CN102198950A - Method for preparing NaY molecular sieve with high aluminum-silicon ratio - Google Patents
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Abstract
The invention relates to a method for preparing a NaY molecular sieve with a high aluminum-silicon ratio, which comprises the following steps of: mixing a silicon source, an aluminum source and deionized water, uniformly mixing two guide agents in different molar ratios, water glass, acidic aluminum salt and sodium aluminate solution in a molar ratio of gel materials to prepare two gels, and crystallizing respectively, wherein the molar ratio of the gel materials is (1.0-6.5)Na2O:Al2O3:(5.0-18)SiO2:(100-280)H2O, and Al2O3 in the guide agents accounts for 0.01 to 15 percent of the total weight of Al2O3; uniformly mixing the two gels in a mass ratio of 1:(0.1-10) to prepare a mixed gel; and crystallizing the prepared mixed gel at the temperature of between 80 and 120 DEG C for 2 to 50 hours to prepare the NaY molecular sieve. Compared with the prior art, the method has the advantages that: the NaY molecular sieve with the high aluminum-silicon ratio can be prepared in shorter time under the condition of the same feeding molar ratio.
Description
Technical field
The present invention relates to the preparation method of a kind of high silica alumina ratio (silica alumina ratio 〉=6.0) NaY molecular sieve.
Background technology
Y zeolite with faujusite crystalline structure is the main active component of industrial FCC catalyzer, and its degree of crystallinity, silica alumina ratio, pore structure and acid distribute and directly influenced the cracking activity of molecular sieve and the product distribution of selectivity and cracking reaction thereof etc.
U.S. GRACE company in 1972 is at first at patent USP3, proposes to use the synthetic NaY molecular sieve of crystallization director method in 639,099, and this method is at first to prepare to consist of
(15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (285～357) H
2O, nucleus particle diameter are generally less than 0.05 micron directed agents slurries, and again this directed agents being mixed with a mole ratio of components with water glass, sodium aluminate, acid aluminium salt etc. is (3～6) Na
2O: Al
2O
3: (8～12) SiO
2: (120～200) H
2The reaction mixture of O, then with this reaction mixture at 100 ℃ of left and right sides hydrothermal crystallizings.This method is because the basicity that feeds intake is bigger, and the silica alumina ratio of the NaY zeolite of preparing is generally 4.0～4.5; And when adopting low basicity (Na
2O/Al
2O
3During=3～4) with raising product silica alumina ratio, then owing to the low colloid of the water yield needs vigorous stirring than thickness.GRACE company improves this method in USP3671191, promptly improves the silica alumina ratio that feeds intake, and increases the water yield that feeds intake, and to obtain silica alumina ratio greater than 5.0 NaY product, wherein the proportioning of reaction mixture is (3.5～7) Na
2O: Al
2O
3: (10～16) SiO
2: (140～280) H
2O, the method for not using the synthetic NaY molecular sieve of template that after this people propose is all similar with aforesaid method, and industrial also all making basically carried out scale operation in this way at present.The shortcoming of this method is that the water yield that feeds intake is higher, SiO in the 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 is lower than 5.2.
In the production process of FCC catalyzer, the NaY molecular sieve need pass through processes such as exchange, roasting and be converted into HY, causes the loss of partial crystallization degree.In the use of FCC catalyzer, the thermal and hydric environment of revivifier can make the framework dealumination of Y zeolite, causes the catalyst activity poor stability.Like this, have good catalytic effect in order to make the FCC catalyzer, just needing increases the content of Y zeolite in catalyzer, and the result is the cost that has improved catalyzer.And the framework of molecular sieve silica alumina ratio links to each other closely with its hydrothermal stability, therefore, improve the framework si-al ratio of Y zeolite, for the quality product that improves the FCC catalyzer, reduce Y zeolite in catalyzer consumption, improve activity of such catalysts stability, significant.
The Y zeolite of high silica alumina ratio can make by last handling process, and main method has high temperature hydro-thermal, chemical dealuminization etc., though these methods respectively have superiority, and some is industrial widely-used, all exists certain deficiency.Because these methods all are the at first synthetic conventional NaY zeolites that has than low silica-alumina ratio, adopt various chemistry or physical method to carry out dealuminzation or aluminium-eliminating and silicon-replenishing then, and then raising silica alumina ratio, its preparation process will repeat repeatedly, the degree of crystallinity loss of molecular sieve is very big, also exist yield low simultaneously, shortcoming such as environmental pollution is serious has limited its application.
At present in the method for the direct synthesizing high-silicon aluminum ratio Y zeolite that proposes, generally need to add the crown ether-like of price comparison costliness or quaternary ammonium salt material as template, and crystallization time is all longer.More representative method is as R.M.Barrer Vaughan; David E.W. (Flemington, NJ); Strohmaier S.J. Miller etc., directly in reactant gel, add template according to certain mol ratio, as TPAOH, tetrabutylammonium hydroxide alkali or 4-propyl bromide, Tetrabutyl amonium bromide etc., synthetic Y type faujusite such as ECR-4, ECR-32 and ECR-35 etc., its silica alumina ratio can reach more than 6.0, can reach about 20.It is comparatively simple that this method has preparation process, and zeolite crystallinity does not incur loss, and technical process is fairly simple, do not have many advantages such as (or few) environmental pollution.But template that these methods are used such as tetrapropyl ammonium alkali price are very expensive, in addition, adopt this method to seek out the NaY molecular sieve of high-crystallinity high silica alumina ratio, need tens days crystallization time, and productive rate are lower.Grace company has developed a kind of method that adds the cesium ion synthetic faujasites in reactant gel, between the CSZ-1 that makes, the CSZ-3 series molecular sieve silica alumina ratio 5.0～7.0.But bad the removing of cesium ion in this kind method product need repeatedly exchange and roasting, increased production cost greatly.
Studies show that compare with the high silica alumina ratio Y zeolite that hydrothermal dealumination, chemical dealuminization and use template directly prepare, the high silica alumina ratio Y molecular sieve that does not use template directly to prepare has more advantage, is more suitable for being applied in the present catalytic cracking process.The high silica alumina ratio Y zeolite that does not use template directly to prepare does not generally contain non-framework aluminum, and thermostability is higher, is difficult for inactivation.After the high silica alumina ratio Y zeolite that direct method is made is incorporated in the catalyzer, can carry out modulation, and can under the situation of low agent-oil ratio, obtain maximum gasoline yield the cracking activity and the isomerization activity of catalyzer.In addition, direct method (not adding template) preparation high silica alumina ratio Y zeolite just can carry out under the appointed condition of the conventional Y of original preparation, does not need to add other device, and production cost is low, technical process is simple, low in the pollution of the environment.
Therefore, template is not used in exploitation, directly the method for synthesizing high-silicon aluminum ratio Y zeolite will have broad application prospects, and also be that present investigators are making great efforts one of difficult problem that solves.
GB1,044,983 disclose the preparation silica alumina ratio 3～7 Y zeolite method.This patent is investigated Na in the reaction mixture
2The amount of O and H
2The amount of O is to the influence of crystallization time, product degree of crystallinity, silica alumina ratio and silicon source utilization ratio, and patent is pointed out H
2O/SiO
2Mol ratio between 5～7, by reducing the Na of reaction system
2O/SiO
2And H
2O/SiO
2But than and the silicon sol of preferred high density as silicon source synthesizing Si-Al than at 5.5～6.8 NaY molecular sieve, but its crystallization time is longer, 2d～4d just can reach maximum degree of crystallinity.
GB1,431,944 have reported that it is 5.5～8.0 molecular sieve product that the method for taking substep to add reactant makes silica alumina ratio.Concrete steps are: react a part of precursor in advance; Add water glass then to improve reaction system silica alumina ratio to 50～135; Next add aluminum chloride and become glue, filter then, remove filtrate, in reaction system, add a certain amount of water again, make the solid content of system reduce by 10～80%; After crystallization, suction filtration, washing, dry product.But patent does not relate to the step that the initial reaction thing adds system simultaneously, and the silica alumina ratio that feeds intake is very high, causes the silicon utilization ratio very low.
JP61-91,013 proposes by the increase Na that feeds intake
2O/Al
2O
3And reduction SiO
2/ Al
2O
3Can prepare SiO
2/ Al
2O
3NaY molecular sieve 5.2～6.0, the products obtained therefrom better heat stability.They are at used raw material: white carbon black or silica gel is as the silicon source, sodium aluminate, sodium hydroxide and distilled water.Silicon source wherein be water-soluble or drying regime all to require the particle diameter of silicon be more than the 8 μ m, preferably more than the 15 μ m.
CN1,621,348A discloses a kind of synthetic method of NaY molecular sieve, first synthesized gel rubber under the situation of the higher basicity that feeds intake, crystallization for some time, after in the crystallization system, forming a large amount of nucleus, add certain acidic cpd,, continue crystallization to reduce the basicity of crystallization system, both crystallization time can be shortened, product NaY molecular sieve silica alumina ratio can be increased again.CN1,621, the disclosed method for preparing the high silica alumina ratio Y zeolite of 349A is, earlier under the situation of the low silica alumina ratio that feeds intake, crystallization for some time, after forming a large amount of nucleus in the crystallization system, add a certain amount of silicon source, to increase the silica alumina ratio of crystallization system, continue crystallization again, both can shorten crystallization time, and can increase product NaY molecular sieve silica alumina ratio again, but the silicon source utilization ratio of this method is not high.
1970, German patent DE 1,951,907 reports use metakaolin, water glass, sodium hydroxide and crystal seed synthesizing Si-Al than the NaY molecular sieve that can reach 4.5 even 6.0.At first metakaolin and water glass are mixed and made into precursor mixture by a certain percentage, again crystal seed and precursor mixture are added in the water glass solution system, obtain reaction product through 60～110 ℃ of crystallization.U.S.P3,574,538 disclose and use specific kaolin or metakaolin, water glass, sodium hydroxide to be raw material, add crystallization director and come synthetic faujasites, and silica alumina ratio is greater than 4.5, sometimes up to 5.90 and 5.95.Thereby the work of producing the high-silicon type faujusite with kaolin broken forward go a step further.Yet in industry, be difficult to obtain to have desired physics, chemical property as this kaolin or metakaolin, recent years, though at the kaolin activation method, high-temperature activation is combined with alkaline hydrolysis (or adding the NaX sintering) to simplify technology, or with the kaolin of high temperature sintering as the silicon source of adding, replace water glass or amorphous silica to improve to some extent with aspect such as reduce cost, but not having important breakthrough, is that raw material is produced the high-Si Y-type molecular sieve industrial problems and is outstanding so far with kaolin.
In addition, Chao Zisheng etc. are when synthetic ultra micro NaY molecular sieve, and after finding to add a certain amount of aluminum complexing agent (ethylenediamine tetraacetic acid (EDTA), citric acid or acetic acid) in conventional directed agents, the crystallization rate of NaY and silica alumina ratio all obviously improve.Jilin University bear cloud dawn, Li Shougui etc. have proposed to use the novel method that the NaY guiding agent for zeolite provides the synthetic NaY zeolite in whole silicon source, not only crystallization rate is fast for (100～140 ℃) synthetic NaY zeolite under the concurrent present hot conditions, and can to synthesize silica alumina ratio under the organic condition be 6.0 zeolite not adding.
In a word, the technology of present existing preparation high silica alumina ratio NaY molecular sieve, though can effectively improve the product silica alumina ratio, have that the silica alumina ratio increase rate is big inadequately, crystallization time is long, technical process is complicated or the not high shortcoming of silicon source utilization ratio, is still waiting further technical progress.
Summary of the invention
The purpose of this invention is to provide a kind of any organic or inorganic template of not using, do not changing substantially under the prerequisite of conventional synthesis technique, directly the method for synthesizing high-silicon aluminum ratio NaY molecular sieve.Compare with existing method, can synthesize high silica alumina ratio NaY molecular sieve in the short period of time.
The method concrete steps of synthetic NaY molecular sieve provided by the invention are as follows:
(1) according to the method for preparing the faujusite directed agents in the prior art, with water glass, sodium aluminate 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, obtained crystallization director in aging 0.5～48 hour in room temperature to 70 ℃;
(2) directed agents, water glass, acid aluminium salt and the sodium aluminate solution of getting two kinds of different mol ratio according to following gel masses mol ratio mixed and makes two kinds of gels, respectively at 80～120 ℃ of following crystallization 0.5～70 hour;
(3) with two kinds of gels making in the step (2) uniform mixing proportionally, make mixed gel;
(4) mixed gel that step (3) is made was 80～120 ℃ of following crystallization 1～50 hour, and filtration, washing, the drying and other steps through routine makes the NaY zeolite product again.
In the method provided by the present invention, the said directed agents of step (1) can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, but preferably prepares according to the at present industrial generally conventional preparation method of the NaY directed agents of employing.For example according to USP3,639,099, USP3, the method that is proposed in 671,191 and USP4,166,099 prepares, so that quality product keeps stable, and can keep technology and equipment not to do bigger change.
In the method provided by the present invention, the said sodium aluminate of step (2) is a sodium metaaluminate; Said acid aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate, wherein Tai-Ace S 150 preferably; Aluminium in sodium aluminate and acid aluminium salt and the directed agents synthesizes the Al of material together as NaY
2O
3The SiO of material is synthesized in source, the silicon in water glass and the directed agents together as NaY
2The source; The basicity that the sodium aluminate of acidic aluminum source and alkalescence can be used to regulate total material, the ratio of the two requires to decide according to the basicity of total material.
In the method provided by the present invention, the mixture that always feeds intake in the step (2) meets (1.0～6.5) Na
2O: Al
2O
3: (5.0～18) SiO
2: (100～280) H
2O, preferred (1.4～4.0) Na
2O: Al
2O
3: (5.5～12) SiO
2: (140～240) H
2The mole proportioning of O is mixed directed agents, water glass, acid aluminium salt and sodium aluminate and stir obtaining gel, wherein the Al of directed agents
2O
3Account for Al
2O
30.01～15 heavy % of total amount, preferred 0.1～10 heavy %.Na among the present invention
2O represents the basicity of mixture, does not comprise the part that is neutralized by acid.In addition, also can be by adding acid or alkali is regulated basicity, but preferably adopt Tai-Ace S 150 and sodium metaaluminate to regulate basicity as the aluminium source and according to the ratio of the two.
In the method provided by the invention, after 0.5～70 hour, according to a certain percentage with two kinds of gel uniform mixing, the blended mass ratio is 1 to the gel in the step (2) 80～120 ℃ of independent crystallization: (0.1～10), preferred 1: (0.2～5).Total molar ratio of mixed even gel should meet (1.0～6.5) Na
2O: Al
2O
3: (5.0～18) SiO
2: (100～280) H
2O, preferred (1.4～4.0) Na
2O: Al
2O
3: (5.5～12) SiO
2: (140～240) H
2O continued crystallization 1～50 hour, more after filtration, washing, drying and other steps make the NaY zeolite product.
Two the different processes of formation and crystalline growth that in the crystallization process of zeolite molecular sieve, comprise nucleus.The forming process of nucleus is commonly referred to as crystallization inductive phase, and macroscopic property such as crystalline degree of crystallinity does not change substantially in this process, but forms a large amount of nucleus in synthetic system, for next step crystalline growth provides the basis.In the crystalline process of growth, apparent degree of crystallinity constantly increases, and until a stationary value, this moment, whole crystallization process was finished.In the preparation process of NaY molecular sieve, in order to improve the silica alumina ratio of products therefrom, can adopt the feed intake method of silica alumina ratio of the basicity that reduces synthetic system or raising, but these two kinds of methods can cause all nucleus to form difficulty, crystallization prolongs inductive phase, finally causes whole crystallization time to prolong greatly.
The inventor finds, selects two kinds of suitable gelling systems for use, and behind the independent crystallization certain hour of its difference, uniform mixing continues crystallization then according to a certain percentage, can guarantee that total crystallization time effectively improves the product silica alumina ratio in short.
According to preferred version of the present invention, select two kinds of systems that basicity is different for use, respectively according to ordinary method (as USP3,639,099 and USP3671191 described) the preparation synthesized gel rubber, and simultaneously or do not begin crystallization simultaneously with two kinds of gels.Close to an end inductive phase or crystal growth when beginning in high basicity system, two kinds of gels are mixed under the temperature identical with crystallization temperature, the blended mass ratio is 1: (0.2～5), the new gel that obtains mixing, under uniform temp, continue crystallization then, complete until crystallization, carry out conventional suction filtration, washing, oven dry again and obtain the NaY zeolite product.
According to method provided by the invention, can be under the prerequisite that does not change existing production technique substantially, do not add any organic or inorganic template,, can directly prepare the Y zeolite of high silica alumina ratio in the short period of time without repeatedly aftertreatment modifying process yet.Compare with ordinary method, under the condition of identical molar ratio, can obviously shorten crystallization time, perhaps the silica alumina ratio of the finished product can be increased to 6.0 or more than.
Embodiment
The following examples are used for that the present invention will be further described, but not thereby limiting the invention.
In each embodiment and Comparative Examples, the lattice constant and the relative crystallinity of zeolite are measured with x-ray powder diffraction, adopt the RIPP145-90 standard method (referring to " petrochemical complex analytical procedure " (RIPP test method), volumes such as Yang Cuiding, Science Press, nineteen ninety version); Framework si-al ratio calculates according to following formula: SiO
2/ Al
2O
3=2 * (25.8575-α
0)/(α
0-24.191);
Embodiment 1
Get 81.50 gram water glass (Beijing Red Star water glass plant 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 %), add 14 gram deionized waters again, mix the back and wore out 5 hours down at 50 ℃, make directed agents.Get 235 gram water glass, add 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 183.24 gram alum liquor (China Changcheng Aluminium Industry Co's product, Al under stirring successively
2O
3Content is 7.1 heavy %), and 70 gram water, mix, make gel A.
Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 235 gram water glass, add 72.50 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 188.24 gram alum liquors under stirring successively, and 70 gram water, mix, make gel B.
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization is after 16 hours under 100 ℃, get A, each 100 gram of B gel 96 ℃ of stirred in water bath mixing, make uniform mixing gel 200 grams, pack into and continue in the tetrafluoroethylene bottle 100 ℃ of following crystallization 24 hours, filter then, wash, dry NaY zeolite product 30.25 grams, record its degree of crystallinity 95%, silica alumina ratio 6.12.
Comparative Examples 1
Each raw material sources is with embodiment 1.Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 235 gram water glass, stir and add 72.50 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 188.24 gram alum liquors down successively, and 70 the gram water, mix and make gel 622.37 grams, pack in the tetrafluoroethylene bottle, 100 ℃ of following crystallization 40 hours, filter then, wash, dry NaY zeolite product 79 grams, record its degree of crystallinity 77%, silica alumina ratio 5.82.
Comparative Examples 2
Each raw material sources is with embodiment 1.Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 253.66 gram water glass, stir and add 85.78 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 199.52 gram alum liquors down successively, and 92.35 the gram water, mix and make gel 687.94 grams, pack in the tetrafluoroethylene bottle, 100 ℃ of following crystallization 40 hours, filter then, wash, dry NaY zeolite product 100.07 grams, record its degree of crystallinity 80%, silica alumina ratio 5.68.
Embodiment 2
Each raw material sources is with embodiment 1.Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 270 gram water glass, add 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 183.24 gram alum liquors under stirring successively, and 70 gram water, mix, make gel A.
Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 278 gram water glass, add 70 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 196 gram alum liquors under stirring successively, and 70 gram water, mix, make gel B.
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization is after 26 hours under 100 ℃, get 140 gram A gels and 70 gram B gels mix 96 ℃ of stirred in water bath, make uniform mixing gel 210 grams, pack into and continue in the tetrafluoroethylene bottle 100 ℃ of following crystallization 26 hours, filter then, wash, dry NaY zeolite product 31.95 grams, record its degree of crystallinity 99%, silica alumina ratio 5.82.
Comparative Examples 3
Each raw material sources is with embodiment 1.Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, mix the back and wear out 5 hours down at 50 ℃, make directed agents.Get 278 gram water glass, stir and add 70 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 196 gram alum liquors down successively, and 70 the gram water, mix, make gel 670.63 grams, in the tetrafluoroethylene bottle of packing into, 100 ℃ of following crystallization 122 hours, filter then, wash, dry NaY zeolite product 103.21 grams, record its degree of crystallinity 79%, silica alumina ratio 5.88.
Claims (6)
1. the preparation method of a high silica alumina ratio NaY molecular sieve, silica alumina ratio 〉=6.0 is characterized in that:
Its step comprises:
(1) with silicon source, aluminium source 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, obtained crystallization director in aging 0.5～48 hour in room temperature to 70 ℃;
(2) directed agents, water glass, acid aluminium salt and the sodium aluminate solution of getting two kinds of different mol ratio according to following gel masses mol ratio mixed and makes two kinds of gels, respectively at 80～120 ℃ of following crystallization 0.5～70 hour;
The gel masses mol ratio is: (1.0～6.5) Na
2O: Al
2O
3: (5.0～18) SiO
2: (100～280) H
2O, the wherein Al of directed agents
2O
3Account for Al
2O
30.01～15% of gross weight;
(3) be 1 with two kinds of gels that make in the step (2) according to mass ratio: (0.1～10) uniform mixing makes mixed gel;
(4) mixed gel that step (3) is made was 80～120 ℃ of following crystallization 2～50 hours, and filtration, washing, the drying step through routine makes the NaY zeolite product again.
2. according to the preparation method of the described high silica alumina ratio NaY molecular sieve of claim 1, it is characterized in that: the said sodium aluminate of step (2) is a sodium metaaluminate, and said acid aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate.
3. according to the preparation method of the described high silica alumina ratio NaY molecular sieve of claim 1, it is characterized in that: the said two kinds of different gels of step (2) are respectively 80～120 ℃ of independent crystallization 0.5～40 hour down.
4. according to the preparation method of the described high silica alumina ratio NaY molecular sieve of claim 1, it is characterized in that: two kinds of gel blended mass ratioes are 1 in the step (3): (0.2～5).
5. according to the preparation method of the described high silica alumina ratio NaY molecular sieve of claim 1, it is characterized in that: mixed gel continued crystallization 5～30 hours down at 80～120 ℃ in the step (4).
6. according to the preparation method of the described high silica alumina ratio NaY molecular sieve of claim 1, it is characterized in that: gel masses mole proportioning is in the step (2): (1.4～4.0) Na
2O: Al
2O
3: (5.5～12) SiO
2: (140～240) H
2O, the wherein Al of directed agents
2O
3Account for Al
2O
30.1～10% of gross weight.
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| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN105084386A (en) * | 2014-05-12 | 2015-11-25 | 中国石油化工股份有限公司 | Small-particle Y-type molecular sieve with silicon-enriched surface and preparation method thereof |
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| CN112591763A (en) * | 2020-12-23 | 2021-04-02 | 正大能源材料(大连)有限公司 | Preparation method for directly synthesizing Y-type molecular sieve with phosphorus-containing framework by utilizing SAPO-34 molecular sieve mother liquor |
| CN113233474A (en) * | 2021-05-31 | 2021-08-10 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
| CN114426285A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Direct synthesis method of Y molecular sieve with high silica-alumina ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN105084386A (en) * | 2014-05-12 | 2015-11-25 | 中国石油化工股份有限公司 | Small-particle Y-type molecular sieve with silicon-enriched surface and preparation method thereof |
| CN105084386B (en) * | 2014-05-12 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of surface Silicon-rich small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN109704356A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The synthetic method of EU-1 zeolite molecular sieve |
| CN109704356B (en) * | 2017-10-26 | 2021-05-11 | 中国石油化工股份有限公司 | Method for synthesizing EU-1 zeolite molecular sieve |
| CN114426285A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Direct synthesis method of Y molecular sieve with high silica-alumina ratio |
| CN114426285B (en) * | 2020-10-13 | 2023-08-29 | 中国石油化工股份有限公司 | Direct synthesis method of high silicon-aluminum ratio Y molecular sieve |
| CN112591763A (en) * | 2020-12-23 | 2021-04-02 | 正大能源材料(大连)有限公司 | Preparation method for directly synthesizing Y-type molecular sieve with phosphorus-containing framework by utilizing SAPO-34 molecular sieve mother liquor |
| CN113233474A (en) * | 2021-05-31 | 2021-08-10 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
| CN113233474B (en) * | 2021-05-31 | 2022-10-28 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
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