CN102963905A - Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel - Google Patents

Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel Download PDF

Info

Publication number
CN102963905A
CN102963905A CN2012104539784A CN201210453978A CN102963905A CN 102963905 A CN102963905 A CN 102963905A CN 2012104539784 A CN2012104539784 A CN 2012104539784A CN 201210453978 A CN201210453978 A CN 201210453978A CN 102963905 A CN102963905 A CN 102963905A
Authority
CN
China
Prior art keywords
sba
triblock copolymer
deionized water
aluminium
synthetic method
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.)
Pending
Application number
CN2012104539784A
Other languages
Chinese (zh)
Inventor
林森
郭鹏
张洪鹏
李湘萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Original Assignee
Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qingdao Institute of Bioenergy and Bioprocess Technology of CAS filed Critical Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Priority to CN2012104539784A priority Critical patent/CN102963905A/en
Publication of CN102963905A publication Critical patent/CN102963905A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention relates to a method for synthetizing Al-SBA-15 containing a plug type silicon/aluminum structure in a pore channel, comprising the steps of: (1) dissolving a triblock copolymer EO20PO70EO20 in deionized water at the room temperature; (2) adding aluminum salt in the solution of the step (1), stirring and dissolving; (3) adding tetraethyl orthosilicate in the solution of the step (2) and stirring; (4) stirring the mixture of the step (3) at the constant temperature of 30-40 DEG C; (5) carrying out static treatment on the mixture of the step (5) under the hydrothermal condition of 80-110 DEG C, filtering, washing by using the deionized water and drying; and (6) heating the product of the step (5) to 100-120 DEG C and maintaining for a while, further heating to 500-550 DEG C and maintaining for a while so as to obtain AlSBA-15 white powder. According to the invention, the Al-SBA-15 is synthetized in a system with no additional acid, so that the defects that the waste liquor treatment problem is brought and the stability of the synthetic material is low due to the massive use of inorganic acid in known methods are overcome.

Description

The duct includes the synthetic method of plug type silicon/constructed of aluminium Al-SBA-15
Technical field
The invention belongs to the molecular sieve technical field of inorganic material, relate to a kind of method that the duct includes plug type silicon/constructed of aluminium Al-SBA-15 of in without the system of outer acid adding, synthesizing.
Background technology
1992, researchist's reported first of the U.S. Mobil company gang have the meso-porous molecular sieve material M41S that bigger serface and high-sequential Jie view hole road are arranged.Subsequently, people are synthetic and in catalysis for it, and the Application Areass such as absorption conduct extensive research.1998, the people such as Zhao (Zhao, D.Y.et al.Science, 1998,297,548.) reported first in the strong acid system synthetic SBA-15 mesoporous material with two-dimentional hexagonal hole road structure, this discovery has further promoted the development of ordered mesoporous material research field.Because SBA-15 has the specific surface area larger than M41S, the handiness that more superior structural stability and active specy mix was so that research synthetic around SBA-15, modification became the focus of mesoporous material research field in recent years.
Existing research work pay close attention to how to improve SBA-15 under heat and hydrothermal condition structural stability and in eco-friendly synthetic system, realize synthesizing of high quality SBA-15 material.2004, Chen etc. (Chen, S.Y.et al.Chem.Mater.2004,16,4174.) utilized the promoter action of positively charged ion and ethanol in the synthetic system without outer acid adding, synthesize the SBA-15 mesoporous material.Subsequently, the people such as Lin add in the acid system in identical nothing, by adjusting template agent/silicon source ratio, directly synthesize Al-SBA-15 (Lin, S.et al.Microporous Mesoporous Mater.2011,139,130.).2011, the people such as Lin further expanded this method, in the system without outer acid adding, only utilized hydrolysis spontaneous acidity in aluminium source to promote the polycondensation process of inorganic species, the one-step synthesis orderly Al-SBA-15 of view hole road structure height that goes out to be situated between.Yet the heat of above-mentioned materials and hydrothermal stability are still lower, and the method for there is no satisfies the chemical reaction process of ask for something harshness.
2002, Yuan and Van Der Voort philosophy are for MCM-41 and SBA-15 mesoporous material, by improving the method for silicon source species content in the reaction soln, synthesize the mesoporous material that the straight hole road includes plug type silicon structure, Plugged Hexagonal Template Silica is called for short: PHTS, (Yuan, Z.et al.Chem.Commun.2002,504; Van Der Voort, P.et al.Chem.Commun.2002,1010.).Because the existence of the inner inorganic species in duct, this material has large micropore volume (＞0.15cm 3/ g) and higher heat/hydrothermal stability.2011, the people such as the people such as Min and Wang adopted respectively the method for introducing hydramine and segmenting cooperation self-assembly to synthesize PHTS ordered mesoporous material (Min, B.-H.et al.Chem.Commun.2011,47,4673 of SBA-15 base; Wang, W.et al.J.Mater.Chem.2011,21,12059.).But at present the synthetic method of report is applicable to the synthetic of pure silicon SBA-15 more, and is also rarely found about the report that other heteroatoms is introduced, and the understanding of the material hole structural changes that the existence of the inorganic species in inside, duct is caused is not also not deeply.In addition, yet there are no so far the report of the synthetic method of the inner inorganic Species Structure in this kind of Effective Regulation material duct in eco-friendly synthetic system.
Summary of the invention
The object of the present invention is to provide a kind of duct to include the synthetic method of plug type silicon/constructed of aluminium Al-SBA-15, to improve a large amount of liquid waste disposal and low defectives of synthetic materials stability of using mineral acids to bring in the known SBA-15 synthetic method.
For achieving the above object, synthetic method provided by the invention, key step is:
1) under the room temperature condition, with triblock copolymer EO 20PO 70EO 20Be dissolved in the deionized water deionized water and triblock copolymer EO 20PO 70EO 20Mol ratio be 8000-112000;
2) add aluminium salt stirring and dissolving, triblock copolymer EO in the solution of step 1 20PO 70EO 20With contained aluminum ion mol ratio in the aluminium salt be 0.05-0.5;
3) add tetraethyl orthosilicate in the solution of step 2, stir triblock copolymer EO 20PO 70EO 20With the mol ratio of tetraethoxy be 0.0020-0.01;
4) mixture of step 3 places 30-40 ℃ of constant temperature to stir;
5) the deionized water wash post-drying is filtered and used to the mixture of step 4 static treatment under 80-110 ℃ of hydrothermal condition;
6) product of step 5 is warming up to 100-120 ℃ and keep to keep for some time at the temperature rise rate with 3-5 ℃/min, then continues temperature rise rate with 3-5 ℃/min and is warming up to 500-550 ℃ and keep for some time, obtains the AlSBA-15 white powder.
Described synthetic method, wherein, aluminium salt is ANN aluminium nitrate nonahydrate (Al (NO 3) 39H 2O), Patent alum (Al 2(SO4) 318H 2O) or Aluminium chloride hexahydrate (AlCl 36H 2O).
Described synthetic method, wherein, step 5 is to carry out hydrothermal treatment consists in the stainless steel synthesis reactor.
Described synthetic method, wherein, the liner of stainless steel synthesis reactor is the polytetrafluoroethyllining lining cover.
Described synthetic method, wherein, step 5 is 80-100 ℃ of lower oven dry.
Environment for use of the present invention has good synthetic method, by the inner quantitative purpose that silicon/constructed of aluminium reaches regulation and control ordered mesoporous material structural parameter that generates in the material duct, a large amount of liquid waste disposal and stable low defectives of synthetic materials of using mineral acid to bring in the SBA-15 prior synthesizing method have been overcome.
Description of drawings
Fig. 1 is little angle XRD spectra and the N of the mesoporous Al-SBA-15 that synthesized among the embodiment 1 2Adsorption isothermal line, wherein Figure 1A is little angle XRD result; Figure 1B is N 2The adsorption-desorption result.
Fig. 2 is little angle XRD spectra and the N of the mesoporous Al-SBA-15 that synthesized among the embodiment 2 2Adsorption isothermal line, wherein Fig. 2 A is little angle XRD result; Fig. 2 B is N 2The adsorption-desorption result.
Fig. 3 is little angle XRD spectra and the N of the mesoporous Al-SBA-15 that synthesized among the embodiment 3 2Adsorption isothermal line, wherein Fig. 3 A is little angle XRD result; Fig. 3 B is N 2The adsorption-desorption result.
Fig. 4 is the pore size distribution curve of gained Al-SBA-15 sample, and wherein curve a is derived from embodiment 1 gained sample; Wherein curve b is derived from embodiment 2 gained samples; Wherein, curve c is derived from embodiment 3 gained samples.
Fig. 5 is the SEM photo of gained Al-SBA-15 sample, and wherein Fig. 5 a is derived from embodiment 1 gained sample; Fig. 5 b is derived from embodiment 2 gained samples; Fig. 5 c is derived from embodiment 3 gained samples.
Fig. 6 is the TEM photo of gained Al-SBA-15 sample, and wherein Fig. 6 a is derived from embodiment 1 gained sample; Fig. 6 b is derived from embodiment 2 gained samples; Fig. 6 c is derived from embodiment 3 gained samples.
Embodiment
The present invention is with triblock copolymer EO 20PO 70EO 20Be template, take tetraethoxy as the silicon source, Al (NO 3) 39H 2O, Al 2(SO4) 318H 2O and AlCl 36H 2Be the aluminium source one of among the O, deionized water is solvent, and by the synthetic Al-SBA-15 mesoporous material of hydro-thermal reaction, the material mesoscopic duct is by two-dimentional Hexagonal array, spacer: p6mm.
The present invention forms by the regulation and control synthesis mother liquid can see Jie of 20-70% the straight hole road with filling in shape silicon/constructed of aluminium obstruction, and synthetic sample 6 hours orderly pore passage structures of roasting in 900 ℃ of air atmospheres are not destroyed; In addition, process 8h with 700 ℃ of saturated vapors after, the material specific surface area reduces less than 10% and is situated between and sees straight hole road order and be not destroyed.
Of the present invention in without acid system synthetic duct include the method for plug type silicon/constructed of aluminium Al-SBA-15, may further comprise the steps:
1) at ambient temperature, in deionized water, adds triblock copolymer EO 20PO 70EO 20(P123), violent stirring is dissolved fully to P123, deionized water and triblock copolymer EO 20PO 70EO 20Molar ratio range be 8000-112000;
2) in the gained settled solution, add aluminium salt, stirring and dissolving, triblock copolymer EO 20PO 70EO 20With contained aluminum ion molar ratio range in the aluminium salt be 0.01-0.5;
3) in the gained settled solution, add tetraethyl orthosilicate, at stirring at room 10-15 hour, triblock copolymer EO 20PO 70EO 20With the molar ratio range of tetraethoxy be 0.0020-0.01;
4) the gained mixture is placed 30-40 ℃ of water bath with thermostatic control, stirred 18-24 hour;
5) the gained mixture is changed in the stainless steel synthesis reactor of inner liner polytetrafluoroethylene cover, under 80-110 ℃ of hydrothermal condition static treatment 2-3 days, after filtration, behind the deionized water wash in 80-100 ℃ of oven dry 10 hours;
6) temperature rise rate with 3-5 ℃/min is warming up to 100-120 ℃ in retort furnace, keeps 1-2 hour, and rear continuation is warming up to 500-550 ℃ with the temperature rise rate of 3-5 ℃/min, keeps 5-7 hour, obtains the AlSBA-15 white powder.
With gained AlSBA-15 sample X-ray diffractometer (XRD), N 2The technology such as adsorption-desorption, scanning electronic microscope (SEM), transmission electron microscope (TEM) characterize.The result shows that adopt present method to make the pore canal system that sample has the two-dimentional Hexagonal array of high-sequential, spacer: P6mm, specific surface area is 675～935m 2/ g.Form according to different resulting solutions, the inner plug shape structure that exists in the mesoscopic size duct, it consists of unbodied silicon-aluminum structure, and blocked mesopore orbit proportion scope in total duct is 20～70%.
For further understanding the solution of the present invention, elaborate below in conjunction with drawings and Examples.
Embodiment 1
At room temperature, in a certain amount of deionized water, add triblock copolymer EO 20PO 70EO (P123), violent stirring is to triblock copolymer EO 20PO 70EO 20Fully dissolving; ANN aluminium nitrate nonahydrate is added to mentioned solution and is stirred to dissolving; In mentioned solution, add tetraethoxy and stir triblock copolymer EO in the mixture 20PO 70The mol ratio of EO, deionized water, tetraethoxy and ANN aluminium nitrate nonahydrate is 0.005: 280: 1: 0.05; Said mixture was kept 15 hours under 40 ℃ of conditions; After change in the stainless steel hydrothermal reaction kettle of inner liner polytetrafluoroethylene cover, reaction is 2 days under 90 ℃ of hydro-thermals price modifications, after filtration, behind the deionized water wash 80 ℃ of dryings 10 hours; Then the temperature rise rate with 3 ℃/min is warming up to 120 ℃ in retort furnace, keeps 1 hour, and rear continuation is warming up to 550 ℃ with the temperature rise rate of 3 ℃/min, keeps 5 hours, obtains the AlSBA-15 white powder.Shown in Figure 1A, be the little angle XRD spectra result of the synthetic mesoporous Al-SBA-15 of embodiment 1, Figure 1B is N 2The adsorption-desorption result.
Embodiment 2: implementation method is described identical with embodiment 1.Substitute ANN aluminium nitrate nonahydrate with Patent alum.Triblock copolymer EO 20PO 70The mol ratio of EO, deionized water, tetraethoxy and Patent alum is 0.005: 280: 1: 0.1.Shown in Fig. 2 A, be the little angle XRD spectra result of the synthetic mesoporous Al-SBA-15 of embodiment 2, Fig. 2 B is N 2The adsorption-desorption result.
Embodiment 3: implementation method is described identical with embodiment 1.Substitute ANN aluminium nitrate nonahydrate with Aluminium chloride hexahydrate.Triblock copolymer EO 20PO 70The mol ratio of EO, deionized water, tetraethoxy and Aluminium chloride hexahydrate is 0.005: 280: 1: 0.05.As shown in Figure 3A, be little angle XRD spectra and the N of the synthetic mesoporous Al-SBA-15 of embodiment 3 2Adsorption isothermal line.As shown in Figure 3A, be the little angle XRD spectra result of the synthetic mesoporous Al-SBA-15 of embodiment 3, Fig. 3 B is N 2The adsorption-desorption result.
The pore size distribution curve of the Al-SBA-15 sample of the embodiment of the invention 1,2 and 3 gained as shown in Figure 4, wherein curve a is derived from embodiment 1 gained sample, curve b is derived from embodiment 2 gained samples, curve c is derived from embodiment 3 gained samples.
Fig. 5 is the SEM photo of embodiment 1,2 and 3 gained Al-SBA-15 samples, and wherein Fig. 5 a is derived from embodiment 1 gained sample, and Fig. 5 b is derived from embodiment 2 gained samples, and Fig. 5 c is derived from embodiment 3 gained samples.
Fig. 6 is the TEM photo of embodiment 1,2 and 3 gained Al-SBA-15 samples, and wherein Fig. 6 a is derived from embodiment 1 gained sample, and Fig. 6 b is derived from embodiment 2 gained samples, and Fig. 6 c is derived from embodiment 3 gained samples.
Table 1 is specific surface area, mean pore size and the pore volume of the embodiment of the invention 1,2 and 3 gained Al-SBA-15 molecular sieves.
The structural parameter of table 1:Al-SBA-15 molecular sieve.

Claims (5)

1. a duct includes the synthetic method of plug type silicon/constructed of aluminium Al-SBA-15, and key step is:
1) under the room temperature condition, with triblock copolymer EO 20PO 70EO 20Be dissolved in the deionized water deionized water and triblock copolymer EO 20PO 70EO 20Mol ratio be 8000-112000;
2) add aluminium salt stirring and dissolving, triblock copolymer EO in the solution of step 1 20PO 70EO 20With contained aluminum ion mol ratio in the aluminium salt be 0.05-0.5;
3) add tetraethyl orthosilicate in the solution of step 2, stir triblock copolymer EO 20PO 70EO 20With the mol ratio of tetraethoxy be 0.0020-0.01;
4) mixture of step 3 places 30-40 ℃ of constant temperature to stir;
5) the deionized water wash post-drying is filtered and used to the mixture of step 4 static treatment under 80-110 ℃ of hydrothermal condition;
6) product of step 5 is warming up to 100-120 ℃ and keep to keep for some time at the temperature rise rate with 3-5 ℃/min, then continues temperature rise rate with 3-5 ℃/min and is warming up to 500-550 ℃ and keep for some time, obtains the AlSBA-15 white powder.
2. synthetic method according to claim 1, wherein, aluminium salt is ANN aluminium nitrate nonahydrate, Patent alum or Aluminium chloride hexahydrate.
3. synthetic method according to claim 1, wherein, step 5 is to carry out hydrothermal treatment consists in the stainless steel synthesis reactor.
4. synthetic method according to claim 3, wherein, the liner of stainless steel synthesis reactor is the polytetrafluoroethyllining lining cover.
5. synthetic method according to claim 1, wherein, step 5 is 80-100 ℃ of lower oven dry.
CN2012104539784A 2012-11-13 2012-11-13 Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel Pending CN102963905A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012104539784A CN102963905A (en) 2012-11-13 2012-11-13 Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012104539784A CN102963905A (en) 2012-11-13 2012-11-13 Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel

Publications (1)

Publication Number Publication Date
CN102963905A true CN102963905A (en) 2013-03-13

Family

ID=47794382

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012104539784A Pending CN102963905A (en) 2012-11-13 2012-11-13 Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel

Country Status (1)

Country Link
CN (1) CN102963905A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056650A (en) * 2013-03-21 2014-09-24 中国科学院青岛生物能源与过程研究所 Nickel group-supported catalyst and preparation method and application thereof
CN105013463A (en) * 2015-07-27 2015-11-04 昆明理工大学 Preparation method for Cu-Zn-Zr supported aluminium-doped mesoporous catalyst
CN108928829A (en) * 2017-05-24 2018-12-04 神华集团有限责任公司 SBA-15 mesopore molecular sieve and its preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1884074A (en) * 2006-06-20 2006-12-27 浙江大学 Method for synthesizing ultra-stable ordered mesoporous Si-Al molecular sieve
CN101531375A (en) * 2009-03-03 2009-09-16 山东科技大学 Method for synthesizing bimodal silicon-aluminum mesoporous material
CN101590424A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1884074A (en) * 2006-06-20 2006-12-27 浙江大学 Method for synthesizing ultra-stable ordered mesoporous Si-Al molecular sieve
CN101590424A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof
CN101531375A (en) * 2009-03-03 2009-09-16 山东科技大学 Method for synthesizing bimodal silicon-aluminum mesoporous material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NA LIN ET AL.: "Tailoring the Al-distribution and performance of mesoporous silica SBA-15 through one-pot synthesis", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 139, 9 November 2010 (2010-11-09) *
ZHENG YING WU ET AL.: "Multiple Functionalization of Mesoporous Silica in One-Pot；Direct Synthesis of Aluminum-Containing Plugged SBA-15 from Aqueous Nitrate Solutions", 《ADVANCED FUNCTIONAL MATERIALS》, vol. 18, 11 December 2007 (2007-12-11) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056650A (en) * 2013-03-21 2014-09-24 中国科学院青岛生物能源与过程研究所 Nickel group-supported catalyst and preparation method and application thereof
CN104056650B (en) * 2013-03-21 2016-06-29 中国科学院青岛生物能源与过程研究所 A kind of Supported Nickel Catalyst and its preparation method and application
CN105013463A (en) * 2015-07-27 2015-11-04 昆明理工大学 Preparation method for Cu-Zn-Zr supported aluminium-doped mesoporous catalyst
CN108928829A (en) * 2017-05-24 2018-12-04 神华集团有限责任公司 SBA-15 mesopore molecular sieve and its preparation method and application

Similar Documents

Publication Publication Date Title
CN104030314B (en) A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof
CN102745708B (en) Synthetic method of mesoporous-microporous molecular sieve by raising hydrothermal stability
CN107597186B (en) Preparation method of water-resistant short mesoporous solid base BG/Zr-SBA-15 for catalytic synthesis of biodiesel
CN101559954B (en) Method for preparing mesoporous molecular sieve with high hydrothermal stability by taking ionic liquid as template agent
CN105153204B (en) Micro-diplopore metal-organic framework materials and preparation method in a kind of CuBTC types
CN102942193B (en) Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework
CN105800634A (en) Nanometer total-silicon beta molecular sieve and preparation method thereof
CN102963905A (en) Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel
Shao et al. Novel synthesis of high hydrothermal stability and long-range order MCM-48 with a convenient method
WO2014125309A2 (en) Supported metal catalyst
CN104016369A (en) Method for synthesizing high-stability ordered mesoporous material A1-SBA-15 by use of kaoline
Liu et al. Further investigations on the modified Stöber method for spherical MCM-41
CN105800624B (en) A kind of synthetic method of total silicon beta molecular sieves
US20100015027A1 (en) Channel-type mesoporous silica material with elliptical pore section
CN1214978C (en) Ordered mesoporous molecnlar sieve material with wltrahigh hydrothermal stability and synthesis method thereof
CN103466653A (en) Preparation method of all-silicon-type silicalite-1 zeolite molecular sieve containing intracrystalline mesoporous
CN102259887A (en) Method for improving regularity of porous channels of mesoporous molecular sieve synthesized in alkali environment
Zhou et al. Effects of alkaline media on the controlled large mesopore size distribution of bimodal porous silicas via sol-gel methods
KR100976084B1 (en) Mesoporous silica substituted with metal and preparing method thereof
CN107814391A (en) A kind of method synthesized with larger aperture and the mesoporous materials of orderly SBA 16 of hole wall high polymeric
CN107138127A (en) A kind of bar-shaped Al of three-dimensional manometer2O3Shell-nuclear compounded material of@molecular sieves and preparation method thereof
CN105366683B (en) A kind of preparation method of mesoporous silicon dioxide micro-sphere
CN110407231B (en) Method for synthesizing copper-containing CHA structure molecular sieve and copper-containing CHA structure molecular sieve
CN103586058A (en) Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method
CN1155518C (en) Proess for preparing mesoporous molecular sieve MCM-48 by using mixture of cationic surfactant and non-ionic surfactant as template agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20130313