CN1393399A - Antiwear spherical NaY molecular sieve and its synthesizing process - Google Patents
Antiwear spherical NaY molecular sieve and its synthesizing process Download PDFInfo
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- CN1393399A CN1393399A CN 01113203 CN01113203A CN1393399A CN 1393399 A CN1393399 A CN 1393399A CN 01113203 CN01113203 CN 01113203 CN 01113203 A CN01113203 A CN 01113203A CN 1393399 A CN1393399 A CN 1393399A
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- molecular sieve
- nay
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- clinoptilolite
- nay molecular
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Abstract
An antiwear spherical NaY molecular sieve is prepared from natural kaolinite and/or clinoptilolite, pore enlarging agent and strengthening agent through spray granulating, calcining and hydrothermal crystallizing. It can be used to prepare microspherical adsorbent or catalyst.
Description
The present invention relates to a kind of synthetic method of antiwear spherical NaY molecular sieve, belong to inorganic synthetic and catalysis technique category.Saying so a kind of more specifically is that kaolin and clinoptilolite are raw material with rich aluminium and persilicic natural mineral, the method for the synthetic wear-resisting NaY molecular sieve of microspheroidal.
Adopting different raw material synthesis of molecular sieve is that the synthetic field of inorganic materials and catalytic material reduces cost and obtains the topmost means of various objectives product.The raw material that usually synthetic NaY molecular sieve adopts is that compositing range is (3.1～6.6) Na
2OAl
2O
3(7.6～16) SiO
2(175～320) H
2The sodium silicoaluminate hydrogel of O.This gel is usually again by liquid soluble glass and Tai-Ace S 150 preparation.The particle diameter of gel method synthetic NaY molecular sieve is 0.3～3 μ m.In order to obtain different sizes and the oarse-grained material that contains molecular sieve of different shapes, normally gel method synthetic molecular sieve is mixed back mechanical presses moulding with other matrix material such as attapulgite, the blue or green powder in field etc., or on the substrate material of selected shape, flood molecular sieve and oxide compound, drying, roasting and make again.
No. 87105499 patent disclosures of CN a kind of technology for preparing the coccoid A type molecular sieve of millimeter level of high mechanical strength, with inorganic ammonium salt, mineral acid, water glass is raw material, prepare the silica hydrogel bead with the oil column spherical container shaping method, through washing, dipping tensio-active agent, drying, roasting, make low bulk silicon-dioxide bead, the silicon-dioxide bead is mixed the back crystallization with sodium metaaluminate, make the silicon-dioxide bead be converted into A type molecular sieve substantially, its profile and size are constant.Its shortcoming is to synthesize spherical model-A molecular sieves.
CN 96112641 patent applications are that a kind of activated water glass solution that adopts is the method for the synthetic NaY type molecular sieve of raw material, and its preparation process is that the conventional directed agents solution that makes in advance (is pressed SiO by 5.0-30.0%
2The mole number meter) joins in the water glass solution, make activated water glass solution, then according to the synthetic NaY type molecular sieve of conventional industry prescription hydro-thermal.The activated water glass solution that adopts can keep its NaY type molecular sieve guiding activity to reach about 15 days under 20-50 ℃ of temperature.The shortcoming of its sintetics is, the sieve particle diameter that gel method obtains is less than 3 μ m, and the mechanical wear intensity of sieve particle is very low.
No. 92109402 patent disclosures of CN a kind of method of preparation of zeolite molecular sieve by kneading method, its preparation process is earlier siliceous and aluminiferous chemical feedstocks such as water glass to be mixed with into gel with Tai-Ace S 150, synthesis of molecular sieve in the presence of no separable mother liquor, also claim extremely dense system synthetic molecules sieve method, do not relate to institute's synthetic sieve particle shape and physical strength.
The CN93115879 patent disclosure a kind of high intensity molecular sieve and preparation method thereof, its preparation method is earlier with molecular sieve or molecular sieve catalyst moulding, molecular sieve that physical strength is very low or molecular sieve catalyst are immersed in and contain in aluminum oxide, silicon oxide, zirconium white or magnesian one or more mixed membrane solvents, improve intensity by dry, roasting then.Its shortcoming is to carry out moulding more earlier with the synthetic mealy molecular sieve of ordinary method.
The preparation method that Chinese patent application discloses a kind of high wearproof granular molecular sieve adsorbent No. 95111956 is with the blue or green powder mixing moulding of commercially available molecular sieve and sodium cellulosate and the field granulin molecule sieve that is certain abrasive wear resistance.But this sample preparation method gained high intensity molecular sieve is when at high temperature (as more than 500 ℃) uses, because the thermolysis of sodium cellulosate and field green grass or young crops powder makes it lose abrasive wear resistance.
In above several method, all do not relate to earlier kaolin and clinoptilolite material forming be 2～400 μ m microballoons after, being converted into the equal diameter of matter in the water glass system is the high strength NaY type sieve technology of 60～90 μ m.
The objective of the invention is, so that one or both are raw material in natural kaolin, the clinoptilolite, provide a kind of synthetic method of antiwear spherical NaY molecular sieve, the microspheroidal molecular sieve of preparation has high wear resistance.
Peculiar noun involved in the present invention is " a sour molten aluminium ": refer to through being dissolved in 10～15% the nitric acid or the aluminum oxide of 10～15% hydrochloric acid in pre-treatment kaolin, the clinoptilolite.
Realize that technical scheme of the present invention is: with rich aluminium and persilicic natural mineral is that kaolin and clinoptilolite are the wear-resisting ball shape NaY molecular sieve of feedstock production, NaY content 25～95%, the SiO of NaY
2/ Al
2O
3=3.7～5.2, the equal diameter of the matter of spherical particle is 60～90 μ m, and abrasion index is 1～15%.The preparation method is: earlier with 5～15% salt acid elutions, wash rich aluminium with 5～20%NaOH again and the persilicic natural mineral promptly is that kaolin (consists of Al
2O
32SiO
22H
2O), clinoptilolite (consists of 4Na
2O4Al
2O
340SiO
232H
2O), or preceding two kinds mixture, blending ratio is a kaolin: clinoptilolite=20: 80～100: 0, after washed product is added expanding agent and strengthening agent and is made slurries, being prepared into mass mean diameter (the equal diameter of matter) with the rotating spraying rapid dry process is 1～400 μ m miniature spherical (microballoon) particle, at 800～1300 ℃ of roasting microballoons, make partial oxidation aluminium wherein from mineral crystal structure, dissociate out, free alumina can be measured (dissolved the aluminum oxide that by acid and claim " sour molten aluminium ") with the nitric acid dissolve standard measure, the microballoon that contains the molten aluminium of quantitative acid after roasting is put in the mixing liquid of water glass and Y zeolite directed agents and is carried out conventional hydrothermal crystallizing reaction, hydrothermal crystallizing 16～36 hours, obtain crystallization product, the active principle mole of each oxide compound consists of (7～15) Na in the crystallization system
2OAl
2O
3(18～30) SiO
2(200～320) H
2O; Measure the degree of crystallinity of institute's synthetic product with x-ray powder diffraction.
Be prepared into satisfactory particle with the rotating spraying rapid dry process, the size distribution gram is 60～90 μ m.
Kaolin: clinoptilolite can be 60: 40, and contain 3.25% Na in the mixture this moment
2O, 29.04% Al
2O
3, 59.34% SiO
2, 8.43% H
2O; Mixture is with 8% salt acid elution, again with 10% NaOH washing.
The expanding agent that adds can be in blue or green powder in field and the yellow soda ash one or both, and addition is 0.1～4.0%; The strengthening agent that adds can be yellow soda ash and TiCl
4In one or both, addition is 0.1～2%.
The temperature range of roasting mineral can be at 900～1100 ℃.
Here the concrete implication of " active principle " is Na
2O refers to total sodium oxide of crystallization system; Al
2O
3The summation that refers to alumina content in sour molten aluminium and the directed agents; SiO
2The summation that refers to crystallization system silicon oxide.Reaction mass is through hydrothermal crystallizing reaction, Na in the roasting mineral microballoon
2O, Al
2O
3, SiO
2Can be converted into the NaY molecular sieve, NaY content can reach 25～95%, the SiO of NaY
2/ Al
2O
3=3.7～5.2, the size and the shape of spherical particle are constant substantially before and after the crystallization, and the abrasion index that the gas lift method is measured is 1～15%.
The present invention is so that one or both are raw material in natural kaolin, the clinoptilolite, a kind of synthetic method of antiwear spherical NaY molecular sieve is provided, microspheroidal molecular sieve with this synthetic method preparation has high wear resistance, is the ideal material of preparation microspheroidal sorbent material, catalyzer.
The present invention is further specified by following examples.
The main analytical procedure that relates in the example sees Table 1.
Example 1: with blending ratio is kaolin: the 1Kg mixed mineral of clinoptilolite=6: 4 grinds, make in the mixture 80% particulate diameter less than 2 μ m, add water then and make slurries, slurries wash with 20% hydrochloric acid soln 200mL, 20% sodium hydroxide solution 200mL washing, washed product add 20g expanding agent Mierocrystalline cellulose, 20g strengthening agent TiCl
4, after the making beating, spraying drying, obtaining particle size distribution is the microballoon of 2～400 μ m, equal diameter 69～90 μ m of matter.This microballoon obtains the grog microballoon after 880～900 ℃ of roastings, the sour molten aluminium of measuring wherein is 17%.The measuring method of the molten aluminium of acid is: take by weighing sample 2.500g, place the 100mL Erlenmeyer flask, add the hydrochloric acid soln of 15mL 10% then, shake up, build stopper, 70 ℃ of constant temperature 2h after-filtration are all collected filtrate in the 200ml volumetric flask, pipette 5mL solution in the 250mL Erlenmeyer flask with transfer pipet, complexometry routinely, with the xylenol orange is indicator, with the titration of standard EDTA solution, can calculate Al in the filtrate according to the EDTA consumption
2O
3Content, and then calculate sour molten aluminium.Get grog microballoon 100g, add directed agents 20ml, add water glass again, make the mole of reaction system active principle consist of 7Na
2OAl
2O
326SiO
2320H
2O, conventional hydrothermal crystallizing obtained crystallization material 117g more than 16 hours, and NaY degree of crystallinity is 66%, and the equal diameter 69 μ m of matter, wet cleaning process obtain coarse particles material 96g after removing the following particle of most of 2 μ m, and NaY degree of crystallinity is 52%, silica alumina ratio is SiO
2/ Al
2O
3Be 4.2, the equal diameter 81 μ m of matter, abrasion index 2.7%
Example 2: with blending ratio is kaolin: the 1Kg mixed mineral of clinoptilolite=9: 1 grinds, other treating processes is fully with example 1, the microballoon of equal diameter 69～90 μ m of preparation matter, this microballoon obtains the grog microballoon after 990～1100 ℃ of roastings, and measuring wherein sour molten aluminium is 12%.Get grog microballoon 100g, add directed agents 20ml, add water glass again, make the mole of reaction system active principle consist of 8Na
2OAl
2O
325SiO
2275H
2O, conventional hydrothermal crystallizing obtained crystallization material 123g more than 20 hours, and NaY degree of crystallinity is 72%, and the equal diameter 65 μ m of matter, wet cleaning process obtain coarse particles material 93g after removing the following particle of most of 2 μ m, and NaY degree of crystallinity is 55%, silica alumina ratio is SiO
2/ Al
2O
3Be 4.7, the equal diameter 80 μ m of matter, abrasion index 2.0%
Example 3: with blending ratio is kaolin: the 1Kg mixed mineral of clinoptilolite=2: 8 grinds, other treating processes is fully with example 1, the microballoon of equal diameter 69～90 μ m of preparation matter, this microballoon obtains the grog microballoon after 800～820 ℃ of roastings, and measuring its sour molten aluminium is 10%.Get grog microballoon 100g, add directed agents 20ml, add water glass again, make the mole of reaction system active principle consist of 8Na
2OAl
2O
326SiO
2223H
2O, conventional hydrothermal crystallizing obtained crystallization material 105g more than 20 hours, and NaY degree of crystallinity is 37%, and the equal diameter 83 μ m of matter, wet cleaning process obtain coarse particles material 91g after removing the following particle of most of 2 μ m, and NaY degree of crystallinity is 35%, and silica alumina ratio is SiO
2/ Al
2O
3Be 3.8, the equal diameter 84 μ m of matter, abrasion index 5.1%.
Table 1 analytical procedure
| Analysis project | Analytical procedure | The method standard code name |
| The molten aluminium of acid is measured | Acid pasting | Q/ALJ2.19 |
| Granular size is measured | The laser particle analyzer method | Q/ALJ2.35 |
| NaY degree of crystallinity | X-ray diffraction method | Q/ALJ2.32 |
| Silica alumina ratio (SiO 2/Al 2O 3) measure | X-ray diffraction method | Q/ALJ2.33 |
| Abrasion index is measured | Fluidisation wearing and tearing method | Q/ALJ2.36 |
Claims (6)
1, a kind of wear-resisting ball shape NaY molecular sieve is characterized in that NaY content 25～95%, the SiO of NaY
2/ Al
2O
3=3.7～5.2, the equal diameter of the matter of spherical particle is 60～90 μ m, and abrasion index is 1～15%.
2, a kind of synthetic method of wear-resisting ball shape NaY molecular sieve is characterized in that with rich aluminium and persilicic natural mineral being that kaolin and clinoptilolite are the feedstock production Y zeolite; The preparation method is: earlier with 5～15% salt acid elutions, wash rich aluminium with 5～20%NaOH again and the persilicic natural mineral promptly is that kaolin (consists of Al
2O
32SiO
22H
2O), clinoptilolite (consists of 4Na
2O4Al
2O
340SiO
232H
2O), or preceding two kinds mixture, blending ratio is a kaolin: clinoptilolite=20: 80～100: 0, after washed product is added expanding agent and strengthening agent and is made slurries, being prepared into mass mean diameter (the equal diameter of matter) with the rotating spraying rapid dry process is 1～400 μ m miniature spherical (microballoon) particle, at 800～1300 ℃ of roasting microballoons, make partial oxidation aluminium wherein from mineral crystal structure, dissociate out, free alumina can be measured (dissolved the aluminum oxide that by acid and claim " sour molten aluminium ") with the nitric acid dissolve standard measure, the microballoon that contains the molten aluminium of quantitative acid after roasting is put in the mixing liquid of water glass and Y zeolite directed agents and is carried out conventional hydrothermal crystallizing reaction, hydrothermal crystallizing 16～36 hours, obtain crystallization product, the active principle mole of each oxide compound consists of (7～15) Na in the crystallization system
2OAl
2O
3(18～30) SiO
2(200～320) H
2O; Measure the degree of crystallinity of institute's synthetic product with x-ray powder diffraction.
3, according to the preparation method of the described wear-resisting ball shape NaY molecular sieve of claim 2, it is characterized in that being prepared into satisfactory particle with the rotating spraying rapid dry process, size distribution is 60～90 μ m.
4, according to the preparation method of the described wear-resisting ball shape NaY molecular sieve of claim 3, it is characterized in that kaolin: clinoptilolite=60: 40, contain 3.25% Na in the mixture this moment
2O, 29.04% Al
2O
3, 59.34% SiO
2, 8.43% H
2O; Mixture is with 8% salt acid elution, again with 10% NaOH washing.
5, according to the preparation method of the described wear-resisting ball shape NaY molecular sieve of claim 4, it is characterized in that the expanding agent that adds be in blue or green powder in field and the yellow soda ash one or both, addition is 0.1～4.0%; The strengthening agent that adds is yellow soda ash and TiCl
4In one or both, addition is 0.1～2%.
6, according to the described preparation method of claim 5, the temperature range that it is characterized in that the roasting mineral is at 900～1100 ℃.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107883B (en) * | 2009-12-23 | 2012-12-26 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| CN110540214A (en) * | 2018-05-28 | 2019-12-06 | 中国石油化工股份有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110589850A (en) * | 2019-10-14 | 2019-12-20 | 北京工业大学 | Synthesis method of clinoptilolite with spherical morphology |
-
2001
- 2001-06-29 CN CN 01113203 patent/CN1393399A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| CN102107883B (en) * | 2009-12-23 | 2012-12-26 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
| CN110540214A (en) * | 2018-05-28 | 2019-12-06 | 中国石油化工股份有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110589850A (en) * | 2019-10-14 | 2019-12-20 | 北京工业大学 | Synthesis method of clinoptilolite with spherical morphology |
| CN110589850B (en) * | 2019-10-14 | 2023-03-28 | 北京工业大学 | Synthesis method of clinoptilolite with spherical morphology |
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