CN1353011A - Molecular sieve containing zinc and its synthesis - Google Patents
Molecular sieve containing zinc and its synthesis Download PDFInfo
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- CN1353011A CN1353011A CN 00130267 CN00130267A CN1353011A CN 1353011 A CN1353011 A CN 1353011A CN 00130267 CN00130267 CN 00130267 CN 00130267 A CN00130267 A CN 00130267A CN 1353011 A CN1353011 A CN 1353011A
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- molecular sieve
- mcm
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Abstract
A molecular sieve MCM-22 containing Zn is disclosed, and it has the X-ray diffraction characteristics and the mole ratio of SiO2 to Al2O3, that the conventional MCM-22 has. It features that the mole ratio of its SiO2 to Al2O3, that the conventional MCM-22 has. It features that the mole ratio of its SiO2 to ZnO is 15-300, and its wave peaks in infrared spectrum (1080-1088/cm and 792-792/cm) move toward low wave number. The said molecular sieve is prepared by hydrothermal synthesis.
Description
The present invention relates to a kind of molecular sieve (MCM-22) with special crystal structure and synthetic, particularly relate to the MCM-22 molecular sieve that contains Zn and synthetic.
The zeolite molecular sieve skeleton is the SiO by the inflexible three-dimensional structure
4Tetrahedron and AlO
4Tetrahedron constitutes, and the sial atomicity is 1: 2 with the ratio of oxygen atomicity.Wherein aluminium is trivalent element, so each AlO
4Negative charge of tetrahedron band.Like this, whole framework of molecular sieve is electronegative, must rely in the hole for this reason and adsorb positively charged ion (as K
+, Na
+, Ca
2+Deng) to keep electric neutrality.These positively charged ions are easy to by ion-exchange, are exchanged for other ion whole or in part (as H
+), this is the source of acidic zeolite.
The silica alumina ratio of zeolite molecular sieve is normally variable.As X type molecular sieve silica alumina ratio about 2～3; Y zeolite silica alumina ratio about 3～6.Some molecular sieve silica alumina ratio even do not have the upper limit is as can directly synthesizing the ZSM-5 molecular sieve that silica alumina ratio is 5～∞.
The synthetic template that needs of many molecular sieves, a kind of template may synthesize the different molecular sieve of several structures, and a kind of molecular sieve also can be synthesized by different template simultaneously.As MCM-22 (US4,954,325) is to be the template synthetic with hexamethylene imine (HMI), with HMI is that template can also be synthesized PSH-3 (US4,439,409), MCM-35 (US4,981,663), MCM-49 (US5,236,575), MCM-56 (US5,362,697), ZSM-12 (US5,021,141) equimolecular sieve.Wherein PSH-3 and MCM-22 belong to MWW type structure, and this is a kind of molecular sieve of laminate structure, and interlayer links to each other with oxo bridge; Though with the former two fine distinction is arranged on MCM-49 and the MCM-56 structure, also be the MWW family member, promptly their basic structural unit is identical, all has the single layer structure of MCM-22.MCM-35 then is the different molecular sieve of structure with ZSM-12.In addition, MWW type molecular sieve also has with N, N, N-trimethylammonium diamantane ammonium ion is template synthetic SSZ-25 (US4,826,667) and with HMI and N, N, the mixture of N-trimethylammonium diamantane ammonium ion is composite mould plate agent synthetic pure silicon molecular sieve ITQ-1 (WO97/19021) etc.
Introduce heteroatoms in the zeolite molecular sieve skeleton and can make heteroatom zeolite.Heteroatom zeolite has unique catalytic performance, be widely used as the catalyzer of petrochemical complex and organic chemical industry's production process, as the zeolite molecular sieve that contains Zn reaction has good catalytic activity and selectivity to aromatization of low carbon hydrocarbon, it can make the refinery gas, Sweet natural gas and the oil field light hydrocarbon that contain C2～C6 alkane be converted into the high aromatic hydrocarbons of added value (BTX) effectively.
MCM-22 synthesizes (US4,954,325) first by Mobil company.It has two kinds independently, mutual disconnected duct system: the one, and the aperture is the sinusoidal duct of ten-ring two dimension of 4.0 * 5.9 ; The 2nd, be the twelve-ring supercage of 7.1 * 7.1 * 18.2 with the ten-ring opening of 4.0 * 5.4 with extraneous that communicate, aperture.MCM-22 has unique pore passage structure, heat/hydrothermal stability and acidity preferably, be the benzene of catalyzer and propylene, the industrialization of vinyl alkyl metallization processes.
N.Kumar and L.Lindfors once reported (Applied Catalysis A:General 147 (1996), p175-187), by with H-MCM-22 with the Zn (NO of 0.1M
3)
2The Zn-MCM-22 molecular sieve that carries out ion-exchange and obtain has the arenes selectivity higher than H-MCM-22 molecular sieve in the normal butane aromatization.
Infrared (IR) antisymmetric stretching vibration range of frequency of Si-O-Al structure is in the framework of molecular sieve: 1050～1150cm-1, the symmetrical stretching vibration range of frequency is: 750～820cm-1.People such as Szostack (J.Catal, 1986,101 (2), p549-552) think, after Al in the framework of molecular sieve among the Si-O-Al is replaced by heteroatoms, its stretching vibration frequency is to the lower wave number displacement, therefore according to the IR stretching vibration frequency of Si-O-Al key whether to the lower wave number displacement, can be used as and judge whether heteroatoms enters the evidence of framework of molecular sieve.
If Zn can be attached in the skeleton of molecular sieve, the height that the degree of scatter of Zn makes than other method in the zeolite molecular sieve that then makes, aromatization activity height; And the Zn in this skeleton can avoid being reduced to metal under hydrogen atmosphere and the volatilization loss causes inactivation to be accelerated, thereby has higher activity stability.
The MCM-22 molecular sieve and the synthetic method thereof that the purpose of this invention is to provide a kind of Zn of containing, Zn wherein shows to have at least part to enter framework of molecular sieve by Infrared spectroscopy.
The MCM-22 molecular sieve of the Zn of containing provided by the present invention has X-ray diffraction (XRD) feature and the SiO of conventional MCM-22 molecular sieve
2/ Al
2O
3Mol ratio, its SiO
2/ ZnO mol ratio is 15～300, it is characterized in that 1082～1086cm occurring in the infrared spectra of this molecular sieve
-1With 792～795cm
-1The spectrum peak, promptly compare this spectrum peak to the lower wave number displacement with conventional MCM-22 molecular sieve.
Its SiO of MCM-22 molecular sieve that contains Zn provided by the invention
2/ Al
2O
3Mol ratio is 12～100, is preferably 15～90; Its SiO
2/ ZnO mol ratio is 15～300, is preferably 20～200.
The preparation method of the MCM-22 molecular sieve of the Zn of containing provided by the invention is (with SiO with the silicon source
2Expression), the aluminium source is (with Al
2O
3Expression), zinc source (representing with ZnO), alkali source are (with OH
-Expression), template (representing with R) and water mixes, make to synthesize and use reaction mixture, then with this reaction mixture according to the ordinary method hydrothermal crystallizing; Wherein the mole of said reaction mixture consists of OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.001～0.03): (0.01～0.1): 1: (0.05～0.5): (5～100) are preferably OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=(0.12～0.4): (0.005～0.025): (0.012～0.01): 1: (0.1～0.35): (8～50).
Said hydrothermal crystallizing carries out according to the condition of prior art in the synthetic method of the MCM-22 molecular sieve of the Zn of containing provided by the present invention, the present invention has no particular limits it, general condition is a hydrothermal crystallizing 10～200 hours under 120～200 ℃ and autogenous pressure, preferably hydrothermal crystallizing 30～150 hours under 130～190 ℃ and autogenous pressure.
The silicon source of being adopted in the synthetic method of the MCM-22 molecular sieve of the Zn of containing provided by the present invention, aluminium source, alkali source, organic formwork agent (R) etc. determine that according to prior art the present invention has no particular limits it; But the preferred raw material of the present invention is to be the silicon source with the solid silicone, or is silicon source and part aluminium source with the solid silicon aluminium glue; With sodium metaaluminate is all or part of aluminium source; Alkali source can be a sodium hydroxide; Organic formwork agent can be hexamethylene imine (HMI) or diamantane quaternary ammonium hydroxide, wherein hexamethylene imine preferably.
Said zinc source can be the salt of zinc oxide, zinc hydroxide or zinc such as zinc nitrate, zinc sulfate, zinc chloride etc. in the synthetic method of the MCM-22 molecular sieve of the Zn of containing provided by the present invention.
The MCM-22 molecular sieve of the Zn of containing provided by the present invention can be used in the reaction such as the aromizing of lower carbon number hydrocarbons.
The MCM-22 molecular sieve of the Zn of containing provided by the invention is owing to adopt direct hydrothermal method that Zn is synthesized in the MCM-22 molecular sieve, infrared spectra shows that the IR stretching vibration frequency of its Si-O-Al key of MCM-22 molecular sieve of the Zn of containing of the present invention obviously to the lower wave number displacement, is 1088.9cm as its IR stretching vibration frequency of MCM-22 molecular sieve (Comparative Examples 1) that does not contain Zn
-1And 797.0cm
-1, its IR stretching vibration frequency of the MCM-22 molecular sieve of the Zn of containing of the present invention is 1082～1086cm
-1With 792～795cm
-1, and adopt its IR stretching vibration frequency of the MCM-22 molecular sieve that contains Zn (Comparative Examples 2) that exchange process obtains not to the lower wave number displacement, can prove that thus the Zn in the MCM-22 molecular sieve of the Zn of containing provided by the invention has entered the skeleton of molecular sieve.The result that Zn enters framework of molecular sieve must bring the characteristics of Zn good dispersity and good stability, to improving reactive behavior and stability is beneficial.
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 are respectively the X-ray diffractogram of embodiment 2,3,4 and 5 gained sieve samples.
Fig. 5, Fig. 6, Fig. 7, Fig. 8, Fig. 9 and Figure 10 are respectively the infrared spectrogram of embodiment 2,3,4,5 and Comparative Examples 1 and Comparative Examples 2 gained sieve samples.
The following examples will the present invention is described further.Said umber is parts by weight in each embodiment and the Comparative Examples.
Embodiment 1
The present embodiment explanation is with the method for the raw silicon aluminium glue microballoon of the synthetic Zn-MCM-22 molecular sieve of NaY mother liquor preparation.
The NaY mother liquor (is taken from Chang Ling oil-refining chemical factory molecular sieve workshop of Catalyst Factory, SiO
2Content is 47 grams per liters, Na
2O content is 25 grams per liters) be that the dilute sulphuric acid of 40 weight % is adjusted to pH=5～6 with concentration, wherein silicon, aluminium element are precipitated out with the form of alumino silica gel.Filter cake after the filtration adds the water making beating, makes the slurries that solid content is 10 weight %.With this slurries spraying drying, obtain the above particle diameter of 60 weight % and be 40～80 microns alumino silica gel microballoon.With of the ammoniumsulphate soln pulp of this microballoon, wash again to Na with 3 weight %
2O content＜0.1 weight %, drying obtains the alumino silica gel microspheres product.The SiO of this alumino silica gel microballoon of analysis revealed
2Content is 92.0 weight %, Al
2O
3Content is 3.16 weight %, and the calcination butt is 85.2 weight %, specific surface area 501m
2/ g.
Embodiment 2
With 1.35 parts of NaOH (Beijing Yili Fine Chemicals Co., Ltd., NaOH 〉=96.0 weight %), 54.7 parts of H
2O, 0.61 part of Zn (NO
3)
26H
2The silicon aluminium microsphere that makes among O (Beijing Chemical Plant, content 〉=99.0 weight %), 4.69 parts of HMI (Tokyo HuaCheng Industry Co., Ltd) and the 18.6 parts of embodiment 1 adds in the autoclave.The gained reaction mixture has following mole and forms: OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=0.14: 0.01: 0.02: 1: 0.19: 13.4.After mixing, this mixture after 66 hours, is stopped crystallization in 154 ℃ of static crystallizations, product is through cooling off, filter, wash and being drying to obtain the Zn-MCM-22 molecular sieve, and its XRD spectra is seen Fig. 1, and skeleton IR spectrogram is seen Fig. 5.
Through x ray fluorescence spectrometry analysis (down together) as can be known: above-mentioned product S iO
2/ Al
2O
3Be 52.6, SiO
2/ ZnO is 109.4; The specific surface area that the BET method records is 421m
2/ g.
Embodiment 3
With 13.8 gram NaOH, 544 gram H
2O, 6.40 gram ZnSO
47H
2O (two swallow chemical plant, Pinggu, Beijing, content 〉=99.5 weight %), 31.3 gram HMI, 1.38 gram NaAlO
2(Jiangpu, Shanghai chemical preparations factory, Al
2O
3〉=43 weight %) and 45.0 gram white carbon blacks add in the autoclaves, mix.Reaction mixture has following mole and forms: OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=0.42: 0.033: 0.013: 1: 0.47: 45.After 83 hours, stop crystallization in 154 ℃ of static crystallizations, product is through cooling off, filter, wash and being drying to obtain the Zn-MCM-22 molecular sieve, and its XRD spectra is seen Fig. 2.Skeleton IR spectrogram is seen Fig. 6.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 81.1, SiO
2/ ZnO is 30.8, and specific surface area is 403m
2/ g.
Embodiment 4
With 1.69 gram NaAlO
2, 3.98 the gram NaOH, 256 the gram H
2O, 3.44 gram Zn (NO
3)
26H
2Silicon aluminium microsphere that makes among O, the 40 gram embodiment 1 and the mixture of 15 gram HMI are in stainless steel autoclave.Reaction mixture has following mole and forms: OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=0.21: 0.022: 0.04: 1: 0.29: 28.In 145 ℃ of static crystallizations stopped reaction after 135 hours, product after filtration, wash and be drying to obtain the Zn-MCM-22 molecular sieve, its XRD spectra is seen Fig. 3.Skeleton IR spectrogram is seen Fig. 7.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 28.1, SiO
2/ ZnO is 45.8, and specific surface area is 408m
2/ g.
With 1.57 gram NaAlO
2, 2.74 the gram NaOH, 123 the gram H
2Silicon aluminium microsphere that makes among O, 0.38 gram ZnO (Beijing Chemical Plant, content 〉=99.5 weight %), the 56 gram embodiment 1 and the mixture of 5.8 gram HMI are in stainless steel autoclave.Reaction mixture has following mole and forms: OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=0.12: 0.007: 0.033: 1: 0.08: 10.In 145 ℃ of static crystallizations stopped reaction after 140 hours, product after filtration, wash and be drying to obtain the Zn-MCM-22 molecular sieve, its XRD spectra is seen Fig. 4.Skeleton IR spectrogram is seen Fig. 8.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 32.6, SiO
2/ ZnO is 157, and specific surface area is 391m
2/ g.
Comparative Examples 1
With 1.25 gram NaOH, 60 gram H
2Silicon aluminium microsphere that makes among O, the 20 gram embodiment 1 and the mixture of 4.9 gram HMI are in stainless steel autoclave.Reaction mixture has following mole and forms: OH
-: Al
2O
3: SiO
2: R: H
2O=0.14: 0.02: 1: 0.19: 13.4.In 155 ℃ of static crystallizations stopped reaction after 85 hours, product after filtration, wash and be drying to obtain the MCM-22 molecular sieve.Its skeleton IR spectrogram is seen Fig. 9.
Comparative Examples 2
Through product, zinc chloride and the water of 4 hours Comparative Examples of 550 ℃ of roastings 1, add in the beaker according to 1: 1: 20 (weight ratio), 90 ℃ of exchanges are after 2 hours, and washing, drying, roasting obtain infrared spectrum such as Figure 10 of sample.
Claims (10)
1, a kind of MCM-22 molecular sieve that contains Zn, X ray diffracting characteristic and SiO with conventional MCM-22 molecular sieve
2/ Al
2O
3Mol ratio, its SiO
2/ ZnO mol ratio is 15～300, it is characterized in that in the infrared spectra of this molecular sieve at 1082～1086cm
-1With 792～795cm
-1Scope in the spectrum peak appears.
2, according to the MCM-22 molecular sieve that contains Zn of claim 1, its SiO
2/ Al
2O
3Mol ratio is 12～100; Its SiO
2/ ZnO mol ratio is 20～200.
3, the described synthetic method that contains the MCM-22 molecular sieve of Zn of claim 1, this method comprise silicon source, aluminium source, zinc source, alkali source, template and water mixed, and makes syntheticly to use reaction mixture, then with this reaction mixture hydrothermal crystallizing; Wherein the mole of said reaction mixture consists of OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.001～0.03): (0.01～0.1): 1: (0.05～0.5): (5～100).
4, according to the synthetic method of claim 3, wherein said silicon source is solid silicone or solid silicon aluminium glue; Said aluminium source is the aluminium in sodium metaaluminate or sodium metaaluminate and the solid silicon aluminium glue; Said alkali source is a sodium hydroxide; Said organic formwork agent is hexamethylene imine or diamantane quaternary ammonium hydroxide.
5, according to the synthetic method of claim 4, wherein said organic formwork agent is a hexamethylene imine.
6, according to the synthetic method of claim 3, wherein said zinc source is the salt of zinc oxide, zinc hydroxide or zinc.
7, according to the synthetic method of claim 6, wherein the salt of said zinc is zinc nitrate, zinc sulfate or zinc chloride.
8, according to the synthetic method of claim 3, wherein the mole of said reaction mixture consists of OH
-: ZnO: Al
2O
3: SiO
2: R: H
2O=(0.12～0.4): (0.005～0.025): (0.012～0.01): 1: (0.1～0.35): (8～50).
9, according to the synthetic method of claim 3, wherein said hydrothermal crystallizing is a hydrothermal crystallizing 10～200 hours under 120～200 ℃ and autogenous pressure.
10, according to the synthetic method of claim 9, wherein said hydrothermal crystallizing is a hydrothermal crystallizing 30～150 hours under 130～190 ℃ and autogenous pressure.
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|---|---|---|---|
| CN 00130267 CN1111087C (en) | 2000-11-02 | 2000-11-02 | Molecular sieve containing zinc and its synthesis |
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|---|---|---|---|
| CN 00130267 CN1111087C (en) | 2000-11-02 | 2000-11-02 | Molecular sieve containing zinc and its synthesis |
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| CN1111087C CN1111087C (en) | 2003-06-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495342A (en) * | 2013-09-25 | 2014-01-08 | 北京钟华鼎盛节能技术有限公司 | Method for separating MEOH-DMC (methanol-dimethyl carbonate) through vapor permeation |
| CN104803397A (en) * | 2014-01-28 | 2015-07-29 | 中国石油化工股份有限公司 | MCM-49 molecular sieve with low silica-alumina ratio, and preparation method thereof |
| WO2015137884A1 (en) * | 2014-03-10 | 2015-09-17 | Agency For Science, Technology And Research | Zeolites with mww framework formed of silicon and zinc or iron, and related methods |
| CN105460948A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Stratified material SCM-7 and preparation method therefor |
-
2000
- 2000-11-02 CN CN 00130267 patent/CN1111087C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495342A (en) * | 2013-09-25 | 2014-01-08 | 北京钟华鼎盛节能技术有限公司 | Method for separating MEOH-DMC (methanol-dimethyl carbonate) through vapor permeation |
| CN103495342B (en) * | 2013-09-25 | 2016-01-20 | 北京钟华鼎盛节能技术有限公司 | A kind of Steam soak is separated the method for MEOH-DMC |
| CN104803397A (en) * | 2014-01-28 | 2015-07-29 | 中国石油化工股份有限公司 | MCM-49 molecular sieve with low silica-alumina ratio, and preparation method thereof |
| WO2015137884A1 (en) * | 2014-03-10 | 2015-09-17 | Agency For Science, Technology And Research | Zeolites with mww framework formed of silicon and zinc or iron, and related methods |
| US20160376159A1 (en) * | 2014-03-10 | 2016-12-29 | Agency For Science, Technology And Research | Zeolites with mww framework formed of silicon and zinc or iron, and related methods |
| CN105460948A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Stratified material SCM-7 and preparation method therefor |
| CN105460948B (en) * | 2014-09-09 | 2017-10-27 | 中国石油化工股份有限公司 | Stratified material SCM 7 and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1111087C (en) | 2003-06-11 |
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Granted publication date: 20030611 |