CN102642847B - Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve - Google Patents
Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve Download PDFInfo
- Publication number
- CN102642847B CN102642847B CN 201210141312 CN201210141312A CN102642847B CN 102642847 B CN102642847 B CN 102642847B CN 201210141312 CN201210141312 CN 201210141312 CN 201210141312 A CN201210141312 A CN 201210141312A CN 102642847 B CN102642847 B CN 102642847B
- Authority
- CN
- China
- Prior art keywords
- crystallization
- molecular sieve
- liquid
- zsm
- zeolite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000010457 zeolite Substances 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 238000000034 method Methods 0.000 title abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 239000006185 dispersion Substances 0.000 title abstract 2
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 238000002425 crystallisation Methods 0.000 claims abstract description 50
- 230000008025 crystallization Effects 0.000 claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012452 mother liquor Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 239000002245 particle Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000009415 formwork Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Abstract
The invention discloses a synthesizing method of a high-dispersion submicron ZSM-5 zeolite molecular sieve. By means of the method adding pre-crystallization liquid in crystallization mother liquid and segmentally adding alkaline in the hydro-thermal synthesis process, the ZSM-5 zeolite molecular sieve with particles mainly concentrated to be 400-500nm is obtained by synthesis and has good industrialized application prospect. The synthesizing method mainly solves the problem that the ZSM-5 zeolite molecular sieve synthesized in an existing template-free method causes large particles to be gathered easily, and the synthesizing method reduces synthesizing cost of the ZSM-5 zeolite molecular sieve in comparison with an organic template method. The synthesized ZSM-5 zeolite molecular sieve does not need roasting, and can manufacture various catalysts by modification such as ion exchange.
Description
Technical field
The present invention relates to the synthetic method of molecular sieve, be specifically related to a kind of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve.
Background technology
The ZSM-5 zeolite is the porous material that a class has the micropore canals homogeneous, extensively is used in catalysis and the parting material.Although the ZSM-5 zeolite has good catalytic performance, its micropore canals is subjected to the influence of diffusional limitation, and reactant molecule is difficult to enter into from the outside surface of catalyzer the active centre in the inner duct of catalyzer.Reducing the catalyzer crystalline size is the effective ways that improve catalyst activity.Particularly work as catalyst particle size and be reduced to 0.5 μ m(C. J. H. Jacobsen, C. Madsen, T. V. W. Janssens, H.J. Jakobsen, J. Skibsted.
Micropor. Mesopor. Mater., 2000,39:393), can effectively reduce the evolving path of micropore canals.Small crystal grain molecular sieve shows in reaction: reactive behavior height, to advantage such as the distinctive selectivity of product, anti-carbon deposition ability be strong.
Mobil Corp. (R. J. Argauer, G. R. Landolt. US 3702886,1972) reported first adopted organic formwork agent successfully to synthesize the ZSM-5 zeolite in 1972.Follow-up a lot of scholar has reported that also the organic formwork agent method synthesizes the ZSM-5 zeolite molecular sieve.The use of organic formwork agent can bring a lot of problems, and such as improving synthetic cost, template is removed not exclusively can stop up the duct, thereby influences activity of such catalysts.The decomposition of template brings environmental problems such as pollution can for big G﹠W.
(R.W. Grose, E.M.Flanigen. US 4257885,1981) such as Flanigen reported that no template agent method synthesized the ZSM-5 zeolite in 1981.1986, Li He extend etc. (Li Hegen, Xiang Shouhe, Liu Shuquan. CN 85100463,1988) patent disclosure " direct method " synthetic ZSM-5.The synthetic ZSM-5 zeolite molecular sieve that obtains of above-mentioned two patents does not need roasting process, can directly carry out ion-exchange and makes various catalyzer.But the synthetic sieve particle that obtains is all at several μ m.
CN85100463, CN97100145, CN5240892 be disclosed not to be used in the method for the synthetic ZSM-5 of organic formwork agent, use water glass to be the silicon source, but the synthetic system viscosity is big, and H feeds intake
2O/SiO
2(mol ratio) is higher, and single-autoclave yield rate is low, and crystal grain is also mostly at several μ m.
No template agent method synthesizes the ZSM-5 zeolite, and operating restraint is narrow, generally at Na
2O:Al
2O
3=0.06 ~ 0.18, be easy to produce the mordenite stray crystal in the building-up process.Therefore this synthesis condition of basicity needs strict control.People such as Ryoo (R. Ryoo, J. M. Kim. J. Chem. Soc., Chem. Commun., 1995, adopt substep to add sour pH value of regulating in the building-up process when 711) synthesizing the MCM-41 molecular sieve in nineteen ninety-five, after this adopting this method to synthesize MCM series mesopore molecular sieve also had report.Li Zhi very waited (Li Zhiliang in 2008, Zhi Jianping, Zhang Wei, Hu Qingxia, Zhang Yulin. silicate journal, 2008,36:246) adopt segmentation to throw alkaline process and synthesized low-silicon X-shaped zeolite, their result shows: alkali is thrown in segmentation can optimizing reaction system basicity environment, regulates nucleation and nucleus growth, thereby make generated time reduce 80 min (amount of decrease is greater than 1/4), product cut size narrowly distributing than ordinary method.
Summary of the invention
The objective of the invention is in order to remedy the deficiency of the synthetic ZSM-5 zeolite molecular sieve of no template agent method, i.e. Basicity Operation narrow range in the building-up process, and synthetic to obtain particle bigger, and a kind of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve is provided.
Technical scheme of the present invention is: for achieving the above object, the present invention adopts the step of no template segmentation alkali adding method synthesizing submicron high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve as follows:
(1) producing of pre-crystallization liquid: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~12 hour, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 0.1~1.0.Autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~5 hour, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling.
Described SiO
2Adopt silicon sol, water glass or white carbon black.Described Al
2O
3Adopt Tai-Ace S 150, aluminum nitrate, aluminum chloride or sodium aluminate.
The MFI type molecular sieve crystallinity height that the present invention synthesizes, particle diameter mainly is distributed in 400~500 nm.The synthetic ZSM-5 zeolite molecular sieve that obtains of said process does not need roasting process, can directly carry out ion-exchange and makes various catalyzer.
Description of drawings
Fig. 1 is the inventive method embodiment 3 synthetic ZSM-5 zeolite molecular sieve SEM figure that obtain;
Fig. 2 is the inventive method embodiment 3 synthetic ZSM-5 zeolite molecular sieve size distribution figure that obtain;
Fig. 3 is the inventive method embodiment 3 synthetic ZSM-5 zeolite molecular sieve XRD spectra that obtain.
Embodiment
The step of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve is as follows:
(1) producing of pre-crystallization liquid: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~12 hour, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 0.1~1.0.Autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~5 hour, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling.
Described SiO
2Adopt silicon sol, water glass or white carbon black.Described Al
2O
3Adopt Tai-Ace S 150, aluminum nitrate, aluminum chloride or sodium aluminate.
The present invention is further elaborated below by a series of embodiment.
Embodiment 1
(1) producing of pre-crystallization liquid: mole consists of 10Na
2O:100SiO
2: 1.25Al
2O
3: 12SO
4 2-: 2000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 100 r/min, and crystallization is after 1 hour, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 10Na
2O:100SiO
2: 1.25Al
2O
3: 12SO
4 2-: 2000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 0.10, and autoclave temp is set to 150 ° of C, rotating speed 100 r/min, and crystallization is after 1 hour, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 1.0Na
2O:100H
2O:10H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01, autoclave temp is set to 150 ° of C, rotating speed 100 r/min, crystallization 1 hour, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 1.0Na
2O:100H
2O:10H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01, autoclave temp is set to 150 ° of C, rotating speed 100 r/min, crystallization 1 hour, chilling.
Described SiO
2Adopt silicon sol.Described Al
2O
3Adopt Tai-Ace S 150.
(1) producing of pre-crystallization liquid: mole consists of 30Na
2O:100SiO
2: 5.0Al
2O
3: 12SO
4 2-: 6000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 400 r/min, and crystallization is after 12 hours, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 30Na
2O:100SiO
2: 5.0Al
2O
3: 12SO
4 2-: 6000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 1.0.Autoclave temp is set to 150 ° of C, rotating speed 400 r/min, and crystallization is after 5 hours, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 5.0Na
2O:500H
2O:200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.2, autoclave temp is set to 150 ° of C, rotating speed 400 r/min, crystallization 12 hours, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 5.0Na
2O:500H
2O:200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.2, autoclave temp is set to 150 ° of C, rotating speed 400 r/min, crystallization 12 hours, chilling.
Described SiO
2Adopt water glass.Described Al
2O
3Adopt aluminum nitrate.
Embodiment 3
(1) producing of pre-crystallization liquid: mole consists of 18Na
2O:100SiO
2: 2.5Al
2O
3: 12SO
4 2-: 4000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 200 r/min, and crystallization is after 4 hours, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 18Na
2O:100SiO
2: 2.5Al
2O
3: 12SO
4 2-: 4000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 0.1.Autoclave temp is set to 150 ° of C, rotating speed 200 r/min, and crystallization is after 2 hours, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 1.4Na
2O:300H
2O:81.7H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.1, autoclave temp is set to 150 ° of C, rotating speed 200 r/min, crystallization 1 hour, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 1.0Na
2O:200H
2O:100H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.1, autoclave temp is set to 150 ° of C, rotating speed 200 r/min, crystallization 1 hour, chilling.
Described SiO
2Adopt white carbon black.Described Al
2O
3Adopt sodium aluminate.
With embodiment 1, described SiO
2Adopt white carbon black.
Embodiment 4
With embodiment 1, described Al
2O
3Adopt aluminum nitrate.
Embodiment 5
With embodiment 1, described Al
2O
3Adopt aluminum chloride.
Embodiment 6
With embodiment 1, described Al
2O
3Adopt sodium aluminate.
Claims (3)
1. high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve is characterized in that its step is as follows:
(1) producing of pre-crystallization liquid: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirs under the room temperature in the stirred autoclave of packing into after 24 hours, and autoclave temp is set to 190 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~12 hour, and chilling obtains pre-crystallization liquid;
(2) preparation of synthetic liquid mother liquor: mole consists of 10~30Na
2O:100SiO
2: 1.25~5.0Al
2O
3: 12SO
4 2-: 2000~6000H
2O stirred 24 hours under the room temperature;
(3) pre-crystallization liquid is joined in the synthetic liquid mother liquor, the mass ratio of pre-crystallization liquid and synthetic liquid mother liquor is 0.1~1.0, and autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, and crystallization is after 1~5 hour, chilling;
(4) add H
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling;
(5) add H again
2O
2With the NaOH mixing solutions, mole consists of 1.0~5.0Na
2O:100~500H
2O:10~200H
2O
2, H
2O
2With the mass ratio of NaOH mixing solutions and synthesis mother liquid be 0.01~0.2, autoclave temp is set to 150 ° of C, rotating speed 100~400 r/min, crystallization 1~12 hour, chilling.
2. according to the described a kind of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve of claim 1, it is characterized in that described SiO
2Adopt silicon sol, water glass or white carbon black.
3. according to the described a kind of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve of claim 1, it is characterized in that described Al
2O
3Adopt Tai-Ace S 150, aluminum nitrate, aluminum chloride or sodium aluminate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201210141312 CN102642847B (en) | 2012-05-09 | 2012-05-09 | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201210141312 CN102642847B (en) | 2012-05-09 | 2012-05-09 | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102642847A CN102642847A (en) | 2012-08-22 |
CN102642847B true CN102642847B (en) | 2013-09-04 |
Family
ID=46655974
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201210141312 Expired - Fee Related CN102642847B (en) | 2012-05-09 | 2012-05-09 | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102642847B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104860333B (en) * | 2014-02-26 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of 5 molecular sieves of ZSM and its synthetic method |
CN106423256A (en) * | 2016-09-19 | 2017-02-22 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of liquid fuel, preparation method and application |
CN106348312B (en) * | 2016-11-04 | 2018-09-28 | 中国科学院上海高等研究院 | A kind of synthesis methods for inorganic compounds of regulation and control ZSM-5 molecular sieve pattern |
CN107265476A (en) * | 2017-07-18 | 2017-10-20 | 大悟县新生农业科技有限公司 | A kind of preparation method of the zeolite little particle type slow release nitrogen fertilizers of ZMS 5 |
CN108298556A (en) * | 2017-09-29 | 2018-07-20 | 鲁西催化剂有限公司 | A kind of preparation method of ZSM-5 zeolite molecular sieve |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101643219B (en) * | 2009-08-27 | 2011-04-20 | 黑龙江大学 | Preparation method of nano-ZSM-5 molecular sieve |
-
2012
- 2012-05-09 CN CN 201210141312 patent/CN102642847B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN102642847A (en) | 2012-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102642847B (en) | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve | |
CN107555446B (en) | Preparation method of hierarchical pore Y-type molecular sieve | |
CN102452666B (en) | Method for synthesizing IM-5 molecular sieve | |
CN103204515B (en) | Preparation method for high-dispersion zeolite molecular sieves | |
EP0643671B1 (en) | Zsm-5 zeolite | |
CN100567152C (en) | Magadiite/ZSM-5 coexisting material and synthetic method thereof | |
CN101884936B (en) | Method for preparing silicoaluminophosphate (SAPO)-34 molecular sieve molded catalyst, product prepared by method and application of product | |
CN105883849B (en) | The synthetic method of the molecular sieves of ZSM 5 of morphology controllable | |
US9827560B2 (en) | Small crystal ferrierite and method of making the same | |
CN102666385A (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
CN102942192A (en) | Preparation method for high-dispersion nanometer zeolite molecular sieve | |
CN102774854A (en) | Synthetic method of novel mesoporous-microporous NaY zeolite | |
CN101311117B (en) | Nano composite meso-microporous molecular sieve and preparation method thereof | |
CN103224242A (en) | Low cost method for rapidly synthesizing ITQ-13 molecular sieve | |
CN104445263A (en) | SCM-3 molecular sieve and preparation method thereof | |
CN105293520B (en) | The Zeolite synthesis methods of special appearance ZSM 5 | |
CN106185978B (en) | A kind of synthetic method of the high silicon b orientations nanometer sheets of ZSM 5 | |
CN104386707B (en) | A kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve | |
CN105668585A (en) | Methods for preparing L-type zeolite guiding agent and zeolite | |
CN101767797B (en) | Synthesizing method of mesoporous zeolite | |
CN102452667B (en) | Method of synthesizing IM-5 molecular sieve by using composite template | |
CN104098108B (en) | A kind of ZSM-5 molecular sieve of rectangle pattern and preparation method thereof | |
CN104891524B (en) | A kind of preparation method of the mesopore molecular sieve of high stability containing rare-earth heteroatoms | |
CN105836756B (en) | A kind of method that Template-free method system prepares the molecular sieves of ZSM 5 of the regular brilliant looks of single dispersing | |
CN105084383B (en) | The preparation method of porous material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130904 |