CN106673000B - The synthetic method of ZSM-11 molecular sieves containing rare earth metal and its molecular sieve of synthesis - Google Patents
The synthetic method of ZSM-11 molecular sieves containing rare earth metal and its molecular sieve of synthesis Download PDFInfo
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Abstract
The synthetic method of the ZSM-11 molecular sieves containing rare earth metal that the present invention relates to a kind of and its molecular sieve of synthesis.The method includes making silicon source, silicon source, alkali source, rare earth metal source, organic formwork agent and water contact under crystallization condition, the step of to obtain molecular sieve；Optionally, the step of roasting the molecular sieve of the acquisition；Wherein, the organic formwork agent R is selected from least one of 1,3- hexamethylenes dimethylamine or Isosorbide-5-Nitrae-hexamethylene dimethylamine, can be used in the industrial production of the ZSM-11 molecular sieves containing rare earth metal.
Description
Technical field
The synthetic method of the ZSM-11 molecular sieves containing rare earth metal that the present invention relates to a kind of and its molecular sieve of synthesis.
Background technology
ZSM-11 molecular sieves are synthesized for the first time the 1970s by mobil oil oil company (Mobil).Subsequently grind
Study carefully and find that ZSM-11 molecular sieves belong to tetragonal crystal system, ZSM-11 belongs to Pentasil families with ZSM-5 molecular sieve.Two kinds of molecules
The structure similarity of sieve is the laminated structure that secondary structure unit has same form；The difference is that neighboring secondary knot
The symmetry of structure unit between layers is different.ZSM-5 meets symmetrical centre correlation；And ZSM-11 meets minute surface correlation, has
It is parallel to the ten-ring two dimension straight hole road in the directions a and the directions b, pore size is 0.54nm × 0.53nm.Compare ZSM-11 molecules
Sieve finds that the XRD spectra of the two has differences at 2 θ=22.4~24.8 ° and 44.5~46 °, sees below with ZSM-5 molecular sieve
Table.
ZSM-11 is compared with ZSM-5 molecular sieve XRD diffraction maximums
Because the pore size of ZSM-11 molecular sieves is less than ZSM-5 molecular sieve, in small molecule selects the reaction of type selective catalysis
It may show catalytic performance more better than ZSM-5 molecular sieve.
The synthesis of ZSM-11 molecular sieves uses tetrabutylammonium bromide or tetrabutylammonium hydroxide for organic formwork agent.The U.S. is special
Sharp US3709979 discloses a kind of using tetraalkyl cation (R4X+, X is N or P, and R is alkyl, can be methyl, ethyl, third
Base, butyl, benzyl or triphenyl) do the method that template synthesizes ZSM-11 molecular sieves.Chinese patent CN201210003750 is public
A kind of method for using tetrabutylammonium bromide for organic formwork agent, while adding crystal seed synthesis ZSM-11 molecular sieves is opened.China
Patent CN201310697846, which is disclosed, a kind of uses tetrabutylammonium hydroxide and 1,8- octamethylenediamines to be closed for compound organic formwork agent
At the method for ZSM-11 molecular sieves.Chinese patent CN201410322401 discloses a kind of using tetrabutylammonium hydroxide or four fourths
Base ammonium bromide is the method that organic formwork agent synthesizes the ZSM-11 molecular sieves containing B element.Chinese patent CN102464335 is disclosed
It is a kind of to use tetrabutylammonium bromide or tetrabutylammonium hydroxide for organic formwork agent, while adding the synthesis of EU-1 molecular sieve seeds
The method of ZSM-11 molecular sieves.Chinese patent CN201110214475, which is disclosed, a kind of uses tetrabutylammonium hydroxide for template
The method that fractional crystallization synthesizes ZSM-11 molecular sieves.
However, Mark E.Davis et al. are the study found that use tetrabutylammonium bromide or tetrabutylammonium hydroxide for template
The ZSM-11 molecular sieves of agent synthesis are not pure phase, but the not net product (Microporous containing ZSM-5 molecular sieve crystalline phase
and Mesoporous Materials,49(2001)163-169).Wherein the content of ZSM-5 molecular sieve can be up to 20 weights
Measure %.
Invention content
One of the object of the invention is intended to provide a kind of synthetic method of the new ZSM-11 molecular sieves containing rare earth metal.The party
The ZSM-11 molecular sieves containing rare earth metal of method synthesis have the characteristics that product purity is high.The two of the object of the invention are intended to provide one
The ZSM-11 molecular sieves containing rare earth metal of kind the method synthesis.
One of for achieving the above object, the technical solution adopted by the present invention is as follows：A kind of ZSM- containing rare earth metal
The synthetic method of 11 molecular sieves, being included under crystallization condition makes silicon source, silicon source, alkali source, rare earth metal source, organic formwork agent and water
Contact, the step of to obtain molecular sieve；Optionally, the step of roasting the molecular sieve of the acquisition；Wherein, the organic formwork
Agent R is selected from least one of 1,3- hexamethylenes dimethylamine or 1,4- hexamethylene dimethylamine.
In above-mentioned technical proposal, the silicon source, source of aluminium, the alkali source, the rare earth metal source, the organic formwork
The molar ratio of agent R and water is 1：(0.0005~0.05)：(0~0.2)：(0.001~0.1)：(0.05~2.0)：(5~100)；
Preferably 1：(0.005~0.04)：(0.01~0.1)：(0.002~0.05)：(0.1~1.0)：(10~50)；More preferably
1：(0.01~0.03)：(0.01~0.09)：(0.005~0.04)：(0.1~0.8)：(12~50).
In above-mentioned technical proposal, the crystallization condition includes：130~190 DEG C of crystallization temperature, crystallization time 1~10 day；It is excellent
It is selected as 145~175 DEG C of crystallization temperature, crystallization time 2~7 days.
In above-mentioned technical proposal, the roasting condition includes：300~800 DEG C of calcination temperature, roasting time 1~10 hour；
Preferably 400~650 DEG C of calcination temperature, roasting time 3~6 hours；Calcination atmosphere is air or oxygen.
In above-mentioned technical proposal, the silicon source is selected from silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, water glass
At least one of glass or white carbon；It is preferably selected from least one of silicic acid, silica gel, Ludox or silicic acid tetraalkyl ester.
In above-mentioned technical proposal, source of aluminium is selected from aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate, aluminum sulfate, kaolin
Or at least one of montmorillonite；It is preferably selected from least one of aluminium hydroxide, sodium aluminate or aluminum nitrate.
In above-mentioned technical proposal, the alkali source is selected from the alkali for cation with alkali or alkaline earth metal；Preferably hydrogen-oxygen
Change sodium.
In above-mentioned technical proposal, the rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium, preferably lanthanum or cerium, more preferable lanthanum.
In above-mentioned technical proposal, in hydrochloride, nitrate or sulfate of the rare earth metal source selected from rare earth metal
It is at least one；It is preferably selected from least one of hydrochloride or the nitrate of rare earth metal；Further preferably it is selected from chlorination
At least one of lanthanum or lanthanum nitrate.
In above-mentioned technical proposal, mode of heating use direct-fired mode, either by the way of microwave heating or
Using the complex method directly heated with microwave heating；It is preferred that using direct-fired mode.
For achieving the above object two, the technical solution adopted by the present invention is as follows：A kind of ZSM- containing rare earth metal
11 molecular sieves, the impurity content in zeolite product are not higher than 10 weight %, preferably no greater than 5 weight %, more preferably no higher than 3
Weight %；The rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium, preferably lanthanum or cerium, more preferable lanthanum.
In above-mentioned technical proposal, the impurity in zeolite product is selected from the unformed SiO containing rare earth metal2, be different from
At least one of at least one molecular sieve of ZSM-11, metal oxide, quartz, tridymite, cristobalite；It is preferably selected from and contains
The unformed SiO of rare earth metal2, ZSM-5, ZSM-23, ZSM-22, Beta, MCM-22, MOR, Y type, X-type, in A type molecular sieve
At least one；The more preferably unformed SiO containing rare earth metal2, at least one of ZSM-5.
In above-mentioned technical proposal, the existence form of the impurity in zeolite product include in physical mixed, cocrystallization extremely
Few one kind.
In above-mentioned technical proposal, it is preferable that the impurity in zeolite product be in the form of cocrystallization existing for content it is not high
In the ZSM-5 molecular sieve containing rare earth metal of 10 weight %.
In above-mentioned technical proposal, in the ZSM-11 molecular sieves containing rare earth metal, the content of rare earth metal is 0.1~10
Weight %.
The method of the present invention is used selected from least one of 1,3- hexamethylenes dimethylamine or 1,4- hexamethylene dimethylamine as organic
Template, has directly synthesized ZSM-11 zeolite product of the high-purity containing rare earth metal, the ZSM-11 containing rare earth metal in product
Molecular sieve purity can be up to 98 weight %.The method of the present invention is simple, and raw material is cheap, is suitble to large-scale industrial production, achieves
Preferable technique effect.
Description of the drawings
Fig. 1 is【Embodiment 1】The XRD spectrum of the ZSM-11 molecular sieves containing rare earth metal of synthesis.
Fig. 2 is【Comparative example 1】The XRD spectrum of the ZSM-11 molecular sieves containing rare earth metal of synthesis.
【Embodiment 1】With【Comparative example 1】In two samples XRD spectra in Nearby there is diffraction maximum, the feature diffraction of these diffraction maximums and the ZSM-11 molecular sieves containing rare earth metal
Peak coincide.However,【Comparative example 1】In sample XRD spectra in(2 θ=24.45 °) nearby have more existing
One diffraction maximum (arrow indicates in figure) for corresponding to the ZSM-5 molecular sieve containing rare earth metal, as the ZSM-11 containing rare earth metal
When the ZSM-5 molecular sieve impurity content containing rare earth metal in molecular sieve is more than 10 mass %, the peak is high-visible, this shows
【Comparative example 1】In sample contain the ZSM-5 molecular sieve crystalline phase containing rare earth metal.
The present invention will be further described below by way of examples.
Specific implementation mode
In the context of the present specification, the existence form of so-called impurity, including physical mixed, cocrystallization.Wherein, physics
Mixing refers to the ZSM-11 molecular sieve crystals containing rare earth metal and between impurity without chemical interaction；Cocrystallization refers to containing rare earth metal
ZSM-11 zeolite products crystal in simultaneously comprising the ZSM-11 molecular sieves containing rare earth metal structure cell and impurity structure cell.
In the context of the present specification, it is included in embodiment below and comparative example, rare earth is contained in zeolite product
The measurement method of the ZSM-11 molecular sieve crystal contents of metal is：Have difference containing rare earth metal using the simulation of DIFFaX softwares
The powder X-ray RD spectrograms of the ZSM-11 molecular sieves of ZSM-11 crystalline phases and ZSM-5 crystal contents containing rare earth metal, by embodiment and right
ZSM-11 zeolite products obtained by ratio containing rare earth metal compare to obtain molecular sieve production with the spectrogram simulated by DIFFaX softwares
The content of ZSM-11 molecular sieves containing rare earth metal in product.
In the case where not clearly indicating, all percentages, number, the ratio etc. that are previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when on the basis of weight.
【Embodiment 1】
By sodium aluminate (Al2O343.0 weight %, Na235.0 weight % of O) 18.6 grams, sodium hydroxide (96.0 weight %)
11.9 grams, 1980.0 grams of deionized water, lanthanum chloride (hydration, La2O345.0 weight %) 23.88 grams, 1,3- hexamethylene dimethylamine
234.7 grams of (99.0 weight %) and Ludox (SiO240.0 weight %) 825.0 grams be uniformly mixed, the material proportion of reactant
(molar ratio) is：
SiO2/Al2O3=70
1,3- hexamethylenes dimethylamine/SiO2=0.3
NaOH/SiO2=0.09
La2O3/SiO2=0.006
H2O/SiO2=25
After mixing, it is fitted into stainless steel cauldron, under agitation in 150 DEG C of crystallization 3 days.Mistake after crystallization
Filter, washing, drying, then 5 hours ZSM-11 molecular sieves that must contain lanthanum are roasted in 550 DEG C of air.ZSM-11 containing lanthanum in product
Molecular sieve content is 94 weight %.The content of lanthanum is 2.7 weight % in product.
【Embodiment 2】
Together【Embodiment 1】, only the material proportion (molar ratio) of reactant be：SiO2/Al2O3=70,1,3- hexamethylene diformazan
Amine/SiO2=0.2, NaOH/SiO2=0.08, La2O3/SiO2=0.005, H2O/SiO2=30, in 150 DEG C of crystallization 60 hours.
The ZSM-11 molecular sieve contents containing lanthanum are 97 weight % in product.The content of lanthanum is 2 weight % in product.
【Embodiment 3】
Together【Embodiment 1】, only use lanthanum nitrate for rare earth metal source, the material proportion (molar ratio) of reactant is：
SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=0.4, NaOH/SiO2=0.09, La2O3/SiO2=0.004, H2O/
SiO2=25, in 150 DEG C of crystallization 70 hours.The ZSM-11 molecular sieve contents containing lanthanum are 96 weight % in product.Lanthanum in product
Content is 1.7 weight %.
【Embodiment 4】
Together【Embodiment 1】, only use lanthanum nitrate for rare earth metal source, the material proportion (molar ratio) of reactant is：
SiO2/Al2O3=60,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.08, La2O3/SiO2=0.002, H2O/
SiO2=25, in 150 DEG C of crystallization 70 hours.The ZSM-11 molecular sieve contents containing lanthanum are 95 weight % in product.Lanthanum in product
Content is 0.9 weight %.
【Embodiment 5】
Together【Embodiment 1】, only use cerous sulfate (Ce (SO4)2·4H2O it is) rare earth metal source, the material of reactant is matched
It is than (molar ratio)：SiO2/Al2O3=50,1,3- hexamethylene dimethylamine/SiO2=0.5, NaOH/SiO2=0.07, CeO2/SiO2
=0.002, H2O/SiO2=25, in 150 DEG C of crystallization 3 days.The ZSM-11 molecular sieve contents containing cerium are 98 weight % in product.Production
The content of cerium is 0.9 weight % in product.
【Embodiment 6】
Together【Embodiment 1】, only use aluminum sulfate for silicon source, the material proportion (molar ratio) of reactant is：SiO2/Al2O3
=70,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.07, La2O3/SiO2=0.005, H2O/SiO2=20,
150 DEG C of crystallization 70 hours.The ZSM-11 molecular sieve contents containing lanthanum are 97 weight % in product.The content of lanthanum is 2.1 weights in product
Measure %.
【Embodiment 7】
Together【Embodiment 6】, only use lanthanum nitrate for rare earth metal source, the material proportion (molar ratio) of reactant is：
SiO2/Al2O3=50,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.08, La2O3/SiO2=0.007, H2O/
SiO2=23, in 150 DEG C of crystallization 70 hours.The ZSM-11 molecular sieve contents containing lanthanum are 97 weight % in product.Lanthanum in product
Content is 3.2 weight %.
【Embodiment 8】
Together【Embodiment 1】, only use aluminum nitrate for silicon source, the material proportion (molar ratio) of reactant is：SiO2/Al2O3
=40,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.09, La2O3/SiO2=0.008, H2O/SiO2=20,
150 DEG C of crystallization 70 hours.The ZSM-11 molecular sieve contents containing lanthanum are 96 weight % in product.The content of lanthanum is 3.6 weights in product
Measure %.
【Embodiment 9】
Together【Embodiment 1】, only use Isosorbide-5-Nitrae-hexamethylene dimethylamine for template, the material proportion (molar ratio) of reactant
For：SiO2/Al2O3=70, Isosorbide-5-Nitrae-hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.09, La2O3/SiO2=0.002,
H2O/SiO2=20, in 150 DEG C of crystallization 72 hours.The ZSM-11 molecular sieve contents containing lanthanum are 98 weight % in product.Lanthanum in product
Content be 0.9 weight %.
【Embodiment 10】
Together【Embodiment 1】, it is template only to use the mixture of 1,3- hexamethylenes dimethylamine and Isosorbide-5-Nitrae-hexamethylene dimethylamine, instead
The material proportion (molar ratio) of object is answered to be：SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=0.2, Isosorbide-5-Nitrae-hexamethylene diformazan
Amine/SiO2=0.2, NaOH/SiO2=0.09, La2O3/SiO2=0.0025, H2O/SiO2=20, in 150 DEG C of crystallization 72 hours.
The ZSM-11 molecular sieve contents containing lanthanum are 98 weight % in product.The content of lanthanum is 1.1 weight % in product.
【Comparative example 1】
Use tetrabutylammonium hydroxide for template, by 204 grams of tetrabutylammonium hydroxide aqueous solutions (TBAOH, 10 weights
Measure %) and 2.87 grams of aluminium hydroxide (Al2O3, 35 weight %) and mixing, molar ratio TBAOH/Al2O3=8, it is small in 150 DEG C of reactions 20
When, 47 grams of silica gel (SiO are added later2, 98.4 weight %), 2.4 grams of ZSM-11 crystal seeds and 1.67 grams of lanthanum chlorides (hydration,
La2O345.0 weight %) mixing, obtaining mixture molar ratio is：SiO2/Al2O3=80, TBAOH/SiO2=0.1, H2O/SiO2=
13, La2O3/SiO2=0.003, in 110 DEG C of constant temperature 5 hours, then it is warming up to 150 DEG C of crystallization 48 hours.Through being filtered, washed, doing
ZSM-11 zeolite products are obtained after dry, roasting, the ZSM-11 molecular sieve contents containing lanthanum are 88 weight % in product.Lanthanum in product
Content is 1.3 weight %.
Claims (17)
1. a kind of synthetic method of the ZSM-11 molecular sieves containing rare earth metal, being included under crystallization condition makes silicon source, silicon source, alkali
Source, rare earth metal source, organic formwork agent and water contact, the step of to obtain molecular sieve；Optionally, point of the acquisition is roasted
The step of son sieve；Wherein, the organic formwork agent R is selected from least one in 1,3- hexamethylenes dimethylamine or Isosorbide-5-Nitrae-hexamethylene dimethylamine
Kind；
The silicon source, source of aluminium, the alkali source, the rare earth metal source, the organic formwork agent R and water molar ratio be 1：
(0.0005~0.05)：(0~0.2)：(0.001~0.1)：(0.05~2.0)：(5~100), wherein the alkali source dosage is not
It is 0；
The crystallization condition includes：130~190 DEG C of crystallization temperature, crystallization time 1~10 day；
And the roasting condition includes：300~800 DEG C of calcination temperature, roasting time 1~10 hour, calcination atmosphere is air
Or oxygen.
2. the synthetic method of the ZSM-11 molecular sieves according to claim 1 containing rare earth metal, which is characterized in that the silicon
Source is selected from least one of silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, waterglass or white carbon；The aluminium
Source is selected from least one of aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate, aluminum sulfate, kaolin or montmorillonite；The alkali source
Selected from the alkali with alkali or alkaline earth metal for cation；The rare earth metal source is selected from hydrochloride, the nitrate of rare earth metal
Or at least one of sulfate；The rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium.
3. the synthetic method of the ZSM-11 molecular sieves according to claim 2 containing rare earth metal, which is characterized in that described dilute
Earth metal is selected from lanthanum or cerium.
4. the synthetic method of the ZSM-11 molecular sieves according to claim 2 containing rare earth metal, which is characterized in that described dilute
Earth metal is lanthanum.
5. the synthetic method of the ZSM-11 molecular sieves according to claim 1 containing rare earth metal, which is characterized in that the silicon
Source, source of aluminium, the alkali source, the rare earth metal source, the organic formwork agent R and water molar ratio be 1：(0.005~
0.04)：(0.01~0.1)：(0.002~0.05)：(0.1~1.0)：(10~50)；
The crystallization condition includes：145~175 DEG C of crystallization temperature, crystallization time 2~7 days；
And the roasting condition includes：400~650 DEG C of calcination temperature, roasting time 3~6 hours；
The silicon source is selected from least one of silicic acid, silica gel, Ludox or silicic acid tetraalkyl ester；Source of aluminium is selected from hydroxide
At least one of aluminium, sodium aluminate or aluminum nitrate；The alkali source is selected from sodium hydroxide.
6. the synthetic method of the ZSM-11 molecular sieves according to claim 5 containing rare earth metal, which is characterized in that the silicon
Source, source of aluminium, the alkali source, the rare earth metal source, the organic formwork agent R and water molar ratio be 1：(0.01~
0.03)：(0.01~0.09)：(0.005~0.04)：(0.1~0.8)：(12~50).
7. the synthetic method of the ZSM-11 molecular sieves according to claim 1 containing rare earth metal, which is characterized in that heating side
Formula uses direct-fired mode, either compound with microwave heating by the way of microwave heating or using directly heating
Mode.
8. the ZSM-11 molecular sieves containing rare earth metal of any the method synthesis of claim 1~7, which is characterized in that molecule
The impurity content sieved in product is not higher than 10 weight %；The rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium.
9. the ZSM-11 molecular sieves according to claim 8 containing rare earth metal, which is characterized in that miscellaneous in zeolite product
Matter content is not higher than 5 weight %.
10. the ZSM-11 molecular sieves according to claim 8 containing rare earth metal, which is characterized in that in zeolite product
Impurity content is not higher than 3 weight %.
11. the ZSM-11 molecular sieves according to claim 8 containing rare earth metal, which is characterized in that the rare earth metal choosing
From lanthanum or cerium.
12. the ZSM-11 molecular sieves according to claim 8 containing rare earth metal, which is characterized in that the rare earth metal is
Lanthanum.
13. the ZSM-11 molecular sieves according to claim 8 containing rare earth metal, which is characterized in that in zeolite product
Impurity is selected from the unformed SiO containing rare earth metal2, at least one molecular sieve different from ZSM-11, metal oxide, quartz,
At least one of tridymite, cristobalite.
14. the ZSM-11 molecular sieves according to claim 13 containing rare earth metal, which is characterized in that in zeolite product
Impurity is selected from the unformed SiO containing rare earth metal2, ZSM-5, ZSM-23, ZSM-22, Beta, MCM-22, MOR, Y type, X-type, A
At least one of type molecular sieve.
15. the ZSM-11 molecular sieves according to claim 13 containing rare earth metal, which is characterized in that in zeolite product
Impurity is selected from the unformed SiO containing rare earth metal2, at least one of ZSM-5.
16. according to any ZSM-11 molecular sieves containing rare earth metal of claim 8~15, which is characterized in that molecular sieve
The existence form of impurity in product includes at least one of physical mixed, cocrystallization.
17. according to any ZSM-11 molecular sieves containing rare earth metal of claim 8~15, which is characterized in that molecular sieve
Impurity in product be in the form of cocrystallization existing for content be not higher than 10 weight % the ZSM-5 molecular sieve containing rare earth metal.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1137022A (en) * | 1994-12-30 | 1996-12-04 | 中国石油化工总公司 | Rare-earth-ZSM5/ZSM11 cocrystallization zeolite |
| CN101717095A (en) * | 2009-12-23 | 2010-06-02 | 中国科学院大连化学物理研究所 | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite |
-
2015
- 2015-11-09 CN CN201510753645.7A patent/CN106673000B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1137022A (en) * | 1994-12-30 | 1996-12-04 | 中国石油化工总公司 | Rare-earth-ZSM5/ZSM11 cocrystallization zeolite |
| CN101717095A (en) * | 2009-12-23 | 2010-06-02 | 中国科学院大连化学物理研究所 | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite |
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