CN101898767A - Synthetic method of high silica ZSM-5 zeolite - Google Patents
Synthetic method of high silica ZSM-5 zeolite Download PDFInfo
- Publication number
- CN101898767A CN101898767A CN2010102318928A CN201010231892A CN101898767A CN 101898767 A CN101898767 A CN 101898767A CN 2010102318928 A CN2010102318928 A CN 2010102318928A CN 201010231892 A CN201010231892 A CN 201010231892A CN 101898767 A CN101898767 A CN 101898767A
- Authority
- CN
- China
- Prior art keywords
- sio
- zeolite
- silicon
- zsm
- sio2
- 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.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a synthetic method of high-silica ZSM-5 zeolite, the method comprises the steps of adopting water glass as a silica source, adopting aluminum salts of aluminum sulfate, aluminum nitrate, aluminum chloride and the like, as well as organic aluminum compounds of sodium metaaluminate, isopropanol and the like as aluminum sources, using sulfuric acid or hydrochloric acid to regulate alkalinity, adding an organic template, simultaneously adding a guide adhesive, carrying out high-temperature crystallization at 120-200 DEG C, and then synthesizing the high-silica ZSM-5 zeolite with the SiO2/Al2O3 ratio which is greater than 100; and the molar ratio of raw materials is as follows: SiO2/Al2O3 is equal to 100-infinity, Na2O/SiO2 is equal to 0.05-0.20, and H2O/SiO2 is equal to 10-100. The organic template comprises tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium hydroxide, n-butylamine, ethylamine, hexamethylene diamine and any other organic matters which can synthesize the ZSM-5 zeolite or the mixture thereof, wherein the using amount of the organic template is that R/SiO2 is equal to 0.005-0.50; and the amount of silicon dioxide in the guide adhesive is 0-5% of the total weight of the silicon dioxide in a synthetic system. The synthetic method can synthesize the high-silica ZSM-5 zeolite with the SiO2/Al2O3 ratio which is greater than 100 and has the advantages of cheap raw materials, a small using amount of the organic template, and capability of realizing the control of product appearance and particle size by changing the relative using amount of the template and the guide adhesive.
Description
Technical field
The present invention relates to the molecular sieve synthesis technical field, specifically a kind of synthetic method of high silica ZSM-5 zeolite.
Technical background
The ZSM-5 zeolite now has been widely used in the petrochemical industries such as shape slective cracking, alkylation, isomerization, disproportionation dewaxing and etherificate of hydro carbons the earliest by the Mobil oil company invention (US3702886) of the U.S..
The silica alumina ratio of ZSM-5 zeolite, pattern and size thereof have very big influence to its catalytic performance.The ZSM-5 zeolite of low silica-alumina ratio can synthesize under the condition of not using organic formwork agent, then needs a large amount of organism to do template but high silica ZSM-5 zeolite is synthetic.The synthetic method of US3702886 report can only synthesizing Si-Al than less than 100 ZSM-5 zeolite, and need to use relatively large expensive TPAOH do organic formwork agent; US3941871 and US4061724 have reported the synthetic of high silica alumina ratio ZSM-5 zeolite, synthesize SiO
2/ Al
2O
3ZSM-5 zeolite greater than 200, but a large amount of expensive quaternary ammonium salt or organic phosphine compounds are done organic formwork agent and still can't be avoided.CN97103679.9 has disclosed a kind of method that adopts alkylamine to do template synthesizing high-silicon ZSM-5 zeolite, template/SiO
2=0.02-0.5 adopts low temperature maturation, the method for high-temperature water thermal crystallisation, reduced water silicon than and the consumption of organic formwork agent, improved single-autoclave yield rate, reduced production cost relatively.CN98101478.X provides and has adopted mother liquor to recycle the synthetic method of synthesizing high-silicon ZSM-5 zeolite, this method with gained filtrate as next time the raw material when synthetic with the required portion water of surrogate response mixture, template, alkali and silicon and aluminum source, more than two kinds of methods the pattern and the grain size of product are not all investigated.(Materials Research Bulletin 2009 such as Banani Kalita, 44,254-258) adopt different silica sources to synthesize the nano-ZSM-5 zeolite of Different Silicon aluminum ratio, the silicon source that it adopts is a silicon sol, be fuming silica gel and positive tetraethyl orthosilicate etc., cost an arm and a leg, and template agent is relatively large.Guiding glue is obtained by template aging certain hour under lower temperature of silicon source under the oligomeric attitude and higher dosage, contain a large amount of molecular sieve protokaryons in the guiding glue, therefore adding guiding glue in the zeolite synthesis process does crystal seed and can shorten induction time, increase crystallization velocity, suppress the stray crystal phase, and can control the size of zeolite, (Ind.Eng.Chem.Res.2009 such as Gerardo Majano, 48,7084-7091) do the silicon source with positive tetraethyl orthosilicate, adopt the method for guiding glue to synthesize the ZSM-5 zeolite that nanometer is piled up, this method can reduce the ZSM-5 zeolite that template agent obtains high-crystallinity, can cause the production prices costliness but use positive tetraethyl orthosilicate to do the silicon source fully, and high silica alumina ratio zeolite author is not made a search; (Microporous and Mesoporous Materials 2010 such as Tang Yi, 131,103-114) adopting the method for guiding glue to synthesize silica alumina ratio is about 40 ZSM-5 zeolite, and its growth mechanism is inquired into, and thinks that crystal seed provides surperficial growth for zeolite.Provide the surface of zeolite growth with guiding glue crystal seed, add a small amount of template and promote the crystallization of zeolite not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of cheap synthetic method of high silica ZSM-5 zeolite, this method is done the silicon source with water glass, the aluminium source can be aluminium salt, sodium metaaluminate or organo-aluminium compound, with sulfuric acid or hydrochloric acid regulation system basicity, add organic formwork agent then, and add guiding glue, in 120~200 ℃ of high temperature crystallization synthesizing Si-Als than greater than 100 high silica ZSM-5 zeolite.This method is used organic formwork agent and directed agents simultaneously, is used for synthetic SiO
2/ Al
2O
3High silica ZSM-5 zeolite greater than 100, the raw material cheapness, the total consumption of organic formwork agent is few, and can realize control to high silica ZSM-5 zeolite pattern and size by changing organic formwork agent and the relative consumption of the glue crystal seed that leads.
The preparation of guiding glue is done template (R) with TPAOH or 4-propyl bromide, after mixing with sodium hydroxide, silicon source, is positioned over room temperature~150 ℃ following wearing out and obtains in 12~72 hours; The silicon source comprises organosilicon acid esters such as positive quanmethyl silicate, positive tetraethyl orthosilicate and silicon sol etc.; The mole ratio range is: R/SiO
2=0.05~0.5, H
2O/SiO
2=10~50, Na
2O/SiO
2=0~0.05.
This method synthesizing high-silicon ZSM-5 zeolite adopts water glass to do the silicon source, the aluminium source can be aluminium salt, sodium metaaluminate or organo-aluminium compounds such as Tributyl aluminate, aluminum isopropylate such as Tai-Ace S 150, aluminum nitrate, aluminum chloride, use sulfuric acid or hydrochloric acid regulation system basicity, the proportioning raw materials scope is: SiO
2/ Al
2O
3=100~∞, Na
2O/Si
2O=0.03~0.20, H
2O/SiO
2=10~100.
Organic formwork agent comprises that 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, n-Butyl Amine 99, ethamine or hexanediamine etc. can synthesize organism or its mixture of ZSM-5 molecular sieve arbitrarily in the synthetic system, and organic formwork agent (R) is R/SiO with the mol ratio of silicon-dioxide
2=0.005~0.50; In the guiding glue amount of silicon-dioxide be in the synthetic system silicon-dioxide total amount 0~5%.
The present invention synthesizes SiO
2/ Al
2O
3High silica ZSM-5 zeolite greater than 100, the raw material cheapness, consumption of template agent is few, and by pattern and the size of change organic formwork agent with the relative consumption may command product of guiding glue.
Description of drawings
Fig. 1 is the sem photograph of Comparative Examples 1 gained sample, spheroidal particle, and size of particles is about 12 microns
Fig. 2 is the sem photograph of Comparative Examples 2 gained samples, aggregated particles, 0.1~0.3 micron of size of particles
Fig. 3 is the sem photograph of embodiment 1 gained sample, discrete particles, 1.0~1.5 microns of size of particles
Fig. 4 is the sem photograph of embodiment 7 gained samples, discrete particles, 0.6~1.0 micron of size of particles
Embodiment
With the following Examples, the present invention is described further, and the present invention is unrestricted in following specific embodiment.
In following each embodiment and each Comparative Examples, the test of molecular sieve relative crystallinity adopts x-ray powder diffraction to measure, and the reference sample is the Comparative Examples counter sample; The pattern of sample and particle diameter have scanning electron microscope to measure; The silica alumina ratio of inductively coupled plasma atomic emission spectrometry working sample.
Comparative Examples 1
With 0.89 gram 18 water Tai-Ace S 150 and 13 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add 4-propyl bromide 2.66 gram (SiO
2/ Al
2O
3=150, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.05, TPA wherein
+Be the tetrapropyl ammonium ion), mix the back in 175 ℃ of crystallization 24 hours, its degree of crystallinity is set at 100%, pattern and size as shown in Figure 1, product be a sphere, particle diameter is about 12 microns, inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2O
3Than being 110.
Comparative Examples 2
The preparation of guiding glue A: the 43.1 positive tetraethyl orthosilicates of gram (Shanghai traditional Chinese medicines, analytical pure) are dropped in the 58.8 gram TPAOH (25%) moisturizing 29.8 gram (SiO
2: 0.35TPAOH: 25H
2O: 4EtOH), be stirred to positive tetraethyl orthosilicate hydrolysis and finish, in 80 ℃ aging 3 days, glue A must lead.
With 0.89 gram 18 water Tai-Ace S 150 and 13 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add above guiding glue 2.6 gram (SiO
2/ Al
2O
3=150, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0175), even back to be mixed was in 175 ℃ of crystallization 24 hours, and its relative crystallinity (Comparative Examples 1 relatively) is 105%, pattern and size as shown in Figure 2, granular size is at 0.1~0.3 micron, inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2O
3Than being 112.
Embodiment 1
The guiding glue that uses is with Comparative Examples 2; With 0.76 gram 18 water Tai-Ace S 150 and 13 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add guiding glue 0.029 gram and organic formwork agent 4-propyl bromide 0.93 gram (SiO
2/ Al
2O
3=150, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0175), even back to be mixed was in 175 ℃ of crystallization 24 hours, and surveying its relative crystallinity (Comparative Examples 1 relatively) is 98%, pattern and size are as shown in Figure 3, be dispersive ZSM-5 zeolite granular, size is at 1~1.5 micron, and inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2O
3Than being 123.
Embodiment 2
Use guiding glue with Comparative Examples 2; With 0.76 gram 18 water Tai-Ace S 150 and 13 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add guiding glue 0.264 gram and organic formwork agent 4-propyl bromide 0.93 gram (SiO
2/ Al
2O
3=150, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0182), even back to be mixed was in 175 ℃ of crystallization 24 hours, and surveying its relative crystallinity (Comparative Examples 1 relatively) is 102%, for dispersive ZSM-5 granular size at 0.5~0.6 micron.
Embodiment 3
The preparation of guiding glue B: silicon sol (30.0%) 30.0 gram and 42.7 gram TPAOH (25.0% aqueous solution) are mixed, be positioned over then 80 ℃ aging 3 days required guiding glue B.Wherein the mole proportioning of directed agents is SiO
2: 0.35TPAOH: 20H
2O.
With 0.47 gram aluminum isopropylate and 13.8 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add above guiding glue 0.193 gram and organic formwork agent 4-propyl bromide 0.93 gram (SiO
2/ Al
2O
3=175, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0182), even back to be mixed is in 175 ℃ of crystallization 24 hours, product ZSM-5 zeolite, surveying its relative crystallinity (Comparative Examples 1 relatively) is 102%, sample is a dispersive ZSM-5 zeolite granular, and size is at 2.5~3.0 microns, and inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2O
3Than being 121.
Embodiment 4
The preparation of guiding glue C: the positive tetraethyl orthosilicate of 48.3 grams is added drop-wise to 0.064 gram NaOH, 28.6 gram TPAOH (25%) and 159.0 gram H
2In the solution of O, mix back 100 ℃ and wore out 24 hours, get required guiding glue C.Wherein the mole proportioning of directed agents is SiO
2: 0.176TPAOH: 0.004Na
2O: 50H
2O.
With 0.55 gram Aluminum Chloride Hexahydrate and 26 milliliters of 4.0molL
-1Dissolving with hydrochloric acid slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 30 gram water; Sodium oxide, 6.9%) in, add above guiding glue 0.483 gram and template 4-propyl bromide 0.93 gram (SiO
2/ Al
2O
3=175, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0178), even back to be mixed is in 175 ℃ of crystallization 24 hours, product ZSM-5 zeolite.Survey its relative crystallinity (Comparative Examples 1 relatively) 96%, product is a dispersive ZSM-5 zeolite granular, and size of particles is about about 2.5 microns, and inductively coupled plasma atomic emission spectrometry is surveyed its SiO
2/ Al
2O
3Be 120.
Embodiment 5
The guiding glue that uses is with embodiment 3, with 14 milliliters of 4.0molL
-1Sulfuric acid and 47 gram water droplets add to 58.8 gram water glass (silicon-dioxide, 20.4%; Sodium oxide, 6.9%) in, add guiding glue 0.196 gram and template tetraethylammonium bromide (Shanghai traditional Chinese medicines, 〉=99%) 1.93 gram (SiO
2/ Al
2O
3=∞, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TEA
+/ SiO
2=0.06), even back to be mixed is in 145 ℃ of crystallization 48 hours, product ZSM-5 zeolite, surveying its relative crystallinity (Comparative Examples 1 relatively) is 110%, sample is a dispersive ZSM-5 zeolite granular, and size is about 4.2 microns, and inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2The O3 ratio is 320.
Embodiment 6
The guiding glue that uses is with embodiment 3, with 0.54 gram 18 water Tai-Ace S 150 and 13.2 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 52 gram water; Sodium oxide, 6.9%) in, add guiding glue 0.195 gram and template n-Butyl Amine 99 (Shanghai traditional Chinese medicines, 〉=98.5%) 0.88 gram (SiO
2/ Al
2O
3=250, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, n-BA/SiO
2=0.06), even back to be mixed is in 175 ℃ of crystallization 24 hours, product ZSM-5 zeolite, surveying its relative crystallinity is 93%, the sample particle size is about 3.5 microns, inductively coupled plasma atomic emission spectrometry is surveyed its SiO
2/ Al
2O
3Than being 155.
Embodiment 7
The guiding glue that uses is with Comparative Examples 2; With 0.76 gram 18 water Tai-Ace S 150 and 13 milliliters of 4.0molL
-1Sulfuric acid dissolution slowly drops to 58.8 gram water glass (silicon-dioxide, 20.4% with this solution in 47 gram water; Sodium oxide, 6.9%) in, add guiding glue 0.145 gram and template 4-propyl bromide 0.93 gram (SiO
2/ Al
2O
3=150, Na
2O/SiO
2=0.05, H
2O/SiO
2=30, TPA
+/ SiO
2=0.0175), even back to be mixed was in 175 ℃ of crystallization 24 hours, and surveying its relative crystallinity (Comparative Examples 1 relatively) is 107%, pattern and size are as shown in Figure 4, be dispersive ZSM-5 zeolite granular, size is at 0.6~1.0 micron, and inductively coupled plasma atomic emission spectrometry is measured its SiO
2/ Al
2O
3Than being 121.
Claims (1)
1. the synthetic method of a high silica ZSM-5 zeolite, it is characterized in that: this method constitutes synthetic system with silicon source, aluminium source, organic formwork agent, guiding glue and sulfuric acid or hydrochloric acid, earlier that aluminium source and sulfuric acid or hydrochloric acid is soluble in water, again this solution is slowly dropped in the silicon source, in the gained mixture, add guiding glue and organic formwork agent then, in 120~200 ℃ of crystallization 24~48 hours, obtain high silica ZSM-5 zeolite;
Wherein: described aluminium source is aluminium salt, sodium metaaluminate or organo-aluminium compound, and aluminium salt is Tai-Ace S 150, aluminum nitrate or aluminum chloride; Organo-aluminium compound is Tributyl aluminate or aluminum isopropylate; The silicon source is a water glass; Organic formwork agent is 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, n-Butyl Amine 99, ethamine or hexanediamine;
The preparation of guiding glue is to do template with TPAOH or 4-propyl bromide, after mixing with sodium hydroxide, silicon source, is positioned over room temperature~150 ℃ following wearing out and obtains in 12~72 hours; The silicon source is positive quanmethyl silicate, positive tetraethyl orthosilicate or silicon sol; Organic formwork agent (R) with the mole proportioning of silicon-dioxide is: R/SiO
2=0.05~0.5; H
2O/SiO
2=10~50; Na
2O/SiO
2=0~0.05;
The mole proportioning of synthetic system is: SiO
2/ Al
2O
3=100~∞, Na
2O/Si
2O=0.03~0.20, H
2O/SiO
2=10~100; Organic formwork agent (R) is R/SiO with the mol ratio of silicon-dioxide
2=0.005~0.50; In the guiding glue amount of silicon-dioxide be in the synthetic system silicon-dioxide total amount 0~5%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102318928A CN101898767B (en) | 2010-07-20 | 2010-07-20 | Synthetic method of high silica ZSM-5 zeolite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102318928A CN101898767B (en) | 2010-07-20 | 2010-07-20 | Synthetic method of high silica ZSM-5 zeolite |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101898767A true CN101898767A (en) | 2010-12-01 |
CN101898767B CN101898767B (en) | 2011-12-28 |
Family
ID=43224754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010102318928A Expired - Fee Related CN101898767B (en) | 2010-07-20 | 2010-07-20 | Synthetic method of high silica ZSM-5 zeolite |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101898767B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102963907A (en) * | 2012-12-03 | 2013-03-13 | 华东师范大学 | Pentasil type zeolite molecular sieve synthetic method |
CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
CN104556132A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 molecular sieve with high silica-alumina ratio |
US20160181010A1 (en) * | 2014-12-23 | 2016-06-23 | Samsung Electro-Mechanics., Ltd. | Composite electronic component |
CN106629768A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Synthetic method for uniform nanosized ZSM-5 molecular sieve |
CN108083953A (en) * | 2018-01-20 | 2018-05-29 | 斯科沃肥业(山东)有限公司 | A kind of saline-alkali land soil conditioner |
CN109592695A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and its synthetic method |
WO2023168271A1 (en) * | 2022-03-01 | 2023-09-07 | Uop Llc | Mfi zeolite and its uses for production of light olefins and/or aromatics |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4606900A (en) * | 1984-01-27 | 1986-08-19 | Sud-Chemie Aktiengesellschaft | Method of preparing crystalline zeolitic aluminosilicates |
CN1915819A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain |
-
2010
- 2010-07-20 CN CN2010102318928A patent/CN101898767B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4606900A (en) * | 1984-01-27 | 1986-08-19 | Sud-Chemie Aktiengesellschaft | Method of preparing crystalline zeolitic aluminosilicates |
CN1915819A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain |
Non-Patent Citations (1)
Title |
---|
《石油冶炼与化工》 20020630 王殿中等 硅源对合成高硅ZSM-5分子筛的影响 16-18 1 第33卷, 第6期 2 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
CN102963907A (en) * | 2012-12-03 | 2013-03-13 | 华东师范大学 | Pentasil type zeolite molecular sieve synthetic method |
CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
CN104556132A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 molecular sieve with high silica-alumina ratio |
US20160181010A1 (en) * | 2014-12-23 | 2016-06-23 | Samsung Electro-Mechanics., Ltd. | Composite electronic component |
CN106629768A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Synthetic method for uniform nanosized ZSM-5 molecular sieve |
CN109592695A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and its synthetic method |
CN108083953A (en) * | 2018-01-20 | 2018-05-29 | 斯科沃肥业(山东)有限公司 | A kind of saline-alkali land soil conditioner |
WO2023168271A1 (en) * | 2022-03-01 | 2023-09-07 | Uop Llc | Mfi zeolite and its uses for production of light olefins and/or aromatics |
US11878292B2 (en) | 2022-03-01 | 2024-01-23 | Uop Llc | MFI zeolite and its uses for production of light olefins and/or aromatics |
Also Published As
Publication number | Publication date |
---|---|
CN101898767B (en) | 2011-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101898767B (en) | Synthetic method of high silica ZSM-5 zeolite | |
CN101717095B (en) | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite | |
CN104903234B (en) | Small crystals ferrierite and preparation method thereof | |
US11260377B2 (en) | Method for synthesizing a FER/MOR composite molecular sieve | |
US20070224113A1 (en) | Process for Preparing Nano Size Zeolites | |
CN102009985A (en) | MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof | |
CN103086399B (en) | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method | |
CN104229826A (en) | ZSM-5 molecular sieve and preparation method thereof | |
CN102616805A (en) | Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 | |
CN105668585A (en) | Methods for preparing L-type zeolite guiding agent and zeolite | |
CN102602959B (en) | Preparation method of pure nano-silicon ZSM-5 zeolite | |
CN101717092A (en) | Method for preparing nanometer high specific surface Beta zeolite | |
JPS5988311A (en) | Crystalline zeolite substance and manufacture | |
CN101462738B (en) | Method for synthesizing high silicon beta zeolite | |
EP0130809B1 (en) | Method of preparing highly siliceous porous crystalline zeolites | |
CN105271287A (en) | Method for preparation of Beta molecular sieve from modified diatomite without organic template | |
CN109437231A (en) | A kind of preparation method of flakes ZSM-5 molecular sieve | |
KR100925851B1 (en) | Preparation method of zeolites with high silica/alumina ratio | |
TWI411578B (en) | Synthesis of a Small Grain Rare Earth - ZSM5 / ZSM11 Co - Crystallized Zeolite | |
CN106517232B (en) | The synthetic method of H-MCM-22 molecular sieve and its molecular sieve of synthesis | |
WO2020227886A1 (en) | Method for rapidly preparing high crystallinity ecr-1 molecular sieve | |
CN102259890A (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof | |
CN106629767A (en) | Method for effectively controlling particle size of ZSM-5 by virtue of silicon polymerization degree and aluminum polymerization degree | |
JP6786876B2 (en) | Method for producing CHA-type zeolite | |
CN110642265B (en) | Method for synthesizing ZSM-5 molecular sieve with framework containing heteroatom |
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: 20111228 Termination date: 20140720 |
|
EXPY | Termination of patent right or utility model |