CN101628721A - Method for preparing ZSM-5 zeolite - Google Patents
Method for preparing ZSM-5 zeolite Download PDFInfo
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Abstract
The invention discloses a method for preparing ZSM-5 zeolite. Under neutrality condition, tetramethyl guanidine is used as a template agent to synthesize the ZSM-5 zeolite. The preparation method comprises the following steps that: a. mixing the tetramethyl guanidine used as the template agent, deionized water, ammonium fluoride and alumina source; b. adding acid to regulate pH to neutrality; c. adding a silicon source; d. crystallizing, and then synthesizing a ZSM-5 zeolite molecular sieve. As the cost of the molecular sieve needs to be considered when the zeolite molecular sieve is used in industry, the zeolite molecular sieve can not be widely applied. The costs of organic template agents and inorganic matters in the ZSM-5 synthesis of the prior art are high. The invention uses tetramethyl guanidine with low cost as the template agents, which performs the significant meaning on the industrialization application of the zeolite molecular sieves. In addition, the ZSM-5 zeolite usually needs to be synthesized under strong alkaline condition, so the invention firstly synthesizes the ZSM-5 zeolite with higher crystallization degree successfully under the neutrality condition.
Description
Technical field
The present invention relates to a kind of zeolite catalyst preparing technical field, particularly a kind of method for preparing the ZSM-5 zeolite.
Background technology
The ZSM-5 molecular sieve adopts organic formwork agent TPAOH synthetic (USP 3,702,886 1972 years) by U.S. MOBIL company first.The ZSM-5 zeolite has complicated duct, and skeleton contains two kinds of intersection ducts, and a kind of is straight, and another kind is " Z " shape approximate ellipsoidal, and two kinds of ducts intersect mutually, and the aperture is to be made of ten members (oxygen) ring.Because ZSM-5 is as the catalytic activity and the shape selective of the uniqueness that characteristic produced of molecular sieve, after this people carry out broad research to this class material, it has unique catalytic performance to reactions such as alkylation, isomerization, disproportionation, selective cracking process and methanol synthesized gasolines, be a kind of catalystic material of extensively being paid attention at present, its technology of preparing also becomes the emphasis of research.
Different with the aluminosilicate zeolite of routine, ZSM-5 generally adopts organic materials synthetic as template.Because TPAOH costs an arm and a leg, in recent years, people seek cheap organic formwork agent always and synthesize ZSM-5, organic amine template commonly used can fall into 5 types: (1) straight chain or cyclic alkyl amine, as benzyl butylamine, tetraethyl-ammonium salt, Tributylamine, triethylamine, Diisopropylamine, isobutylamine, diisobutylamine, tert-Octylamine, neo-pentyl amine, hexahydroaniline, cycloheptylamine, 1,2-diamino-cyclohexane, 2-or 4-methyl cyclohexylamine, tetramethyl-ethyl diamines, R4N+-spiralization compound etc.; (2) oxygen-containing organic compound, as hydroxyl diamines, sodium-chlor-trolamine, contain 1 or 2 Sauerstoffatom saturated cyclic amines, with ether (particularly cyclic ethers class), thanomin, the saturated low-carbon alcohol of IV family metal complex; (3) nitrogen-containing heterocycle compound is as pyridine, 2-aminopyridine, methyl violet etc.; (4) alkylsulfonate; (5) ionene of nitrogenous positive ion or its ionomer etc.Relevant patent has: the method for (Chinese patent) 01140181.8 1 kinds of synthetic ZSM-5 molecular sieves; The preparation method of (Chinese patent) 200410048353.5 1 kinds of ZSM-5 molecular sieves; (United States Patent (USP)) 3,702,886Crystalline Zeolite ZSM-5and Method of Preparing theSame.
Can synthesize ZSM-5 though found cheap organic formwork agent, people are still studying always and are using cheaper material to prepare ZSM-5.
Because organic amine synthesizes costing an arm and a leg of ZSM-5 molecular sieve and has bigger toxicity, a lot of scholars do not use organic formwork agent to synthesize the ZSM-5 molecular sieve.Usually adopt inorganic substance such as methyl alcohol, ethanol and ammoniacal liquor to replace organic amine to synthesize, but these organic formwork agents and inorganics price are still relatively more expensive.Usually synthetic ZSM-5 molecular sieve is synthetic under strong alkaline condition, also is not synthesized under neutrallty condition.
Summary of the invention
Technical problem to be solved by this invention is, synthetic ZSM-5 zeolite needs in the prior art organic formwork agent and inorganic substance price comparison costliness, and the present invention adopts cheap template tetramethyl guanidine successfully to synthesize ZSM-5, greatly reduces production cost.In addition, usually ZSM-5 need synthesize under strong alkaline condition, the present invention successfully synthesizes the higher ZSM-5 zeolite of degree of crystallinity first under neutrallty condition, for other recruit sieve or some need to provide new method and thinking with the molecular sieve of organic formwork agent synthetic.
For solving the problems of the technologies described above, the invention provides a kind of method of the ZSM-5 of preparation zeolite, under neutrallty condition, be the synthetic ZSM-5 zeolite of template with the tetramethyl guanidine.
Described preparation method preferably includes following steps:
A. the template tetramethyl guanidine is mixed with deionized water, Neutral ammonium fluoride, alumina source;
B. add acid for adjusting pH to neutral;
C. add the silicon source;
D. crystallization is synthesized the ZSM-5 zeolite molecular sieve.
Described alumina source can be Tai-Ace S 150 or aluminum isopropylate.
Described silicon source can be tetraethoxy or silicon sol.
Described step a is preferably: the 6.6-11.2ml deionized water is added in the 2.5-3.7ml tetramethyl guanidine, to wherein adding the 0.2-1g Neutral ammonium fluoride, stirred 1.5-2.5 hour then, until the Neutral ammonium fluoride dissolving, add the 0.8-1.4ml alum liquor again, stirred 4-6 hour.
Described step b is preferably: add the salt acid for adjusting pH value to neutral.
Described step c is preferably: add the 10.3-12.6ml tetraethoxy, stirred 12-14 hour, obtain the gel of transparence.
Described steps d is preferably: the reactant that will add behind the silicon source is incorporated with in the reactor of tetrafluoroethylene, and at 160-200 ℃ of following crystallization 10-15 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.
Described steps d may further include following steps: after crystallization finished, the cold filtration reactant was used deionized water wash, and 80-100 ℃ of drying, obtains crystallization product, through its structure of X-ray diffraction analysis.
Described steps d can also for: will add reactant behind the silicon source and be incorporated with crystallization in the reactor of tetrafluoroethylene, until reacting completely, hydro-thermal synthesizes molecular sieve ZSM-5; The molar ratio range of described hydrothermal synthesis reaction is: SiO
2/ Al
2O
3=90-110, H
2O/SiO
2=8-12, tetramethyl guanidine/SiO
2=0.4-0.6.
Because industrial application zeolite molecular sieve must consider to obtain the cost problem of molecular sieve, this is the reason that they can not widespread use, organic formwork agent and inorganic substance price comparison that usually synthetic ZSM-5 needs are expensive, the present invention adopts cheap template tetramethyl guanidine, and this industrial applications for zeolite molecular sieve has great significance.In addition, ZSM-5 need synthesize under strong alkaline condition in the prior art, and the present invention successfully synthesizes the higher ZSM-5 zeolite of degree of crystallinity first under neutrallty condition.
Description of drawings
Fig. 1 is the crystallization product ZSM-5 that the employing embodiment of the invention 1 described method prepares, and analyzes the thing phasor of its structure through X-ray diffraction (XRD).
Embodiment
The invention provides a kind of method of under neutrallty condition, synthesizing ZSM-5 with cheap template, template tetramethyl guanidine (TMG), deionized water, Neutral ammonium fluoride and alumina source are mixed, add appropriate hydrochloric acid and be adjusted to neutrality, add the silicon source then, at 160-200 ℃ of following crystallization certain hour, until reacting completely, hydro-thermal synthesizes molecular sieve; Hydro-thermal reaction proportioning (mol ratio) scope is: SiO
2/ Al
2O
3=90-110, H
2O/SiO
2=8-12, TMG/SiO
2=0.4-0.6.
Embodiment 1:
The 8.9ml deionized water is added in the 3.1ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.3ml), add the 11.5ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 12 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, and analyzing its structure through X-ray diffraction (XRD) is ZSM-5, its XRD thing phasor is seen Fig. 1.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=100, H
2O/SiO
2=10, TMG/SiO
2=0.5.
Embodiment 2:
The 7.1ml deionized water is added in the 2.5ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 2.6ml), add the 10.3ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 10 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings.Analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=90, H
2O/SiO
2=8, TMG/SiO
2=0.4.
Embodiment 3:
The 10.7ml deionized water is added in the 3.7ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 4.0ml), add the 12.6ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 15 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=110, H
2O/SiO
2=12, TMG/SiO
2=0.6.
Embodiment 4:
The 6.5ml deionized water is added in the 2.5ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 2.6ml), add the 11.5ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 10 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=90, H
2O/SiO
2=8, TMG/SiO
2=0.4.
Embodiment 5:
The 8.2ml deionized water is added in the 3.1ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.3ml), add the 12.8ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 12 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=100, H
2O/SiO
2=10, TMG/SiO
2=0.5.
Embodiment 6:
The 9.8ml deionized water is added in the 3.7ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 1.1ml alum liquor again, stirred 5 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 4.0ml), add the 14.0ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 15 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=110, H
2O/SiO
2=12, TMG/SiO
2=0.6.
Embodiment 7:
The 7.5ml deionized water is added in the 2.5ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 2.5ml), add the 10.3ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 10 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=90, H
2O/SiO
2=8, TMG/SiO
2=0.4.
Embodiment 8:
The 9.4ml deionized water is added in the 3.1ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.2ml), add the 11.5ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 12 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=100, H
2O/SiO
2=10, TMG/SiO
2=0.5.
Embodiment 9:
The 11.2ml deionized water is added in the 3.7ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.8ml), add the 12.6ml tetraethoxy at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 15 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=110, H
2O/SiO
2=12, TMG/SiO
2=0.6.
Embodiment 10:
The 7.5ml deionized water is added in the 2.5ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 2.4ml), add the 11.5ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 10 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=90, H
2O/SiO
2=8, TMG/SiO
2=0.4.
Embodiment 11:
The 9.4ml deionized water is added in the 3.1ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.1ml), add the 12.8ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 12 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=100, H
2O/SiO
2=10, TMG/SiO
2=0.5.
Embodiment 12:
The 11.2ml deionized water is added in the 3.7ml tetramethyl guanidine, to wherein adding the 0.5g Neutral ammonium fluoride, stirred 2 hours then, until the Neutral ammonium fluoride dissolving, add the 0.20g aluminum isopropylate again, stirred 7 hours, add hydrochloric acid and regulate pH value to neutral (hydrochloric acid content of adding is about 3.7ml), add the 14.0ml silicon sol at last, stirred 13 hours, obtain the gel of transparence, be incorporated with in the reactor of tetrafluoroethylene, 180 ℃ of following crystallization 15 days, until reacting completely, hydro-thermal synthesized molecular sieve ZSM-5.After crystallization finishes, the washing of cold filtration product with deionized water, and, obtain crystallization product 100 ℃ of dryings, analyzing its structure through X-ray diffraction (XRD) is ZSM-5.
Each component by the mol ratio of oxide compound is in the gel: SiO
2/ Al
2O
3=110, H
2O/SiO
2=12, TMG/SiO
2=0.6.
The synthetic method of ZSM-5 zeolite of the present invention belongs to technical field of catalysis chemistry.A kind of method that adopts the synthetic ZSM-5 zeolite of cheap masterplate agent under neutrallty condition is provided, organic formwork agent tetramethyl guanidine (TMG), deionized water, Neutral ammonium fluoride and alumina source are mixed, add appropriate hydrochloric acid and be adjusted to neutrality, add the silicon source then, at 180 ℃ of following crystallization certain hours, until reacting completely, hydro-thermal synthesizes molecular sieve; Hydro-thermal reaction proportioning (mol ratio) scope is: SiO
2/ Al
2O
3=90-110, H
2O/SiO
2=8-12, TMG/SiO
2=0.4-0.6.Method of the present invention is simple, and synthetic ZSM-5 compares with common adding organic formwork agent, and this method adopts cheap template tetramethyl guanidine first and be successfully synthetic under neutrallty condition, has reduced production cost widely.
Claims (10)
1, a kind of method for preparing the ZSM-5 zeolite is characterized in that, under neutrallty condition, is the synthetic ZSM-5 zeolite of template with the tetramethyl guanidine.
2, according to the described method for preparing the ZSM-5 zeolite of claim 1, it is characterized in that described preparation method may further comprise the steps:
A. the template tetramethyl guanidine is mixed with deionized water, Neutral ammonium fluoride, alumina source;
B. add acid for adjusting pH to neutral;
C. add the silicon source;
D. crystallization is synthesized the ZSM-5 zeolite molecular sieve.
According to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that 3, described alumina source is Tai-Ace S 150 or aluminum isopropylate.
According to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that 4, described silicon source is tetraethoxy or silicon sol.
5, according to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that, described step a is: the 6.6-11.2ml deionized water is added in the 2.5-3.7ml tetramethyl guanidine, then to wherein adding the 0.2-1g Neutral ammonium fluoride, stirred 1.5-2.5 hour, until the Neutral ammonium fluoride dissolving, add the 0.8-1.4ml alum liquor again, stirred 4-6 hour.
6, according to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that described step b is: add the salt acid for adjusting pH value to neutral.
7, according to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that described step c is: add the 10.3-12.6ml tetraethoxy, stirred 12-14 hour, obtain the gel of transparence.
8, according to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that described steps d is: the reactant that will add behind the silicon source was incorporated with in the reactor of tetrafluoroethylene, at 160-200 ℃ of following crystallization 10-15 days, until reacting completely, hydro-thermal synthesizes molecular sieve ZSM-5.
9, the described according to Claim 8 method for preparing the ZSM-5 zeolite is characterized in that, described steps d further may further comprise the steps: after crystallization finishes, the cold filtration reactant is used deionized water wash, and 80-100 ℃ of drying, obtain crystallization product, through its structure of X-ray diffraction analysis.
10, according to the described method for preparing the ZSM-5 zeolite of claim 2, it is characterized in that described steps d is: will add reactant behind the silicon source and be incorporated with crystallization in the reactor of tetrafluoroethylene, until reacting completely, hydro-thermal synthesizes molecular sieve ZSM-5; The molar ratio range of described hydrothermal synthesis reaction is: SiO
2/ Al
2O
3=90-110, H
2O/SiO
2=8-12, tetramethyl guanidine/SiO
2=0.4-0.6.
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| CN102897789A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-5 molecular sieve |
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| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| CN1171791C (en) * | 2001-11-29 | 2004-10-20 | 中国石油化工股份有限公司 | ZSM-s molecular sieve synthesizing process |
| CN1307102C (en) * | 2004-06-29 | 2007-03-28 | 中国石油化工股份有限公司 | Process for preparing ZSM-5 molecular sieve |
| CN100457623C (en) * | 2005-10-26 | 2009-02-04 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 zeolite molecular sieve |
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| CN102951656A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | Method for synthesizing even-grained ZSM-5 molecular sieves |
| CN102951656B (en) * | 2012-10-16 | 2014-06-04 | 大连瑞克科技有限公司 | Method for synthesizing even-grained ZSM-5 molecular sieves |
| CN103787368A (en) * | 2013-12-30 | 2014-05-14 | 温州大学 | Mesoporous ZSM-5 zeolite, mesoporous ZSM-5 zeolite-loaded metal sulfide catalyst and application |
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| CN112624146A (en) * | 2021-01-12 | 2021-04-09 | 国家能源集团宁夏煤业有限责任公司 | Molecular sieve and preparation method and application thereof |
| CN114229867A (en) * | 2022-01-13 | 2022-03-25 | 黑龙江大学 | Method for synthesizing hierarchical pore ZSM-22 molecular sieve by adopting single template method |
| CN114229867B (en) * | 2022-01-13 | 2023-08-11 | 黑龙江大学 | Method for synthesizing hierarchical pore ZSM-22 molecular sieve by adopting single template method |
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