CN104556127A - Synthetic method for small-crystal-size high-silicon Y-type molecular sieve - Google Patents
Synthetic method for small-crystal-size high-silicon Y-type molecular sieve Download PDFInfo
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Abstract
The invention provides a synthetic method for a small-crystal-size high-silicon Y-type molecular sieve. The method comprises the following steps: stirring water, inorganic base, an aluminum source and part of a silicon source for 2-4 days; then adjusting the basicity of the system with acid; and adding a silicon source, and finally synthesizing the Y-type molecular sieve by hydrothermal crystallization. The small-crystal high-silicon Y-type molecular sieve synthesized by the method provided by the invention has the characteristics of small crystal size and high silicon-aluminum ratio, is suitable for serving as an adsorbent for separation of a gas and liquid mixture and can also serve as a catalyst carrier or an acid catalyst component.
Description
Technical field
The invention belongs to molecular sieve catalytic material synthesis field, particularly relate to a kind of little grain high-Si Y-type molecular sieve synthetic method.
Background technology
Y zeolite is most important a kind of catalytic material in petroleum refining industry, and its invention and application instead of clay mineral and amorphous silico-aluminate, causes the revolution of oil refining industry one field technology in the sixties in 20th century.So far, Y zeolite remains the major catalytic constituent element of catalytic cracking and hydrocracking, is a kind of industrialization molecular screen material that usage quantity is maximum.
At present, adopt the silica alumina ratio of Y zeolite of routine techniques synthesis all lower than 6, usually below 5.0, thermostability and hydrothermal stability poor, so need to carry out aftertreatment to it in industry to improve silica alumina ratio.But also can pass through the direct synthesizing high-silicon Y zeolite of some other technologies means, such as in building-up process, add organic formwork agent, or adopt special gel process for preparation etc.As patent US4965059High silica faujasite aluminosilicate, ECR-4, and a process for making it, disclose a kind of synthetic method of high silicon FAU structure molecular screen, the method mainly in synthetic system, introduce the organic formwork agents such as tripropyl ammonium, synthesize silica alumina ratio higher than 6 Y zeolite.Patent US 4,931,267Process for preparing a high silica zeolite having the faujasite topology, ECR-32, then introduce the organic formwork agents such as butyl ammonium in synthetic system, hydrothermal crystallizing go out silica alumina ratio higher than 6 Y zeolite.
The preparation method of a patent CN1621349A NaY molecular sieve, discloses a kind of synthetic method of high-Si Y-type molecular sieve.The method does not use machine template, and crystallization is divided into two steps.Feature is after the first step crystallization terminates, and adds silicon-containing material more again through row second time crystallization to reaction system.But the SiO given by the raw material of this patent
2/ A1
2o
3preferable range 6.5 ~ 14, with the SiO of common Y zeolite
2/ A1
2o
3close, in theory and be unfavorable for generate high-Si Y-type molecular sieve.Synthesized by this patent Example 4, the silica alumina ratio of Y zeolite reaches 6.17, but is through the embodiment repeating this patent, and products obtained therefrom silica alumina ratio not more than 6, but is as good as with common low Si Y-type molecular sieve.
The preparation method of a patent CN101254929A high silica alumina ratio NaY molecular sieve, disclose a kind of synthetic method of high-Si Y-type molecular sieve, the method is also do not use machine template, crystallization is divided into two steps to carry out, after the first step crystallization terminates, add silica-alumina gel again to reaction system, finished product oxide silicon aluminum ratio is 5 ~ 6.
In addition such as patent US5549881, US5116590, US4965059, US4931267, US4714601, EP0887310, CN1226875, CN1145278 etc., also direct synthesizing high-silicon Y zeolite is all related to, but in building-up process, all add the organic formwork agent such as quaternary ammonium salt, quaternary ammonium hydroxide of carbon one to carbon four, also have interpolation crown ether or other organism as template.But the organic formwork agent of costliness considerably increases synthesis cost undoubtedly, and the problem of environmental pollution and harm producers health also cannot be avoided, and these are all that all molecular sieve production firms are unaffordable.
At present, Industrial Catalysis also compares concern to Y zeolite crystal size.Because the Y zeolite size of ordinary method synthesis is generally even larger at about 1000nm, be extremely unfavorable for the material diffusion in catalytic process, and outer surface area is low, macromole conversion capability is weak, easy coking etc.The Y zeolite therefore with little crystal grain is more praised highly.
In prior art, in little crystal grain zeolite synthesis method, adopt adds organic formwork agent or other organic additive more, the manner of formulation and the crystal pattern that control gel also can reduce granularity, these technology have been reported in the synthesis of small-grain ZSM-5, MOR, BETA equimolecular sieve, in the synthesis of small crystal grain Y-shaped molecular sieve, also have application.
Patent US3755538 PREPARATION OF ZEOLITES, discloses a kind of method of small crystal grain Y-shaped molecular sieve, this patent mainly by adding the crystal size that the materials such as B, V, P, Mo, Co, Ge, Ga reduce zeolite in directed agents.
The preparation method of a patent CN1840475 A NaY molecular sieve, mainly by being added with the crystal size that organic compounds crown ether reduces zeolite in directed agents.
Patent CN102049306A mono-kind, containing small crystal grain Y-shaped molecular sieve carrier of hydrocracking catalyst and method for making thereof, relates to small crystal grain Y-shaped molecular sieve synthesis.The key step of this patent is that the preparation of directed agents and the preparation of synthesized gel rubber are carried out in low temperature environment, and required temperature is: 0 ~ 10 DEG C, thinks that low temperature can reduce the granularity of molecular sieve.
The synthetic method of a patent CN 101468802A small crystal grain NaY molecular sieve, also directing agent method is adopted to synthesize small crystal grain Y-shaped molecular sieve, but its technical characteristic and patent CN102049306A have certain paradox, its feature mainly synthesized gel rubber prepares under the environment of room temperature to 70 DEG C.
The preparation method of patent CN1081425A small crystal grain NaY molecular sieve, disclose a kind of method of small crystal grain Y-shaped molecular sieve, the preparation process of this patent is: first the silica-alumina gel not containing directed agents is thrown people's directed agents in crystallization 1-10 hour again at 80 ~ 180 DEG C, then continues crystallization 5-25 hour at 90 ~ 100 DEG C.Principal character is through twice crystallization to obtain small crystal grain Y-shaped molecular sieve.
Nano level y-type zeolite that patent CN1533982A synthesizes with kaolin and preparation method thereof, uses conventional directed agents, silicon and aluminum source, and the kaolin after pyroprocessing synthesizes the different small-grain Y-type zeolite of crystal shape.
At present, the technology of direct synthesizing high-silicon aluminum ratio small crystal grain Y-shaped molecular sieve also has report, as the synthetic method of a patent CN 101468803A small crystal grain NaY molecular sieve, adopt directing agent method synthesizing small-grain high-Si Y-type molecular sieve, its technical characteristic in synthesized gel rubber, adds the additive such as chitin and/or oligosaccharides to reduce the silica alumina ratio of crystallite size and raising product.
The preparation method of patent CN1079444A small crystal grain NaY molecular sieve, disclose a kind of method of little grain high-Si Y-type molecular sieve, the principal character of this patent improves traditional directed agents, first the conventional directed agents of transmittance <30% is prepared according to a conventional method, then sodium silicate solution is joined in the conventional directed agents of transmittance <30%, the directed agents of obtained transmittance >75%.
The preparation method of patent CN1160676A fine-grain NaY zeolite, disclose a kind of method of little grain high-Si Y-type molecular sieve, this patent first conventionally prepares directed agents, then the whole silicon sources using the silicon in this directed agents as synthesis material, directed agents mixed with aluminium source, last hydrothermal crystallizing obtains little grain high-Si Y-type molecular sieve again.
Patent CN1785807A high silicon aluminium ratio small crystal NaY molecular sieve, disclose a kind of method of little grain high-Si Y-type molecular sieve, this patent is by directed agents, the mixing such as silicon and aluminum source, adopt the first step dynamic crystallization again, second step static crystallization, obtain little grain high-Si Y-type molecular sieve.
At present, direct synthesizing small-grain and the technology with the Y zeolite of high silica alumina ratio also exists many defects, therefore, has very important realistic meaning to the development research of this type of technology.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of synthetic method of little grain high-Si Y-type molecular sieve, Y zeolite provided by the invention has the feature of little crystal grain and high silica alumina ratio.
The synthetic method of little grain high-Si Y-type molecular sieve of the present invention, comprises the steps:
(1) first by silicon source, aluminium source, mineral alkali and water according to mol ratio 9 ~ 16Na
2o:18 ~ 34SiO
2: A1
2o
3: 300 ~ 550H
2o mixes successively, then stirs 48 ~ 96 hours at 30 ~ 50 DEG C;
(2) slowly mineral acid is dripped in the mixture obtained to step (1);
(3) add excess silicon source in the mixture obtained to step (2), then stir 1 ~ 2h, then at 80 ~ 130 DEG C of crystallization 10 ~ 80h, finally by separation, washing and dry, obtain little grain high-Si Y-type molecular sieve.
The synthetic method of little grain high-Si Y-type molecular sieve of the present invention, wherein said mineral alkali is NaOH; Aluminium source can be one or more in sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate; Silicon source can be White Carbon black or silica gel.
In step (1), material mol ratio is preferably silicon source, aluminium source, mineral alkali and water according to mol ratio 9 ~ 16Na
2o:18 ~ 34SiO
2: A1
2o
3: 300 ~ 550H
2o, is preferably 11 ~ 15Na
2o:20 ~ 30SiO
2: A1
2o
3: 350 ~ 500H
2o.
Mineral acid described in step (2) is hydrochloric acid, sulfuric acid, nitric acid, preferably hydrochloric acid.Slowly drip in the mixture that step (1) obtains and add in mineral acid process, mixture be prevented because local ph change is violent and Morphological Transitions occurs.
In step (3), material mol ratio is: 7 ~ 13Na
2o:20 ~ 40SiO
2: A1
2o
3: 300 ~ 550H
2o:3 ~ 5.5H
+, preferably 8 ~ 11Na
2o:25 ~ 35SiO
2: A1
2o
3: 350 ~ 500H
2o:3.5 ~ 5H
+.
Described in step (3), crystallization temperature is 80 ~ 130 DEG C, preferably 90 ~ 120 DEG C; Crystallization time is 10 ~ 80h, preferably 20 ~ 70h.
Drying described in step (3) is dry 5 ~ 15h at 100 ~ 140 DEG C.
The little grain high-Si Y-type molecular sieve prepared according to the inventive method has following feature: synthetic product characterizes through x-ray diffractometer, and its crystal formation is Y zeolite, not containing other Crystal impurity; Its oxide silicon al mole ratio scope is 5 ~ 6; Characterize through electron microscope, its crystal size scope is 100 ~ 400nm; Measure through physical adsorption, specific surface area is 500 ~ 800 m
2/ g.
The sorbent material that Y zeolite provided by the invention can be used as gas, liquid mixture is separated, also as the carrier of catalyzer or an acidic catalyst component, can be particularly suitable as catalytic cracking and hydrocracking catalyst use.
Compared with existing synthetic technology, the synthetic method of little grain high-Si Y-type molecular sieve provided by the invention has the following advantages:
1, synthetic method provided by the invention, can synthesize little grain high-Si Y-type molecular sieve when not using organic formwork agent or other expensive additive, and synthesis cost is low, is beneficial to suitability for industrialized production.
2, in the inventive method, by the mode of Multistep feeding, the little grain high-Si Y-type molecular sieve that usual way cannot obtain successfully is synthesized.First the nucleus of a large amount of Y zeolite is obtained, nucleus quantity the more, the granularity of molecular sieve end product is less, so the present invention can obtain the small crystal grain Y-shaped molecular sieve of particle diameter at 100 ~ 400nm, far below the granularity of the micron-sized Y zeolite of current commercial synthesis.And comprise the secondary structure unit being beneficial to synthesizing high-silicon aluminum ratio product in the nucleus of the Y zeolite obtained by the step of high-temperature stirring process, be beneficial to generation high-Si Y-type molecular sieve.Regulate synthetic system basicity, the dissolution rate of sial element in the hierarchy of control, and the state of sial element in liquid phase, make it more be beneficial to synthesizing small-grain high-Si Y-type molecular sieve.Finally by interpolation silicon source, whole synthetic system is made to be in high reactivity state, reach the rigors of synthesizing high-silicon Y zeolite, so the Y zeolite only synthesizing high silica alumina ratio under the situation ability of organic formwork agent or other additive can be synthesized, silica alumina ratio scope is 5 ~ 6, far above the Y zeolite (silica alumina ratio about 4.9) of current commercial synthesis, and there is the feature of little crystal grain, there is higher catalytic activity.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the little grain high-Si Y-type molecular sieve that embodiment 1 obtains.
Fig. 2 is the SEM photo of the little grain high-Si Y-type molecular sieve that embodiment 1 obtains.
Embodiment
Below by specific embodiment, detailed description is given to little grain high-Si Y-type molecular sieve synthetic method of the present invention, but be not limited to embodiment.The sial raw material used in the embodiment of the present invention, acid, alkali and solvent are analytical pure chemical reagent.
Embodiment 1
(1) first 40mL distilled water is mixed with 6g sodium hydroxide, after to be dissolved, add 1.5g sodium aluminate, dissolve completely and add 8g white carbon black, be then placed in 40 DEG C of water bath and stir 72h.
(2) slowly drip hydrochloric acid 10 mL of 3.75 mol/L in the mixture obtained to step (1), mixture should be prevented in dropping process because local ph change is violent and Morphological Transitions occurs.
(3) in the mixture obtained to step (2), 6g white carbon black is added in mixing, then under normal temperature state, 1h is stirred, then reaction mixture is loaded reactor, closed reactor, is placed in baking oven crystallization 50h at 100 DEG C by reactor, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL1, for pure Y zeolite, silica alumina ratio is 5.9, and granularity is 210nm.
Embodiment 2
(1) first 40mL distilled water is mixed with 6g sodium hydroxide, after to be dissolved, add 9g aluminum nitrate, dissolve completely and add 8g white carbon black, be then placed in 35 DEG C of water bath and stir 72h.
(2) slowly drip hydrochloric acid 9 mL of 3.75 mol/L in the mixture obtained to step (1), mixture should be prevented in dropping process because local ph change is violent and Morphological Transitions occurs.
(3) in the mixture obtained to step (2), 6g white carbon black is added in mixing, then under normal temperature state, 1h is stirred, then reaction mixture is loaded reactor, closed reactor, reactor is placed in baking oven crystallization 55h at 100 DEG C, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL2, is little grain high-Si Y-type molecular sieve.
Embodiment 3
(1) first 45mL distilled water is mixed with 5.5g sodium hydroxide, after to be dissolved, add 7g aluminum nitrate, dissolve completely and add 8g white carbon black, be then placed in 45 DEG C of water bath and stir 60h.
(2) slowly drip hydrochloric acid 10 mL of 3.75 mol/L in the mixture obtained to step (1), mixture should be prevented in dropping process because local ph change is violent and Morphological Transitions occurs.
(3) in the mixture obtained to step (2), 5g white carbon black is added in mixing, then under normal temperature state, 1.5h is stirred, then reaction mixture is loaded reactor, closed reactor, reactor is placed in baking oven crystallization 39 h at 110 DEG C, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL3, is little grain high-Si Y-type molecular sieve.
Embodiment 4
(1) first 40mL distilled water is mixed with 5.2g sodium hydroxide, after to be dissolved, add 1.2 sodium aluminates, dissolve completely and add 7 g white carbon blacks, be then placed in 35 DEG C of water bath and stir 72h.
(2) slowly drip the hydrochloric acid 7.5mL of 3.75 mol/L in the mixture obtained to step (1), mixture should be prevented in dropping process because local ph change is violent and Morphological Transitions occurs.
(3) in the mixture obtained to step (2), 4.5g white carbon black is added in mixing, then under normal temperature state, 1h is stirred, then reaction mixture is loaded reactor, closed reactor, reactor is placed in baking oven crystallization 60h at 95 DEG C, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL4, is little grain high-Si Y-type molecular sieve.
Comparative example 1
Adopt the material proportion consistent with embodiment 1, conveniently directing agent method synthesizes Y zeolite.
(1) first 21mL distilled water is mixed with 4.82 g sodium hydroxide, after to be dissolved, add 1.26 sodium aluminates.Dissolve water glass 10 mL adding 8mol/L completely, stir, be then placed in 35 DEG C of baking oven static state and place 1 d, obtain Y structure directing agent.
(2) 45mL distilled water is mixed with 4.5g sodium hydroxide, after to be dissolved, add 1.5g sodium aluminate, dissolve completely and add 14g white carbon black, then add Y structure directing agent 5mL, stir 1h.Then reaction mixture is loaded reactor, closed reactor, reactor is placed in baking oven at 100 DEG C of crystallization 50h, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL5, is Y zeolite, and silica alumina ratio is 4.9, and granularity is 1100nm.Even if illustrate and adopt the material proportion consistent with the present invention, ordinary method also can only obtain the Y zeolite of micron-sized low silica-alumina ratio.
Comparative example 2
Adopt the material proportion consistent with embodiment 1, without step (2) sour control method synthesis Y zeolite.
(1) first 40mL distilled water is mixed with 6g sodium hydroxide, after to be dissolved, add 1.5g sodium aluminate, dissolve completely and add 8g white carbon black, be then placed in 40 DEG C of water bath and stir 72h.
(2) in the mixture obtained to step (2), 6g white carbon black is added in mixing, then under normal temperature state, 1h is stirred, then reaction mixture is loaded reactor, closed reactor, is placed in baking oven crystallization 50h at 100 DEG C by reactor, finally by solid product at 120 DEG C of dry 12h, gained sample number into spectrum is CL6, for Y zeolite, silica alumina ratio is 4.9, and granularity is 1160nm.The method of description of step (2) regulation system acidity can reduce the particle diameter of product and increase the silica alumina ratio of product.
Table 1 embodiment of the present invention and comparative example products obtained therefrom character
By contrasting with comparative example, illustrate that the inventive method can synthesize the small crystal grain Y-shaped molecular sieve of high silica alumina ratio, its physico-chemical property obtains Y zeolite far above ordinary method.
Claims (10)
1. a synthetic method for little grain high-Si Y-type molecular sieve, comprises the steps:
(1) first by silicon source, aluminium source, mineral alkali and water according to mol ratio 9 ~ 16Na
2o:18 ~ 34SiO
2: A1
2o
3: 300 ~ 550H
2o mixes successively, then stirs 48 ~ 96 hours at 30 ~ 50 DEG C; (2) slowly mineral acid is dripped in the mixture that step (1) obtains;
(3) add excess silicon source in the mixture that step (2) obtains, then stir 1 ~ 2 h, then at 80 ~ 130 DEG C of crystallization 10 ~ 80h, finally by separation, washing and drying, obtain little grain high-Si Y-type molecular sieve.
2. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: described mineral alkali is NaOH; Aluminium source is one or more in sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate; Silicon source is White Carbon black or silica gel.
3. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: in step (1), material mol ratio is preferably silicon source, aluminium source, mineral alkali and water according to mol ratio 11 ~ 15Na
2o:20 ~ 30SiO
2: A1
2o
3: 350 ~ 500H
2o.
4. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: the mineral acid described in step (2) is hydrochloric acid, sulfuric acid, nitric acid.
5. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: in step (3), material mol ratio is 7 ~ 13Na
2o:20 ~ 40SiO
2: A1
2o
3: 300 ~ 550H
2o:3 ~ 5.5H
+.
6. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: in step (3), material mol ratio is 8 ~ 11Na
2o:25 ~ 35SiO
2: A1
2o
3: 350 ~ 500H
2o:3.5 ~ 5H
+.
7., according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that described in step (3), crystallization temperature is 80 ~ 130 DEG C, crystallization time is 10 ~ 80h.
8., according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that described in step (3), crystallization temperature is 90 ~ 100 DEG C, crystallization time is 20 ~ 70h.
9. according to the synthetic method of little grain high-Si Y-type molecular sieve according to claim 1, it is characterized in that: rapid drying described in (3) is 5 ~ 15h dry at 100 ~ 140 DEG C.
10. the little grain high-Si Y-type molecular sieve prepared in accordance with the method for claim 1, described little grain high-Si Y-type molecular sieve has following feature: synthetic product characterizes through x-ray diffractometer, and its crystal formation is Y zeolite; Its oxide silicon al mole ratio scope is 5 ~ 6; Characterize through electron microscope, its crystal size scope is 100 ~ 400nm; Measure through physical adsorption, specific surface area is 500 ~ 800 m
2/ g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698460A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nano Y molecular sieve |
| CN112744827A (en) * | 2021-01-05 | 2021-05-04 | 江南大学 | Method for synthesizing ferrierite molecular sieve by seed crystal method |
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| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN1354133A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for preparing small-grain Y-type molecular sieve |
| CN101041442A (en) * | 2007-03-19 | 2007-09-26 | 天津元山科技开发有限公司 | Fine grain strong acid type molecular sieve and method for synthesizing same |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
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Patent Citations (4)
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| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN1354133A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for preparing small-grain Y-type molecular sieve |
| CN101041442A (en) * | 2007-03-19 | 2007-09-26 | 天津元山科技开发有限公司 | Fine grain strong acid type molecular sieve and method for synthesizing same |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
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| CN106698460A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nano Y molecular sieve |
| CN106698460B (en) * | 2015-11-12 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of synthetic method of nanometer of Y molecular sieve |
| CN112744827A (en) * | 2021-01-05 | 2021-05-04 | 江南大学 | Method for synthesizing ferrierite molecular sieve by seed crystal method |
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