CN102198950B - 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 affected 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 the 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 diamter are generally less than 0.05 micron directed agents slurries, and again this directed agents being mixed with into 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.The method is because the basicity that feeds intake is larger, and the silica alumina ratio of the NaY zeolite of preparing is generally 4.0～4.5; And when adopting lower 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, namely 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 basically all making carried out scale operation in this way at present.The shortcoming of the 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 to pass through the processes such as exchange, roasting and be converted into HY, causes the loss of partial crystallization degree.In the use procedure 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 the activity stability of catalyzer, 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., although these methods respectively have superiority, and some has been widely used industrial, all exists certain deficiency.Because these methods all are at first to synthesize the conventional NaY zeolite that has than low silica-alumina ratio, then adopt various chemistry or physical method to carry out dealuminzation or aluminium-eliminating and silicon-replenishing, and then raising silica alumina ratio, its preparation process will be repeatedly, the degree of crystallinity loss of molecular sieve is very large, also exist simultaneously yield low, the shortcoming such as environmental pollution is serious has limited its application.
In the method for the direct synthesizing high-silicon aluminum ratio Y zeolite that proposes at present, 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 such 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, such 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, without many advantages such as (or few) environmental pollutions.But the template that these methods are used such as tetrapropyl ammonium alkali price are very expensive, in addition, adopt the method to want to obtain 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 Molecules sieve silica alumina ratio 5.0～7.0.But bad the removing of cesium ion in this kind method product need to repeatedly exchange and roasting, greatly increased production cost.
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 advantages, 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 to cracking activity and the isomerization activity of catalyzer, and can in the situation of low agent-oil ratio, obtain maximum gasoline yield.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 on the impact 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 in advance a part of precursor; Then add water glass to improve reaction system silica alumina ratio to 50～135; Next add aluminum chloride and become glue, then filter, remove filtrate, in reaction system, add a certain amount of water again, make the solid content of system reduce by 10～80%; Finally by crystallization, suction filtration, washing, the dry product that gets.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 in 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, to reduce the basicity of crystallization system, continue crystallization, both crystallization time can be shortened, product NaY molecular sieve silica alumina ratio can be increased again.CN1, the disclosed method for preparing the high silica alumina ratio Y zeolite of 621,349A is, first in 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 again crystallization, both can shorten crystallization time, and can increase again product NaY molecular sieve silica alumina ratio, 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, although in the activation of kaoline method, high-temperature activation is combined to simplify technique with alkaline hydrolysis (or adding the NaX sintering), 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 to reduce the aspects such as cost, but do not have important breakthrough, be outstanding so far take kaolin as waste high-Si Y-type molecular sieve industrial problems.
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, although can Effective Raise product silica alumina ratio, the shortcoming such as have that the silica alumina ratio increase rate is large not, crystallization time is long, technical process is complicated or silicon source utilization ratio is not high 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, substantially do not changing 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 in the short period of time high silica alumina ratio NaY molecular sieve.
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 make two kinds of gels, respectively at 80～120 ℃ of lower crystallization 0.5～70 hour;
(3) two kinds of gels that make in the step (2) are proportionally evenly mixed, make mixed gel;
(4) mixed gel that step (3) is made was 80～120 ℃ of lower 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 proposes in 671,191 and USP4,166,099 prepares, so that quality product keeps stable, and can keep technology and equipment not do larger change.
In the 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; 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, the gel in the step (2), evenly mixes two kinds of gels after 0.5～70 hour according to a certain percentage 80～120 ℃ of independent crystallization, and the mass ratio of mixing is 1: (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 growth that in the crystallization process of zeolite molecular sieve, comprise nucleation and crystal.The nucleation process is commonly referred to as crystallization inductive phase, and the macroscopic properties such as degree of crystallinity of crystal do not change substantially in this process, but forms a large amount of nucleus in synthetic system, for the growth of next step crystal provides the basis.In the process of growth of crystal, apparent degree of crystallinity constantly increases, 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 greatly to prolong.
The inventor finds, selects two kinds of suitable gelling systems, and respectively behind the independent crystallization certain hour, evenly then mixing continues crystallization according to a certain percentage at it, can guarantee total crystallization time short in Effective Raise product silica alumina ratio.
According to preferred version of the present invention, select two kinds of systems that basicity is different, respectively according to ordinary method (such as USP3,639,099 and USP3671191 described) the preparation synthesized gel rubber, and with two kinds of gels simultaneously or do not begin simultaneously crystallization.Close to an end inductive phase or during crystal growth beginning in the high alkalinity system, two kinds of gels are mixed under the temperature identical with crystallization temperature, the mass ratio that mixes is 1: (0.2～5), the new gel that obtains mixing, then under uniform temp, continue crystallization, until crystallization is complete, carries out again conventional suction filtration, washing, oven dry and obtain the NaY zeolite product.
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 repeatedly aftertreatment modifying process, 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, 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, lattice constant and the relative crystallinity of zeolite are measured with x-ray powder diffraction, adopt the RIPP145-90 standard method (referring to " Petrochemical Engineering Analysis method " (RIPP test method), the 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 again 14 gram deionized waters, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 235 gram water glass, stir lower 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, the Al of adding 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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 235 gram water glass, stir the lower 72.50 gram high alkali deflection aluminium acid sodiums, 56.63 that add successively and restrain above-mentioned directed agents, 188.24 gram alum liquors, and 70 gram water, mix, make gel B.
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization are after 16 hours under 100 ℃, get A, each 100 gram of B gel 96 ℃ of stirred in water bath mixing, make even mixed gel 200 grams, pack into and continue in the tetrafluoroethylene bottle 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 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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 235 gram water glass, stir lower 72.50 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, the 188.24 gram alum liquors of adding successively, and 70 the 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 5.82.
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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 253.66 gram water glass, stir lower 85.78 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, the 199.52 gram alum liquors of adding successively, and 92.35 the 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 5.68.
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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 270 gram water glass, stir the lower 83.58 gram high alkali deflection aluminium acid sodiums, 56.63 that add successively and restrain above-mentioned directed agents, 183.24 gram alum liquors, 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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 278 gram water glass, stir the lower 70 gram high alkali deflection aluminium acid sodiums, 56.63 that add successively and restrain above-mentioned directed agents, 196 gram alum liquors, and 70 gram water, mix, make gel B.
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization are after 26 hours under 100 ℃, get 140 gram A gels and 70 gram B gels mix 96 ℃ of stirred in water bath, make even mixed gel 210 grams, pack into and continue in the tetrafluoroethylene bottle 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 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, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing.Get 278 gram water glass, stir lower 70 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, the 196 gram alum liquors of adding successively, and 70 the 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 5.88.
Claims (2)
1. the preparation method of a high silica alumina ratio NaY molecular sieve is characterized in that:
Get 81.50 gram water glass, this water glass SiO
2Content is 28.08 heavy %, and modulus 3.28 adds 80.16 gram high alkali deflection aluminium acid sodiums, this high alkali deflection aluminium acid sodium Al
2O
3Content is 3.16 heavy %, Na
2O content is 21.11 heavy %, adds 14 gram deionized waters again, 50 ℃ of lower wearing out 5 hours, makes directed agents after mixing; Get 235 gram water glass, stir lower 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 183.24 gram alum liquors, this alum liquor Al of adding successively
2O
3Content is 7.1 heavy %, and 70 gram water, mixes, and makes gel A;
Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing; Get 235 gram water glass, stir the lower 72.50 gram high alkali deflection aluminium acid sodiums, 56.63 that add successively and restrain above-mentioned directed agents, 188.24 gram alum liquors, and 70 gram water, mix, make gel B;
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization are after 16 hours under 100 ℃, get A, each 100 gram of B gel 96 ℃ of stirred in water bath mixing, make even mixed gel 200 grams, pack into and continue in the tetrafluoroethylene bottle 100 ℃ of lower crystallization 24 hours, then filter, wash, dry NaY molecular sieve.
2. the preparation method of a high silica alumina ratio NaY molecular sieve is characterized in that:
Get 81.50 gram water glass, this water glass SiO
2Content is 28.08 heavy %, and modulus 3.28 adds 80.16 gram high alkali deflection aluminium acid sodiums, this high alkali deflection aluminium acid sodium Al
2O
3Content is 3.16 heavy %, Na
2O content is 21.11 heavy %, adds 14 gram deionized waters again, 50 ℃ of lower wearing out 5 hours, makes directed agents after mixing; Get 270 gram water glass, stir lower 83.58 gram high alkali deflection aluminium acid sodiums, the above-mentioned directed agents of 56.63 grams, 183.24 gram alum liquors, this alum liquor Al of adding successively
2O
3Content is 7.1 heavy %, and 70 gram water, mixes, and makes gel A;
Get 81.50 gram water glass, adding 80.16 gram high alkali deflection aluminium acid sodiums add 14 gram deionized waters again, 50 ℃ of lower wearing out 5 hours, make directed agents after mixing; Get 278 gram water glass, stir the lower 70 gram high alkali deflection aluminium acid sodiums, 56.63 that add successively and restrain above-mentioned directed agents, 196 gram alum liquors, and 70 gram water, mix, make gel B;
Two kinds of gels of A, B are respectively charged in the tetrafluoroethylene bottle, independent crystallization are after 26 hours under 100 ℃, get 140 gram A gels and 70 gram B gels mix 96 ℃ of stirred in water bath, make even mixed gel 210 grams, pack into and continue in the tetrafluoroethylene bottle 100 ℃ of lower crystallization 26 hours, then filter, wash, dry NaY molecular sieve.
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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 |
| 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 |
| 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 |
| 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 |
| CN112591763B (en) * | 2020-12-23 | 2022-10-04 | 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 |
| 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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| CN102198950A (en) | 2011-09-28 |
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