CN102515198A - Integral-type heteroatom replacing hierarchical porous molecular sieve and synthesis method thereof - Google Patents
Integral-type heteroatom replacing hierarchical porous molecular sieve and synthesis method thereof Download PDFInfo
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- CN102515198A CN102515198A CN2011103706747A CN201110370674A CN102515198A CN 102515198 A CN102515198 A CN 102515198A CN 2011103706747 A CN2011103706747 A CN 2011103706747A CN 201110370674 A CN201110370674 A CN 201110370674A CN 102515198 A CN102515198 A CN 102515198A
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- molecular sieve
- heteroatoms
- pore canal
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Abstract
The invention discloses an integral-type heteroatom replacing hierarchical porous molecular sieve. The chemical formula of the integral-type heteroatom replacing hierarchical porous molecular sieve is (M<n+>)(x+y)/n[(MexAlySil-(x+y))O2].wH2O, wherein M<n+> is one or a mixture of several of cations: Na<+>, K<+>, H<+>, Ca<2+> and Mg<2+>; Me which enters a molecular sieve framework is one or a mixture of several of the following metal atoms: Cu, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Pt, Pd, Ce, La and Y; x, y and 1-(x+y) respectively represent mole fractions of Me, Al and Si; x ranges from 0.001 to 0.05, and y ranges from 0 to 0.6; w represents the number of water molecules in each mole of (MexAlySil-(x+y))O2; and w ranges from 1 to 80, and n is equal to 1 or 2. The preparation process is simple, and is low in cost.
Description
Technical field
The present invention relates to a kind of monolithic devices heteroatoms and replace multistage pore canal molecular sieve and one-step method for synthesizing thereof.
Background technology
But zeolite molecular sieve has the duct of rule, the catalytic performance of good shape selectivity, stability and modulation, fields such as being widely used in catalysis, IX, adsorbing and separating.Metals ion is introduced hydrothermal stability and the catalytic performance that molecular sieve can further improve molecular sieve.The investigator often is scattered in metallic element in molecular sieve surface or the duct through methods such as IX, dipping and vapour depositions at present.But in these three kinds of preparation process, part is scattered in molecular sieve surface or the duct because metallic element can not get into framework of molecular sieve fully, thereby under hydrogen atmosphere, is reduced to metal unavoidably and is run off, and causes catalyst stability to descend.Though isomorphous substitution method can overcome the shortcoming of aforesaid method; But metals ion in the synthetic normally used alkaline medium of molecular sieve water heat very easily hydrolysis generate indissoluble oxyhydroxide or oxide precipitation; Stop metallic element effectively to get into framework of molecular sieve, therefore must adopt new synthesis path just might metallic element be incorporated in the framework of molecular sieve.Recently, a kind of multistep of proposition such as Wu is regulated the method that the synthetic skeleton of pH method contains the MCM-22 molecular sieve of rare-earth heteroatoms.At first, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, using the pH value of HCl control solution is 2, in above-mentioned hydrolysate, adds the template of hexamethylene imine then, and the pH value that obtains solution is 5-6.Add solution before the last crystallization and mix that to contain the pH value that aluminium source and NaOH obtain solution be 11.6.(Y. Wu, J. Wang, P. Liu; W. Zhang, J. Gu, X. Wang. Framework-Substituted Lanthanide MCM-22 Zeolite:Synthesis and Characterization. J. AM. CHEM. SOC. 2010; 132; 17989 – 17991) though. this method helps rare-earth heteroatoms and gets into framework of molecular sieve, and the preparation process is complicated, difficult control pH.The heteroatomic molecular sieve of gained skeleton containing metal generally is a powder.Though in industrial application, it is whole column or sheet shape that zeolite [molecular sieve adopts usually, also there is not the monolithic devices heteroatoms to replace any patent and the bibliographical information of multistage pore canal molecular sieve at present.
Summary of the invention
The purpose of this invention is to provide a kind of monolithic devices heteroatoms and replace multistage pore canal molecular sieve and one-step method for synthesizing thereof.
Monolithic devices heteroatoms of the present invention replaces the multistage pore canal molecular sieve, and its chemical constitution is expressed as (M
N+ )
(x+y)/n [(Me
x Al
y Si
1
-(
X+y)
) O
2].
wH
2O; Wherein, M
N+ Be positively charged ion Na
+, K
+, H
+, Ca
2+And Mg
2+In one or more mixing; Me is for getting into the atoms metal Cu of framework of molecular sieve, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Pt, Pd, Ce, one or more mixing among La and the Y;
x,
Y,1-(
x+
y) represent Me respectively, the x of Al and Si,
x=0.001 – 0.05,
y=0 – 0.6;
wRepresent every mole of (Me
x Al
y Si
1
-(
X+y)
) O
2Middle water molecule number,
w=1 – 80,
n=1 or 2, its heteroatoms replaces the crystal of molecular sieve from unifying, and has the mesoporous of micropore less than 2nm, 2-50nm and greater than three grades of ducts of macropore of 50nm.
Monolithic devices heteroatoms of the present invention replaces the method for multistage pore canal molecular sieve, employing be single stage method, its concrete steps are following:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred 2 ~ 24 hours, to wherein adding alkali source, and then added metal-salt and got gel mixture, this gel mixture was moved in stainless steel synthesis reactor seal, 80 ~ 200
oBehind the C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours gets the monolithic devices heteroatoms and replaces the multistage pore canal molecular sieve;
The mol ratio of above-mentioned silicon source, aluminium source, water, template, metal-salt and alkali source is 1:0 ~ 0.1:5 ~ 80:0.1 ~ 0.8:0.002 ~ 0.05:0.08 ~ 0.4.
Among the present invention, described alkali source is NaOH, KOH and NH
4The mixture of one or more among the OH.Described silicon source is one or more mixing in silicon sol, water glass, silicon gel, positive tetraethyl orthosilicate and the positive silicic acid propyl ester.Described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and the tertiary butyl aluminium.Described template is organic amine (C
nH
2n+1)
4One or more mixing among the NX, wherein n=1 – 22; X=OH, Br or Cl.Described metal-salt is a kind of or any several kinds mixture in the nitrate salt of Cu, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Ce, La and Y.
Beneficial effect of the present invention:
The present invention adopts one-step synthesis, in building-up process, generates oxyhydroxide or water and oxide precipitation for fear of metal heteroatom because of hydrolysis, and it is to promote gelating agent that the present invention adopts alkali source, and first gelation mother liquor adds metal-salt then; Atoms metal Me is existed with the form of Si-O-Me, need not add any unbodied carrier, need not mesoporous or macropore template; Technology is simple, reduces water, and crystallization time is short; Temperature is low, and production cost is low, is suitable for the characteristics of suitability for industrialized production etc.The pure multistage pore canal heteroatoms of prepared monolithic devices replaces the crystal self join of molecular sieve.The hole is from the micropore to the macropore, and size distribution is wide, active, good hydrothermal stability, and physical strength is high.Can be used for petrochemical complex, fields such as fine chemicals preparation and environmental catalysis.
Description of drawings
Fig. 1 is the XRD spectra of sintetics, and wherein a is the XRD spectra of embodiment 1, and b is the XRD spectra of embodiment 4;
Fig. 2 is the low temperature conditioning adsorption-desorption isothermal map of sintetics.1 is adsorption curve among the figure, and 2 is the desorption curve.
Fig. 3 obtains pore volume and aperture graph of a relation adsorbing by BJH of sintetics.
Fig. 4 is the stereoscan photograph of sintetics, and wherein a is the stereoscan photograph of embodiment 1, and b is the stereoscan photograph of embodiment 4;
Fig. 5 is the UV-vis spectrogram of sintetics, and wherein a is the UV-vis spectrogram of embodiment 1, and b is the UV-vis spectrogram of embodiment 4.
Embodiment
Embodiment 1:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, to wherein adding 3.5ml 6% NaOH solution, added 0.06g Fe (NO again
3)
3.9H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 155
oC crystallization 24 hours, the product that obtains the monolithic devices molecular sieve is through washing, drying and 550
oAfter the C roasting 6 hours, promptly obtain the integral body that heteroatoms replaces multistage pore canal Fe-ZSM-5 molecular sieve.Its chemical formula is Na
+ 0..073[(Fe
0.006Al
0.067 Si
0.927) O
2]. 60H
2O.
Fig. 1 a is the XRD characterization result of product, can see that by Fig. 1 a product has typical MFI ZSM-5 molecular sieve structure, and sample has very high percent crystallinity, shows that product has hydrothermal stability preferably.
Fig. 2 and Fig. 3 are respectively the low temperature conditioning adsorption-desorption thermo-isopleth of product and obtain pore volume and aperture graph of a relation by BJH absorption.Can see that from spectrogram sample has mesoporous part (nitrogen adsorption isotherm line chart belongs to the H4 type).Mesoporous distribution of sizes is wide.
Fig. 4 a is the SEM photo of sample, can see from the SEM photo, and the Fe-ZSM-5 molecular sieve crystal is from joining together, has the integral body of micropore, mesoporous and macropore multistage pore canal simultaneously, shows that product has higher physical strength.
Fig. 5 a is the UV-vis spectrogram, can see that from figure the Fe atom all is present in the ZSM-5 framework of molecular sieve with the four-coordination form.
Embodiment 2:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, to wherein adding 3.5ml 6% NaOH solution, added 0.06g Fe (NO again
3)
3.9H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 170
oThe C crystallization obtained the product of monolithic devices molecular sieve in 24 hours through washing, drying and 550
oAfter the C roasting 6 hours, promptly obtain heteroatoms and get the integral body of multistage pore canal for the Fe-ZSM-5 molecular sieve.Its chemical formula is Na
+ 0..073[(Fe
0.006Al
0.067 Si
0.927) O
2]. 60H
2O.
Embodiment 3:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 2g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, to wherein adding 3.5ml 6% NaOH solution, added 0.12g Fe (NO again
3)
3.9H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 170
oThe C crystallization obtained the product of monolithic devices molecular sieve in 24 hours through washing, drying and 550
oAfter the C roasting 6 hours, promptly obtain the integral body that heteroatoms replaces multistage pore canal Fe-ZSM-5 molecular sieve.Its chemical formula is Na
+ 0.067[(Fe
0.023Al
0.044 Si
0.933) O
2]. 60H
2O.
Embodiment 4:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, to wherein adding 3.5ml 6% NaOH solution, added 0.07g Ce (NO again
3)
3.6H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 155
oThe C crystallization obtained the product of monolithic devices molecular sieve in 24 hours through washing, drying and 550
oAfter the C roasting 6 hours, promptly obtain the integral body that heteroatoms replaces multistage pore canal Ce-ZSM-5 molecular sieve.Its chemical formula is (Na
+ 0..073[(Ce
0.006Al
0.067 Si
0.927) O
2]. 60H
2O.
Fig. 1 b is the XRD characterization result of product, can see that by Fig. 1 b product has typical MFI ZSM-5 molecular sieve structure, and sample has very high percent crystallinity, shows that product has hydrothermal stability preferably.
Fig. 4 a is the SEM photo of sample, can see from the SEM photo, and the Ce-ZSM-5 molecular sieve crystal shows that from join the integral body form the Ce-ZSM-5 molecular sieve that the duct varies in size together product has higher physical strength.
Fig. 5 b is the UV-vis spectrogram of sample, can see that from figure the Ce atom is present in the four-coordination form all that (250nm belongs to Ce the ZSM-5 framework of molecular sieve
3+Four-coordination, 300nm belongs to Ce
4+Four-coordination).
Embodiment 5:
The positive tetraethyl orthosilicate of 5.13g, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, to wherein adding 3.5ml 6% NaOH solution, added 0.07g Ce (NO again
3)
3.6H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 170
oThe C crystallization obtained the product of monolithic devices molecular sieve in 24 hours through washing, drying and 550
oAfter the C roasting 6 hours, promptly obtain the integral body that heteroatoms replaces multistage pore canal Ce-Silicalite-1 molecular sieve.Its chemical formula is Na
+ 0..006[(Ce
0.006Si
0.994) O
2]. 60H
2O.
The above only is several kinds of case study on implementation of the present invention, is not that the present invention is done any pro forma restriction.Protection scope of the present invention is not limited thereto.
Claims (7)
1. a monolithic devices heteroatoms replaces the multistage pore canal molecular sieve, it is characterized in that chemical constitution is expressed as (M
N+ )
(x+y)/n [(Me
x Al
y Si
1
-(
X+y)
) O
2].
wH
2O; Wherein, M
N+ Be positively charged ion Na
+, K
+, H
+, Ca
2+And Mg
2+In one or more mixing; Me is for getting into the atoms metal Cu of framework of molecular sieve, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Pt, Pd, Ce, one or more mixing among La and the Y;
x,
Y,1-(
x+
y) represent Me respectively, the x of Al and Si,
x=0.001 – 0.05,
y=0 – 0.6;
wRepresent every mole of (Me
x Al
y Si
1
-(
X+y)
) O
2Middle water molecule number,
w=1 – 80,
n=1 or 2, its heteroatoms replaces the crystal of molecular sieve from unifying, and has the mesoporous of micropore less than 2nm, 2-50nm and greater than three grades of ducts of macropore of 50nm.
2. the described monolithic devices heteroatoms of synthetic claim 1 replaces the method for multistage pore canal molecular sieve, it is characterized in that step is following:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred 2 ~ 24 hours, to wherein adding alkali source, and then added metal-salt and got gel mixture, this gel mixture was moved in stainless steel synthesis reactor seal, 80 ~ 200
oBehind the C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours gets the monolithic devices heteroatoms and replaces the multistage pore canal molecular sieve;
The mol ratio of above-mentioned silicon source, aluminium source, water, template, metal-salt and alkali source is 1:0 ~ 0.1:5 ~ 80:0.1 ~ 0.8:0.002 ~ 0.05:0.08 ~ 0.4.
3. replace the method for multistage pore canal molecular sieve according to the described synthetic monolithic devices heteroatoms of claim 2, it is characterized in that described alkali source is NaOH, KOH and NH
4The mixture of one or more among the OH.
4. the method that replaces the multistage pore canal molecular sieve according to the described synthetic monolithic devices heteroatoms of claim 2 is characterized in that described silicon source is one or more mixing in silicon sol, water glass, silicon gel, positive tetraethyl orthosilicate and the positive silicic acid propyl ester.
5. replace the method for multistage pore canal molecular sieve according to the described synthetic monolithic devices heteroatoms of claim 2, it is characterized in that described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and the tertiary butyl aluminium.
6. replace the method for multistage pore canal molecular sieve according to the described synthetic monolithic devices heteroatoms of claim 2, it is characterized in that described template is organic amine (C
nH
2n+1)
4One or more mixing among the NX, wherein n=1 – 22; X=OH, Br or Cl.
7. the method that replaces the multistage pore canal molecular sieve according to the described synthetic monolithic devices heteroatoms of claim 2 is characterized in that used metal-salt is a kind of or any several kinds mixture in the nitrate salt of Cu, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Ce, La and Y.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105451881A (en) * | 2013-06-13 | 2016-03-30 | 巴斯夫欧洲公司 | Process for the preparation of butadiene |
| CN107537555A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The catalyst of Mo/HZSM 5, preparation method and applications |
| CN107876084A (en) * | 2017-10-23 | 2018-04-06 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of the molecular sieve catalysts of integrated nano hetero atom ZSM 22 |
| CN110586176A (en) * | 2019-09-27 | 2019-12-20 | 中国环境科学研究院 | Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof |
| CN111408402A (en) * | 2020-04-10 | 2020-07-14 | 福建龙净环保股份有限公司 | Titanium modified SSZ-13 type molecular sieve catalyst slurry, preparation method thereof, modified molecular sieve catalyst and catalytic ceramic filter tube |
| WO2022116379A1 (en) * | 2020-12-03 | 2022-06-09 | 万华化学集团股份有限公司 | Method for preparing catalyst and method for reducing voc content in polyether polyol |
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Cited By (7)
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|---|---|---|---|---|
| CN105451881A (en) * | 2013-06-13 | 2016-03-30 | 巴斯夫欧洲公司 | Process for the preparation of butadiene |
| CN107537555A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The catalyst of Mo/HZSM 5, preparation method and applications |
| CN107876084A (en) * | 2017-10-23 | 2018-04-06 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of the molecular sieve catalysts of integrated nano hetero atom ZSM 22 |
| CN110586176A (en) * | 2019-09-27 | 2019-12-20 | 中国环境科学研究院 | Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof |
| CN110586176B (en) * | 2019-09-27 | 2020-11-17 | 中国环境科学研究院 | Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof |
| CN111408402A (en) * | 2020-04-10 | 2020-07-14 | 福建龙净环保股份有限公司 | Titanium modified SSZ-13 type molecular sieve catalyst slurry, preparation method thereof, modified molecular sieve catalyst and catalytic ceramic filter tube |
| WO2022116379A1 (en) * | 2020-12-03 | 2022-06-09 | 万华化学集团股份有限公司 | Method for preparing catalyst and method for reducing voc content in polyether polyol |
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