CN103964460A - Microporous composite silicon aluminum molecular sieve and preparation method thereof - Google Patents
Microporous composite silicon aluminum molecular sieve and preparation method thereof Download PDFInfo
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- CN103964460A CN103964460A CN201310035287.7A CN201310035287A CN103964460A CN 103964460 A CN103964460 A CN 103964460A CN 201310035287 A CN201310035287 A CN 201310035287A CN 103964460 A CN103964460 A CN 103964460A
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Abstract
The invention relates to a microporous composite silicon aluminum molecular sieve and a preparation method thereof. The method is as below: adding an inorganic alkali source into deionized water, stirring for dissolving, adding an aluminum source and a template agent to prepare an operating fluid A; adding a silicon source into the operating fluid A to obtain a silicon aluminum initial sol B, adjusting the pH value to 9-13, aging at the room temperature for 4-36h, and crystallizing at 130-180 DEG C for 40-120 h; and filtering the crystallization products, washing until the pH value filtrate reaching 7-9, drying the filter cake at 80-140 DEG C for 1-4 h, and calcining at 450-700 DEG C for 2-6 h. The molecular sieve has TON / MTT micro composite topology structure, and can be used for processing processes including isomerization-visbreaking, hydrocracking and catalytic cracking of petroleum fractions.
Description
Technical field
The present invention relates to a kind of micropore comprehensive silicon aluminum molecular screen and preparation method thereof, is a kind of Si-Al molecular sieve with micropore composite structure concretely.
Background technology
Molecular sieve is one of most important integral part in inorganic microporous crystalline material, it has the pore size of uniform composition, regular structure, adjustable surface acidity and molecular size and has special shape selective catalysis performance, is used as catalytic material, gas delivery and sorbent material, ion-exchanger etc. and is widely applied in oil and gas processing, fine chemistry industry, environmental protection and nuclear waste disposal field.Therefore, design and synthesis zeolite have become the focus of new catalytic material exploitation.
ZSM-22 and ZSM-23 molecular screen are the representatives of molecular sieve shape selective catalysis technical field.ZSM-22 molecular sieve belongs to TON topological framework, has the one-dimensional tunnel structure of ten-ring, and port size is
zSM-23 molecular screen belongs to MTT topological framework, also has the one-dimensional tunnel structure of ten-ring, and port size is
due to the special pore passage structure of these two kinds of molecular sieves and stronger surface acid characteristic, in alkene and alkane isomerization reaction, show very high catalytic activity and selectivity, especially in alkane isomerization reaction, there is the incomparable superiority of other catalyzer, have good application prospect.But due to nuances such as pore passage structure and physico-chemical properties, the isomeric effect of two kinds of molecular sieves is not quite similar again.
The patents such as CN1693196, CN1762807, CN1769173 and CN1772611 disclose the synthetic method of ZSM-22/ZSM-23 molecular sieve, its technical characterstic is all to add another molecular sieve in a kind of initial gel of molecular sieve, and this mixture is carried out to hydrothermal crystallizing, and then obtain composite molecular screen.The composite molecular screen product that these class methods obtain exists and forms skewness, and the composite irregular shortcoming of pore passage structure, cannot give full play to the compound catalytic performance of molecular sieve.
Summary of the invention
The object of this invention is to provide a kind of TON/MTT micropore comprehensive silicon aluminum molecular screen and preparation method thereof.This molecular sieve has pore passage structure feature and the acidic character of ZSM-22 and two kinds of molecular sieves of ZSM-23 concurrently, has embodied good synergistic effect.
TON/MTT micropore comprehensive silicon aluminum molecular screen provided by the invention, its SiO
2/ Al
2o
3=30 ~ 180.
The preparation method of TON/MTT micropore comprehensive silicon aluminum molecular screen provided by the invention, the steps include:
A) inorganic alkali source is added in deionized water, after stirring and dissolving, add aluminium source, template, make working fluid A; Silicon source is added in working fluid A, stir, obtain the initial sol B of sial, its mole consists of: SiO
2/ Al
2o
3=30 ~ 180, R/SiO
2=0.1 ~ 3, (M
1+ M
2)/SiO
2=0.1 ~ 100, M
1/ M
2=0.1 ~ 2, OH
-/ SiO
2=0.05 ~ 100, H
2o/SiO
2=20 ~ 100, M is metal ion, and R is organic amine template;
The pH value of the initial sol B of sial of b) with mineral acid or organic acid, step a being made is adjusted between 9 ~ 13, obtains silicon-aluminum sol C;
C) by silicon-aluminum sol C in step b in aged at room temperature 4 ~ 36h, obtain silicon-aluminum sol D;
D) silicon-aluminum sol D in step c is carried out to hydrothermal crystallizing, 130 ~ 180 ℃ of crystallization temperatures, crystallization time is 40 ~ 120h;
E) crystallization product that makes in steps d is filtered, wash to filtrate pH value 7 ~ 9, filter cake is dried 1 ~ 4h in 80 ~ 140 ℃, then at 450 ~ 700 ℃ roasting 2 ~ 6h.
Organic amine used is one or more mixtures in triethylamine, quadrol, Tri N-Propyl Amine, Isopropylamine.
Silicon source is one or more mixtures in silicon sol, water glass, water glass, solid silicone.
Aluminium source is one or more mixtures in Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, pseudo-boehmite, aluminium hydroxide.
Mineral alkali is two or more mixture in basic metal, alkaline-earth metal or ammoniacal liquor.
Mineral acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; Organic acid is citric acid, acetic acid, propionic acid, butyric acid, oxalic acid or tartrate.
Micropore comprehensive silicon aluminum molecular screen of the present invention has TON/MTT Compound Topology skeleton structure.For obtaining TON/MTT Compound Topology structure, adopt the organic amines such as triethylamine that structure rigidity is stronger, quadrol as template, and by composite, make template molecule group and sial inorganic silicon-aluminum skeleton form geometric configuration and electronic configuration compactness is mated; Meanwhile, adopt mineral alkali or alkalimetal ion, adjust the charge matching of inorganic silicon-aluminum skeleton and organic formwork agent, and by regulating different Na
+, K
+plasma content, regulates the variation of compound skeleton ratio.After definite synthetic system proportioning, by regulating ageing condition, complete elementary gel restructuring and polycondensation, the secondary gel that formation can crystallization, increases nucleus quantity; And according to the feature of TON/MTT composite molecular sieves system, determined suitable crystallization condition.
This micropore comprehensive silicon aluminum molecular screen has TON/MTT basic skeleton structure, and its chemical constitution is expressed as SiO with sieve and silica-sesquioxide mol ratio
2/ Al
2o
3=30 ~ 180, and at least there is the characteristic of following X-ray powder diffraction pattern:
In note: a. table, listed 2 θ values all ± 0.20.
B.I/I
0≤ 20% be a little less than; 20%<I/I
0≤ 40% is medium; 40%<I/I
0≤ 60% is strong;
60%<I/I
0≤ 80% for very strong; 80%<I/I
0≤ 100% is extremely strong.
This kind of micro porous molecular sieve can be used for the courses of processing such as the isomerization-visbreaking, hydrocracking, catalytic cracking of petroleum fractions.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction pattern (XRD) of micropore comprehensive silicon aluminum molecular screen.
Embodiment
Embodiment 1
15.7g potassium hydroxide is added in deionized water, after stirring and dissolving, add 1.72g sodium metaaluminate, 30.3g triethylamine, make working fluid A; By 120g silicon sol (SiO
2content is 30%) add in working fluid A, vigorous stirring, obtains the initial sol B of sial, and its mole consists of: SiO
2/ Al
2o
3=60, R/SiO
2=0.5, (M
1+ M
2)/SiO
2=0.5, M
1/ M
2=14, OH
-/ SiO
2=0.5, H
2o/SiO
2=50, M
1for K
+, M
2for Na
+, R is triethylamine.
With 98% sulfuric acid, the pH value of the initial sol B of sial is adjusted to 12.0, obtains silicon-aluminum sol C; Silicon-aluminum sol C, in aged at room temperature 24h, is obtained to silicon-aluminum sol D; Silicon-aluminum sol D is heated to after 175 ℃ of temperature to thermostatic crystallization 90h.
Crystallization product is filtered, wash to filtrate pH value=8, filter cake is in 120 ℃ of dry 2h, then at 500 ℃ roasting 6h, obtain object product TON/MTT micropore comprehensive silicon aluminum molecular screen.
Fig. 1 is shown in by the XRD diffraction pattern of product.
Embodiment 2
67.2g potassium hydroxide is added in deionized water, after stirring and dissolving, add 1.72g sodium metaaluminate, 121.2g triethylamine, make working fluid A; By 240g silicon sol (SiO
2content is 30%) add in working fluid A, vigorous stirring, obtains the initial sol B of sial, and its mole consists of: SiO
2/ Al
2o
3=120, R/SiO
2=1, (M
1+ M
2)/SiO
2=1, M
1/ M
2=60, OH
-/ SiO
2=1, H
2o/SiO
2=50, M
1for K
+, M
2for Na
+, R is triethylamine.
With 98% sulfuric acid, the pH value of the initial sol B of sial is adjusted to 13.0, obtains silicon-aluminum sol C; Silicon-aluminum sol C, in aged at room temperature 24h, is obtained to silicon-aluminum sol D; Silicon-aluminum sol D is heated to after 170 ℃ of temperature to thermostatic crystallization 75h.
Crystallization product is filtered, wash to filtrate pH value=8, filter cake is in 120 ℃ of dry 2h, then at 600 ℃ roasting 4h, obtain object product TON/MTT micropore comprehensive silicon aluminum molecular screen.
Embodiment 3
16.8g potassium hydroxide, 12.0g sodium hydroxide are added in deionized water, after stirring and dissolving, add 2.3g Tai-Ace S 150,121.2g triethylamine, make working fluid A; By 240g silicon sol (SiO
2content is 30%) add in working fluid A, vigorous stirring, obtains the initial sol B of sial, and its mole consists of: SiO
2/ Al
2o
3=60, R/SiO
2=0.5, (M
1+ M
2)/SiO
2=0.5, M
1/ M
2=1, OH
-/ SiO
2=0.5, H
2o/SiO
2=50, M
1for K
+, M
2for Na
+, R is triethylamine.
With 98% sulfuric acid, the pH value of the initial sol B of sial is adjusted to 11.0, obtains silicon-aluminum sol C; Silicon-aluminum sol C, in aged at room temperature 12h, is obtained to silicon-aluminum sol D; Silicon-aluminum sol D is heated to after 170 ℃ of temperature to thermostatic crystallization 60h.
Crystallization product is filtered, wash to filtrate pH value=8, filter cake is in 120 ℃ of dry 2h, then at 600 ℃ roasting 4h, obtain object product TON/MTT micropore comprehensive silicon aluminum molecular screen.
Embodiment 4
112.0g potassium hydroxide, 40.0g sodium hydroxide are added in deionized water, after stirring and dissolving, add 2.3g Tai-Ace S 150,45.0g quadrol, make working fluid A; 90g gross porosity solid silicone is added in working fluid A, and vigorous stirring, obtains the initial sol B of sial, and its mole consists of: SiO
2/ Al
2o
3=150, R/SiO
2=0.5, (M
1+ M
2)/SiO
2=2, M
1/ M
2=2, OH
-/ SiO
2=2, H
2o/SiO
2=70, M
1for K
+, M
2for Na
+, R is quadrol.
With 98% sulfuric acid, the pH value of the initial sol B of sial is adjusted to 11.0, obtains silicon-aluminum sol C; Silicon-aluminum sol C, in aged at room temperature 12h, is obtained to silicon-aluminum sol D; Silicon-aluminum sol D is heated to after 150 ℃ of temperature to thermostatic crystallization 90h.
Crystallization product is filtered, wash to filtrate pH value=8, filter cake is in 120 ℃ of dry 2h, then at 600 ℃ roasting 4h, obtain object product TON/MTT micropore comprehensive silicon aluminum molecular screen.
Claims (7)
1. a micropore comprehensive silicon aluminum molecular screen preparation method, is characterized in that:
Step is as follows:
A) inorganic alkali source is added in deionized water, after stirring and dissolving, add aluminium source, template, make working fluid A; Silicon source is added in working fluid A, stir, obtain the initial sol B of sial, its mole consists of: SiO
2/ Al
2o
3=30 ~ 180, R/SiO
2=0.1 ~ 3, (M
1+ M
2)/SiO
2=0.1 ~ 100, M
1/ M
2=0.1 ~ 2, OH
-/ SiO
2=0.05 ~ 100, H
2o/SiO
2=20 ~ 100, M is metal ion, and R is organic amine template;
The pH value of the initial sol B of sial of b) with mineral acid or organic acid, step a) being made is adjusted between 9 ~ 13, obtains silicon-aluminum sol C;
C) by silicon-aluminum sol C in step b) in aged at room temperature 4 ~ 36h, obtain silicon-aluminum sol D;
D) silicon-aluminum sol D in step c) is carried out to hydrothermal crystallizing, 130 ~ 180 ℃ of crystallization temperatures, crystallization time is 40 ~ 120h;
E) crystallization product that makes in step d) is filtered, wash to filtrate pH value 7 ~ 9, filter cake is dried 1 ~ 4h in 80 ~ 140 ℃, then at 450 ~ 700 ℃ roasting 2 ~ 6h.
2. micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1, is characterized in that: described organic amine is one or more mixtures in triethylamine, quadrol, Tri N-Propyl Amine, Isopropylamine.
3. micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1, is characterized in that: silicon source is one or more mixtures in silicon sol, water glass, water glass, solid silicone.
4. micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1, is characterized in that: aluminium source is one or more mixtures in Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, pseudo-boehmite, aluminium hydroxide.
5. micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1, is characterized in that: mineral alkali is two or more mixture in basic metal, alkaline-earth metal or ammoniacal liquor.
6. micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1, is characterized in that: mineral acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; Organic acid is citric acid, acetic acid, propionic acid, butyric acid, oxalic acid or tartrate.
7. a micropore comprehensive silicon aluminum molecular screen, is characterized in that: it is prepared by micropore comprehensive silicon aluminum molecular screen preparation method according to claim 1.
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Cited By (9)
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|---|---|---|---|---|
| CN104512902A (en) * | 2015-01-06 | 2015-04-15 | 华东理工大学 | Microporous molecular sieve and preparation method and application thereof |
| CN106334514A (en) * | 2016-10-31 | 2017-01-18 | 华东理工大学 | Method for preparing alkane adsorption separation material |
| CN107416860A (en) * | 2017-07-25 | 2017-12-01 | 中国科学院山西煤炭化学研究所 | A kind of zeolite molecular sieve containing TON/MTT matrix topologies and preparation method thereof |
| CN107570216A (en) * | 2016-07-04 | 2018-01-12 | 中国石油天然气股份有限公司 | Catalyst used for hydrogenation of distilled oil fraction carrier and preparation method thereof |
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| CN110683558A (en) * | 2018-07-06 | 2020-01-14 | 中国石油天然气股份有限公司 | Synthesis method of MTT zeolite molecular sieve with short shaft morphology |
| CN111153413A (en) * | 2020-01-15 | 2020-05-15 | 延长中科（大连）能源科技股份有限公司 | Preparation method of ZSM-11 molecular sieve |
Citations (1)
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| CN101045212A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Catalyst of naphtha catalytic pyrolysis preparing ethylene propylene |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101045212A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Catalyst of naphtha catalytic pyrolysis preparing ethylene propylene |
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| CN104512902A (en) * | 2015-01-06 | 2015-04-15 | 华东理工大学 | Microporous molecular sieve and preparation method and application thereof |
| CN107570216A (en) * | 2016-07-04 | 2018-01-12 | 中国石油天然气股份有限公司 | Catalyst used for hydrogenation of distilled oil fraction carrier and preparation method thereof |
| CN107570206A (en) * | 2016-07-04 | 2018-01-12 | 中国石油天然气股份有限公司 | Diesel oil hydrogenation pour point depression catalyst and preparation method thereof |
| CN107570207A (en) * | 2016-07-04 | 2018-01-12 | 中国石油天然气股份有限公司 | Base metal distillate hydrogenation heterogeneous catalyst and preparation method thereof |
| CN106334514A (en) * | 2016-10-31 | 2017-01-18 | 华东理工大学 | Method for preparing alkane adsorption separation material |
| CN106334514B (en) * | 2016-10-31 | 2019-07-23 | 华东理工大学 | A kind of preparation method of alkane adsorption and separation material |
| CN107416860A (en) * | 2017-07-25 | 2017-12-01 | 中国科学院山西煤炭化学研究所 | A kind of zeolite molecular sieve containing TON/MTT matrix topologies and preparation method thereof |
| CN107416860B (en) * | 2017-07-25 | 2019-11-05 | 中国科学院山西煤炭化学研究所 | A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology |
| CN110683558A (en) * | 2018-07-06 | 2020-01-14 | 中国石油天然气股份有限公司 | Synthesis method of MTT zeolite molecular sieve with short shaft morphology |
| CN110683558B (en) * | 2018-07-06 | 2022-02-01 | 中国石油天然气股份有限公司 | Synthesis method of MTT zeolite molecular sieve with short shaft morphology |
| CN108950438A (en) * | 2018-08-06 | 2018-12-07 | 浙江工贸职业技术学院 | A kind of light foam aluminium and preparation method thereof |
| CN111153413A (en) * | 2020-01-15 | 2020-05-15 | 延长中科（大连）能源科技股份有限公司 | Preparation method of ZSM-11 molecular sieve |
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