CN102515198B - 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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- CN102515198B CN102515198B CN 201110370674 CN201110370674A CN102515198B CN 102515198 B CN102515198 B CN 102515198B CN 201110370674 CN201110370674 CN 201110370674 CN 201110370674 A CN201110370674 A CN 201110370674A CN 102515198 B CN102515198 B CN 102515198B
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- -1 butyl aluminium Chemical group 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000002910 rare earth metals Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
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 Integral-type heteroatom replacing hierarchical porous molecular sieve and one-step method for synthesizing thereof.
Background technology
But the catalytic performance of the well-regulated duct of zeolite molecular sieve tool, good shape selectivity, stability and modulation, fields such as being widely used in catalysis, ion-exchange, adsorbing and separating.Metal 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 duct by methods such as ion-exchange, dipping and vapour depositions at present.But in these three kinds of preparation process, part is scattered in molecular sieve surface or duct because metallic element can not enter framework of molecular sieve fully, thereby is reduced to unavoidably metal and is run off under hydrogen atmosphere, causes catalyst stability to descend.Although isomorphous substitution method can overcome the shortcoming of aforesaid method, but metal ion very easily is hydrolyzed in the normally used alkaline medium of zeolite-water thermal synthesis and generates indissoluble oxyhydroxide or oxide precipitation, stop metallic element effectively to enter framework of molecular sieve, therefore must adopt new synthesis path just metallic element might be incorporated in framework of molecular sieve.Recently, Wu etc. proposes a kind of method that multistep is regulated the MCM-22 molecular sieve of the synthetic containing rare earth heteroatoms in skeleton of pH method.At first, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, the pH value of controlling solution with HCl is 2, then adds the template of hexamethylene imine in the above-mentioned hydrolysate, and the pH value that obtains solution is 5-6.Add solution before 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) although. the method is conducive to rare-earth heteroatoms and enters framework of molecular sieve, and preparation process is complicated, the difficult pH that controls.The heteroatomic molecular sieve of gained skeleton containing metal is generally powder.Although in industrial application, it is whole column or sheet shape that zeolite [molecular sieve adopts usually, also there is no any patent and the bibliographical information of Integral-type heteroatom replacing hierarchical porous molecular sieve at present.
Summary of the invention
The purpose of this invention is to provide a kind of Integral-type heteroatom replacing hierarchical porous molecular sieve and one-step method for synthesizing thereof.
Integral-type heteroatom replacing hierarchical porous molecular sieve of the present invention, 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 the atoms metal Cu that enters framework of molecular sieve, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Pt, Pd, Ce, one or more mixing in La and Y;
x,
y，1-(
x+
y) represent respectively Me, the molar fraction 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.
The method of Integral-type heteroatom replacing hierarchical porous molecular sieve of the present invention, employing be single stage method, its concrete steps are as follows:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred 2 ~ 24 hours, added wherein alkali source, and then added metal-salt to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 80 ~ 200
oAfter C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours gets Integral-type heteroatom replacing hierarchical porous 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.
In the present invention, described alkali source is NaOH, KOH and NH
4The mixture of one or more in OH.Described silicon source is one or more mixing in silicon sol, water glass, silicon gel, tetraethyl orthosilicate and positive silicic acid propyl ester.Described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and tertiary butyl aluminium.Described template is organic amine (C
nH
2n+1)
4One or more mixing in NX, wherein n=1 – 22; X=OH, Br or Cl.Described metal-salt is a kind of in the nitrate of Cu, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Ce, La and Y or several mixture arbitrarily.
Beneficial effect of the present invention:
The present invention adopts one-step synthesis, generates oxyhydroxide or water and oxide precipitation for fear of metal heteroatom because of hydrolysis in building-up process, and it is to promote gelating agent that the present invention adopts alkali source, then first gelation mother liquor adds metal-salt, atoms metal Me is existed with the form of Si-O-Me, need not add any unbodied carrier, need not mesoporous or macropore template, technique is simple, reduce water, crystallization time is short, and temperature is low, 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, the 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 nitrogen absorption under low temperature-desorption isotherm figure of sintetics.In figure, 1 is adsorption curve, 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 5.13g tetraethyl orthosilicate, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution, then added 0.06g Fe (NO
3)
3.9H
2O gets gel mixture, this gel mixture is moved in the stainless steel synthesis reactor seal, 155
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve through washing, drying and 550
oAfter C roasting 6 hours, namely 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 degree of crystallinity, shows that product has hydrothermal stability preferably.
Fig. 2 and Fig. 3 are respectively the nitrogen absorption under low temperature-desorption isotherm 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 being linked togather, and has simultaneously the integral body of micropore, mesoporous and macropore multistage pore canal, 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 molecular sieve skeleton with the four-coordination form.
Embodiment 2:
Colloidal sol (2.8 wt.% Al with 5.13g tetraethyl orthosilicate, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution, then added 0.06g Fe (NO
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 C roasting 6 hours, namely obtain heteroatoms and get multistage pore canal for the integral body of 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 5.13g tetraethyl orthosilicate, 2g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution, then added 0.12g Fe (NO
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 C roasting 6 hours, namely 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 5.13g tetraethyl orthosilicate, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution, then added 0.07g Ce (NO
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 C roasting 6 hours, namely 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 degree of 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 being linked togather the integral body that forms the Ce-ZSM-5 molecular sieve that the duct varies in size 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 the ZSM-5 molecular sieve skeleton, (250nm belongs to Ce
3+Four-coordination, 300nm belongs to Ce
4+Four-coordination).
Embodiment 5:
5.13g tetraethyl orthosilicate, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution, then added 0.07g Ce (NO
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 C roasting 6 hours, namely 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 is only several 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 to this.
Claims (6)
1. an Integral-type heteroatom replacing hierarchical porous molecular sieve, 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 the atoms metal Cu that enters framework of molecular sieve, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Pt, Pd, Ce, one or more mixing in La and Y;
x,
y，1-(
x+
y) represent respectively Me, the molar fraction 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. synthesize the method for Integral-type heteroatom replacing hierarchical porous molecular sieve claimed in claim 1, it is characterized in that step is as follows:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred 2 ~ 24 hours, added wherein alkali source, and then added metal-salt to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 80 ~ 200
oAfter C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours gets Integral-type heteroatom replacing hierarchical porous 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; Described template is TPAOH.
3. the method for described synthetic Integral-type heteroatom replacing hierarchical porous molecular sieve according to claim 2, is characterized in that described alkali source is NaOH, KOH and NH
4The mixture of one or more in OH.
4. the method for described synthetic Integral-type heteroatom replacing hierarchical porous molecular sieve according to claim 2 is characterized in that described silicon source is one or more mixing in silicon sol, water glass, silicon gel, tetraethyl orthosilicate and positive silicic acid propyl ester.
5. the method for described synthetic Integral-type heteroatom replacing hierarchical porous molecular sieve according to claim 2 is characterized in that described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and tertiary butyl aluminium.
6. the method for described synthetic Integral-type heteroatom replacing hierarchical porous molecular sieve according to claim 2 is characterized in that metal-salt used is a kind of in the nitrate of Cu, Mo, Fe, Co, Ti, Ni, Mn, W, V, Zn, Mg, Sn, Ce, La and Y or several mixture arbitrarily.
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| CN107537555B (en) * | 2016-06-29 | 2020-09-04 | 中国石油化工股份有限公司 | Mo/HZSM-5 catalyst, preparation method and application thereof |
| CN107876084B (en) * | 2017-10-23 | 2021-02-23 | 中海油天津化工研究设计院有限公司 | Preparation method of integral nano heteroatom ZSM-22 molecular sieve catalyst |
| 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 |
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|---|---|---|---|---|
| EP0251589A2 (en) * | 1986-06-26 | 1988-01-07 | Mobil Oil Corporation | Synthesis of crystalline binary oxides |
| CN101054182A (en) * | 2007-05-31 | 2007-10-17 | 吉林大学 | Method of preparing ordered mesoporous molecular sieve with high hydrothermal stability |
| CN101121525A (en) * | 2007-05-31 | 2008-02-13 | 吉林大学 | Method for synthesizing ordered mesoporous molecular sieve by anion effect |
| CN101327935A (en) * | 2008-07-18 | 2008-12-24 | 山西大学 | Ordered organic/inorganic hybridization mesoporous material and method for preparing the same |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0251589A2 (en) * | 1986-06-26 | 1988-01-07 | Mobil Oil Corporation | Synthesis of crystalline binary oxides |
| CN101054182A (en) * | 2007-05-31 | 2007-10-17 | 吉林大学 | Method of preparing ordered mesoporous molecular sieve with high hydrothermal stability |
| CN101121525A (en) * | 2007-05-31 | 2008-02-13 | 吉林大学 | Method for synthesizing ordered mesoporous molecular sieve by anion effect |
| CN101327935A (en) * | 2008-07-18 | 2008-12-24 | 山西大学 | Ordered organic/inorganic hybridization mesoporous material and method for preparing the same |
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