CN103449468A - Synthesis method of NaY molecular sieve - Google Patents
Synthesis method of NaY molecular sieve Download PDFInfo
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- CN103449468A CN103449468A CN2012101684201A CN201210168420A CN103449468A CN 103449468 A CN103449468 A CN 103449468A CN 2012101684201 A CN2012101684201 A CN 2012101684201A CN 201210168420 A CN201210168420 A CN 201210168420A CN 103449468 A CN103449468 A CN 103449468A
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- molecular sieve
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Abstract
The invention relates to a synthesis method of an NaY molecular sieve. The method includes: mixing water glass, sodium metaaluminate and deionized water, conducting aging at 15-70DEG C for 0.5-48h to obtain a crystallization guiding agent; mixing the crystallization guiding agent, water glass, an acidic aluminum salt and a sodium aluminate solution uniformly to obtain a silica-alumina gel; crystallizing the silicon-aluminum gel at 80-140DEG C for 0.1- 80h; adding a peroxide into the crystallized silicon-aluminum gel, making molar ratio of the 02<2-> in the peroxide to the Al2O3 in the gel at 0.05-20, then further conducting crystallization for 5-20h, thus obtaining the NaY molecular sieve. Without adding any organic or inorganic template and being free of multiple after-treatment modification processes, the method can directly prepare the Y type molecular sieve with a high silicon-aluminum ratio. The obtained molecular sieve has crystallinity up to over 80%, a silicon-aluminum ratio of not less than 5.8, and an average grain size of 200-300.
Description
Technical field
The present invention relates to a kind of synthetic method of NaY molecular sieve, relate to specifically and synthetic having than the method for the NaY zeolite of high silica alumina ratio.
Background technology
In recent years, it is heavy that stock oil becomes increasingly, uses conventional cracking catalyst to be difficult to gradually meet the requirement of development.How more fully, more effective make good use of the focal issue that limited petroleum resources become refining of petroleum.The catalytic cracking catalyst of China mainly be take the Y-type rare earth catalyzer as main, and Y zeolite is the main active component of cracking catalyst, the product that the cracking activity of molecular sieve and selectivity have directly affected cracking reaction distributes, and its degree of crystallinity, silica alumina ratio, pore structure and acid distribution etc. are paid close attention to by people the research of catalytic performance impact always.
The Grace company of the U.S. early proposes to utilize the synthetic NaY molecular sieve of method of crystallization director.At disclosed patent USP3, the synthetic NaY molecular sieve of use crystallization director method has been proposed in 639,099 and USP3,671,191, the method is at first to prepare to consist of (15 ~ 17) Na
2o:Al
2o
3: (14 ~ 16) SiO
2: (285 ~ 357) H
2the crystallization director of O, the directed agents nucleus diamter obtained is generally less than 0.05 micron, then this directed agents is mixed with into and consists of (3 ~ 6) Na with water glass, sodium aluminate, acid aluminium salt etc.
2o:Al
2o
3: (8 ~ 12) SiO
2: (120 ~ 200) H
2the reaction mixture of O, then by this reaction mixture 100 ℃ of left and right crystallization.The shortcoming of the method is that the water yield that feeds intake is higher, SiO in mother liquor
2quantity discharged is higher, has reduced the utilization ratio of silicon, and synthetic NaY framework of molecular sieve silica alumina ratio (below be SiO
2/ Al
2o
3mol ratio) generally lower than 5.2.After this people are improved on this method basis, develop into the synthetic method that adds the different templates agent, but, due to the restriction that is subject to electrochemical conditions in building-up process, the silica alumina ratio of the NaY molecular sieve that the method obtains is all in 5.0 left and right, generally lower than 5.5.
Structure and the character of the framework silicon-aluminum comparison of Y zeolite self have a direct impact.Improve skeleton Si/Al ratio, reduce Al center density, improve the relative intensity in acid site, contribute to change the ratio of cracking/hydrogen transfer activity, reduce catalysis Jiao's generation; Because high silica alumina ratio Y molecular sieve structure cell shrinks, there is good hydrothermal stability and acid acceptance, can bear reaction-regeneration condition harsh in catalytic cracking process; In addition, its catalytic selectivity is good, contributes to increase yield of gasoline, improves octane value.
Current, the active component of the heavy oil fluid catalytic cracking of widespread use generally adopts the method for the aftertreatments such as dealuminzation or dealumination complement silicon, is that the parent NaY that alkaline system is synthetic carries out dealuminzation, dealumination complement silicon to obtain high silicon Y molecular sieve.Advantage is easy industrialization, and shortcoming is the technical process complexity, and the degree of crystallinity of NaY molecular sieve descends, and generates a large amount of non-framework aluminum etc.
Adopt the method for template method high silica alumina ratio NaY molecular sieve, mainly contain following reported in literature.
Patent USP 4,714,601, and USP 4,931,267, and USP 5,116,590, and USP 5,549, and the people such as Vanghan and DavidE.W have synthesized a series of high silicon faujusite isomorphs in 881, respectively called after ECR-4, ECR-32 and ECR-35.Its silica alumina ratio (SiO2/Al2O3 mol ratio) is between 6.0-30.0.The principal feature of this technology is exactly in silica-alumina gel, to add organic formwork agent as a kind of or its mixture in Tetramethylammonium hydroxide, TPAOH or TBAH.The mol ratio of each oxide compound for preparing the reaction mixture of this molecular sieve is: 0.02～0.40T
2o:0.60～0.98Na
2o:Al
2o
3: 4～12SiO
2: 0～25H
2o, T means the alkyl ammonium ion.Silicon used source can be white carbon black, silica gel, silicon sol and water glass etc., and the aluminium source can be alchlor, intends rich diaspore, sodium aluminate or Tai-Ace S 150 etc.It is comparatively simple that this method has preparation process, and zeolite crystallinity does not incur loss, and technical process is fairly simple, without many advantages such as (or few) environmental pollutions.But these methods template used is as very expensive as tetrapropyl ammonium alkali price, in addition, adopt the method to want to obtain the NaY molecular sieve of high-crystallinity high silica alumina ratio, need the crystallization time of tens days, and productive rate is lower.Grace company (USP4,333,859) has developed a kind of method that adds the cesium ion synthetic faujasites in reactant gel, between the CSZ-1 made, CSZ-3 Series Molecules sieve silica alumina ratio 5.0～7.0.But bad the removing of cesium ion in this kind of method product, need to repeatedly exchange and roasting, greatly increased production cost.
Exploitation is without the synthetic method of template, and directly synthesizing Si-Al is than more than 5.5, and even the NaY zeolite product of the high silica alumina ratio of 6.0 left and right has great importance.
Patent GB1,044,983 discloses and prepares silica alumina ratio and be about: Y zeolite method between 3～7.This patent is pointed out, if think the y-type zeolite of high silica alumina ratio processed, be necessary to make silica alumina ratio in reactant between 7～40, silica alumina ratio in reaction-ure mixture is between 7～40, just need to place the longer time (approximately 20～40 hours or longer) in room temperature, time of high temperature crystallization also long (4～6 days) just can obtain the product of expection.Its shortcoming is that crystallization time is long, institute's preferred feedstock silicon sol high cost, and silicon source utilization ratio is also very low.
USP3574538 has reported a kind of use metakaolin, water glass, and sodium hydroxide, and the crystal seed synthesizing Si-Al is than the method that reaches 6.0 NaY zeolite.Its advantage is that raw material availability is high, and shortcoming is that the character of raw material metakaolin is had relatively high expectations, and industry is difficult for reaching requirement.
CN 1785807 patents disclose employing non-template agent direct synthesis technique two step crystallization and have synthesized SiO
2/ Al
2o
3it is 6.0～6.5 high-silicon Y-Zeolite.Product degree of crystallinity is high, and crystal grain is little, has satisfactory stability and catalytic activity.
, CN 1789125A[31 in 2006] patent discloses a kind of method of high silica alumina ratio, small crystal grain NaY molecular sieve.At first according to the synthetic NaY molecular sieve guiding agent of prior art, then with water glass, directed agents, acid aluminium salt and sodium metaaluminate, make gel, by gel after 50～100 ℃ of lower crystallization 0～70h, add the silicon source, continue crystallization 0.5～50h at 90～120 ℃ again,, product silica alumina ratio 5.5～7.0.The shortcoming of the method is that silicon source utilization ratio is on the low side, and production cost significantly increases.
Summary of the invention
The purpose of this invention is to provide a kind ofly substantially not changing under the prerequisite of conventional synthesis technique, can improve the novel synthesis of NaY zeolite product silica alumina ratio.Compared with the conventional method, can synthesize in the short period of time high silica alumina ratio NaY molecular sieve, obtain the NaY molecular sieve of little crystal grain simultaneously.
The method concrete steps of synthetic NaY molecular sieve provided by the invention are as follows:
(1) by water glass, sodium metaaluminate and deionized water according to 11 ~ 18Na
2o:Al
2o
3: 11 ~ 18SiO
2: 200 ~ 380H
2the mixed in molar ratio of O, after stirring, obtain crystallization director in aging 0.5 ~ 48 hour at 15-70 ℃;
(2) crystallization director, water glass, acid aluminium salt and sodium aluminate solution are mixed and make silica-alumina gel; In silica-alumina gel, material mole proportioning is 1.0 ~ 6.5Na
2o:Al
2o
3: 5.0 ~ 18SiO
2: 100 ~ 280H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.01 ~ 15 % by weight of total amount;
(3) by silica-alumina gel in 80 ~ 140 ℃ of lower crystallization; Crystallization 0.1 ~ 80 hour;
(4) add superoxide in the Crystallized Silicon alumina gel obtained in (3), make 0 in superoxide
2 2-with the Al in gel
2o
3mol ratio be 0.05-20, then continue crystallization 5-20 hour and obtain.
In said silica-alumina gel, material mole proportioning is 1.4 ~ 4.6Na
2o:Al
2o
3: 6.5～12SiO
2: 140 ~ 240H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.1 ~ 10 % by weight of total amount.
In method provided by the present invention, can prepare by the whole bag of tricks of preparation NaY molecular sieve guiding agent in prior art by the said directed agents of step (1), but preferably according to the at present industrial generally conventional preparation method of the NaY directed agents of employing, prepare.For example, according to USP3,639,099, USP3, prepared by disclosed method in 671,191 and USP4,166,099, to obtaining stay-in-grade product, can keep technology and equipment not do larger change simultaneously.In present method, crystallization director used is according to industrial ordinary method, by water glass, sodium metaaluminate and deionized water according to (11 ~ 18) Na
2o:Al
2o
3: (10 ~ 17) SiO
2: (200 ~ 380) H
2the mixed in molar ratio of O, after stirring, obtain at 15-70 ℃ in aging 0.5 ~ 48 hour.
In method provided by the present invention, in step 4, to adding peralcohol in gel, can be hydrogen peroxide, sodium peroxide, or one or more mixtures in Potassium peroxide.Afterwards the mixture gel is continued to crystallization and obtain zeolite product.
In method provided by the present invention, the said sodium aluminate of step (2) is sodium metaaluminate; Said acid aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate, wherein Tai-Ace S 150 preferably; Sodium aluminate with together with aluminium in acid aluminium salt and directed agents as the Al of the synthetic material of NaY
2o
3source, the silicon in water glass and directed agents synthesizes the SiO of material together as NaY
2source; The basicity that acidic aluminum source and alkaline sodium aluminate can be used to regulate total material, the ratio of the two requires to decide according to the basicity of total material.
According to method provided by the invention, can be under the prerequisite that does not substantially change existing production technique, do not add any organic or inorganic template,, without aftertreatment modifying process repeatedly, can directly prepare in the short period of time the Y zeolite of high silica alumina ratio yet.Compare with ordinary method, under the condition of identical molar ratio, can obviously shorten crystallization time, simultaneously the silica alumina ratio of the finished product can be increased to 5.5, generally more than 5.8, the small crystal grain molecular sieve that resulting product is 200-300nm.
The accompanying drawing explanation
Fig. 1 embodiment 2 gained NaY molecular sieve electron microscope picture.
Embodiment
The following examples are for the present invention will be further described, but not thereby limiting the invention.
Embodiment 1
Get 81.50 gram water glass (Red Star water glass plant, Beijing product, SiO
2content is 28.08 heavy %, modulus 3.28), add 80.16 gram high alkali deflection aluminium acid sodium (Shandong Aluminium Industrial Corp's product, Al
2o
3content is 3.16 heavy %, Na
2o content is 21.11 heavy %), then add 14 gram deionized waters, the last mixing under 50 ℃ aging 5 hours, make directed agents.Get 235 gram water glass, add successively 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 gram, 183.24 gram alum liquor (China Changcheng Aluminium Industry Co's product, Al under stirring
2o
3content is 7.1 heavy %), and 70 gram water, mix, make the mixture gel.
The mixture gel is packed in the tetrafluoroethylene bottle, 100 ℃ of lower crystallization, after 16 hours, in gelling system, add 20 gram hydrogen peroxide (Beijing Chemical Plant, H
2o
2content is 30 heavy %) in be uniformly mixed, make even gel, in the tetrafluoroethylene bottle of packing into, continue 100 ℃ of lower crystallization 24 hours, then filter, wash, dry NaY zeolite product 30.25 grams, record its degree of crystallinity 95%, silica alumina ratio 5.91.
Comparative Examples 1
Each raw material sources are with embodiment 1.Get 81.50 gram water glass, add 80.16 gram high alkali deflection aluminium acid sodiums, then add 14 gram deionized waters, the last mixing under 50 ℃ aging 5 hours, make directed agents.Get 235 gram water glass, add successively 72.50 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 gram, 188.24 gram alum liquors under stirring, and 70 gram water, mix and make gel 622.37 grams, pack in the tetrafluoroethylene bottle, 100 ℃ of lower crystallization 40 hours, then filter, wash, dry NaY zeolite product 79 grams, record its degree of crystallinity 77%, silica alumina ratio 5.22.
Comparative Examples 2
Each raw material sources are with embodiment 1.Get 81.50 gram water glass, add 80.16 gram high alkali deflection aluminium acid sodiums, then add 14 gram deionized waters, the last mixing under 50 ℃ aging 5 hours, make directed agents.Get 253.66 gram water glass, add successively 85.78 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 gram, 199.52 gram alum liquors under stirring, and 92.35 gram water, mix and make gel 687.94 grams, pack in the tetrafluoroethylene bottle, 100 ℃ of lower crystallization 40 hours, then filter, wash, dry NaY zeolite product 100.07 grams, record its degree of crystallinity 80%, silica alumina ratio 5.18.
Embodiment 2
Each raw material sources are with embodiment 1.Get 81.50 gram water glass, add 80.16 gram high alkali deflection aluminium acid sodiums, then add 14 gram deionized waters, the last mixing under 50 ℃ aging 5 hours, make directed agents.Get 270 gram water glass, add successively 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 gram, 183.24 gram alum liquors under stirring, and 70 gram water, mix, make gel.
To make gel and pack in the tetrafluoroethylene bottle, 100 ℃ of lower crystallization, after 26 hours, in gelling system, add 50 gram hydrogen peroxide (Beijing Chemical Plant, H
2o
2content is 30 heavy %) in be uniformly mixed, in the tetrafluoroethylene bottle of packing into, continue 100 ℃ of lower crystallization 26 hours, then filter, wash, dry NaY zeolite product 31.95 grams, record its degree of crystallinity 99%, silica alumina ratio 6.12, zeolite crystal is the 300nm left and right.Shown in following scanning electron microscope (SEM) photograph:
Comparative Examples 3
Each raw material sources are with embodiment 1.Get 81.50 gram water glass, add 80.16 gram high alkali deflection aluminium acid sodiums, then add 14 gram deionized waters, the last mixing under 50 ℃ aging 5 hours, make directed agents.Get 278 gram water glass, add successively 70 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 gram, 196 gram alum liquors under stirring, and 70 gram water, mix, make gel 670.63 grams, in the tetrafluoroethylene bottle of packing into, 100 ℃ of lower crystallization 122 hours, then filter, wash, dry NaY zeolite product 103.21 grams, record its degree of crystallinity 79%, silica alumina ratio 5.30.
Claims (4)
1. the synthetic method of a NaY molecular sieve is characterized in that:
(1) by water glass, sodium metaaluminate and deionized water according to 11 ~ 18Na
2o:Al
2o
3: 11 ~ 18SiO
2: 200 ~ 380H
2the mixed in molar ratio of O, after stirring, obtain crystallization director in aging 0.5 ~ 48 hour at 15-70 ℃;
(2) crystallization director, water glass, acid aluminium salt and sodium aluminate solution are mixed and make silica-alumina gel; In silica-alumina gel, material mole proportioning is 1.0 ~ 6.5Na
2o:Al
2o
3: 5.0 ~ 18SiO
2: 100 ~ 280H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.01 ~ 15 % by weight of total amount;
(3) by silica-alumina gel in 80 ~ 140 ℃ of lower crystallization; Crystallization 0.1 ~ 80 hour;
(4) add superoxide in the Crystallized Silicon alumina gel obtained in (3), make 0 in superoxide
2 2-with the Al in gel
2o
3mol ratio be 0.05-20, then continue crystallization 5-20 hour and obtain.
2. according to the synthetic method of NaY molecular sieve claimed in claim 1, it is characterized in that: in said silica-alumina gel, material mole proportioning is 1.4 ~ 4.6Na
2o:Al
2o
3: 6.5 ~ 12SiO
2: 140 ~ 240H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.1 ~ 10 % by weight of total amount.
3. according to the synthetic method of NaY molecular sieve claimed in claim 1, it is characterized in that: the superoxide added in step (4) is hydrogen peroxide, sodium peroxide, or one or more mixtures in Potassium peroxide.
4. according to the synthetic method of NaY molecular sieve claimed in claim 1, it is characterized in that: the said sodium aluminate of step (1) is sodium metaaluminate, and said acid aluminium salt is one or more mixtures in Tai-Ace S 150, aluminum chloride or aluminum nitrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2535584A (en) * | 2014-12-01 | 2016-08-24 | China Petroleum & Chem Corp | Na-Y Molecular Sieve, H-Y Molecular Sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN114655965A (en) * | 2020-12-23 | 2022-06-24 | 中国石油化工股份有限公司 | Method for preparing small-grain NaY |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785808A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101767799A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon small grain NaY molecular sieve |
-
2012
- 2012-05-28 CN CN201210168420.1A patent/CN103449468B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785808A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101767799A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon small grain NaY molecular sieve |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2535584A (en) * | 2014-12-01 | 2016-08-24 | China Petroleum & Chem Corp | Na-Y Molecular Sieve, H-Y Molecular Sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| GB2535584B (en) * | 2014-12-01 | 2017-02-08 | China Petroleum & Chem Corp | Na-Y Molecular Sieve and preparation methods thereof |
| US10265687B2 (en) | 2014-12-01 | 2019-04-23 | China Petroleum & Chemical Corporation | Na—Y molecular sieve, H—Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| US10525452B2 (en) | 2014-12-01 | 2020-01-07 | China Petroleum & Chemical Corporation | Na-Y molecular sieve, H-Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN114655965A (en) * | 2020-12-23 | 2022-06-24 | 中国石油化工股份有限公司 | Method for preparing small-grain NaY |
| CN114655965B (en) * | 2020-12-23 | 2023-10-10 | 中国石油化工股份有限公司 | Method for preparing small-grain NaY |
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