CN1137049C - Synthesis of MCM-49 zeolite - Google Patents

Synthesis of MCM-49 zeolite Download PDF

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CN1137049C
CN1137049C CNB00136197XA CN00136197A CN1137049C CN 1137049 C CN1137049 C CN 1137049C CN B00136197X A CNB00136197X A CN B00136197XA CN 00136197 A CN00136197 A CN 00136197A CN 1137049 C CN1137049 C CN 1137049C
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zeolite
mcm
template
described synthetic
synthetic mcm
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CN1361060A (en
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谢素娟
彭建彪
王清遐
徐龙伢
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a method for synthesizing MCM-49 zeolite. An adopted template agent mainly comprises the mixture of 76.0% to 84.0% of weight percentage of hexamethylene imine, 1.0 to 10.0% of caprolactam and surplus water; other synthetic raw materials are a compound of silicon and/or germanium, aluminum and/or boron salt or aluminum and/or boron oxide, alkali metal or alkaline earth metal hydroxide and deionized water. The substances are crystallized for 1 to 18 days at the temperature of 85 DEG C to 200 DEG C for preparing a molecular sieve by hydrothermal synthesis. By adopting the method, the synthetic cost of MCM-49 zeolite can be effectively reduced.

Description

A kind of method of synthetic MCM-49 zeolite
The present invention relates to a kind of method of synthetic MCM-49 zeolite.
The MCM-49 zeolite is a kind of novel molecular sieve (USP5,236,575) that U.S. Mobil company succeeded in developing in phase earlier 1990s.The skeleton structure of roasting type MCM-49 and roasting type MCM-22 is basic identical, is difficult to distinguish on X-ray diffraction (XRD) spectrogram, has only the MCM-49 of synthesis type and MCM-22 to differentiate, this also is the special character of this zeolite.MCM-49 can be used for many chemical conversion processes, as alkylation of aromatic hydrocarbons and low-carbon alkene, long-chain olefin etc.
The template of at present synthetic MCM-49 zeolite is pure hexamethylene imine substantially, and adopting other material is that template is difficult to obtain pure MCM-49 zeolite.Hexamethylene imine generally be by with the product behind the caprolactam hydrogenation again separation and Extraction obtain, thereby cause the synthetic expense of MCM-49 zeolite higher.Application number provides a kind of preparation and application that is used for synthetic MCM-22 zeolite template for 99112979.2 Chinese patent, this template is the mixture of water for mainly containing (weight percent) 76.0～84.0% hexamethylene imines, 1.0～10.0% hexanolactams, surplus, the technological process of this mixture of relevant preparation, this application has been described in detail.But, have not yet to see and use this mixture to make the report that template can be synthesized MCM-49.
The object of the present invention is to provide a kind of method of improved synthetic MCM-49 zeolite, it is template that this method adopts liquid mixture, can obtain highly purified MCM-49 zeolite equally, and can obviously reduce synthetic cost.
The method of synthetic MCM-49 zeolite provided by the invention is that to adopt oxyhydroxide, template and the deionized water of oxide compound, basic metal or the alkaline-earth metal of the salt of aluminium and/or boron or oxide compound, silicon and/or germanium be raw material, under 85～200 ℃, after the crystallization 1～20 day, hydro-thermal synthesizes molecular sieve, said template adopts the liquid mixing template based on hexamethylene imine, promptly, this template is for mainly containing the aqueous mixture of hexamethylene imine and hexanolactam, and the proportioning raw materials of this zeolite synthesis (molecular ratio) scope is: YO 2/ X 2O 3=11～34, OH -/ X 2O 3=0.6～17.0, M/X 2O 3=0.6～102, R/X 2O 3=2.0～34.0, H 2O/X 2O 3=100～2400, wherein X is aluminium and/or boron, and Y is silicon and/or germanium, and R is the organism in the liquid mixture, and M is basic metal or alkaline-earth metal.
The main component hexamethylene imine is obtained by the caprolactam shortening in the employed in the present invention mixture template, and directly should react back solution and do the template use.The weight percent that accounts for reaction solution owing to resultant hexamethylene imine after reaction can reach 76.0～84.0%, and the reactant hexanolactam is about 1.0～10.0%, surplus is a water, is that the aqueous solution of the caprolactam mixture of 76.0～84.0% hexamethylene imine and 1.0～10.0% is made template so can adopt weight content %.
The synthetic MCM-49 zeolite of the present invention proportioning raw materials (molecular ratio) scope preferably is: YO 2/ X 2O 3=16～30, OH -/ X 2O 3=0.6～10.0, M/X 2O 3=0.6～32, R/X 2O 3=5.4～17.0, H 2O/Al 2O 3=150～1800.
X described in the inventive method 2O 3Can adopt compounds such as Tai-Ace S 150 and sodium aluminate.
The described YO of the inventive method 2Can adopt compounds such as silicon-dioxide, silicic acid, alkoxyl silicone.
The present invention since the mixture that contains materials such as hexamethylene imine (HMI) and hexanolactam that the hexanolactam shortening is obtained directly as template, and will this hydrogenation products separation and Extraction HMI wherein, thereby can obviously reduce the synthetic expense of MCM-49 zeolite, and to synthesize the degree of crystallinity of MCM-49 molecular sieve suitable with the result who adopts pure HMI.The X-ray diffract spectral line and the USP5 of the synthetic MCM-49 zeolite of the present invention, 236,575 unanimity as a result.
The synthetic MCM-49 of institute zeolite of the present invention, its primary positively charged ion (as basic metal or alkaline earth metal cation) can be by ion exchange technique by other cationic moiety or replacement fully.These replace precursor such as ammonium ion and their mixture that positively charged ion comprises metal ion, hydrogen ion, hydrogen, and wherein metal ion can be the metal ion among IIA, IIIA, IVA, IB, IIB, IIIB, IVB and the VIII in the rare earth metal and the periodic table of elements.Typical ion-exchange techniques, be with the cationic salt of replacement such as halogenide, nitrate and vitriol, contact with synthesis type MCM-49 zeolite,, can obtain containing the MCM-49 zeolite of required cationic again through washing, 1～48 hour, 220～550 ℃ roastings of 60～220 ℃ of dryings 1～48 hour.
The present invention will be further described below by example, but application of the present invention is not subjected to the restriction of these examples.
Example 1: the preparation of template
In a series connection, multistage, cold shock fixed-bed reactor, be divided into four sections 280ml hydrogenation catalyst JH-01 that pack into (production of the Dalian Chemistry and Physics Institute), respectively adorn 70ml for one to four section, hydrogen is divided into four parts and enters from every section top, and hexanolactam adds from first section top.The temperature of reaction of controlling each section is 265 ℃, reaction pressure 1.0MPa, total hydrogen and the mol ratio of hexanolactam 90, the liquid air speed 0.1h of total hexanolactam -1Obtain the transformation efficiency 98% of hexanolactam, contain 82.5% (weight percentage, as follows) hexamethylene imine, 2.0% (w) hexanolactam, 0.5% (w) by product and 15.0% (w) water in the product liquid, this liquid mixture called after L.
Synthesizing of example 2:MCM-49 zeolite
1) raw material:
A. sodium aluminate solution [contains 15.0% (w) Al 2O 3, 21.8% (w) Na 2O, as follows]: 3.40 grams;
B. sodium hydroxide solution [containing 10% (w) NaOH, as follows]: 2.80 grams;
C. liquid mixture L (product of example 1, as follows): 2.90 grams;
D. solid silicone [contains 89.0% (w) SiO 2, as follows]: 8.40 grams;
E. deionized water: 40.80 grams.
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=25; OH -/ Al 2O 3=6.2; H 2O/Al 2O 3=520; Na/Al 2O 3=6.2; R/Al 2O 3=5.0 (R refers to the organism among the L).
2) operation steps:
Earlier with raw material (A) with (B) in 200 milliliters of stainless steel cauldrons, mix, under agitation add successively in the still, continue to stir after 60 minutes, reactor is sealed with raw material (C), (D) with (E), be warming up to 144 ℃, crystallization 4 days, after the cooling, with solid and mother liquor with the 5000rpm centrifugation, solid through deionized water wash to PH8～9,120 ℃ of following dry airs 10 hours, make MCM-49 (former powder), record its SiO 2/ Al 2O 3Be 19.8 (molecular ratios, as follows).This sample has the X-ray diffraction spectral line shown in the table 1, other this sample that takes a morsel, and at 540 ℃ of following roasting 6h, it is as shown in table 2 to record its X-ray diffraction spectral line.
The X-ray diffract spectral line of table 1 example 2 samples of the present invention (former powder)
2θ(°) Spacing d () I/I 0(×100)
3.2 27.5 29
6.80 12.99 39sh *
7.13 12.39 54
7.92 11.15 34
9.77 9.04 31
12.79 6.91 21
15.72 5.63 18
20.11 4.41 35
21.53 4.12 30
21.84 4.07 48
22.59 3.93 68
23.55 3.77 34
25.93 3.43 100
26.84 3.32 44
27.67 3.22 32
28.30 3.15 26
*" sh " refers to acromion (as follows).
X-ray diffract spectral line after the table 2 example 2 sample roastings of the present invention
2θ(°) Spacing d () I/I 0(×100)
3.23 27.33 20
7.10 12.44 65
7.98 11.07 31
9.78 9.04 43
12.81 6.91 17
14.25 6.21 39
15.86 5.58 22
20.18 4.40 28
21.83 4.07 37
22.61 3.93 57
23.60 3.77 36
24.89 3.57 30
25.94 3.43 100
26.93 3.31 32
27.70 3.22 31
28.64 3.12 19
Synthesizing of example 3:MCM-49 zeolite
In example 2, change the add-on of liquid mixture L into 3.40 grams, the add-on of solid silicone changes 6.70 grams into, and the add-on of deionized water changes 47.90 grams into, hydro-oxidation sodium solution not, all the other components are constant, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=20; OH -/ Al 2O 3=4.8; H 2O/Al 2O 3=570; Na/Al 2O 3=4.8; R/Al 2O 3=5.8 (R refers to the organism among the L).147 ℃ of following crystallization 3.5 days, product was the MCM-49 molecular sieve, records its SiO 2/ Al 2O 3Be 16.9.X-ray diffraction spectral line behind the former powder of this sample and the 540 ℃ of roasting 6h is similar with table 1 and table 2 respectively.Synthesizing of example 4:MCM-49 zeolite
In example 2, use Al instead 2(SO 4) 3.18H 2O is the aluminium source, and its add-on is 3.30 grams, and the add-on of sodium hydroxide solution changes 20.80 grams into, and the add-on of liquid mixture L changes 3.20 grams into, and the add-on of deionized water changes 22.40 grams into, and the add-on of solid silicone is constant.In the synthetic operation process, from the deionized water of metering, take out on a small quantity earlier, make Al 2(SO 4) 3.18H 2O is dissolved in wherein, constitutes raw material (A), and following operation steps is identical with example 2.The mole of reaction mixture consists of: SiO 2/ Al 2O 3=25; OH -/ Al 2O 3=4.4; H 2O/Al 2O 3=490; Na/Al 2O 3=10.4; R/Al 2O 3=5.5 (R refers to the organism among the L).150 ℃ of following crystallization 3 days, product was the MCM-49 molecular sieve, records its SiO 2/ Al 2O 3Be 19.3.The X-ray diffraction spectral line of synthesis type sample is shown in table 3.
The X-ray diffraction spectral line of synthesis type sample in table 3 example 4
2θ(°) Spacing d () I/I 0(×100)
3.19 27.67 37
6.78 13.03 47sh *
7.10 12.44 66
7.90 11.18 37
9.86 8.96 33
12.79 6.91 23
14.03 6.31 24
15.92 5.56 22
20.12 4.41 40
21.83 4.07 52
22.58 3.93 73
23.40 3.80 35
24.88 3.57 36
25.94 3.43 100
26.87 3.31 39
27.50 3.23 31
28.40 3.13 21
Synthesizing of example 5:MCM-49 zeolite
In example 2, with the purity that liquid mixture L rectifying is obtained is that 99% hexamethylene imine is a template, add-on is 3.40 grams, the add-on of sodium hydroxide solution changes 1.30 grams into, the add-on of deionized water changes 49.70 grams into, all the other components are constant, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=25; OH -/ Al 2O 3=5.4; H 2O/Al 2O 3=600; Na/Al 2O 3=5.4; R/Al 2O 3=6.9 (R refers to hexamethylene imine),, 147 ℃ of following crystallization 3 days, product was the MCM-49 molecular sieve, records its SiO 2/ Al 2O 3Be 19.6.The X-ray diffraction spectral line of synthesis type sample is shown in table 4.
The X-ray diffraction spectral line of sample in table 4 example 5
2θ(°) Spacing d () I/I 0(×100)
3.15 28.04 22
6.82 12.96 38sh *
7.06 12.51 54
7.94 11.13 31
9.79 9.03 33
12.79 6.92 20
14.09 6.29 17
15.71 5.64 19
20.04 4.43 33
21.77 4.08 49
22.59 3.93 67
23.56 3.77 33
24.88 3.57 39
25.91 3.43 100
26.82 3.32 39
27.64 3.22 35
28.30 3.14 21
Synthesizing of example 6:MCM-49 zeolite
In example 2, with boric acid (H 3BO 3) be the boron source, H 3BO 3Add-on be 0.07 gram, change the add-on of sodium aluminate solution into 3.10 grams, the add-on of sodium hydroxide solution changes 4.10 grams into, the add-on of liquid mixture L changes 3.70 grams into, the add-on of deionized water changes 45.00 grams into, and all the other components are constant, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=28; SiO 2/ B 2O 3=227; OH -/ Al 2O 3=6.4; H 2O/Al 2O 3=580; Na/Al 2O 3=6.4; R/Al 2O 3=6.3 (R refers to the organism among the L),, 140 ℃ of following crystallization 5 days, product was the MCM-49 molecular sieve, records its SiO 2/ Al 2O 3Be 21.8.The X-ray diffraction spectral line of synthesis type sample is shown in table 5.
The X-ray diffraction spectral line of sample in table 5 example 6
2θ(°) Spacing d () I/I 0(×100)
3.16 27.97 28
6.78 13.03 30sh *
7.10 12.44 58
7.92 11.15 31
9.70 9.11 31
12.84 6.89 17
14.31 6.18 18
15.89 5.57 20
20.01 4.43 33
21.79 4.07 47
22.56 3.94 65
23.58 3.77 31
24.91 3.57 36
25.93 3.43 100
26.84 3.32 40
27.53 3.24 30
28.23 3.15 22

Claims (8)

1, a kind of method of synthetic MCM-49 zeolite, preparation process be adopt silicon/or the salt of compound, aluminium and/or the boron of germanium or oxyhydroxide, template and the deionized water of oxide compound, basic metal or alkaline-earth metal be raw material, hydro-thermal synthesizes molecular sieve, it is characterized in that employed template is the aqueous solution that contains hexamethylene imine and caprolactam mixture; The proportioning raw materials scope is: YO 2/ X 2O 3=11-34, M/X 2O 3=0.6-102, OH -/ X 2O 3=0.6-17, R/X 2O 3=2.0-34, H 2O/X 2O 3=100-2400;
Wherein Y is silicon and/or germanium, and X is aluminium and/or boron, and M is basic metal or alkaline-earth metal, and R is the organism in the template;
Wherein template is the aqueous solution that contains the organic mixture of weight percent 76.0-84.0% hexamethylene imine and 1.0-10.0% hexanolactam.
2,, it is characterized in that the proportioning raw materials scope is: YO according to the method for the described synthetic MCM-49 zeolite of claim 1 2/ X 2O 3=16-31, M/X 2O 3=0.6-32, OH -/ X 2O 3=0.6-10.0, R/X 2O 3=5.0-34, H 2O/X 2O 3=150-1800.
3,, it is characterized in that X is an aluminium according to the method for the described synthetic MCM-49 zeolite of claim 1.
4,, it is characterized in that Y is a silicon according to the method for the described synthetic MCM-49 zeolite of claim 1.
5,, it is characterized in that described X according to the method for the described synthetic MCM-49 zeolite of claim 1 2O 3Adopt sodium aluminate.
6, according to the method for the described synthetic MCM-49 zeolite of claim 1, it is characterized in that YO 2Adopt silicon-dioxide, silicic acid or alkoxyl silicone.
7, according to the method for the described synthetic MCM-49 zeolite of claim 2, it is characterized in that X 2O 3Adopt sodium aluminate or Tai-Ace S 150.
8, according to the method for the described synthetic MCM-49 zeolite of claim 2, it is characterized in that YO 2Adopt silicon-dioxide.
CNB00136197XA 2000-12-27 2000-12-27 Synthesis of MCM-49 zeolite Expired - Fee Related CN1137049C (en)

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CN103086387B (en) * 2011-10-28 2014-12-03 中国石油化工股份有限公司 Porous silica microsphere preparation method
CN104591203B (en) * 2013-10-31 2017-10-27 中国科学院大连化学物理研究所 Solvent process for thermosynthesizing of the molecular sieves of MCM 22 and products thereof and purposes
CN107597179A (en) * 2017-09-29 2018-01-19 钦州学院 A kind of MCM 49 molecular sieve catalysts of isooctane and preparation method thereof

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