic base, fluoride, rare earth compound etc., need not to adopt organic amine to do the template agent, need not crystal seed, and crystallization makes at a certain temperature.RE represents rare earth element.
According to the molecular sieve that contains rare earth and have the MOR structure provided by the invention, it has following feature:
1. has MOR structural zeolite molecular sieve feature X-ray diffracting spectrum (XRD) as shown in table 1.
Table 1
d(×10
-1nm) I/I
0
13.59±0.10 W-VW
12.02±0.10 VW
9.04±0.05 S-M
7.05±0.05 W-VW
6.59±0.05 W
6.39±0.05 W
6.00±0.05 VW
5.79±0.05 W-VW
4.53±0.05 W
4.25±0.05 W
4.00±0.05 M-W
3.83±0.05 M-VW
3.76±0.05 W
3.47±0.05 M-W
3.42±0.05 W
3.39±0.05 VS-S
3.22±0.05 M-W
3.05±0.03 W
2.89±0.03 VW
The represented relative intensity of each symbol is worth as follows in the table: VS:80～100%; S:60～80%; M:40～60%; W:20～40%; VW＜20%.
2. has lattice constant as shown in table 2.
Table 2 RE-MOR zeolite molecular sieve lattice constant
RE-MOR MOR
a/nm 1.358 1.811
b/nm 2.174 2.053
c/nm 0.797 0.753
v/nm
3 2.352 2.800
3. its anhydrous chemical composition (in oxide mol ratio) expression formula is:
xRE
2O
3·yNa
2O·Al
2O
3·zSiO
2
Wherein: x=0.01～5.0;
y＝0.005～16.0；
z＝5～300。
4. the rare earth during it is formed can be a single rare earth, also can be mishmetal.
5. has the outer ion-exchange RE of general skeleton
3+Not available redox active.
According to method provided by the invention, a kind of MOR structural zeolite molecular sieve that contains rare-earth heteroatoms prepares through the following steps: with waterglass, aluminium source, inorganic base, fluoride, rare earth compound etc. is raw material anabolic reaction system, do not add organic amine and crystal seed, mix the back and under 80～250 ℃, carried out hydrothermal crystallizing 8 hours～10 days, will promptly obtain the described zeolite product of claim 1 after the washing of gained crystallization product, the drying.
Reaction system has following mol ratio and forms: SiO
2/ Al
2O
3=5～500, Na
2O/SiO
2=0.30～0.60, H
2O/SiO
2=12～60, F
-/ SiO
2=0～0.50, Re
2O
3/ SiO
2=0.002～0.25.
In the fluoride that synthetic used fluoride is an IA family element in the periodic table of elements, ammonium fluoride, the ammonium acid fluoride one or more.
Synthetic used aluminium source is one or more in alchlor, aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum phosphate, aluminium hydroxide, the boehmite.
Synthetic used inorganic base is one or more in NaOH, potassium hydroxide, the ammoniacal liquor.NaOH can be replaced by the hydroxides of other alkali metal that does not influence reaction or alkaline-earth metal.
The nitrate that synthetic used rare earth compound is rare earth chloride or rare earth, sulfate, acetate etc.
Used rare earth compound can be the compound that contains single rare earth, also contains the compound that mixes rare earth.
In the synthetic method of this zeolite provided by the invention,, need not crystal seed, and use industry water glass to do the silicon source, thereby production cost is low owing to do the template agent without organic amine.Simultaneously synthetic method of the present invention also can be regulated as required and be contained rare-earth heteroatoms MOR structural zeolite molecule and be sieved to high silica alumina ratio, and content of rare earth is adjustable.
Can regulate the crystallization process parameter by changing the mol ratio of reactant mixture, synthetic have Different Silicon al mole ratio, different content of rare earth, different grain sizes contain rare-earth heteroatoms MOR structural zeolite molecular sieve series of products.
Rare-earth heteroatoms MOR structural zeolite molecular sieve provided by the invention can be used as the catalyzed conversion of adsorbent and multiple organic compound, as process catalyst such as the transalkylation of catalytic cracking, aromatic hydrocarbons, alkylation, isomerization, disproportionation, particularly organic mitigation oxidation reduction catalyst.
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
ICP (plasma coupling light spectrometry) method is adopted in the elementary analysis of embodiment mesolite.
Embodiment 1
Get 69.0g waterglass, add the solution that 2.468g KOH and 1.289g NaF are dissolved in 16.9g water; Stir and successively to add 1.006g aluminum sulfate down and be dissolved in the solution of 6g water and the solution that the 1.321g lanthanum nitrate is dissolved in 5.6g water, continue to stir 1 hour, 140 ℃ of crystallization 9 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and lattice constant sees Table 2, and its silica alumina ratio is 22, La
2O
3/ Al
2O
3=1.45.
Embodiment 2
After 5.00g phenol is dissolved in the 16.0g deionized water, add the La-MOR zeolite molecular sieve that 0.25g embodiment 1 synthesizes, press hydrogen peroxide/phenol mol ratio=0.8 and drip 26.40% aqueous hydrogen peroxide solution, in 60 ℃ of reactions 4 hours, getting phenol conversion is 35%, contain catechol 65.0% in the product, hydroquinones 33.5%, 1,4-benzoquinone 1.5%.
Embodiment 3
Get 69.0g waterglass, add the solution that 2.468g KOH and 2.573g NaF are dissolved in 19.9g water; Stir and successively to add 1.012g aluminum sulfate down and be dissolved in the solution of 6g water and the solution that the 1.321g lanthanum nitrate is dissolved in 6g water, continue to stir 1 hour, 140 ℃ of crystallization 9 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 21, La
2O
3/ Al
2O
3=1.14.
Embodiment 4
Water intaking glass 69.3g adds the solution that 2.460g KOH and 1.305g NaF are dissolved in 18.4g water; Stir and successively to add 1.003g aluminum sulfate down and be dissolved in the solution of 6g water and the solution that the 1.312g lanthanum nitrate is dissolved in 6g water, continue to stir 3 hours, 140 ℃ of crystallization 6 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 17.5, La
2O
3/ Al
2O
3=1.02.
Embodiment 5
Get 69.0g waterglass, add the solution that 3.071g KOH and 1.738g NaF are dissolved in 16g water; Stir and successively to add 2.020g aluminum sulfate down and be dissolved in the solution of 6g water and the solution that the 2.621g lanthanum nitrate is dissolved in 7g water, continue to stir 1 hour, 140 ℃ of crystallization 7 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 32.5, La
2O
3/ Al
2O
3=1.89.
Embodiment 6
Get 69.0g waterglass, add the solution that 3.070g KOH is dissolved in 10g water; Stir and successively to add 2.020g aluminum sulfate down and be dissolved in the solution of 8g water and the solution that the 2.621g lanthanum nitrate is dissolved in 7g water, continue to stir 1 hour, 140 ℃ of crystallization 7 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 19.3, La
2O
3/ Al
2O
3=1.25.
Embodiment 7
69.4g add 33.8g water and 2.572g NaF in the waterglass, stir and successively to add 2.020g aluminum sulfate down and be dissolved in the solution of 12g water and the solution that the 7.875g lanthanum nitrate is dissolved in 14g water, continue to stir 1 hour 170 ℃ of crystallization 2 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 61.7, La
2O
3/ Al
2O
3=2.93.
Embodiment 8
Get 40.5g waterglass, add 17.8g water, 1.19g KOH and 1.5g NaF; Stir and successively to add 1.680g aluminum sulfate down and be dissolved in the solution of 10g water and the solution that the 5.462g lanthanum nitrate is dissolved in 10g water, continue to stir 1 hour, 170 ℃ of crystallization 2 days.Through washing, 120 ℃ of drying 2 hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 44.2, La
2O
3/ Al
2O
3=2.77.
Embodiment 9
Get 40.5g waterglass, add 17.8g water, 1.19g KOH and 1.5g NaF; Stir and successively to add 1.680g aluminum sulfate down and be dissolved in the solution of 10g water and the solution that the 4.433g lanthanum sulfate is dissolved in 10g water, continue to stir 1 hour, 170 ℃ of crystallization 2 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 42.5, La
2O
3/ Al
2O
3=2.65.
Embodiment 10
Get 40.5g waterglass, add 17.8g water, 1.19g KOH and 1.5g NaF; Stir and successively to add 1.680g aluminum sulfate down and be dissolved in the solution of 10g water and the solution that the 4.415g mixed chlorinated rare earth is dissolved in 10g water, continue to stir 1 hour, 170 ℃ of crystallization 2 days.Through washing, 120 ℃ of drying 2 hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 48.5, La
2O
3/ Al
2O
3=2.83.
Embodiment 11
Get 69.2g waterglass, add 34.0g water and 2.3g NaF; Stir and successively to add 2.020g aluminum sulfate down and be dissolved in the solution of 12g water and the solution that the 7.972g cerous nitrate is dissolved in 14g water, continue to stir 1 hour, 200 ℃ of crystallization 2 days.Through washing, 120 ℃ of dry 2hr, get zeolite provided by the invention.
This zeolite has the XRD data shown in the table 1, and its silica alumina ratio is 55.4, Ce
2O
3/ Al
2O
3=2.95.
Claims (10)
1. a skeleton contains the MOR structural zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that: have the zeolite structured characteristic X ray diffracting spectrum figure (XRD) of MOR and a=1.358nm, b=2.174nm, c=0.797nm, v=2.352nm
3The crystallography parameter; Its anhydrous chemical composition (in oxide mol ratio) expression formula is xRE
2O
3.yNa
2O.Al
2O
3.zSiO
2, x=0.01～5.0 wherein, y=0.005～16.0, z=5～300, RE represents rare earth element.
2. according to the described zeolite molecular sieve of claim 1, it is characterized in that its rare earth in forming both can be single also can be the rare earth element that mixes.
3. the method for the described zeolite molecular sieve of synthetic claim 1, it is characterized in that: with waterglass, aluminium source, inorganic base, inorganic acid, fluoride, rare earth compound is the reaction system that raw material is formed, do not add organic amine and crystal seed, mix the back in 80～250 ℃ of following hydrothermal crystallizings 8 hours～10 days under strong agitation, the gained crystallization product promptly obtains the described zeolite molecular sieve product of claim 1 after washing, drying.
4. according to the described preparation method of claim 3, it is characterized in that reaction system has following mol ratio and forms: SiO
2/ Al
2O
3=5～500, Na
2O/SiO
2=0.30～0.60, H
2O/SiO
2=12～60, F
-/ SiO
2=0～0.50, RE
2O
3/ SiO
2=0.002～0.25.
5. according to claim 3 or 4 described methods, it is characterized in that described fluoride is one or more in the fluoride, ammonium fluoride, ammonium acid fluoride of IA family element in the periodic table of elements.
6. according to claim 3 or 4 described methods, it is characterized in that described aluminium source is one or more in alchlor, aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum phosphate, aluminium hydroxide, the boehmite.
7. according to claim 3 or 4 described methods, it is characterized in that described inorganic base is one or more in NaOH, the ammoniacal liquor.
8. in accordance with the method for claim 7, it is characterized in that described NaOH can be replaced by the hydroxides of other alkali metal or alkaline-earth metal.
9. according to claim 3 or 4 described methods, it is characterized in that described inorganic acid be selected from sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid any or several.
10. according to claim 3 or 4 described methods, it is characterized in that described rare earth compound is single or the chloride of mixed rare-earth elements, or nitrate, or sulfate, or acetate.
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| WO2014174416A2 (en) * | 2013-04-22 | 2014-10-30 | Basf Se | Dehydration of sugars on zeolites obtainable from an organotemplate-free synthetic process |
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