CN1406870A - Heteroatomic molecular sieve and its synthesis - Google Patents
Heteroatomic molecular sieve and its synthesis Download PDFInfo
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- CN1406870A CN1406870A CN 01130975 CN01130975A CN1406870A CN 1406870 A CN1406870 A CN 1406870A CN 01130975 CN01130975 CN 01130975 CN 01130975 A CN01130975 A CN 01130975A CN 1406870 A CN1406870 A CN 1406870A
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Abstract
A molecular sieve MCM-49 containing heteroatoms is prepared by direct hydrothermal synthesis. Said molecular sieve has the X-ray diffraction characteristics and the mole ratio of SiO2 to Al2O3 of conventional molecular sieve MCM-49 and contains the heteroatoms of transition metal chosen from Ti, V, Cr, Mo, W, Co, Ni, Cu and Zn.
Description
Technical field
The present invention relates to a kind of molecular sieve (MCM-49) with special crystal structure and synthetic, particularly relate to the MCM-49 molecular sieve that contains transition metal hetero-atom and synthetic.
Background technology
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.
USP5,236,575 (1993) have reported the synthetic of MCM-49 first.The roasting sample of MCM-22 has similar structure cell c shaft size among MCM-49 molecular screen primary powder (the undressed molecular sieve that synthesizes) and this family member, and its interlamellar spacing is less, in conjunction with stronger, and can not be in the effect UR of expanding agent; The former powder of MCM-22 (being designated as MCM-22 (p)) interlamellar spacing is bigger, a little less than, and can reaming under the effect of expanding agent; MCM-22 (p) roasting can be obtained the MCM-22 molecular sieve, and its interlamellar spacing is that structure cell c shaft size diminishes.The nuance of axial dimension has tangible reflection on X-ray diffraction (XRD) collection of illustrative plates, wherein the former powder d of MCM-49 value is that the peak of～12.8 and this three kinds of materials are can both observed d value very close for the strong peak of～12.4 .MCM-22 is usually expressed as the acromion that d value is the strong peak of～12.4 in the d value for the peak of～12.6 .In addition, the XRD of MCM-22 (p) composes the peak, and especially the d value is that～4.1 arrive the spectrum peak between～3.6 , and the disperse broadening is also overlapped; And the former powder of MCM-49 spectrum peak and the spectrum peak of the MCM-22 after the roasting during this time is similar, and spectral line comes to a point, clear in structure.
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.The zeolite molecular sieve that contains Mo has very high activity and selectivity in oxygen-free aromatization reaction of methane.
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.Known to the inventor, except people's such as above-mentioned Kumar report and have trivalent element Ga and Fe are synthesized to the report in the MCM-22 molecular sieve, also do not find to contain the report of heteroatomic MCM-49 molecular sieve.
If heteroatoms can be attached in the skeleton of molecular sieve, the height that heteroatomic degree of scatter makes than other method in the zeolite molecular sieve that then makes, reactive behavior height; And the heteroatoms 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.
Summary of the invention
The purpose of this invention is to provide a kind of heteroatomic MCM-49 molecular sieve and synthetic method thereof of containing.
Provided by the present inventionly contain X-ray diffraction (XRD) feature and the SiO that heteroatomic MCM-49 molecular sieve has conventional MCM-49 molecular sieve
2/ Al
2O
3Mol ratio is characterized in that this molecular sieve contains the transition metal hetero-atom that is selected from Ti, V, Cr, Mo, W, Co, Ni, Cu or Zn, its SiO
2/ heteroatomic mol ratio is 15～300.
The preparation method who contains heteroatomic MCM-49 molecular sieve provided by the present invention comprises silicon source, aluminium source, heteroatoms 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
-: heteroatoms: 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).
In the reactions such as the aromizing that contains hydrofining that heteroatomic MCM-49 molecular sieve can be used for hydro carbons, hydrocracking, lower carbon number hydrocarbons provided by the present invention, desulfurization.
Feature of the present invention is to adopt direct hydrothermal method that heteroatoms is synthesized in the MCM-49 molecular sieve.
MCM-49 molecular sieve provided by the invention can expect that it has special activity and selectivity in some hydrocarbon reaction owing to contain heteroatoms.
Following embodiment will be described in more detail the present invention.
Embodiment
As previously mentioned, provided by the present inventionly contain X-ray diffraction (XRD) feature and the SiO that heteroatomic MCM-49 molecular sieve has conventional MCM-49 molecular sieve
2/ Al
2O
3Mol ratio is characterized in that this molecular sieve contains the transition metal hetero-atom that is selected from Ti, V, Cr, Mo, W, Co, Ni, Cu or Zn, its SiO
2/ heteroatomic mol ratio is 15～300.
Provided by the inventionly contain heteroatomic its SiO of MCM-49 molecular sieve
2/ Al
2O
3Mol ratio is 12～100, is preferably 15～80; Its SiO
2/ heteroatoms mol ratio is 15～300, is preferably 20～200.
Provided by the inventionly contain that said heteroatoms is preferably Ti, VNi, W, Mo or Zn in the heteroatomic MCM-49 molecular sieve.
The preparation method who contains heteroatomic MCM-49 molecular sieve provided by the invention is (with SiO with the silicon source
2Expression), the aluminium source is (with Al
2O
3Expression), heteroatoms source (representing with element M), 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
-: M: 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
-: M: 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 that contains heteroatomic MCM-49 molecular sieve 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 heteroatomic MCM-49 molecular sieve, aluminium source, alkali source, organic formwork agent (R) etc. of containing provided by the present invention determines 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.
In the synthetic method that contains heteroatomic MCM-49 molecular sieve provided by the present invention said heteroatoms source can be its oxide compound, oxyhydroxide or described heteroatomic salt such as nitrate, vitriol, muriate with and the salt of oxygen acid root negatively charged ion (as the metatungstic acid root) etc.Description of drawings
Fig. 1 a, b, c and d are respectively the X-ray diffractogram of embodiment 2,3,4 and 5 gained sieve samples.
The present invention is described further below by embodiment, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In each embodiment, x ray fluorescence spectrometry is adopted in ultimate analysis, and the BET surface-area is pressed the GB/T5816-1995 method with low-temperature nitrogen adsorption method and measured.
Embodiment 1
The present embodiment explanation is with the synthetic method that contains the alumino silica gel microballoon of heteroatoms MCM-49 molecular sieve raw material 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 47g/L, Na
2O content is 25g/L) 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 particle diameter 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 0.28gNaOH (Beijing Yili Fine Chemicals Co., Ltd., NaOH 〉=96.0 weight %), 60gH
2O, 1.1gZn (NO
3)
26H
2The silicon aluminium microsphere that makes among O (Beijing Chemical Plant, content 〉=99.0 weight %), 3.4gHMI (Tokyo HuaCheng Industry Co., Ltd) and the 20g embodiment 1 adds in the autoclave, mixes, and reaction mixture has following mole and forms: OH
-: Al
2O
3: ZnO: SiO
2: R: H
2O=0.14: 0.067: 0.014: 1: 0.13: 13.5.In 160 ℃ of static crystallizations 58 hours, stop crystallization.Product is through cooling off, filter, wash and being drying to obtain the Zn-MCM-49 molecular sieve, and its XRD spectra is seen accompanying drawing 1a.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 15.3, SiO
2/ ZnO is 74, and specific surface area is 458m
2/ g.
Embodiment 3
With 0.56gNaAlO
2, 3.69gNaOH, 185gH
2O, 1.52gNi (NO
3)
26H
2The silicon aluminium microsphere that makes among O, 12.9gHMI and the 20g embodiment 1 adds in the autoclave, mixes, and reaction mixture has following mole and forms: OH
-: Al
2O
3: NiO: SiO
2: R: H
2O=0.4: 0.033: 0.02: 1: 0.5: 40.In 168 ℃ of static crystallizations 53 hours, stopped reaction, product is through cooling off, filter, wash and being drying to obtain the Ni-MCM-22 molecular sieve, and its XRD spectra is seen accompanying drawing 1b.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 31.2, SiO
2/ NiO is 50.5, and specific surface area is 445m
2/ g.
Embodiment 4
With 3.6gNaOH, 200gH
2O, 1.04gTiOSO
4(TiO
2Content is 20 weight %), the silicon aluminium microsphere that makes among 11.6gHMI and the 30g embodiment 1 adds in the autoclave, mixes, reaction mixture has following mole and forms: OH
-: Al
2O
3: TiO
2: SiO
2: R: H
2O=0.25: 0.02: 0.0067: 1: 0.3: 29.In 175 ℃ of static crystallizations 44 hours, stop crystallization, product is through cooling off, filter, wash and being drying to obtain the Ti-MCM-22 molecular sieve, and its XRD spectra is seen accompanying drawing 1c.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 50.6, SiO
2/ TiO
2Be 155.1, specific surface area is 409m
2/ g.
Embodiment 5
With 0.77gNaAlO
2, 2.17gNaOH, 134gH
2O, 1.16ml ammonium metatungstate aqueous solution (73.2g/100mlWO
3), the white carbon black of 7.4gHMI and 25g adds in the autoclave, mixes, reaction mixture has following mole and forms: OH
-: Al
2O
3: WO
3: SiO
2: R: H
2O=0.17: 0.013: 0.01: 1: 0.20: 20.In 180 ℃ of static crystallizations 40 hours, stop crystallization, product is through cooling off, filter, wash and being drying to obtain the W-MCM-22 molecular sieve, and its XRD spectra is seen accompanying drawing 1d.
By analysis as can be known: above-mentioned product S iO
2/ Al
2O
3Be 80.7, SiO
2/ WO
3Be 102.2, specific surface area is 391m
2/ g.
Claims (10)
1, a kind of MCM-49 molecular sieve, X ray diffracting characteristic and SiO with conventional MCM-49 molecular sieve
2/ Al
2O
3Mol ratio is characterized in that this molecular sieve contains the transition metal hetero-atom that is selected from Ti, V, Cr, Mo, W, Co, Ni, Cu or Zn.
2, according to the MCM-49 molecular sieve of claim 1, the SiO of this molecular sieve
2/ heteroatomic mol ratio is 15～300.
3, according to the MCM-49 molecular sieve of claim 1, its SiO
2/ Al
2O
3Mol ratio is 12～100; Its SiO
2/ heteroatoms mol ratio is 20～200.
4, the preparation method of the described MCM-49 molecular sieve of claim 1, this method comprise silicon source, aluminium source, heteroatoms 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
-: heteroatoms: 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).
5, according to the preparation method of claim 4, wherein said silicon source is the silicon in solid silicone or the 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.
6, according to the preparation method of claim 5, wherein said organic formwork agent is a hexamethylene imine.
7, according to the preparation method of claim 4, wherein said heteroatoms source is described heteroatomic oxide compound, oxyhydroxide or described heteroatomic salt.
8, according to the preparation method of claim 7, wherein said heteroatomic salt be nitrate, vitriol, muriate with and the anionic salt of oxygen acid root.
9, according to the preparation method of claim 4, wherein the mole of said reaction mixture consists of OH
-: heteroatoms: 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).
10, according to the preparation method of claim 4, wherein said hydrothermal crystallizing is a hydrothermal crystallizing 10～200 hours under 120～200 ℃ and autogenous pressure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411736C (en) * | 2005-10-27 | 2008-08-20 | 中国科学院过程工程研究所 | Chronmium-containing mesoporous mobecular sieve and its preparation method and use |
| 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 |
-
2001
- 2001-08-29 CN CNB01130975XA patent/CN1171792C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411736C (en) * | 2005-10-27 | 2008-08-20 | 中国科学院过程工程研究所 | Chronmium-containing mesoporous mobecular sieve and its preparation method and use |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1171792C (en) | 2004-10-20 |
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