CN1176018C - Method for synthesizing small-grain Y-type molecular sieve - Google Patents
Method for synthesizing small-grain Y-type molecular sieve Download PDFInfo
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- CN1176018C CN1176018C CNB011356855A CN01135685A CN1176018C CN 1176018 C CN1176018 C CN 1176018C CN B011356855 A CNB011356855 A CN B011356855A CN 01135685 A CN01135685 A CN 01135685A CN 1176018 C CN1176018 C CN 1176018C
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- molecular sieve
- silica gel
- silicon
- crystallization
- alumino silica
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Abstract
The present invention relates to a method for synthesizing a molecular sieve. The method comprises the following steps: firstly, a silicon aluminum collosol is prepared from the components of the following molar proportion: 1 of Al2O3, 10 to 20 of SiO2, 12 to 18 of Na2O and 150 to 450 of H2O at a temperature of 0 to 40 DEG C, and the silicon aluminum collosol is aged so that a crystallization directing agent is obtained; then reactive alumino silica gel is prepared from the components of the following molar proportion: 1 of Al2O3, 5 to 20 of SiO2, 2 to 5 of Na2O and 200 to 600 of H2O at a temperature of 0 to 40 DEG C; the quantity of guiding agents added into the reactive alumino silica gel accounts for 10 mol% of the total quantity of Al2O3 in a synthetic system measured by Al2O3. The reactive alumino silica gel is transferred into a pressure kettle, sealed and crystallized statically at a temperature of 90 to 110 DEG C for 15 to 60 hours. Because the mixing process of raw materials is carried out at a low temperature and silicon sources and alkalis are mixed firstly, more smaller crystal nucleuses are formed, and the average grain size of the molecular sieve is smaller than 300 nm.
Description
The present invention relates to a kind of synthetic method of molecular sieve.
Molecular sieve can have very important use as catalyst activity constituent element or support of the catalyst because of its unique hole/basket structure, ion-exchange performance and potential are acid in the hydrocarbon processing industry process.
The preparation method of Y zeolite classics is described at first by the patent US3130007 of U.S. Union Carbide company: be with the reaction mixture direct crystallization, or earlier in room temperature or a little more than the room temperature ageing, and then carry out the high temperature crystallization.And the at present industrial crystallization director method that widely adopts, then based on the patent US3510258 of U.S. Engehard company and the patent US3671191 and the US3639099 of C.W.R.Grace company: be the reaction mixture for preparing a small amount of high basicity earlier, carry out ageing in room temperature or a little more than room temperature again, and with this as crystallization director.Prepare the reaction mixture of a large amount of low basicity then, again crystallization director is added on wherein, at high temperature carry out crystallization then.In patent US3671191 and US3639099, adopted mineral acid (as sulfuric acid) and aluminium salt (as Tai-Ace S 150, aluminum chloride etc.) respectively, with the basicity of reduction reaction system, thus the silica alumina ratio of raising product molecular sieve.By the technology that above-mentioned patent is introduced, the Y for preparing has the grain fineness number of 1000-3000 μ m.
There are some patents once to report to reducing the zeolite crystal degree.The preparation method that patent US3755538 reported is to add a small amount of B in alumino silica gel, V, and P, Mo, W, Ge and Ga element, the prepared Y that goes out has the grain fineness number of 200-600 nanometer; By in the preparation system, introducing the organic solvent that can dissolve each other, can reduce to prepare the grain fineness number of Y effectively, as in patent US4372931 with water, then used glucose, prepared Y with the nanocrystalline granularity of 40-60, but after adding organic solvent, the skeleton SiO of molecular sieve
2/ Al
2O
3Lower, generally be lower than 2.5.
It is shorter that purpose of the present invention aims to provide a kind of crystallization time, and the Y zeolite average grain size that is synthesized is less than the synthetic method of the small crystal grain Y-shaped molecular sieve of 300nm.
The method of the said synthesizing small-grain Y zeolite of the present invention is as follows:
According to 1Al
2O
3: (10-20) SiO
2: (12-18) Na
2O: (150-450) H
2The mole proportioning of O is preferably pressed 1Al
2O
3: (14-16) SiO
2: (14-18) Na
2O: (200-350) H
2The mole proportioning of O at 0-40 ℃, is preferably under 0-4 ℃ the ice-water bath and mechanical stirring condition, silicon source, aluminium source, sodium hydroxide and water are mixed, and it is even to continue to be stirred to mixing of materials, obtains silicon-aluminum sol, this silicon-aluminum sol after at room temperature still aging 48 hours, is got crystallization director.Then according to 1Al
2O
3: (5-20) SiO
2: (2-5) Na
2O: (200-600) H
2The mole proportioning of O is preferably pressed 1Al
2O
3: (8-12) SiO
2: (2.5-4) Na
2O: (300-500) H
2The mole proportioning of O at 0-40 ℃, is preferably under 0-4 ℃ the ice-water bath and mechanical stirring condition, be pre-mixed crystallization director, silicon source and sodium hydroxide in order, slowly add aluminium source and water then, and it is even to continue to be stirred to mixing of materials, makes the reaction alumino silica gel.The addition of directed agents is with Al in the reaction alumino silica gel
2O
3Meter accounts for total Al in the synthetic system
2O
3The 10mol% of amount.To react alumino silica gel and change in the autoclave pressure, the sealing back was preferably in 100 ℃ of following static crystallizations 35 hours at 90-110 ℃ of following static crystallization 15-60 hour.Product to neutral and oven dry under 120 ℃, obtains sieve sample through suction filtration, washing.Said silicon source is silicon sol, water glass, is preferably water glass; Said aluminium source is Tai-Ace S 150, sodium metaaluminate, is preferably Tai-Ace S 150.
Raw material mixing process of the present invention all is to carry out being lower than under the room temperature.During owing to preparation feedback mixture under being lower than room temperature, earlier all alkali and silicon source are mixed, make that the abundant depolymerization under sufficiently high basicity of silicon source is oligomeric activated silica species, generate the polycondensation and the rearrangement of alumino silica gel and alumino silica gel when helping further mixing fast with the aluminium source, thereby make and to form the crystallization rate quickening that more littler nucleus make molecular sieve in the synthetic system, shortened crystallization time, the Y zeolite that is synthesized has the average grain size less than 300nm, the framework of molecular sieve silica alumina ratio is greater than 5.0, and degree of crystallinity is greater than 90%.
Fig. 1,2 is the TEM photo of embodiment 1Y type sieve sample.
The present invention will be further described below by embodiment:
Embodiment 1: press 1Al
2O
3: 15SiO
2: 16Na
2O: 300H
2The mole proportioning of O, (autogamy reagent with silicon sol and sodium hydroxide preparation, contains 5molSiO in every liter of solution with 37.5ml water glass
2And 5molNaOH, down with), 11.5g sodium hydroxide, 12.5ml Tai-Ace S 150 (1mol/l, down with) solution and 24.4ml deionized water in 0-4 ℃ of ice-water bath and mechanical stirring mix, and continue to be stirred to raw material and mix, mixture after at room temperature still aging 48 hours, is obtained directed agents.Press 1Al then
2O
3: 10SiO
2: 3.3Na
2O: 300H
2The mole proportioning of O, 16.3g directed agents, 34ml water glass and 0.3g sodium hydroxide are reached mechanical stirring in 0-4 ℃ of ice-water bath mix, slowly add 18ml alum liquor and 52ml deionized water then, and continue to be stirred to raw material and mix, obtain reacting alumino silica gel.To react alumino silica gel and change in the autoclave pressure, crystallization was left standstill 35 hours in the sealing back under 100 ℃.The also quick cooling pressure still of taking-up, product, characterizes with technology such as XRD, TEM to neutrality and after drying under 120 ℃ through suction filtration, washing.X-ray diffraction analysis shows (main XRD diffraction peak data such as table 1), and the sample that above-mentioned synthetic method makes is a Y zeolite, SiO
2/ Al
2O
3Than being 5.6, relative crystallinity is 97.4%.Show that as Fig. 1,2TEM photo this Y zeolite sample has the average grain size of 150nm.
Embodiment 2: according to 1Al
2O
3: 10SiO
2: 12Na
2O: 150H
2The mole proportioning of O, with 41.5ml silicon sol (25wt%, 22g sodium hydroxide and 40ml sodium aluminate solution (1mol/l down together),, down with) under 0-4 ℃ and mechanical stirring, mix, and continue to be stirred to raw material and mix, with at room temperature still aging 48 hours of mixture, obtain crystallization director.Press then
The XRD main diffraction peak position and the intensity of table 1 embodiment 1 products molecule sieve
2θ h2+k2+l2 d I/IO
6.16 3 14.348 100
10.11 8 8.749 15
11.88 11 7.449 24
15.65 19 5.662 41
18.69 27 4.748 23
20.37 32 4.360 35
22.81 40 3.899 11
23.68 43 3.757 47
25.81 51 3.452 9
27.08 56 3.293 37
27.81 59 3.208 8
29.67 67 3.011 14
30.79 72 2.904 20
31.45 75 2.845 48
32.51 80 2.754 21
33.13 83 2.704 7
34.15 88 2.626 19
34.74 91 2.582 11
37.97 108 2.370 13 according to 1Al
2O
3: 5SiO
2: 2Na
2O: 600H
2The mole proportioning of O with 9.7g directed agents, 16.6ml silicon sol, 5.4g sodium hydroxide, 9ml sodium aluminate solution and 180ml deionized water, is mixed under 0-4 ℃ and churned mechanically condition, and continues to be stirred to raw material and mix, and obtains reacting alumino silica gel.To react alumino silica gel and change in the autoclave pressure, crystallization was left standstill 35 hours in the sealing back under 100 ℃.After product such as embodiment 1 handle, characterize with XRD, TEM technology.Characterization result shows that the sample that above-mentioned synthetic method makes is a Y zeolite, SiO
2/ Al
2O
3Than being 4.3, relative crystallinity is 90.2%, and average grain size is 220nm.
Embodiment 3: according to 1Al
2O
3: 20SiO
2: 18Na
2O: 450H
2The mole proportioning of O, 50ml water glass, 11g sodium hydroxide, 12.5ml alum liquor and 47.8ml deionized water are mixed under 0-4 ℃ and mechanical stirring, and continue to be stirred to raw material and mix, mixture at room temperature still aging 48 hours, is obtained crystallization director.According to 1Al
2O
3: 20SiO
2: 5Na
2O: 200H
2The mole proportioning of O is mixed 22.6g directed agents and 72ml water glass under 0-4 ℃ and churned mechanically condition, slowly add 18ml alum liquor and 6ml deionized water then, and continues to be stirred to raw material and mix, and obtains reacting alumino silica gel.To react alumino silica gel and change in the autoclave pressure, crystallization was left standstill 35 hours in the sealing back under 100 ℃.After product such as embodiment 1 handle, characterize with XRD, TEM technology.Characterization result shows that the sample that above-mentioned synthetic method makes is a Y zeolite, SiO
2/ Al
2O
3Than being 5.2, relative crystallinity is 94.5%, and average grain size is 180nm.
Embodiment 4: it is all identical with embodiment 1 with consumption to synthesize the used raw material of directed agents and reaction alumino silica gel, but has prepared directed agents and reaction alumino silica gel respectively under 40 ℃, and the reaction alumino silica gel of gained left standstill crystallization 30 hours under 110 ℃.After product such as embodiment 1 handle, characterize with XRD, TEM technology.Characterization result shows that the sample that above-mentioned synthetic method makes is Y zeolite SiO
2/ Al
2O
3Than being 5.3, relative crystallinity is 93%, and average grain size is 250nm.
Claims (4)
1. the synthetic method of a small crystal grain Y-shaped molecular sieve is characterized in that at first by 1Al
2O
3: (14-16) SiO
2: (14-18) Na
2O: (200-350) H
2The mole proportioning of O, under 0-4 ℃ ice-water bath and mechanical stirring condition, silicon source, aluminium source, sodium hydroxide and water are mixed, and continue to be stirred to raw material and mix, obtain silicon-aluminum sol, silicon-aluminum sol is got crystallization director after at room temperature still aging 48 hours; Press 1Al then
2O
3: (8-12) SiO
2: (2.5-4) Na
2O: (300-500) H
2The mole proportioning of O under 0-4 ℃ of ice-water bath and mechanical stirring condition, is mixed crystallization director, silicon source and sodium hydroxide earlier in order, slowly add aluminium source and water then, and it is even to continue to be stirred to mixing of materials, makes the reaction alumino silica gel; The addition of directed agents is with Al in the reaction alumino silica gel
2O
3Meter accounts for total Al in the synthetic system
2O
3The 10mol% of amount; To react alumino silica gel and change in the autoclave pressure, the sealing back was at 90-110 ℃ of following static crystallization 15-60 hour, and product to neutrality and 120 ℃ of oven dry down, obtains sieve sample through suction filtration, washing; Said silicon source is silicon sol, water glass; Said aluminium source is Tai-Ace S 150, sodium metaaluminate.
2. the synthetic method of small crystal grain Y-shaped molecular sieve as claimed in claim 1, the crystallization condition that it is characterized in that molecular sieve are 100 ℃ of following static crystallizations 35 hours.
3. the synthetic method of small crystal grain Y-shaped molecular sieve as claimed in claim 1 is characterized in that said silicon source is a water glass.
4. the synthetic method of small crystal grain Y-shaped molecular sieve as claimed in claim 1 is characterized in that said aluminium source is a Tai-Ace S 150.
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|---|---|---|---|
| CNB011356855A CN1176018C (en) | 2001-10-19 | 2001-10-19 | Method for synthesizing small-grain Y-type molecular sieve |
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|---|---|---|---|
| CNB011356855A CN1176018C (en) | 2001-10-19 | 2001-10-19 | Method for synthesizing small-grain Y-type molecular sieve |
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| CN1176018C true CN1176018C (en) | 2004-11-17 |
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Families Citing this family (16)
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|---|---|---|---|---|
| CN1308238C (en) * | 2004-06-08 | 2007-04-04 | 太原理工大学 | Double microporous zeolite molecular sieves and preparing method thereof |
| CN1331748C (en) * | 2004-09-08 | 2007-08-15 | 中国科学院大连化学物理研究所 | Production of Y-shaped molecular sieve |
| CN101723400B (en) * | 2008-10-29 | 2013-01-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN103449469B (en) * | 2012-06-01 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of NaY molecular sieve preparation method that improves stability |
| CN104556127B (en) * | 2013-10-24 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of synthetic method of little grain high-Si Y-type molecular sieve |
| CN105084388B (en) * | 2014-05-20 | 2017-05-24 | 中国石油化工股份有限公司 | Method for preparing and modifying Y-type molecular sieve |
| CN105523567B (en) * | 2016-01-19 | 2018-06-05 | 菏泽学院 | A kind of preparation method of the NaY molecular sieve of controlled dimensions |
| RU2627900C1 (en) * | 2016-12-05 | 2017-08-14 | Федеральное государственное бюджетное учреждение науки Институт проблем переработки углеводородов Сибирского отделения Российской академии наук (ИППУ СО РАН) | Method of preparing microcrystalline nay zeolite |
| CN108408737A (en) * | 2018-05-29 | 2018-08-17 | 王子韩 | A method of quickly preparing Y type molecular sieve |
| CN111087001A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation method of small-grain NaY type molecular sieve |
| CN109264743A (en) * | 2018-11-23 | 2019-01-25 | 福州大学 | A kind of preparation method of little crystal grain high silica alumina ratio NaY molecular sieve |
| CN112723375B (en) * | 2019-10-28 | 2023-02-03 | 中国石油化工股份有限公司 | Y-type molecular sieve and preparation method and application thereof |
| CN112744840B (en) * | 2019-10-31 | 2023-02-07 | 中国石油化工股份有限公司 | NaY molecular sieve synthesis device and NaY molecular sieve synthesis method |
| JP2023546276A (en) * | 2020-10-15 | 2023-11-01 | 中国石油化工股▲ふん▼有限公司 | m-xylene adsorbent and its preparation method |
| CN114604875A (en) * | 2020-12-09 | 2022-06-10 | 成都理工大学 | Fast green synthesis method of NaY molecular sieve with small crystal grains and large specific surface area |
| CN112320816A (en) * | 2020-12-09 | 2021-02-05 | 成都理工大学 | Low-temperature green synthesis method of NaY molecular sieve with small crystal grains and large specific surface area |
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