CN104692412A - A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve - Google Patents
A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve Download PDFInfo
- Publication number
- CN104692412A CN104692412A CN201310656066.1A CN201310656066A CN104692412A CN 104692412 A CN104692412 A CN 104692412A CN 201310656066 A CN201310656066 A CN 201310656066A CN 104692412 A CN104692412 A CN 104692412A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- gel
- directed agents
- nay molecular
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve. The method includes following steps: a step of synthesizing a directing agent, namely a step of subjecting a silicon source and NaOH to mixing pretreatment, adding water and an aluminum source, mixing uniformly and ageing to obtain the directing agent, with the mole ratio of Na2O, Al2O3, SiO2 and H2O being 15-25:1:10-30:250-450; a step of preparing reactive gel, namely a step of adding a solid silicon source into a NaOH solution, pretreating to prepare hydrous silica gel, adding an aluminum source, mixing uniformly, adding the directing agent, stirring and mixing uniformly to obtain flow type solid-like reactive gel, with the total adding mole ratio of the Na2O, the Al2O3, the SiO2 and the H2O being 2-6:1:5.5-10.5:50-150; and a step of crystallizing, performing suction filtration and drying, namely a step of crystallizing the prepared solid-like reactive gel, filtering after crystallization is finished, washing and drying to obtain a product.
Description
Technical field
The present invention relates to the preparation of molecular sieve, specifically, relate to and a kind ofly synthesize the method for NaY molecular sieve and the NaY molecular sieve of synthesis thereof, more particularly, that solid-state silicon and aluminum source, deionized water and directed agents are uniformly mixed, obtained flowable state class solid state reaction gel, the novel method of efficient synthesis NaY molecular sieve.
Background technology
Y zeolite is industrially used widely due to its high-temperature stability and good catalytic activity.At the end of the fifties, MILTON R M and BRECK D W successfully synthesizes Y zeolite.Y zeolite replaces with its high stability, high reactivity, anti-metallic contamination and anti-caking power the main active component that X-type zeolite becomes catalyzer.At the beginning of the seventies, GRACE company of the U.S. synthesizes NaY molecular sieve with directing agent method, and raw material instead of expensive silicon sol with water glass, Simplified flowsheet, shortens the production cycle, thus makes NaY molecular sieve be widely used in petroleum catalytic cracking field rapidly.
The ordinary method of current industrial production NaY molecular sieve adopts water glass to do preparation of raw material epoxy glue, carries out the synthesis that crystallization completes Y zeolite.Because water glass system raw material itself is containing a large amount of water, wherein the massfraction of silicon-dioxide only has 28%, and its synthetic system viscosity cannot improve greatly the solids content of system, cause the method solid content low, so the single still yield preparing Y zeolite in each reaction process is also low lower than 10-12%, silicon source utilization ratio, silicon source and course is caused to lose serious.It is reported, large Alternative carries out repeatedly reuse to the mother liquor preparing Y zeolite, compensate for silicon sources and courses a large amount of in above-mentioned technique to a certain extent and lose, but this brings the complicacy of Y zeolite preparation technology and the uncontrollable of product property virtually.
The directing agent method for example proposed in US3639099 and US3671191.This route technical maturity, technical qualification easily control, and quality product is higher, but it is lower to there is single-autoclave yield rate, and silicon source utilization ratio is lower, the defects such as pollutant discharge amount is large.Therefore how to improve reaction gel solid content, to improve silicon source utilization ratio and output per single reactor, reduce pollutant emission, synthesize the NaY molecular sieve had compared with high silica alumina ratio and appropriate particle size simultaneously, become the focus of this area research.
The research of high-level efficiency synthesis NaY molecular sieve is mainly reflected in two aspects.
The first, by increasing the solid content in gel, improve single still yield.
In order to solve, the combined coefficient existed in the synthesis of above-mentioned Y zeolite is low, silicon source and course loses the problems such as serious, develops and utilizes solid state si source to prepare the technology of Y zeolite under solid system, increased substantially silicon source utilization ratio, single-autoclave yield rate.But solid system prepares material stirring difficulty in Y zeolite process to be increased, the synthesis device of existing Y zeolite cannot be utilized to carry out amplification and to produce, limit its industrial application.In addition, this technology comprises in zeolite product quality and to need in degree of crystallinity, grain-size and dispersiveness thereof etc. to be improved further.
1964, US3130007 proposed to adopt unformed solid silicone to provide silicon source, and solid sodium metaaluminate provides aluminium source, and by filling into sodium hydroxide and water prepares gel mixture, obtaining degree of crystallinity is 93%, and silica alumina ratio is the NaY product of 4.42.This method reduce the water-content in gel, but digestion time and crystallization time longer, synthesis of molecular sieve silica alumina ratio is lower.
1984, USP4436708 proposed a kind of method that low temperature plastic prepares NaY molecular sieve.The method introduces NaY crystal seed in gelling system.First by crystal seed, a small amount of water and water glass mix and blend 5h at normal temperatures, be cooled to-5 ~ 10 DEG C and make water glass system, then add sodium aluminate solution at room temperature ageing 24h, be then heated to 80 ~ 120 DEG C and carry out crystallization.The method can improve single-autoclave yield rate, but single still production cycle is long.
1986, US4576807 proposed a kind of method preparing NaY molecular sieve.First adopt water glass process crystal seed, then add sodium aluminate solution and prepare gel, be warming up to 100 DEG C and stir crystallization more than 12 hours, NaY product can be obtained.The method is prepared in gelation process and is reduced water-content, improves single still yield.But because the basicity fed intake is higher, product silica alumina ratio is lower.
1998, CN1185996 proposed a kind of high-efficiency synthesis method of NaY molecular sieve.The method and ordinary method similar, just preparing gelation process, reduced the viscosity of colloid by the method improving raw water glass temperature.Throw the water yield owing to decreasing in gel, although improve single still yield of NaY molecular sieve to a certain extent, in silicon source utilization ratio, still there is certain defect in the aspects such as pollutant emission, and heat riser adds cost, and economic benefit reduces.
2000, CN1266742 proposes the preparation method of another kind of NaY molecular sieve, compared with ordinary method, acid aluminium salt is added in gel several times, form repeatedly thickness point, but gel consistency during each thickness point, viscosity when all once adding lower than existing bialuminate and form a thickness point.Therefore can reduce the solid content fed intake in water yield raising gel, the method can improve the single-autoclave yield rate of NaY relatively, but complex process, be unfavorable for industrial production.
2008, CN101190795 provided a kind of method adopting solid phase transformation to prepare NaY molecular sieve, be reaction mixture was the novel method preparing NaY molecular sieve under the condition of solid state.The method is different from the method for conventional hydrothermal crystallization production NaY molecular sieve, has silicon source utilization ratio high.But synthesis of molecular sieve exists certain defect in degree of crystallinity and grain-size, and stir difficulty, be unfavorable for industrial production.
The second, carry out recycle by the silicon source in the mother liquor of NaY molecular sieve that synthesizes water glass system, improve the utilization ratio in silicon source.
1998, Li Zhong county etc. described the industrial application of silicon recycle to extinction NaY molecular sieve synthesis technique.Adopt the fresh silicon of silicon Substitute For Partial of disposing mother liquor to synthesize NaY molecular sieve, the utilization ratio of silicon can be brought up to more than 95% by 51 ~ 54% by the method, and supplies consumption obviously declines, and can reduce the quantity discharged of pollutent by a relatively large margin.But circulation device adds complex process degree, cost raises.
1999, Lanzhou oil-refining chemical head factory water fine jade etc. has carried out transforming thoroughly to NaY molecular sieve synthesis technique, develops silicon recycle to extinction NaY molecular sieve new synthetic process, achieves maximization and the intensive manufacture of NaY molecular sieve, quantity of wastewater effluent reduces, and reduces environmental pollution.But silicon recycle to extinction device adds the input of cost, reduces economic benefit.
2008, when Yue Huxiu, Zhang Jihua etc. synthesize NaY molecular sieve, after taking the mother liquor that the NaY molecular sieve washing filtering stage produces all to recycle and improve strainability two Cleaning production measures of gel, the suspension content of externally discharged waste water reduced.Further, two sections of washing lotions and gel filtrate are recycled, the cyclic utilization rate of silicon can be made to improve, the starting material unit consumption of synthesis NaY molecular sieve product is reduced, improve silicon source utilization ratio.But disposing mother liquor adds technological process, improve production cost.
2009, CN101549874 proposed a kind of synthesis technique improving generation rate of nano Y-shaped molecular sieve.This technique adopts the synthesis of water glass material system.First by gel hydrothermal crystallizing 60-110h at 90-130 DEG C of preparation; The solidliquid mixture obtained is separated, and wherein mother liquor retains, and solid is nano Y-shaped molecular sieve; To the mother liquor postreaction raw material obtained, then continue crystallization, solid-liquid separation, again obtain nano Y-shaped molecular sieve and reaction mother liquor.The productive rate of postreaction raw material, crystallization, solid-liquid separation raising nano Y-shaped molecular sieve repeatedly.This method, by the reuse of mother liquor repeatedly, can improve silicon source utilization ratio, but the yield of technique single process is not high, needs cyclic process process repeatedly, and overall cost increases, and economy reduces.
In sum, prepare Y zeolite at present and mainly adopt water glass to do preparation of raw material epoxy glue, carry out crystallization and complete Y zeolite synthesis.Because water glass system raw material itself is containing a large amount of water, wherein the massfraction of silicon-dioxide only has 28%, and viscosity cannot improve greatly the solids content of system under synthetic system condition, cause the method solid content low, thus prepare the low 10-12% of single still yield of Y zeolite in each reaction process, silicon source utilization ratio is also low.In order to avoid a large amount of silicon sources and courses loses in above-mentioned technique, mostly adopt Y molecular sieve to prepare the repeatedly reuse of mother liquor, virtually bring the uncontrollable of process complexity and product property.
Summary of the invention
One object of the present invention is to provide a kind of method of synthesizing NaY molecular sieve, the present invention emphasizes the epoxy glue adopting high reactivity directed agents, high reactivity hydrated silica gel is prepared into flowable state, not only increase its combined coefficient, improve zeolite product quality, also help and implement industry amplification.
Another object of the present invention is to the NaY molecular sieve providing described method to synthesize.Under class solid system, this invention exploits the method efficiently preparing Y zeolite, the physico-chemical property of product meets or exceeds the molecular sieve of current method synthesis, namely obtain that crystalline phase is complete, high silica alumina ratio, high-specific surface area, hole is flourishing, finely dispersed submicron-scale NaY molecular sieve.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of method of synthesizing NaY molecular sieve, described method comprises the steps:
(1) directed agents is synthesized: according to Na
2o:Al
2o
3: SiO
2: H
2o mol ratio is 15-25:1:10-30:250-450, and silicon source is for subsequent use with NaOH mixing pre-treatment; Add remaining water and aluminium source successively, mix, mixture ageing is obtained directed agents;
(2) preparation feedback gel: according to Na
2o:Al
2o
3: SiO
2: H
2total molar ratio of O is 2-6:1:5.5-10.5:50-150, solid silicon source is added pre-treatment in NaOH solution and prepares hydrated silica gel, add aluminium source, mix, add directed agents, be uniformly mixed, obtained flowable state class solid state reaction gel;
(3) crystallization, suction filtration, drying: the class solid state reaction gel crystallization obtained by step (2), after crystallization completes, filtration, washing, drying, obtained product.
Be understandable that, the mole number in step (2) in said total molar ratio refers to the total mole number that step (1) adds step (2) and all feeds intake.
Wherein, according to method of the present invention, in step (2), introduce H by adding deionized water
2the amount of O accounts for the 30-50% of class solid phase gel total amount, introduces Al by directed agents
2o
3amount account for Al in gel
2o
3the 5-20wt% of total amount.
According to method of the present invention, the ageing in step (1) can adopt the ageing of prior art to operate, and is improve NaY molecular sieve performance prepared by the present invention further, the present invention preferably by mixture 0-40 DEG C of ageing at least 12 hours, obtained directed agents.
Wherein can also preferably by mixture 0-40 DEG C of ageing after at least 12 hours, more static ageing 12-120 hour, obtained directed agents;
Wherein the present invention is preferred further stirs ageing more than 12 hours by mixture at 10-30 DEG C;
Wherein mixture preferably can also be stirred ageing after more than 12 hours at 10-30 DEG C by the present invention, more static ageing 48-96 hour.
According to method of the present invention, in the further preferred steps of the present invention (2) at 15-60 DEG C, make uniform dispersion respectively to adding deionized water in solid state si source and solid aluminum source and stirring.
According to method of the present invention, Na in the further preferred steps of the present invention (2)
2o:Al
2o
3: SiO
2: H
2total molar ratio of O is 2.5-4:1:7.5-9.5:80-120;
Wherein more preferably 2.5-4:1:8-9:85-95.
For improving reaction effect further, it is that 10-60 drips/min that preferred steps of the present invention (2) adds directed agents speed.
Wherein the NaOH solution pH of the present invention also described in further preferred steps (2) is 12-13.
According to method of the present invention, the crystallization in step (3) can with reference to prior art crystallization working method, and the present invention preferably adopts, reaction gel under the condition of 90-110 DEG C the crystallization 24-72 hour obtained by step (2).
According to method of the present invention, in step (1), the silicon source of synthesis directed agents is the mixture of one or more of water glass and silicon sol, and aluminium source is the mixture of one or more of sodium metaaluminate, Tai-Ace S 150 and aluminum nitrate.
According to method of the present invention, in step (2), preparation flowable state class solid state reaction gel silicon source is the mixture of one or more of silochrom, shrend water glass and white carbon black; Aluminium source is the mixture of one or more of sodium metaaluminate, Tai-Ace S 150 and aluminum nitrate.
Wherein water glass is this area conventional reagent; For example conventional commercial water glass wherein SiO
2content is 28.08wt%, Na
2o content is 8.83wt%; The water glass of for example Red Star chemical plant, Beijing production again.
Silicon sol is this area conventional reagent; For example conventional commercial silicon sol SiO
2content is 40.00wt%, Na
2o content is 0.40wt%, median size 10-20nm; The silicon sol of for example Qingdao Marine Chemical Co., Ltd.'s production again.
Be understandable that, the water in step of the present invention (1) said molar ratio comes from the water in deionized water and silicon source.
Silochrom is again C type silica gel, is the one of silica gel, and the present invention adopts any commercially available silochrom.Any silochrom meeting commercial available quality standard all can be used for the present invention.For example pore volume >=0.78ml/g.
Microsphere silica gel wherein, shrend water glass and white carbon black are conventional commercial chemical reagent, and any mentioned reagent meeting commercial available quality standard all can be used for the present invention, and realizes the object of the invention.
According to method of the present invention, the further preferred steps of the present invention (1) described pre-treatment for stir 2-4h at 10-30 DEG C.
According to method of the present invention, the further preferred steps of the present invention (2) described pre-treatment for process 2-4h at 0-60 DEG C.
Wherein the present invention can also the middle NaOH solution pH value of preferred steps (2) be further 12-13.
On the other hand, present invention also offers the NaY molecular sieve of any described method synthesis of the present invention.
According to NaY molecular sieve of the present invention, wherein said molecular sieve silica alumina ratio is 5.3-6.3, and grain-size is in 200-600nm scope.
The all right NaY molecular sieve relative crystallinity preferably described further of the present invention is more than 95%; Wherein be more preferably 95%-100%.
The present invention can also preferred described NaY molecular sieve specific surface area be further 700-850m
2/ g.
In sum, the invention provides a kind of synthesize NaY molecular sieve method and the NaY molecular sieve that obtains of synthesis.Method tool of the present invention has the following advantages:
Method provided by the invention is uniformly mixed solid-state silicon and aluminum source, deionized water and directed agents, and obtained flowable state class solid state reaction gel, improves reaction gel solid content, efficiently synthesize NaY molecular sieve.This system improves single still yield and single still utilization ratio, and simultaneously in order to improve the performance of product, silicon source is carried out pre-treatment and is prepared into high reactivity hydration sodium silicate solution by the present invention's employing when preparing directed agents, then prepares high reactivity directed agents further; When preparation feedback gel, solid silicon source is carried out the high reactivity hydrated silica gel that pre-treatment prepares by employing.The method technique is simple, cost is lower, crystallization time is short, the single-autoclave yield rate of single preparation process can reach 20-30%, the silicon source utilization ratio of single preparation process reaches 70-90%, 15-20 percentage point is improve than the productive rate of traditional hydrothermal crystallization method, synthesizing Si-Al is than being 5.5-6.5, grain-size is in 200-800nm scope, and finely dispersed NaY molecular sieve;
Based on the existing problems solved in the synthesis of above-mentioned Y zeolite, adopt solid-state silicon source to carry out solid phase method and prepare Y zeolite, in order to be reduced in the uniform engineering issues such as mass transfer, heat transfer in amplification process, modulation of the present invention is standby can the epoxy glue of flowable state, is conducive to industry and amplifies.On the other hand, the physico-chemical property completing the Y zeolite of preparation under high efficiency preparation system meets or exceeds the molecular sieve of current method synthesis, and namely the silica alumina ratio of molecular sieve is higher, and specific surface area is high, and hole is flourishing.
Accompanying drawing explanation
Fig. 1 is the XRD figure sheet of the NaY molecular sieve that embodiment 1 prepares;
Fig. 2, Fig. 3 are the SEM photo of the NaY molecular sieve that embodiment 1 prepares; Wherein Fig. 2 is amplification 20000 times, Fig. 3 is amplification 100000 times.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
In each embodiment, the relative crystallinity of NaY molecular sieve and silica alumina ratio all adopt Japanese SIMADU Lab XRD-6000 type X-ray diffractometer.Experiment condition is: CuKa radiation, Ni filtering, continuous sweep, and tube voltage is 40kv, and tube current is 30mA, walks wide by 0.02.Adopt (311), (511,333), (440), (642), (822,660), (555,751), (664) crystallographic plane diffraction peak area sum, by following formulae discovery Y zeolite relative crystallinity Xi
Xi=Xr(∑Ai/∑Ar)
Xr is the degree of crystallinity 93% of standard specimen, and ∑ Ai is eight peak area sums of testing sample, and ∑ Ar is eight peak area sums of standard specimen.
The measuring method of silica alumina ratio is according to SH/T0339-92 standard method (see " standard of chemical industry compilation ", China Standards Press, version in 2000).(555) diffraction peak is adopted to calculate the silica alumina ratio of Y zeolite: the diffraction angle calculated value 2 θ Si=28.443 ° getting silica flour, in order to correct the position of testing sample diffraction peak:
2 θ (school)=2 θ (survey)-(2 θ Si (survey)-2 θ Si)
Then lattice constant a is calculated:
In formula: a-lattice constant/
λ-Cu-K α 1 radiation wavelength (
);
(h
2+ k
2+ l
2the interference index sum of squares of)-diffracted ray.
Under this experiment condition, a=6.671/sin (θ (school)).
According to Breck-Flanigen formula:
Si/Al=(25.858-a)/(a-24.191)
Calculate Y zeolite silica alumina ratio.
Embodiment 1
First, take 57.81g water glass and be placed in beaker, then take 8.81g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) be placed in beaker, by both mixing and stirring, and stir 2 hours in room temperature (27 DEG C), prepare high reactivity hydration sodium silicate solution; Add 54.11g deionized water successively again, 3.12g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 36 hours, prepare directed agents in room temperature (27 DEG C) ageing, the constitutive molar ratio in this directed agents is 15.3Na
2o:Al
2o
3: 19SiO
2: 376H
2o.
Taking 5.00g sodium hydrate solid is dissolved in 45g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 42.54g gross porosity microsphere silica gel again joins in basic solution, stir 3 hours at constant temperature 20 DEG C, prepare highly active hydrated silica gel, then 21.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 83.38g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 249.9g, and proportioning is 2.73Na
2o:Al
2o
3: 8.53SiO
2: 87.21H
2o, solid content is 35.31%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 54.56g, a silicon source utilization ratio of synthesis NaY molecular sieve is 80.13%, and single still yield is 22.29%.It is 96%, specific surface area 745m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.57, and grain-size is within the scope of 200-600nm.Physical and chemical performance and preparation process analysis in table 1.This product XRD spectra is as Fig. 1, and Electronic Speculum spectrogram as shown in Figure 2 and Figure 3.
Embodiment 2
The preparation of directed agents and various raw material sources are all with embodiment 1
Taking 2.50g sodium hydrate solid is dissolved in 24g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 15.01g gross porosity microsphere silica gel again joins in basic solution, stir 4 hours at constant temperature 10 DEG C, prepare highly active hydrated silica gel, then 7.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 37.79g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 86.3g, and proportioning is 5.74Na
2o:Al
2o
3: 10.05SiO
2: 73.02H
2o, solid content is 38.89%.Loaded in the stainless steel cauldron of liner zellon, at 90 DEG C of static crystallization 60h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 18.32g, a silicon source utilization ratio of synthesis NaY molecular sieve is 81.69%, and single-autoclave yield rate is 26.25%.It is 98%, specific surface area 813m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.53, and grain-size is within the scope of 200-600nm.
Embodiment 3
The preparation of directed agents and various raw material sources are all with embodiment 1
Taking 2.00g sodium hydrate solid is dissolved in 20g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 16.21g gross porosity microsphere silica gel again joins in basic solution, stir 2.5 hours at constant temperature 30 DEG C, prepare highly active hydrated silica gel, then 8.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 39.71g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 83.91g, and proportioning is 3.31Na
2o:Al
2o
3: 8.76SiO
2: 69.26H
2o, solid content is 41.17%.Loaded in the stainless steel cauldron of liner zellon, at 105 DEG C of static crystallization 32h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 25.33g, a silicon source utilization ratio of synthesis NaY molecular sieve is 81.88%, and single-autoclave yield rate is 27.35%.XRD test relative crystallinity is 95%, specific surface area 710m2/g silica alumina ratio is 5.51, and grain-size is within the scope of 200-600nm.
Embodiment 4
Various raw material sources are with embodiment 1
First, 73.00g silicon sol (Qingdao Marine Chemical Co., Ltd., SiO is taken
2content is 40.00wt%, Na
2o content is 0.40wt%, median size (10-20nm)) be placed in beaker, take 14.28g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd. again, analytical pure) be placed in this beaker, by both mixing and stirring, and stir 3 hours in 15 DEG C, prepare high reactivity hydration sodium silicate solution; Add 86.07g deionized water successively again, 4.70g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 120 hours, prepare directed agents in constant temperature temperature (10 DEG C) ageing, the constitutive molar ratio in this directed agents is 16.5Na
2o:Al
2o
3: 21SiO
2: 388H
2o.
Taking 6.00g sodium hydrate solid is dissolved in 65g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 30.39g gross porosity microsphere silica gel again joins in basic solution, stir 2 hours at constant temperature 50 DEG C, prepare highly active hydrated silica gel, then 15.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 59.56g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 169.95g, and proportioning is 3.47Na
2o:Al
2o
3: 8.92SiO
2: 89.69H
2o, solid content is 35.39%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 40.32g, a silicon source utilization ratio of synthesis NaY molecular sieve is 82.71%, and single-autoclave yield rate is 23.73%.It is 95%, specific surface area 706m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.67, and grain-size is within the scope of 200-600nm.
Embodiment 5
Various raw material sources are with embodiment 1
First, take 55.80g water glass and be placed in beaker, then take 9.66g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) be placed in beaker, by both mixing and stirring, and stir 1 hour in room temperature (50 DEG C), prepare high reactivity hydration sodium silicate solution; Add 47.39g deionized water successively again, 2.82g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 120 hours, prepare directed agents in 15 DEG C of ageings, the constitutive molar ratio in this directed agents is 17.6Na
2o:Al
2o
3: 21SiO
2: 369H
2o.
Taking 3.10g sodium hydrate solid is dissolved in 35.00g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 20.31g gross porosity microsphere silica gel again joins in basic solution, stir 3 hours at constant temperature 50 DEG C, prepare highly active hydrated silica gel, then 12.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 47.65g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 118.06g, and proportioning is 3.44Na
2o:Al
2o
3: 7.00SiO
2: 72.59H
2o, solid content is 40.59%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 32.80g, a silicon source utilization ratio of synthesis NaY molecular sieve is 84.11%, and single-autoclave yield rate is 27.58%.It is 95%, specific surface area 723m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.24, and grain-size is within the scope of 200-600nm.
Embodiment 6
Various raw material sources are with embodiment 1
5L amplification test, first, take 372.00g water glass and be placed in beaker, take 64.95g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd. again, analytical pure) be placed in this beaker, by both mixing and stirring, and stir 4 hours in 20 DEG C, prepare high reactivity hydration sodium silicate solution; Add 371.77g deionized water successively again, 23.21g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is wt41%), be uniformly mixed, within 60 hours, prepare directed agents in 25 DEG C of ageings, the constitutive molar ratio in this directed agents is 14.6Na
2o:Al
2o
3: 17SiO
2: 329H
2o.
Taking 18.75g sodium hydrate solid is dissolved in 300g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 303.87g gross porosity microsphere silica gel again joins in basic solution, stir 3 hours at constant temperature 45 DEG C, prepare highly active hydrated silica gel, then 150.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 595.59g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 1668.21g, and proportioning is 3.39Na
2o:Al
2o
3: 8.66SiO
2: 84.27H
2o, solid content is 37.40%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 450g, a silicon source utilization ratio of synthesis NaY molecular sieve is 92.76%, and single-autoclave yield rate is 27.29%.It is 96%, specific surface area 764m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.57, and grain-size is within the scope of 200-600nm.
Embodiment 7
Various raw material sources are with embodiment 1
Take 93.00g water glass and be placed in beaker, take 13.92g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) again and be placed in this beaker, by both mixing and stirring, and stir 3 hours in 24 DEG C, prepare high reactivity hydration sodium silicate solution; Add 68.63g deionized water successively again, 4.11g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 18 hours, prepare directed agents in 40 DEG C of ageings, the constitutive molar ratio in this directed agents is 18.4Na
2o:Al
2o
3: 24SiO
2: 390H
2o.
Taking 18.75g sodium hydrate solid is dissolved in 300g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 303.87g gross porosity microsphere silica gel again joins in basic solution, stir 3 hours at constant temperature 45 DEG C, prepare highly active hydrated silica gel, then 150.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 63.53g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 195.69g, and proportioning is 3.42Na
2o:Al
2o
3: 9.18SiO
2: 85.71H
2o, solid content is 37.11%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 42.67g, a silicon source utilization ratio of synthesis NaY molecular sieve is 82.48%, and single-autoclave yield rate is 24.11%.It is 97%, specific surface area 730m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.58, and grain-size is within the scope of 200-600nm.
Embodiment 8
Various raw material sources are with embodiment 1
Take 74.40g water glass and be placed in beaker, take 11.21g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) again and be placed in this beaker, by both mixing and stirring, and stir 4 hours in 18 DEG C, prepare high reactivity hydration sodium silicate solution; Add 62.95g deionized water successively again, 5.27g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 72 hours, prepare directed agents in 24 DEG C of ageings, the constitutive molar ratio in this directed agents is 12.1Na
2o:Al
2o
3: 15SiO
2: 263H
2o.
Taking 3.13g sodium hydrate solid is dissolved in 50.00g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 22.28g gross porosity microsphere silica gel again joins in basic solution, stir 3 hours at constant temperature 30 DEG C, prepare highly active hydrated silica gel, then 11.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 43.68g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 130.09g, and proportioning is 2.97Na
2o:Al
2o
3: 8.40SiO
2: 81.84H
2o, solid content is 36.04%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 29.33g, a silicon source utilization ratio of synthesis NaY molecular sieve is 80.09%, and single-autoclave yield rate is 23.10%.It is 96%, specific surface area 745m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.47, and grain-size is within the scope of 200-600nm.
Embodiment 9
Various raw material sources are with embodiment 1
First, take 55.80g water glass and be placed in beaker, then take 9.66g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) be placed in this beaker, by both mixing and stirring, and stir 4 hours in 15 DEG C, prepare high reactivity hydration sodium silicate solution; Add 36.24g deionized water successively again, 1.97g sodium metaaluminate (Tianjin, Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), be uniformly mixed, within 120 hours, make high reactivity directed agents in 15 DEG C of ageings.Constitutive molar ratio in this directed agents is 24.5Na
2o:Al
2o
3; 30SiO
2: 450H
2o.
Taking 4.38g sodium hydrate solid is dissolved in 70g deionized water, stirring makes it fully dissolve, prepare basic solution, taking 30.39g gross porosity microsphere silica gel again joins in basic solution, stir 3.5 hours at constant temperature 30 DEG C, prepare highly active hydrated silica gel, then 15.00g sodium metaaluminate is taken in high reactivity hydrated silica gel, after stirring, add above-mentioned directed agents 59.56g, stir obtained flowable state class solid state reaction gel, and reaction gel mixture total mass is 179.33g, and proportioning is 3.21Na
2o:Al
2o
3: 9.08SiO
2: 86.67H
2o, solid content is 36.53%.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 42.32g, a silicon source utilization ratio of synthesis NaY molecular sieve is 82.26%, and single-autoclave yield rate is 24.07%.It is 96%, specific surface area 719m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 6.01, and grain-size is within the scope of 200-600nm.
Comparative example 1
This comparative example illustrates that various raw material sources are with embodiment 1 with reference to CN1185996 conventional hydrothermal method synthesis NaY type molecular sieve.
First, take 55.80g water glass and join a certain amount of deionization dilution with water, fully stir, activation for some time is for subsequent use; Then, take 14.96g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) and be dissolved in 73.63g deionized water, after being cooled to room temperature, add sodium metaaluminate 3.97g(Tianjin Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41%), make high alkalinity sodium aluminate solution; Finally, be slowly added in high alkalinity sodium aluminate solution by the water glass of activation and stir, ageing for some time is for subsequent use.Constitutive molar ratio in this directed agents is 16.7Na
2o:Al
2o
3: 14.9SiO
2: 345H
2o.
Get 100ml water glass, be heated to 95 DEG C, stop heating, then under agitation add the low sodium aluminate solution of 42.4ml wherein, after 34ml alum liquor and above-mentioned directed agents mix, loaded in the stainless steel cauldron of liner zellon, gel cumulative volume is 193ml, at 100 DEG C of static crystallization 48h, then obtains NaY molecular sieve product through filtration washing drying, quality is 28.7g, and silicon source utilization ratio is 55.7%.It is 90%, specific surface area 703m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.00.Physical and chemical performance and preparation process analysis in table 1.
Comparative example 2
This comparative example illustrates that the preparation of directed agents and various raw material sources are all with comparative example 1 with reference to patent 200610114668.4 Solid phase synthesis NaY molecular sieve.
First, take 8.1g sodium hydrate solid (Beijing Century Red Star Chemical Co., Ltd., analytical pure) and be dissolved in 26.2g deionized water, after being cooled to room temperature, add sodium metaaluminate 2.46g(Tianjin Tianjin section chemical institute, Al
2o
3content be 45wt%, Na
2the content of O is 41wt%), make high alkalinity sodium aluminate solution; Finally, take 55.80g water glass and be slowly added in high alkalinity sodium aluminate solution and stir, room temperature ageing obtains directed agents in 14 hours.Constitutive molar ratio in this directed agents is 14Na
2o:Al
2o
3: 14SiO
2: 248H
2o.
Take 9.3g silochrom and be placed in beaker, then take 4.54g sodium metaaluminate in beaker, by both mixing and stirring, add above-mentioned directed agents 19.6g, stir obtained moistening solid state reaction mixture, and reaction mixture total mass is 33.44g, and proportioning is 3Na
2o:Al
2o
3: 8SiO
2: 34H
2o.Loaded in the stainless steel cauldron of liner zellon, at 100 DEG C of static crystallization 48h, then obtain NaY molecular sieve product through filtration, washing, drying, quality is 10.98g, a silicon source utilization ratio of synthesis NaY molecular sieve is 82.48%, and single-autoclave yield rate is 32.54%.It is 81%, specific surface area 651m that XRD tests relative crystallinity
2/ g silica alumina ratio is 5.3, and grain-size is at about 1000nm.
Comparative example 3
This comparative example illustrates that the preparation of directed agents and various raw material sources are all with comparative example 1 with reference to USP3671191 conventional hydrothermal method synthesis NaY molecular sieve.
Get 102.5ml water glass and put into container, the directed agents that 11.3g is prepared according to comparative example 1 method is added under whipped state, the low sodium aluminate solution of 26.6ml (with comparative example 1), 22.3ml alum liquor (with comparative example 1) and 31.1ml water, mix, loaded in the stainless steel cauldron of liner zellon, gel cumulative volume is 193ml, at 100 DEG C of static crystallization 48h, then NaY molecular sieve product is obtained through filtration washing drying, quality is 18.2g, and silicon source utilization ratio is 55.17%.It is 92%, specific surface area 615m that XRD tests relative crystallinity
2/ g, silica alumina ratio is 5.10.Physical and chemical performance and preparation process analysis in table 1.
Table 1
Claims (10)
1. synthesize a method for NaY molecular sieve, it is characterized in that, described method comprises the steps:
(1) directed agents is synthesized: according to Na
2o:Al
2o
3: SiO
2: H
2o mol ratio is 15-25:1:10-30:250-450, and silicon source is for subsequent use with NaOH mixing pre-treatment; Add water and aluminium source successively, mix, mixture ageing is obtained directed agents;
(2) preparation feedback gel: according to Na
2o:Al
2o
3: SiO
2: H
2total molar ratio of O is 2-6:1:5.5-10.5:50-150, solid silicon source is added pre-treatment in NaOH solution and prepares hydrated silica gel, add aluminium source, mix, add directed agents, be uniformly mixed, obtained flowable state class solid state reaction gel; Preferred described NaOH solution pH is 12-13; It is that 10-60 drips/min that preferred described directed agents adds speed;
(3) crystallization, suction filtration, drying: the class solid state reaction gel crystallization obtained by step (2), after crystallization completes, filtration, washing, drying, obtained product; Preferred described crystallization is by the obtained reaction gel crystallization 24-72 hour under the condition of 90-110 DEG C of step (2).
2. method according to claim 1, is characterized in that, by adding the H that deionized water is introduced in step (2)
2the weight of O accounts for the 30-50% of class solid phase gel gross weight, introduces Al by directed agents
2o
3weight account for Al in gel
2o
3the 5-20wt% of gross weight.
3. method according to claim 1 and 2, is characterized in that, in step (1) by mixture in 0-40 DEG C of ageing at least 12 hours obtained directed agents; Wherein preferred in 10-30 DEG C of ageing at least 12 hours obtained directed agents; Wherein preferred 10-30 DEG C of ageing 48-96 hour, obtained directed agents.
4. method according to claim 1 and 2, is characterized in that, Na in step (2)
2o:Al
2o
3: SiO
2: H
2total molar ratio of O is 2.5-4:1:7.5-9.5:80-120; Wherein be preferably 2.5-4:1:8-9:85-95.
5. method according to claim 1 and 2, is characterized in that, in step (1), the silicon source of synthesis directed agents is the mixture of one or more of water glass and silicon sol, and aluminium source is the mixture of one or more of sodium metaaluminate, Tai-Ace S 150 and aluminum nitrate.
6. method according to claim 1 and 2, is characterized in that, in step (2), the solid silicon source of preparation flowable state class solid state reaction gel is the mixture of one or more of silochrom, shrend water glass and white carbon black; Aluminium source is the mixture of one or more of sodium metaaluminate, Tai-Ace S 150 and aluminum nitrate.
7. method according to claim 1 and 2, is characterized in that, step (1) described pre-treatment for stir 2-4h at 10-30 DEG C.
8. method according to claim 1 and 2, is characterized in that, step (2) described pre-treatment for process 2-4h at 0-60 DEG C.
9. the NaY molecular sieve of method synthesis described in claim 1 ~ 8 any one.
10. NaY molecular sieve according to claim 9, is characterized in that, described molecular sieve silica alumina ratio is 5.3-6.3, and grain-size is in 200-600nm scope; Preferred described molecular sieve relative crystallinity is greater than 95%; More preferably described molecular sieve specific surface area is 700-850m
2g
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310656066.1A CN104692412A (en) | 2013-12-06 | 2013-12-06 | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310656066.1A CN104692412A (en) | 2013-12-06 | 2013-12-06 | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104692412A true CN104692412A (en) | 2015-06-10 |
Family
ID=53340031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310656066.1A Pending CN104692412A (en) | 2013-12-06 | 2013-12-06 | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104692412A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439167A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing 3A molecular sieve from potassium feldspar |
| RU2627900C1 (en) * | 2016-12-05 | 2017-08-14 | Федеральное государственное бюджетное учреждение науки Институт проблем переработки углеводородов Сибирского отделения Российской академии наук (ИППУ СО РАН) | Method of preparing microcrystalline nay zeolite |
| CN107399743A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of preparation method of NaY molecular sieve |
| CN107777698A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | B NaY molecular sieves and its production and use |
| CN108529644A (en) * | 2017-03-01 | 2018-09-14 | 中国石油天然气集团公司 | A kind of NaY molecular sieve and preparation method thereof |
| CN108569705A (en) * | 2017-03-14 | 2018-09-25 | 中国石油天然气集团公司 | A kind of high silica alumina ratio NaY type molecular sieve and preparation method thereof |
| CN108862309A (en) * | 2017-05-11 | 2018-11-23 | 中国石油大学(北京) | A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure |
| CN109264743A (en) * | 2018-11-23 | 2019-01-25 | 福州大学 | A kind of preparation method of little crystal grain high silica alumina ratio NaY molecular sieve |
| CN110078093A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of NaY molecular sieve and its preparation method and application |
| CN110078084A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of high silicon aluminium ratio small crystal NaY molecular sieve and preparation method thereof |
| CN111410206A (en) * | 2020-04-13 | 2020-07-14 | 邹凌峰 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
| 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 |
| CN112744840A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | NaY molecular sieve synthesis device and NaY molecular sieve synthesis method |
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 |
| US20080154083A1 (en) * | 2002-02-05 | 2008-06-26 | Xingtao Gao | Hydrocarbon conversion using nanocrystalline zeolite Y |
| CN102198950A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve with high aluminum-silicon ratio |
-
2013
- 2013-12-06 CN CN201310656066.1A patent/CN104692412A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080154083A1 (en) * | 2002-02-05 | 2008-06-26 | Xingtao Gao | Hydrocarbon conversion using nanocrystalline zeolite Y |
| 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 |
| CN102198950A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve with high aluminum-silicon ratio |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439167A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing 3A molecular sieve from potassium feldspar |
| CN107399743A (en) * | 2016-05-20 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of preparation method of NaY molecular sieve |
| CN107777698B (en) * | 2016-08-30 | 2020-09-04 | 中国石油化工股份有限公司 | B-NaY molecular sieve and preparation method and application thereof |
| CN107777698A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | B NaY molecular sieves and its production and use |
| RU2627900C1 (en) * | 2016-12-05 | 2017-08-14 | Федеральное государственное бюджетное учреждение науки Институт проблем переработки углеводородов Сибирского отделения Российской академии наук (ИППУ СО РАН) | Method of preparing microcrystalline nay zeolite |
| CN108529644A (en) * | 2017-03-01 | 2018-09-14 | 中国石油天然气集团公司 | A kind of NaY molecular sieve and preparation method thereof |
| CN108529644B (en) * | 2017-03-01 | 2020-12-25 | 中国石油天然气集团公司 | NaY molecular sieve and preparation method thereof |
| CN108569705B (en) * | 2017-03-14 | 2021-02-05 | 中国石油天然气集团公司 | NaY type molecular sieve with high silicon-aluminum ratio and preparation method thereof |
| CN108569705A (en) * | 2017-03-14 | 2018-09-25 | 中国石油天然气集团公司 | A kind of high silica alumina ratio NaY type molecular sieve and preparation method thereof |
| CN108862309B (en) * | 2017-05-11 | 2020-12-08 | 中国石油大学(北京) | NaY molecular sieve aggregate with nano-micro structure and preparation method thereof |
| CN108862309A (en) * | 2017-05-11 | 2018-11-23 | 中国石油大学(北京) | A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure |
| CN110078093A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of NaY molecular sieve and its preparation method and application |
| CN110078084A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of high silicon aluminium ratio small crystal NaY molecular sieve and preparation method thereof |
| CN110078084B (en) * | 2018-01-25 | 2020-12-08 | 中国石油天然气集团有限公司 | High-silica-alumina-ratio small-grain NaY molecular sieve and preparation method thereof |
| CN110078093B (en) * | 2018-01-25 | 2022-02-01 | 中国石油天然气集团有限公司 | NaY molecular sieve and preparation method and application thereof |
| CN109264743A (en) * | 2018-11-23 | 2019-01-25 | 福州大学 | A kind of preparation method of little crystal grain high silica alumina ratio NaY molecular sieve |
| CN112744840A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | NaY molecular sieve synthesis device and NaY molecular sieve synthesis method |
| CN112744840B (en) * | 2019-10-31 | 2023-02-07 | 中国石油化工股份有限公司 | NaY molecular sieve synthesis device and NaY molecular sieve synthesis method |
| CN111410206A (en) * | 2020-04-13 | 2020-07-14 | 邹凌峰 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104692412A (en) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve | |
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| CN104525245B (en) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application | |
| CN107640775B (en) | Method for preparing ZSM-5 molecular sieve by using solid waste | |
| CN101177282A (en) | Method for synthesizing high-crystallinity ZSM-5 molecular sieve without organic template | |
| CN103204516A (en) | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio | |
| CN109701619A (en) | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method | |
| CN104556094A (en) | Y/Silicalite-1 composite molecular sieve and preparation method thereof | |
| CN110217804B (en) | ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method | |
| CN102198950B (en) | Method for preparing NaY molecular sieve with high aluminum-silicon ratio | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN101993091B (en) | Method for synthesizing ZSM-5 zeolite | |
| CN106276950B (en) | A method of preparing NU-88 molecular sieve | |
| CN103140445A (en) | Hydrothermal synthesis of zeolites or zeolite-like materials using modified mixed oxides | |
| CN100390060C (en) | High-silica octagonal zeolite and synthesizing method thereof | |
| CN112174164B (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN102701232B (en) | Preparation method of NaY molecular sieve | |
| CN104649294B (en) | Method for improving relative crystallinity of synthetic NaY zeolite | |
| CN110790283A (en) | Synthesis method of mordenite with high silicon-aluminum ratio | |
| CN106830005A (en) | The method of the zeolite molecular sieves of solvent-free route high temperature Fast back-projection algorithm EU 1 | |
| CN101723395B (en) | Method for preparing double-micropore composite molecular sieve | |
| CN106976889B (en) | Si-Al zeolite molecular sieve and preparation method thereof with BOG structure | |
| CN103204505B (en) | Preparation method of aluminum-containing layered kenyaite | |
| CN102259890B (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof | |
| CN105776245A (en) | Synthesis method of ZSM-5 molecular sieve and application of ZSM-5 molecular sieve in methanol synthesis to prepare propylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150610 |