CN102050466B - Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material - Google Patents
Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material Download PDFInfo
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- CN102050466B CN102050466B CN200910188124A CN200910188124A CN102050466B CN 102050466 B CN102050466 B CN 102050466B CN 200910188124 A CN200910188124 A CN 200910188124A CN 200910188124 A CN200910188124 A CN 200910188124A CN 102050466 B CN102050466 B CN 102050466B
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Abstract
The invention relates to a method for in-suit synthesis of a Y-type molecular sieve by taking silicon-aluminum as a base material. The method comprises the following steps of: (1) adding water to dissolve or uniformly mixing a basic sodium-containing compound, an aluminum-containing compound and water glass; (2) adding amorphous silicon aluminum and kaolin and pulping; (3) aging the mixed slurry under stirring; (4) adding a Y-type molecular sieve guiding agent; (5) transferring the mixture into a reaction kettle for crystallization; and (6) filtering and washing by using water to obtain an in-suit crystallized product. By the method for in-suit crystallization synthesis of the Y-type molecular sieve, the amorphous silicon aluminum base material can be effectively used and converted to obtain the product with a larger aperture; moreover, the Y-type molecular sieve is applicable for catalytic reaction of heavy oil.
Description
Technical field
The present invention relates to a kind of method of in-situ crystallization synthetic Y zeolite, belong to the catalytic material field, specifically belong to the molecular screen material field.
Technical background
Zeolite molecular sieve extensively is present in nature, and the realization of molecular sieve synthetic has then promoted the development of materials chemistry and Industrial Catalysis technology.In the heavy oil deep process technology of petroleum refining process, landmark leap is exactly the heavy oit pyrolysis technological revolution that alternative natural clay of molecular sieve and amorphous acidic silicic acid aluminium are caused.
The molecular sieve original position is synthetic to be grown directly upon the preparation method on certain matrix with molecular sieve component exactly; It is synthetic the same in synthetic liquid phase with traditional in essence; Different is, and it is growth and attached to the dispersion system of the zeolite crystal on the matrix, says on certain meaning that it is a kind of matrix material.
It is that base starting material prepares active constituent and the symbiotic NaY in-situ crystallization technology of matrix that Heden etc. at first disclose with kaolin at US3391994, and main consideration is applied on the FCC catalyzer.In order to obtain the excellent in-situ crystallization catalyzer of active good catalysis selection type, substrate material there is particular requirement, disclose a kind of like EP0209332A2 and be the in-situ crystallization technology of raw material with kaolin, use the 550-925 ℃ of metakaolin that roasting obtains.CN1549746A; CN1232862A; Do matrix and carry out the synthetic preparation of original position Y molecular sieve though CN1334318A has also related to the employing roasting kaolin; Preparation is loaded down with trivial details adds a large amount of Y crystal seeds as needing but they all show, and the disclosed in-situ crystallization time of these patents is all long, generally all at 20h even more than the 30h.
Amorphous aluminum silicide is a kind of porous material, is a kind of catalytic material commonly used, and is particularly more commonly used in hydrocracking process.The chemical constitution of amorphous aluminum silicide is silicon oxide and aluminum oxide; But amorphous aluminum silicide is not the raw material of the synthetic Y zeolite of routine; Because under the condition of the synthetic Y zeolite of hydrothermal crystallizing, can't utilize amorphous aluminum silicide; Therefore the synthetic Y zeolite of in-situ crystallization is not base starting material with the amorphous aluminum silicide, and majority is a base starting material with kaolin.
Summary of the invention
The object of the present invention is to provide a kind of is matrix and the method for passing through growth in situ acquisition Y zeolite with amorphous aluminum silicide and kaolin.
The present invention comprises following content with the sial for the method for the synthetic Y zeolite of matrix original position:
(1) alkaline compounds containing sodium, aluminum contained compound, water glass are dissolved in water or mix;
(2) add the making beating of amorphous aluminum silicide and kaolin;
(3) under agitation that mixed serum is aging;
(4) add the Y zeolite directed agents;
(5) change said mixture over to reaction kettle and carry out crystallization;
(6) filter washing and obtain the in-situ crystallization product.
In the inventive method, alkaline compounds containing sodium can be a kind of or mixtures such as sodium hydroxide, sodium aluminate, and aluminum contained compound is one or more in aluminum oxide, white lake, Tai-Ace S 150, aluminum chloride and the aluminum nitrate etc.The synthetic Y zeolite synthetic feed molar proportioning of original position is (8～15) Na
2O: Al
2O
3: (12～30) SiO
2: (80～380) H
2O, wherein kaolin: the amorphous aluminum silicide weight ratio was at 0.1: 1～1: 1.Amorphous aluminum silicide and kaolin account for 15%～65% of the anhydrous composition of synthesis material by weight, are preferably 25%～45%.The silicon oxide weight content is 10%-90% in the amorphous aluminum silicide, and specific surface area is 300-600m
2/ g, pore volume are 0.6-1.4ml/g.
In the inventive method, the aging condition of step (3) is to wear out 1～18 hour at 30～70 ℃.The preparation process of the Y zeolite directed agents in the step (4) is: with silicon source, sodium metaaluminate, sodium hydroxide and deionized water according to (15～18) Na
2O: Al
2O
3: (15～17) SiO
2: (280～380) H
2The mixed in molar ratio of O evenly after, under room temperature to 70 ℃, leave standstill and made directed agents in aging 0.5～48 hour, the silicon source is a water glass.Y zeolite directed agents add-on is 0.1%～10% of synthetic weight of material.The condition of step (5) crystallization is autogenous pressure and 90～120 ℃ of following crystallization 6～20 hours.In the inventive method, kaolin is through the product behind the 500-1300 ℃ of calcination processing 1-10h.
What the present invention relates to is the synthetic Y zeolite of in-situ crystallization of matrix with amorphous aluminum silicide and kaolin, and mean pore size is not less than 2nm, and specific surface area is 100-400m
2/ g, pore volume are 0.2-0.5ml/g.Y zeolite crystal grain is not more than 700nm.
What prior art was produced conventional Y molecular sieve employing also is directing agent method, and general crystallization time is more than 20h, usually all about 30h.The method that the in-situ crystallization of prior art prepares Y molecular sieve mainly is on method, to introduce kaolin as matrix, but synthetic ratio is to apply mechanically industry to go up sophisticated condition basically, and its proportioning is generally at 4-12SiO
2: 2-5Na
2O: 100-250H
2O, crystallization time are also long, and the conventional molecular sieve of fundamental sum is synthetic similar, generally about 30h.
In industrial production, cost is very important factor, comprises raw materials cost and time cost, if can synthesize apace, means higher combined coefficient, high plant factor and running cost undoubtedly.Adopt original position of the present invention to synthesize Y zeolite, existing relatively FCC in-situ techniques, generated time shortens significantly; Generally be no more than 20h; Even below 16h, generally speaking, the synthetic Y zeolite crystallization time of solid phase original position of the present invention is for usually at 6～20 hours.
The in-situ crystallization Y zeolite material building-up process that the present invention relates to is a matrix with amorphous aluminum silicide and kaolin; Experimental result shows; Synergy has taken place in amorphous aluminum silicide and kaolin under crystallization condition; Unserviceable amorphous aluminum silicide and kaolin have carried out the crystallization conversion effectively under common Y zeolite synthesis condition, and XRD analysis shows that the amorphous aluminum silicide after the crystallization is different fully with the amorphous silicon constructed of aluminium that feeds intake, and big portion crystallization is converted into Y zeolite; Simultaneously because the original skeleton of amorphous aluminum silicide does not have completely destroy; Therefore this original position synthetic Y zeolite is compared with existing method in-situ crystallization synthetic Y zeolite, and mean pore size obviously increases, and heavy oil cracking is useful to this catalytic material for macromole.
Embodiment
Following examples further specify essence of the present invention and effect, do not constitute the restriction to the requirement of right of the present invention, and the composition percentage composition that relates to is a weight percentage.
The preparation process of Y zeolite directed agents is: with water glass, sodium metaaluminate, sodium hydroxide and deionized water according to 16Na
2O: Al
2O
3: 16SiO
2: 300H
2After the mixed in molar ratio of O is even, under 50 ℃, leaves standstill and making the Y zeolite directed agents in aging 18 hours.
Embodiment 1
Be the synthetic Y zeolite of original position of the present invention.Get 5 liters of beakers, add 165.6g Tai-Ace S 150 and add water 300g dissolving, get the 56.3g solid sodium hydroxide in addition and add water 171g dissolving, under agitation the former is slowly added the latter.After mixing, add the water glass 842g of silica content 24%, add silica content 75%, specific surface 278m
2The kaolin 50g that 550 ℃ of roasting 2h of granularity 200 purposes obtain is produced in the amorphous aluminum silicide 240g of/g, pore volume 0.72ml/g and Anhui.Rest on behind the continuously stirring 1h and add Y directed agents 33g behind 50 ℃ of aging 4h, change said mixture over to reaction kettle after stirring and, filter washing and obtain the in-situ crystallization product at 95 ℃ of following crystallization 16h.Be decided to be typical Y molecular sieve through the XRD flash ranging, percent crystallinity 33%, specific surface 280m
2/ g, pore volume 0.24ml/g, mean pore size 4.2nm, sem analysis shows the about 580nm of grain size of products therefrom.
Embodiment 2
Be in-situ crystallization molecular sieve of the present invention.Get 5 liters of beakers, add 60.9g solid sodium hydroxide and 55.8g sodium aluminate and add water 670g, be stirred to the water glass 742g that the dissolving back adds silica content 27%, add silica content 25%, specific surface 518m
2The amorphous aluminum silicide 150g of/g, pore volume 1.22ml/g and Mongolia produce the Coaseries kaolin 100g behind 1350 ℃ of roasting 2h of granularity 600 orders.Add Y directed agents 25g after leaving standstill aging 2h behind the continuously stirring 1h.Change said mixture over to reaction kettle after stirring and under 100 ℃ of hydrothermal conditions crystallization 18h, filter washing and obtain the in-situ crystallization product.Be decided to be typical Y molecular sieve through the XRD flash ranging, percent crystallinity 26%, specific surface 303m
2/ g, pore volume 0.29ml/g, mean pore size 3.1nm, sem analysis shows the about 650nm of grain size of products therefrom.
Comparative example
Press embodiment 2 described methods, just amorphous aluminum silicide is all replaced with kaolin, the percent crystallinity that obtains the Y zeolite product is 31%, specific surface 310m
2/ g, pore volume 0.24ml/g, mean pore size 2.1nm, sem analysis shows the about 2.5 μ m of grain size of products therefrom.
Embodiment 3
Be the embodiment 1 product Hydrogen original position Y zeolite that exchange obtains for twice through ammonium salt; And adopt this Hydrogen original position Y molecular sieve to adopt conventional catalyst prepared A for the cracking component; Contain Hydrogen original position Y zeolite 50% in the catalyst A; Tungsten oxide 99.999 22%, nickel oxide 8%, surplus is an aluminum oxide.
Embodiment 4
The reference catalyst B that adopts a kind of conventional Hydrogen Y molecular sieve to prepare according to embodiment 3 identical proportionings.Wherein, this routine Y molecular sieve percent crystallinity 96%, specific surface 683m
2/ g, pore volume 0.28ml/g, mean pore size 1.6nm, about 2 microns of the grain size of sem analysis demonstration products therefrom.
Embodiment 5
For the heavy-oil hydrogenation cracking of hydrocracking catalyst A of the present invention and reference catalyst B is estimated.Catalyzer is a raw material with heavy Iran's vacuum distillate (density 0.921g/ml, boiling range 352-541 ℃), carries out the hydrogen cracking evaluation experimental.Appreciation condition is hydrogen dividing potential drop 15MPa, hydrogen to oil volume ratio 1000, volume space velocity 1.5h during cracking liquid
-1, carry out hydrogenation split before raw material be not more than 10 μ g/g through conventional unifining control cracking zone charging organonitrogen content.
Experimental result shows: handle above-mentioned heavy feed stock, under the same situation of temperature of reaction, CA catalyzer of the present invention is suitable basically with conventional reference catalyst CB per pass conversion; The intermediate oil selectivity of CA catalyzer is up to 87.2; And the CB catalyzer has only 83.3, explains because the wide aperture of molecular sieve of the present invention helps the diffusion of resultant; Reduced the probability of second pyrolysis, shown that therefore the intermediate oil selectivity is high.
Claims (10)
1. one kind is the method that the matrix original position is synthesized Y zeolite with the sial, comprises following content:
(1) alkaline compounds containing sodium, aluminum contained compound, water glass are dissolved in water or mix;
(2) add the making beating of amorphous aluminum silicide and kaolin;
(3) under agitation that mixed serum is aging;
(4) add the Y zeolite directed agents;
(5) change said mixture over to reaction kettle and carry out crystallization;
(6) filter washing and obtain the in-situ crystallization product.
2. according to the described method of claim 1; It is characterized in that: described alkaline compounds containing sodium is a kind of or mixture in sodium hydroxide, the sodium aluminate, and aluminum contained compound is one or more in aluminum oxide, white lake, Tai-Ace S 150, aluminum chloride and the aluminum nitrate.
3. according to the described method of claim 1, it is characterized in that: the synthetic Y zeolite synthetic feed molar proportioning of original position is (8～15) Na
2O: Al
2O
3: (12～30) SiO
2: (80～380) H
2O.
4. according to the described method of claim 1, it is characterized in that kaolin: the amorphous aluminum silicide weight ratio is 0.1: 1～1: 1.
5. according to claim 1 or 4 described methods, it is characterized in that: the silicon oxide weight content is 10%-90% in the amorphous aluminum silicide, and specific surface area is 300-600m
2/ g, pore volume are 0.6-1.4ml/g; Kaolin is through the product behind the 500-1300 ℃ of calcination processing 1-10h.
6. according to the described method of claim 1, it is characterized in that: the aging condition of step (3) is for wearing out 1～18 hour at 30～70 ℃.
7. according to the described method of claim 1, it is characterized in that: the preparation process of the Y zeolite directed agents in the step (4) is: with silicon source, sodium metaaluminate, sodium hydroxide and deionized water according to (15～18) Na
2O: Al
2O
3: (15～17) SiO
2: (280～380) H
2The mixed in molar ratio of O evenly after, under room temperature to 70 ℃, leave standstill and made directed agents in aging 0.5～48 hour, the silicon source is a water glass.
8. according to claim 1 or 7 described methods, it is characterized in that: Y zeolite directed agents add-on is 0.1%～10% of synthetic weight of material.
9. according to the described method of claim 1, it is characterized in that: the condition of step (5) crystallization is for autogenous pressure and 90～120 ℃ of following crystallization 6～20 hours.
10. the Y zeolite of the said method preparation of a claim 1, mean pore size is not less than 2nm, and specific surface area is 100-400m
2/ g, pore volume are 0.2-0.5ml/g.
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|---|---|---|---|
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|---|---|---|---|
| CN200910188124A CN102050466B (en) | 2009-10-27 | 2009-10-27 | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material |
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| CN102050466B true CN102050466B (en) | 2012-08-29 |
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|---|---|---|---|---|
| CN104556123B (en) * | 2013-10-23 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of in-situ crystallization Y type molecular sieve and synthetic method thereof |
| CN104556121B (en) * | 2013-10-23 | 2017-07-14 | 中国石油化工股份有限公司 | One kind load crystallized nano Y type molecular sieve and its synthetic method |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN105621445B (en) * | 2014-11-03 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of NaY types molecular sieve and preparation method thereof |
| CN105645433B (en) * | 2016-03-29 | 2017-12-12 | 东北大学 | A kind of method for synthesizing Y type molecular sieve with kaolin dynamic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
Non-Patent Citations (1)
| Title |
|---|
| 王雪静等.合成条件对偏高岭土水热合成Y型分子筛结构的影响.《信阳师范学院学报：自然科学版》.2009,第22卷(第1期),56-59. * |
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