CN1093513C - Process for synthesizing zeolite with mordenite structure - Google Patents
Process for synthesizing zeolite with mordenite structure Download PDFInfo
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- CN1093513C CN1093513C CN 98123237 CN98123237A CN1093513C CN 1093513 C CN1093513 C CN 1093513C CN 98123237 CN98123237 CN 98123237 CN 98123237 A CN98123237 A CN 98123237A CN 1093513 C CN1093513 C CN 1093513C
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- zeolite
- sio
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- fluorochemical
- water glass
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Abstract
The present invention discloses a method for synthesizing a crystallized aluminium silicate zeolite in an MOR structure, whose anhydrous chemical composition expressed in the molar ratio of oxides comprises 0.8 to 10.0 of Na2O and Al2O3 and 15 to 60 of SiO2. In the method of the present invention, organic amines, mineral acids and inorganic hydroxides are not needed, and inexpensive and easily obtained water glasses, aluminum salt or aluminate are directly processed in the existence of fluorides at a certain temperature by a crystallizing reaction to obtain the crystallized aluminum silicate zeolite. The zeolite prepared by the method of the present invention is suitable to be used in various application fields of mordenites. The present invention has the advantages that raw materials with low cost are used to directly synthesize a high silicon zeolite; the technical process is simpleness simple, and the corrosion to equipment is little.
Description
The present invention relates to a kind of method of synthetic crystalline aluminosilicate zeolite with MOR structure and the crystalline aluminosilicate zeolite that can obtain by this method.
Mordenite is the crystalline aluminosilicate zeolite that typically has the MOR structure, has good heat-resisting, acidproof and anti-steam performance, be widely used as the isolating sorbent material of gas and liquid mixture, being particularly useful for catalytic processs such as isomerization, disproportionation, transalkylation, alkylation and catalytic cracking, is crucial catalytic material.
Zeolite with MOR structure is generally by SiO
2/ Al
2O
3Mol ratio 10～12 is divided into two classes for the boundary, and according to existing most synthetic technologys, that does not use that template makes mostly is SiO greatly
2/ Al
2O
3The low silicon content mordenite of mol ratio 5～10 (US 3,996, and 337; US 4,503, and 023; US4,511,547; US 4,581, and 216), suitable with natural mordenite zeolite.High silicon mordenite can pass through the method acquisition that water vapor, acid and title complex etc. are handled dealuminzation, and operating process is long and complicated; Better method is that direct hydro-thermal is synthetic, but generally all needs to add the organic amine template.Japan Japan Cao Da industrial uses the benzyl Trimethylamine 99 and adds the mordenite crystal seed and synthesizes high silicon (silica alumina ratio 25.8) mordenite, EP 80,615 reports add bromination diethyl piperidines and make template can to prepare silica alumina ratio be 31 supersiliceous zeolite, the employed organic formwork agent of patented technology of other synthetic this class zeolite also has indicator, and (US 4,585,640), oxyamine, the hydroxyl diamines, the saturated cyclic amine that contains 1 or 2 Sauerstoffatom, the ether that cooperates with IA family metal, especially cyclic ethers class (US4,377,502) etc., and straight chain alkyl amine and cyclic alkyl amine such as 2-aminopyridine, 2-or 4-methyl cyclohexane alkanamine etc. (US 4,376, and 104; US 4,390, and 457; US 4,707, and 345; US 4,788, and 380; US 5,219, and 546).
Uop Inc. has announced that the 1st does not add organic amine and make the patented technology of high silicon mordenite (US 3,677,973), adopts SiO
2/ Al
2O
3It is synthetic that the amorphous silicic acid aluminium glue of mol ratio 15～30 adds alkali, but the aluminosilicagel process complexity of preparation high silicon content, long flow path needs equipment also many; (zeolite (Zeolites), 1986,6 (1): 30) report can synthesize SiO with amorphous silica gel to Itabashi etc.
2/ Al
2O
3Mol ratio is about 15 mordenite, and the silica alumina ratio that feeds intake must be very high, and raw materials cost is unreasonable economically; The clear 58-88119 of Japanese kokai publication sho 56-160316 and Te Kai also reports with water glass, Tai-Ace S 150 and sulfuric acid and synthesized silica alumina ratio near 30 mordenite in the presence of sodium-chlor, but XRD detects and exists the significant quantity stray crystal.Chinese patent application prospectus CN1050011 discloses a kind of method for preparing high silica mordenite, and it does not use organic amine, at NH
3Have the crystalline aluminosilicate that synthesizes silica alumina ratio nearly 30 down, XRD identifies the genus mordenite, and is simple although this method was compared technology with former method, NH
3Use certain environmental pollution of still failing to reduce production costs effectively and caused, and, therefore still leave some room for improvement because of having used mineral acid or inorganic strong alkali to cause heavy corrosion in process of production to equipment; In addition, the not open more crystalline silicate of high silica alumina ratio of this application.Chinese patent application prospectus CN1147479 discloses a kind of technology of synthetic crystalline aluminosilicate zeolite, with amorphous aluminum silicide microballoon and NaOH is raw material, but use sodium-chlor or sodium-chlor-trolamine to make the zeolite that the template crystallization makes high silica alumina ratio with MOR structure, although this method has reduced the environmental pollution that causes in the zeolite synthesis process, but because the silicon aluminium microsphere that this method adopts is Industrial products, zeolite product at the Different Silicon aluminum ratio, need to use the silicon aluminium microsphere of Different Silicon aluminum ratio, thereby can not reduce production costs effectively, it is complicated loaded down with trivial details that the control of the silica alumina ratio that feeds intake also seems; In addition, also owing to having used inorganic strong alkali to cause heavy corrosion in process of production to equipment.
The objective of the invention is on the prior art basis, a kind of synthetic supersiliceous zeolite technology with MOR structure of non-amine method of using water glass is provided, need organic amine to overcome prior art, though perhaps do not have amine because of adding NH
3Or the use silicon aluminium microsphere, and must use mineral acid or inorganic strong alkali to cause environmental pollution or cost is higher, equipment corrosion and technology are comparatively complicated deficiency.
According to the present invention, a kind of synthetic method with zeolite of MOR structure is provided, it need not add any organic formwork agent, only makes water glass and aluminium source carry out the crystalline aluminosilicate zeolite that crystallization just can obtain high silica alumina ratio at a certain temperature in the presence of fluorochemical.The specific embodiments of synthetic method of the present invention is: after water glass and fluorochemical are mixed, add aluminium source or its aqueous solution; Perhaps add aluminium source and fluorochemical in water glass, the back that stirs was 120～250 ℃ of crystallization 20～80 hours.The crystallization thing that obtains washs after filtration, drying, promptly gets zeolite product.
In the method for the invention, the mole of reaction system consists of: SiO
2/ Al
2O
3=15～60, Na
2O/SiO
2=0.30～0.60, H
2O/SiO
2=12～50, F
-/ SiO
2=0.02～0.30.Synthetic used aluminium source can be any aluminium salt in aluminum chloride, Tai-Ace S 150 or the aluminum nitrate, also can be aluminates such as sodium aluminate.Used fluorochemical is alkali-metal fluorochemical or Neutral ammonium fluoride or its mixture.
Synthetic of the present invention has the XRD feature of the zeolite of MOR structure and lists in table 1, with CN1147479 provide zeolite structured identical, and with natural (CaNaKM) or synthetic (NaM) mordenite slightly different (table 2), be 0.8～10.0Na with the anhydrous chemical expression of oxide mol ratio formation
2OAl
2O
315～60SiO
2
Table 1
d/nm I/I
0
1.359±0.10 W-VW
1.024±0.10 VW
0.904±0.08 M
0.657±0.05 M-W
0.639±0.05 W-VW
0.607±0.05 VW
0.579±0.02 VW
0.453±0.02 W
0.400±0.02 S
0.383±0.02 W-VW
0.376±0.02 VW
0.352±0.02 VW
0.347±0.02 VS
0.339±0.02 S-M
0.329±0.02 VW
0.322±0.02 VS-M
0.294±0.02 VW
0.289±0.02 W
0.257±0.02 VW
0.252 intensity: VS 80～100% in ± 0.02 VW table; S 60～80%; M 40～60%; W 20～40%; VW＜20%
Table 2
CaNaKM NaM zeolite D/nm of the present invention I/I
0D/nm I/I
0D/nm I/I
01.370 50 -- 1.359 W-VW- - -- 1.024 VW0.910 90 0.896 50 0.904 M0.661 90 0.655 20 0.657 M-W0.638 40 -- 0.639 W-VW0.610 50 -- 0.607 VW0.579 50 0.574 10 0.579 VW0.503 10 -- 0.504 VW0.487 20 -- 0.487 VW0.453 80 0.449 30 0.453 W0.414 30 - - 0.414 VW0.400 90 0.398 70 0.400 S 0.384 60 - - 0.383 W-VW0.376 20 0.375 10 0.376 VW0.362 10 - - 0.363 VW0.356 10 - - 0.352 VW0.347 100 0.345 100 0.347 VS0.339 90 0.339 50 0.339 S-M0.331 10 - - 0.329 VW0.322 100 0.321 60 0.322 VS-M- -- - 0.315 VW0.310 20 - - 0.311 VW- - 0.304 40 0.300 VW0.2946 20 - - 0.2942 VW0.2896 60 - - 0.2891 W0.2700 30 - - 0.2696 W0.2560 40 - - 0.2565 W0.2522 50 0.2526 30 0.2518 VW0.2465 20 - - 0.2461 VW0.2437 20 - - 0.2431 VW0.2343 20 - - - -0.2299 10 - - - -0.2275 10 - - - -0.2228 20 - - 0.2229 VW- - - - 0.2164 VW0.2123 10 - - 0.2121 VW0.2047 40 0.2048 20 0.2052 VW
Because the synthetic technology with high silica alumina ratio zeolite of MOR structure of the present invention is not used organic formwork agent and NH
3, adopt water glass to do silicon source and aluminium salt or aluminate, thereby can reduce cost, simplify technical process significantly and shorten crystallization time, but also help controlling the silica alumina ratio that feeds intake as the aluminium source.In addition, because the inventive method need not be used in the prior art mineral acid or the inorganic strong alkali that must use, thereby the corrosion that equipment is caused seldom.
The crystalline aluminosilicate zeolite of the MOR of having structure provided by the invention can be used as the processes such as transalkylation, alkylation, isomerization, disproportionation and catalytic cracking of the catalytic conversion process of sorbent material and multiple organic compound, particularly aromatic hydrocarbons.
The following examples will be further specified the present invention, but these embodiment do not limit the scope of the invention.The ICP method is adopted in the ultimate analysis of embodiment mesolite.
Embodiment 1
In 46.3 gram water glass, add 60.43 gram water and 1.715 gram NaF, under agitation add 4.489 gram Al
2(SO
4)
318H
2O is dissolved in the solution of 13.51 grams in the water, 170 ℃ of following crystallizations 54 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 15.1, Na
2O/SiO
2Mol ratio is 3.14.
Embodiment 2
In 46.32 gram water glass, add 55.60 gram water, under agitation add 0.634 gram NaF and 0.625 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 30 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 28.40.
Embodiment 3
In 46.32 gram water glass, add 55.60 gram water, under agitation add 0.634 gram NaF and 0.625 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 48 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 31.20.
Embodiment 4
In 47.15 gram water glass, add 57.25 gram water, under agitation add 0.701 gram NaF and 0.714 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 30 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 32.03.
Embodiment 5
In 46.11 gram water glass, add 56.05 gram water, under agitation add 0.860 gram NaF and 0.679 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 30 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 35.80.
Embodiment 6
In 46.11 gram water glass, add 56.05 gram water, under agitation add 0.860 gram NaF and 0.679 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 48 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 38.40.
Embodiment 7
In 46.81 gram water glass, add 55.89 gram water, under agitation add 1.725 gram NaF and 1.343 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 48 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 41.4.
Embodiment 8
In 46.81 gram water glass, add 55.89 gram water, under agitation add 1.725 gram NaF and 1.343 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 72 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 55.27.
Embodiment 9
In 56.416 gram water glass, add 68 gram water, under agitation add 2.097 gram NaF and 1.625 gram Al
2(SO
4)
318H
2O, the back that stirs is in 150 ℃ of following crystallizations 80 hours, through washing, at 120 ℃ down after dry 2 hours, promptly gets zeolite of the present invention.
This zeolite has XRD data as shown in table 1, its SiO
2/ Al
2O
3Mol ratio is 58.29.
Claims (7)
1. one kind synthetic have XRD data shown in the following table 1 and has the method for the crystalline aluminosilicate zeolite of MOR structure, and the anhydrous chemical constitution of described zeolite is expressed as 0.8～10.0Na with oxide mol ratio
2OAl
2O
315～60SiO
2, it is characterized in that this method is to make water glass and aluminium source crystallization in the presence of fluorochemical.
Table 1
d/nm I/I
0
1.359±0.10 W-VW
1.024±0.10 VW
0.904±0.08 M
0.657±0.05 M-W
0.639±0.05 W-VW
0.607±0.05 VW
0.579±0.02 VW
0.453±0.02 W
0.400±0.02 S
0.383±0.02 W-VW
0.376±0.02 VW
0.352±0.02 VW
0.347±0.02 VS
0.339±0.02 S-M
0.329±0.02 VW
0.322±0.02 VS-M
0.294±0.02 VW
0.289±0.02 W
0.257±0.02 VW
0.252±0.02 VW
Intensity in the table: VS 80～100%; S 60-80%; M 40～60%; W 20～
40％；VW＜20％
2. in accordance with the method for claim 1, after it is characterized in that water glass and fluorochemical mixed, add aluminium source or its aqueous solution; Perhaps add aluminium source and fluorochemical in water glass, the back that stirs was 120～250 ℃ of following crystallization 20～80 hours.
3. according to claim 1 or 2 described methods, it is characterized in that reaction system has following molar ratio: SiO
2/ Al
2O
3=15～60, Na
2O/SiO
2=0.30～0.60, H
2O/SiO
2=12～50, F
-/ SiO
2=0.02～0.30.
4. according to claim 1 or 2 described methods, it is characterized in that described fluorochemical is alkali-metal fluorochemical or Neutral ammonium fluoride or its mixture.
5. according to claim 1 or 2 described methods, it is characterized in that described aluminium source is aluminium salt or aluminate.
6. according to the method for claim 5, wherein said aluminium salt is any in aluminum chloride, Tai-Ace S 150 or the aluminum nitrate, and described aluminate is a sodium aluminate.
7. the crystalline aluminosilicate zeolite that can be obtained by each described method among the claim 1-6 has the XRD data shown in the following table 1.
Table 1
d/nm I/I
0
1.359±0.10 W-VW
1.024±0.10 VW
0.904±0.08 M
0.657±0.05 M-W
0.639±0.05 W-VW
0.607±0.05 VW
0.579±0.02 VW
0.453±0.02 W
0.400±0.02 S
0.383±0.02 W-VW
0.376±0.02 VW
0.352±0.02 VW
0.347±0.02 VS
0.339±0.02 S-M
0.329±0.02 VW
0.322±0.02 VS-M
0.294±0.02 VW
0.289±0.02 W
0.257±0.02 VW
0.252 intensity: VS 80～100% in ± 0.02 VW table; S 60～80%; M 40～60%; W 20～40%; VW＜20%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98123237 CN1093513C (en) | 1998-12-22 | 1998-12-22 | Process for synthesizing zeolite with mordenite structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98123237 CN1093513C (en) | 1998-12-22 | 1998-12-22 | Process for synthesizing zeolite with mordenite structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1257831A CN1257831A (en) | 2000-06-28 |
| CN1093513C true CN1093513C (en) | 2002-10-30 |
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ID=5228101
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98123237 Expired - Fee Related CN1093513C (en) | 1998-12-22 | 1998-12-22 | Process for synthesizing zeolite with mordenite structure |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039152B (en) * | 2009-10-13 | 2012-10-10 | 中国石油化工股份有限公司 | Preparation method of binder-free mordenite catalyst |
| CN107758686A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Anion is oriented to nano mordenite and preparation method thereof |
| CN108217679B (en) * | 2016-12-09 | 2020-03-27 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve, and preparation method and application thereof |
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1998
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