CN1724363A - High silicon super stabilizing natural foresite and it preparation process - Google Patents
High silicon super stabilizing natural foresite and it preparation process Download PDFInfo
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- CN1724363A CN1724363A CN 200510027083 CN200510027083A CN1724363A CN 1724363 A CN1724363 A CN 1724363A CN 200510027083 CN200510027083 CN 200510027083 CN 200510027083 A CN200510027083 A CN 200510027083A CN 1724363 A CN1724363 A CN 1724363A
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Abstract
A natural high-Si desmine with super thermal stability (more than 1000 deg. C) and open artery structure is prepared from natural STI zeolite through acid exchange, ammonium exchange, calcining, ammonium fluorosilicate exchange and calcining.
Description
Technical field
The invention belongs to natural zeolite material modification technical field, be specifically related to natural stilbite of a kind of high silicon super stabilizing and preparation method thereof.With the natural STI zeolite is raw material, through the dealumination complement silicon method of modifying, exchanges as acid, ammonium exchanges roasting again, and ammonium silicofluoride exchanges roasting again etc., obtains high silicon natural STI zeolite (Si/Al＞7.0), its pore passage structure is open perfect, and structure thermal stability reaches more than 1000 ℃.
Background technology
Zeolite molecular sieve is a kind of inorganic silicon-aluminum hydrochlorate or phosphate crystal, the duct or the cage (ca.0.3-1.5nm) that contain the molecular dimension of regular and ordered arrangement in the skeleton, has the effect of grading of shape selective catalysis, ion-exchange and molecular sieve, be widely used in Industrial Catalysis, fractionation by adsorption and ion-exchange etc.
Be found in a kind of natural stilbite in China Beijing area, of high grade, reserves are big, and cost of winning is low, are a kind of new natural mineral resources that has wide application prospects.This natural zeolite belongs to the zeolite structured type of STI (Stilbite), have the ten-ring duct (along [100] direction, 0.49 * 0.62nm) and the octatomic ring duct that intersects (along [101] direction, 0.27 * 0.56nm).Its single crystal structure is measured by Galli at first, and desirable structure cell consists of Na
4Ca
8[Al
20Si
52O
144] 56H
2O belongs to rich calcium type STI zeolite [Galli, E.Acta Cryst.1971, B27,833].At present domestic to the studying in great detail seldom of this zeolite, use and also only rest in the very low primary industry of added value.
The zeolite structured poor heat stability of former Ca-STI, 350 ℃ of roasting 2h skeletons are destroyed fully, and the application in fields such as catalysis and absorption is subjected to very big restriction [Qiu Jin etc., chemical journal, 1999,57 (4), 377].People such as Mortier find, the position and the relevant [Mortier of kind of exchangeable cation in the zeolite structured stability of STI and the dehydration, W.J.etc.Am.Meneral.1981,66,309], wherein Ca-STI zeolite stability is the poorest, and H-STI the most stable zeolite structured [Jacobs, P.A.etc.Faraday.Trans.1979, I 75,883].The stability of STI zeolite after the modification of systematic study ammonium exchange once of this seminar finds that simultaneously the 700 ℃ of roasting structures of Na-STI zeolite after the modification still keep perfect.STI zeolite after the modification (Na-STI and H-STI) has the selection adsorptivity to the alkene and the alcohols of different chain length, and its surface has hydrophobicity and solid acid character [Li Jun etc., chemical journal, 2000,58 (8), 988].Compare with H-FER zeolite (ferrierite), it is that the catalyzed reaction transformation efficiency of iso-butylene is lower that the H-STI zeolite aligns isomerization of butene, but selectivity higher [Li, J.etc.Microporous Mesoporous Mater.2000,37 (3), 365.Hong，S.B.etc.J.Am.Chem.Soc.2004，126(18)，5817]。The H-STI zeolite also can be used as material of main part assembling function material, the functional materials of preparation Stability Analysis of Structuresization.The LiCl/H-STI host-guest material of this seminar preparation has good wet quick performance, and [ZL 01 1 12692.2 for Zou Jing, an imperial outstanding person.Zou waits quietly, chemical journal, 2001,59 (6), 862.Zou，J.etc.J.Mater.Chem.2004，14，2405]。The acid resistance of H-STI zeolite also is used for antiacid ion-exchanger and sorbent material by successful exploitation, and [an imperial outstanding person etc., ZL 03 141 604.7.Long，Y.-C.etc.Chin.J.Chem.2004，22(7)，668]。Be of the application of these high-quality natural resource of deep level development, further improve the thermostability and the hydrothermal stability of this zeolite, realize that its skeleton structure super stabilizing is very necessary in fields such as catalysis, absorption and functional materialss.
Usually preparation H type zeolite has two kinds of approach, i.e. roasting again after acid exchange and the ammonium exchange.The former requires zeolite itself to have good acid resistance, and the latter then has high requirement to its thermostability.Usually used HY zeolite prepares by the latter exactly in the petroleum catalytic cracking.Obviously, these two kinds of methods all are applicable to natural STI zeolite and prepare the H-STI zeolite.Simultaneously, these two kinds of methods all can cause skeleton part dealuminzation, thereby framework si-al ratio is obviously improved, but simultaneously the skeleton defective are increased.Generally speaking, silica alumina ratio improves the thermostability help improving zeolite framework, but the skeleton defective increases and can make its stability decreases, and this is a competition process.Concerning natural STI zeolite, acid exchange and roasting all easily make framework dealumination, and the existence meeting of a large amount of non-framework aluminums obviously reduces its exchange capacity and absorption property.Hong etc. are with 1, and 4-lutidine butane is template synthesizing high-silicon aluminum ratio (Si/Al=7.1) STI zeolite first, and its thermostability is [Hong, S.B.etc.J.Am.Chem.Soc.2004,126 (18), 5817] up to 1100 ℃.But template used dose of preparation of document is difficult, cost is higher, and the composition ratio range of building-up reactions thing is very narrow, the product silica alumina ratio is difficult to continue to improve.We once chemically handled the Na-STI zeolite that natural STI zeolite obtains sial atomic ratio 6.81, and its thermostability is verified have been reached more than 800 ℃.This points out us, might further improve the framework si-al ratio of natural STI zeolite by chemical treatment method, the implementation structure super stabilizing.We once obtained the H-STI zeolite of framework si-al ratio 4.5-7.3 method by chemical modification, its skeleton structure with and positively charged ion form product thermostability all reach 1000 ℃, basic implementation structure super stabilizing [Zhong Ying etc., the chemistry journal, 2005,63 (8), 720-724.Cheng，X.W.etc.Microporous Mesoporous Mater.2005，83，233-243]。
The present invention adopts the dealumination complement silicon method of modifying, is raw material with the natural STI zeolite, by acid exchange, ammonium exchange back roasting in air, prepares high silicon super stabilizing STI zeolite with ammonium silicofluoride exchange back method of roasting in air again.Its used natural mineral resource is of high grade, reserves abundant, cost of winning is low, and the preparation method is easy, less investment during industrialization, and production cost is lower, and as sorbent material, catalyzer and functional materials have extensive market prospects.
Summary of the invention
The objective of the invention is to propose a kind of natural stilbite of high silicon super stabilizing (STI) and preparation method thereof, the product framework si-al ratio is obviously improved, pore passage structure keeps perfect open simultaneously, and thermostability reaches super stabilizing.
The high silicon that the present invention the proposes natural stilbite of steadyization (ST1) that becomes is to be raw material with the natural STI zeolite, roasting in air again after acid exchange, ammonium exchange, again after ammonium silicofluoride exchanges in air process such as roasting, obtain high silicon super stabilizing STI zeolite.
The resulting high silicon super stabilizing STI zeolite of the present invention, its framework si-al ratio reaches 7.1-11.4, specific surface area 200-510m
2/ g, micropore volume are 0.06-0.19m
3/ g, thermostability reaches 1000 ℃.
High silicon super stabilizing STI prepare zeolite method of the present invention is as follows:
Natural stilbite (ST1) with the acid heat exchange, is washed oven dry; Use the ammonium heat exchange again, the washing oven dry; Roasting in air atmosphere in the tube furnace of both ends open then; With the ammonium fluosilicate solution exchange, washing is dried again; After roasting obtains high silicon super stabilizing STI zeolite.
In the aforesaid method, used natural STI sample former state (Ca-STI zeolite) is provided by China geology department, and its structure cell consists of Na
0.2Mg
0.1Ca
8.4[Al
17.2Si
54.8O
144] 65H
2O, chemical ingredients is m (SiO
2): m (Al
2O
3): m (MgO): m (CaO): m (Na
2O)=and 56.86: 14.83: 0.11: 8.13: 8.85 * 10
-2, sial atomic ratio 3.08, grain-size is 5～10 μ m.
In the aforesaid method, used acid is hydrochloric acid (HCl), sulfuric acid (H
2SO
4), nitric acid (HNO
3) or acetic acid (HAc) etc., concentration is 0.1-1mol/L, solid-to-liquid ratio is 1: 10-1: and 20, the exchange temperature is 80-100 ℃, each 1-3h, exchange number of times 1-4 time.
In the aforesaid method, used ammonium is ammonium chloride (NH
4Cl), ammonium nitrate (NH
4NO
3), ammonium sulfate ((NH
4)
2SO
4) or ammonium acetate (NH
4Ac) etc., concentration is 0.1-1mol/L, and solid-to-liquid ratio is 1: 10-1: 20, and the exchange temperature is 80-100 ℃, each 1-3h, exchange number of times 1-4 time.
In the aforesaid method, ammonium silicofluoride ((NH
4)
2SiF
6) concentration is 0.1-1mol/L, solid-to-liquid ratio is 1: 10-1: 20, and the exchange temperature is 20-50 ℃, each 40-50h, exchange number of times 1-4 time.
In the aforesaid method, maturing temperature is 400-600 ℃, and roasting time is 0.5-2h, and air flow quantity is 1-10mL/min.
The feature of high silicon super stabilizing STI zeolite provided by the present invention can characterize with the following method:
1. powder x-ray diffraction (XRD).In powder x-ray diffraction, reference standard STI collection of illustrative plates, not destroyed after treatment to determine product structure.
2. segmented program intensification roasting (TPH).Be used to measure the zeolite sample of thermostability, it is 2h temperature programming to 600 ℃ in muffle furnace, constant temperature 1h postcooling is to room temperature, with same heat-up rate and constant temperature time this sample is carried out the calcination process of higher temperature again behind the relative crystallinity of this sample of XRD determining, obtain the relative crystallinity data of this sample after 700,800,900,1000 ℃ of processing successively.
3. cryogenic nitrogen absorption.Calculate product specific surface area and pore volume by the BJH method.
4.X ray fluorescence scattering analysis (XRF).Calculate product chemistry silica alumina ratio.
5.
27Al high resolving power evil spirit angle solid-state nuclear magnetic resonance spectrum (
27Al MAS NMR).Calculate product non-framework aluminum content.
Description of drawings
Fig. 1 be respectively the Ca-STI zeolite after acid exchange again through ammonium exchange roasting after product (H-STI) and with the XRD spectra of ammonium silicofluoride exchange roasting after product (H-STI ').Therefrom as can be seen, product structure all keeps perfect after treatment.XRF result shows that its chemical silica alumina ratio is 4.63, the deduction non-framework aluminum (content is 34.6%, by
27Al MAS NMR calculates), its framework silicon-aluminum atomic ratio is 7.1; And exchange roasting after product chemistry silica alumina ratio through ammonium silicofluoride is 9.09, the deduction non-framework aluminum (content is 20.2%, by
27Al MAS NMR calculates), its framework silicon-aluminum atomic ratio reaches 11.4.
Fig. 2 is respectively (b) the cryogenic nitrogen absorption spectrogram of zeolite of H-STI (a) and H-STI '.All present the typical type I adsorption curve, but the former specific surface area and micropore volume are respectively 509m
2/ g and 0.190cm
3/ g, this illustrates its perfect structure and duct opening, and latter's specific surface area and micropore volume are respectively 199m
2/ g and 0.061cm
3/ g illustrates that its duct is partly stopped up.
Fig. 3 is the TPH collection of illustrative plates of product H-STI zeolite (1) and H-STI ' (2) zeolite.Its relative crystallinity still keeps more than 75% after 1000 ℃ of roastings as can be seen, zeolite structured basic realization super stabilizing after the modification is described, especially H-STI ', relative crystallinity after the differing temps roasting will illustrate that its thermostability obviously improves with the raising of silica alumina ratio apparently higher than corresponding H-STI.
Embodiment
The invention is further illustrated by the following examples:
| Embodiment | The acid exchange | The ammonium exchange | Roasting | The ammonium silicofluoride exchange | |||||||
| The acids type | Concentration/temperature | Solid-to-liquid ratio/number of times | Ammonium type | Concentration/temperature | Solid-to-liquid ratio/number of times | Temperature | Flow | Time | Concentration/temperature | Solid-to-liquid ratio/number of times | |
| One | HCl | 0.1/80 | 1∶10/4 | NH 4Cl | 0.1/80 | 1∶10/4 | 400 | 1 | 2 | 0.1/20 | 1∶10/4 |
| Two | HCl | 0.5/90 | 1∶15/2 | NH 4Cl | 0.5/90 | 1∶15/2 | 500 | 5 | 1 | 0.5/30 | 1∶15/2 |
| Three | H 2SO 4 | 0.2/100 | 1∶10/4 | (NH 4) 2SO 4 | 0.5/100 | 1∶10/4 | 550 | 10 | 0.5 | 0.8/40 | 1∶20/1 |
| Four | H 2SO 4 | 1.0/90 | 1∶20/1 | (NH 4) 2SO 4 | 1.0/100 | 1∶20/1 | 600 | 8 | 0.5 | 1.0/50 | 1∶18/1 |
| Five | HNO 3 | 1.0/100 | 1∶20/3 | NH 4NO 3 | 0.8/95 | 1∶18/3 | 450 | 9 | 1 | 0.9/45 | 1∶15/3 |
| Six | HNO 3 | 0.8/95 | 1∶10/4 | NH 4NO 3 | 0.3/95 | 1∶20/4 | 500 | 4 | 1.5 | 0.3/50 | 1∶20/4 |
| Seven | HAc | 0.5/85 | 1∶15/2 | NH 4Ac | 0.9/85 | 1∶15/3 | 550 | 6 | 0.8 | 0.6/35 | 1∶16/3 |
| Eight | HAc | 1.0/100 | 1∶20/1 | NH 4Ac | 0.5/80 | 1∶10/4 | 600 | 3 | 2 | 1.0/50 | 1∶20/2 |
| Nine | HCl | 1.0/80 | 1∶20/4 | NH 4NO 3 | 1.0/100 | 1∶10/4 | 450 | 10 | 1 | 0.7/40 | 1∶10/4 |
| Ten | HAc | 0.5/100 | 1∶10/3 | NH 4Cl | 1.0/90 | 1∶20/2 | 550 | 8 | 1.5 | 0.5/45 | 1∶20/2 |
Illustrate: unit is as follows in the form:
Concentration---mol/L;
Solid-to-liquid ratio---mass ratio;
Temperature---℃;
Flow---mL/min;
Time---h.
Claims (5)
1, a kind of high silicon super stabilizing modified natural stilbite is characterized in that its framework si-al ratio is 7.1-11.4, specific surface area 200-510m
2/ g, micropore volume are 0.06-0.19m
3/ g, thermostability reaches 1000 ℃.
2, a kind of preparation method of high according to claim 1 silicon super stabilizing modified natural stilbite is characterized in that concrete steps are as follows:
Natural stilbite (ST1) with the acid heat exchange, is washed oven dry; Use the ammonium heat exchange again, the washing oven dry; Roasting in air atmosphere in the tube furnace of both ends open then; With the ammonium fluosilicate solution exchange, washing is dried again; After roasting obtains high silicon super stabilizing STI zeolite; Wherein, maturing temperature is 400-600 ℃, and roasting time is 0.5-2h, and air flow quantity is 1-10mL/min.
3, preparation method according to claim 2 is characterized in that used acid is hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and used ammonium is ammonium chloride, ammonium nitrate, ammonium sulfate or ammonium acetate.
4, preparation method according to claim 2, the concentration that it is characterized in that acid or ammonium is 0.1-1mol/L, solid-to-liquid ratio is 1: 10-1: 20, the exchange temperature is 80-100 ℃, each 1-3h, exchange number of times 1-4 time.
5, preparation method according to claim 2 is characterized in that ammonium silicofluoride concentration is 0.1-1mol/L, and solid-to-liquid ratio is 1: 10-1: 20, and the exchange temperature is 20-50 ℃, each 40-50h, exchange number of times 1-4 time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009539747A (en) * | 2006-06-08 | 2009-11-19 | シェブロン ユー．エス．エー． インコーポレイテッド | Molecular sieve SSZ-75 composition and its synthesis |
| CN102285665A (en) * | 2011-06-07 | 2011-12-21 | 天津大学 | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water |
| CN101759197B (en) * | 2008-12-26 | 2012-11-14 | 复旦大学 | Mesopore USSTI zeolite with high silicon content and high hydrothermal stability and preparation method thereof |
| CN106809849A (en) * | 2017-02-15 | 2017-06-09 | 上海浦东路桥建设股份有限公司 | For the zeolite and its extracting method of purified industrial sewage |
| CN112403433A (en) * | 2020-09-21 | 2021-02-26 | 复榆(张家港)新材料科技有限公司 | Preparation method and application of novel sub-mesoporous zeolite molecular sieve adsorbent |
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| CN1169717C (en) * | 2001-01-05 | 2004-10-06 | 中国石油化工股份有限公司 | Y-zeolite modifying method with RE ion and its product |
| CN1393401A (en) * | 2001-07-04 | 2003-01-29 | 北京运衡兴源科技发展有限公司 | Modified zeolite and its preparing process, application and regeneration |
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- 2005-06-23 CN CNB2005100270834A patent/CN1319857C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009539747A (en) * | 2006-06-08 | 2009-11-19 | シェブロン ユー．エス．エー． インコーポレイテッド | Molecular sieve SSZ-75 composition and its synthesis |
| CN101759197B (en) * | 2008-12-26 | 2012-11-14 | 复旦大学 | Mesopore USSTI zeolite with high silicon content and high hydrothermal stability and preparation method thereof |
| CN102285665A (en) * | 2011-06-07 | 2011-12-21 | 天津大学 | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water |
| CN106809849A (en) * | 2017-02-15 | 2017-06-09 | 上海浦东路桥建设股份有限公司 | For the zeolite and its extracting method of purified industrial sewage |
| CN112403433A (en) * | 2020-09-21 | 2021-02-26 | 复榆(张家港)新材料科技有限公司 | Preparation method and application of novel sub-mesoporous zeolite molecular sieve adsorbent |
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