CN106672999B - The synthetic method of ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal and its composite molecular screen of synthesis - Google Patents
The synthetic method of ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal and its composite molecular screen of synthesis Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic method of ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal and its composite molecular screens of synthesis.The method includes making silicon source, silicon source, alkali source, halogen 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/ZSM-5 composite molecular screens containing halogen and rare earth metal.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal and its
The composite molecular screen 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.
Invention content
One of the object of the invention is intended to provide a kind of new ZSM-11/ZSM-5 compound molecules containing halogen and rare earth metal
The synthetic method of sieve.The ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal of this method synthesis have containing halogen and
The ZSM-11 crystal contents of rare earth metal are high, and the controllable range of the content of the ZSM-11 crystalline phases containing halogen and rare earth metal is wide
The characteristics of.The two of the object of the invention are intended to provide a kind of ZSM-11/ZSM-5 containing halogen and rare earth metal of the method synthesis
Composite molecular screen.
One of for achieving the above object, the technical solution adopted by the present invention is as follows：One kind containing halogen and rare earth metal
ZSM-11/ZSM-5 composite molecular screens synthetic method, being included under crystallization condition makes silicon source, silicon source, alkali source, halogen source, dilute
Earth metal source, organic formwork agent and water contact, the step of to obtain molecular sieve；Optionally, the molecular sieve of the acquisition is roasted
The step of；Wherein, the organic formwork agent R is selected from least one of 1,3- hexamethylenes dimethylamine or Isosorbide-5-Nitrae-hexamethylene dimethylamine.
In above-mentioned technical proposal, the silicon source, source of aluminium, the alkali source, the halogen source, the rare earth metal source,
The molar ratio of the organic formwork agent R and water is 1：(0.0005~0.05)：(0.001~0.8)：(0.001~0.2)：
(0.001~0.1)：(0.05~2.0)：(5~100)；Preferably 1：(0.005~0.04)：(0.05~0.6)：(0.01~
0.1)：(0.002~0.05)：(0.05~1.0)：(10~50)；More preferably 1：(0.003~0.025)：(0.09~0.5)：
(0.01~0.1)：(0.005~0.04)：(0.08~0.8)：(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 2~10 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 halogen source is selected from ammonium fluoride, sodium fluoride, potassium fluoride, sodium chloride, ammonium chloride, chlorination
At least one of potassium, sodium bromide, ammonium bromide, potassium bromide, sodium iodide, ammonium iodide or potassium iodide；It is preferably selected from ammonium fluoride, fluorine
Change at least one of sodium, potassium fluoride, sodium chloride, ammonium chloride or potassium chloride；Further preferably be selected from ammonium fluoride, sodium fluoride or
At least one of potassium fluoride.
In above-mentioned technical proposal, in hydrochloride of the rare earth metal source selected from rare earth metal, nitrate, sulfate extremely
Few one kind；It is preferably selected from least one of hydrochloride, the nitrate of rare earth metal；Further preferably be selected from lanthanum chloride,
At least one of lanthanum nitrate.
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, 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：One kind containing halogen and rare earth metal
ZSM-11/ZSM-5 composite molecular screens, in the composite molecular screen, the content of the ZSM-11 crystalline phases containing halogen and rare earth metal
Not less than 90 weight %, preferably 75 weight %, more preferable 60 weight %, more preferable 45 weight %, more preferable 30 weight %；It is described
Rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium, preferably lanthanum or cerium, more preferable lanthanum.
In above-mentioned technical proposal, impurity is contained in the composite molecular screen, impurity content is not higher than 10 weight %, preferably not
Higher than 5 weight %, more preferably no higher than 3 weight %.
In above-mentioned technical proposal, the impurity is selected from the unformed SiO containing halogen and rare earth metal2, be different from ZSM-11
With at least one of at least one molecular sieve of ZSM-5, metal oxide, halide, quartz, tridymite, cristobalite.It is preferred that
Unformed SiO containing halogen and rare earth metal2, ZSM-23, ZSM-22, Beta, MCM-22, MOR, Y type, X-type, A type molecular sieve
At least one of；The more preferably unformed SiO containing halogen and rare earth metal2, at least one of MOR.
In above-mentioned technical proposal, the ZSM-11/ZSM-5 compound molecules containing halogen and rare earth metal in the composite molecular screen
The existence form of sieve and impurity includes at least one of physical mixed, cocrystallization.
In above-mentioned technical proposal, it is preferable that the impurity is that content contains halogen and rare earth metal not higher than 10 weight %
Unformed SiO2。
In above-mentioned technical proposal, in the ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal, halogen
Content is 0.01~10 weight %, and 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 the high-purity ZSM-11/ZSM-5 composite molecular screen products containing halogen and rare earth metal, has contained in product
The purity of the ZSM-11/ZSM-5 composite molecular screens of halogen and rare earth metal can be up to 98 weight %, contain halogen and rare earth metal
ZSM-11 crystalline phases content it is adjustable within the scope of 30~98 weight %.The method of the present invention is simple, and raw material is cheap, is suitble to extensive
Industrial production achieves preferable technique effect.
Description of the drawings
Fig. 1 is【Embodiment 1】The XRD diagram of the ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal of synthesis
Spectrum.
The present invention will be further described below by way of examples.
Specific implementation mode
In the context of the present specification, so-called ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal and miscellaneous
The existence form of matter, including physical mixed, cocrystallization.Wherein, physical mixed refers to the ZSM-11/ZSM- containing halogen and rare earth metal
Without chemical interaction between 5 composite molecular screen crystal and impurity；Cocrystallization refers to the ZSM-11/ZSM- containing halogen and rare earth metal
Include the structure cell of the ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal in the crystal of 5 composite molecular screen products simultaneously
With the structure cell of impurity.
In the context of the present specification, it is included in embodiment below and comparative example, contains in composite molecular screen product
The assay method of the ZSM-11 molecular sieve crystal contents of halogen and rare earth metal is：It is simulated using DIFFaX softwares and is contained with difference
The ZSM-11 crystalline phases of halogen and rare earth metal and the ZSM-5 crystal contents containing halogen and rare earth metal contain halogen and rare earth metal
ZSM-11/ZSM-5 composite molecular screens powder X-ray RD spectrograms, by the ZSM-11/ containing halogen and rare earth metal obtained by embodiment
ZSM-5 composite molecular screens product and the spectrogram simulated by DIFFaX softwares compare to obtain in composite molecular screen product containing halogen and dilute
The content of the ZSM-11 molecular sieves of earth metal.
In the context of the present specification, it is included in embodiment below and comparative example, it is miscellaneous in composite molecular screen product
The assay method of the content of matter is：Content based on object phase is directly proportional to the X-ray diffraction peak intensity of the object phase, by XRD spectra
In the peak intensities of all diffraction maximums be added, obtain total I, ZSM-11 containing halogen and rare earth metal will be corresponded in spectrogram and contain halogen
It is added with the peak intensity of the characteristic diffraction peak of the ZSM-5 molecular sieve of rare earth metal, obtains total I ', (1-I '/I) × 100% is
Impurity content 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, 10.2 grams of ammonium fluoride, lanthanum chloride (hydration, La2O345.0 weight %) 23.88 grams, 1,3-
234.7 grams of hexamethylene dimethylamine (99.0 weight %) and Ludox (SiO240.0 weight %) 825.0 grams be uniformly mixed, reactant
Material proportion (molar ratio) is：
SiO2/Al2O3=70
1,3- hexamethylenes dimethylamine/SiO2=0.3
NaOH/SiO2=0.09
NH4F/SiO2=0.05
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 the fluorine-containing ZSM-11/ZSM-5 composite molecular screens with lanthanum are roasted 5 hours to obtain in 550 DEG C of air.Product
In the ZSM-11 molecular sieve contents of fluorine-containing and lanthanum be 94 weight %, impurity content is 1 weight %, and the content of fluorine is 1.0 weight %,
The content of lanthanum is 2.7 weight %.
【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=0.15, NH4F/SiO2=0.02, La2O3/SiO2=0.005, H2O/SiO2=30,
150 DEG C of crystallization 72 hours.Fluorine-containing and lanthanum ZSM-11 molecular sieve contents are 80 weight % in product, and impurity content is 1 weight %,
The content of fluorine is 0.4 weight %, and the content of lanthanum is 2 weight %.
【Embodiment 3】
Together【Embodiment 1】, it for halogen source, lanthanum nitrate is rare earth metal source only to use ammonium chloride, and the material of reactant is matched
It is than (molar ratio)：SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=0.4, NaOH/SiO2=0.18, NH4Cl/SiO2
=0.1, La2O3/SiO2=0.004, H2O/SiO2=25, in 150 DEG C of crystallization 70 hours.ZSM-11 points containing chlorine and lanthanum in product
Son sieve content is 50 weight %, and impurity content is 0.5 weight %, and the content of chlorine is 5.5 weight %, and the content of lanthanum is 1.7 weights
Measure %.
【Embodiment 4】
Together【Embodiment 1】, it for halogen source, lanthanum nitrate is rare earth metal source only to use ammonium chloride, and the material of reactant is matched
It is than (molar ratio)：SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.28, NH4Cl/SiO2
=0.01, La2O3/SiO2=0.002, H2O/SiO2=25, in 150 DEG C of crystallization 70 hours.ZSM-11 containing chlorine and lanthanum in product
Molecular sieve content is 40 weight %, and impurity content is 2 weight %, and the content of chlorine is 0.6 weight %, and the content of lanthanum is 0.9 weight
Measure %.
【Embodiment 5】
Together【Embodiment 1】, only use ammonium chloride for halogen source, cerous sulfate (Ce (SO4)2·4H2O) it is rare earth metal source,
The material proportion (molar ratio) of reactant is：SiO2/Al2O3=50,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=
0.18, NH4Cl/SiO2=0.04, CeO2/SiO2=0.002, H2O/SiO2=25, in 150 DEG C of crystallization 3 days.In product containing chlorine and
The ZSM-11 molecular sieve contents of cerium are 79 weight %, and impurity content is 1 weight %, and the content of chlorine is 2.2 weight %, the content of cerium
For 0.9 weight %.
【Embodiment 6】
Together【Embodiment 1】, only use aluminum sulfate for silicon source, the material proportion (molar ratio) of reactant is：SiO2/Al2O3
=200,1,3- hexamethylene dimethylamine/SiO2=0.2, NaOH/SiO2=0.35, NH4F/SiO2=0.06, La2O3/SiO2=
0.005, H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.Fluorine-containing and lanthanum ZSM-11 molecular sieve contents are 65 weights in product
% is measured, impurity content is 2 weight %, and the content of fluorine is 1.2 weight %, and the content of lanthanum is 2.1 weight %.
【Embodiment 7】
Together【Embodiment 6】, it for halogen source, lanthanum nitrate is rare earth metal source only to use ammonium chloride, and the material of reactant is matched
It is than (molar ratio)：SiO2/Al2O3=80,1,3- hexamethylene dimethylamine/SiO2=0.5, NaOH/SiO2=0.6, NH4Cl/SiO2
=0.02, La2O3/SiO2=0.007, H2O/SiO2=23, in 150 DEG C of crystallization 60 hours.ZSM-11 containing chlorine and lanthanum in product
Molecular sieve content is 57 weight %, and impurity content is 3 weight %, and the content of chlorine is 1.1 weight %, and the content of lanthanum is 3.2 weights
Measure %.
【Embodiment 8】
Together【Embodiment 1】, it for silicon source, ammonium chloride is halogen source only to use aluminum nitrate, the material proportion of reactant (mole
Than) be：SiO2/Al2O3=90,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.19, NH4Cl/SiO2=0.06,
La2O3/SiO2=0.008, H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.ZSM-11 molecular sieves containing chlorine and lanthanum in product contain
Amount is 85 weight %, and impurity content is 2 weight %, and the content of chlorine is 3.2 weight %, and the content of lanthanum is 3.6 weight %.
【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=0.14, NH4F/SiO2=0.09,
La2O3/SiO2=0.002, H2O/SiO2=20, in 150 DEG C of crystallization 72 hours.Fluorine-containing and lanthanum ZSM-11 molecular sieves contain in product
Amount is 74 weight %, and impurity content is 1 weight %, and the content of fluorine is 1.7 weight %, and the content of lanthanum is 0.9 weight %.
【Embodiment 10】
Together【Embodiment 1】, it is template, chlorine only to use the mixture of 1,3- hexamethylenes dimethylamine and Isosorbide-5-Nitrae-hexamethylene dimethylamine
Change ammonium is halogen source, and the material proportion (molar ratio) of reactant is：SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=
0.2, Isosorbide-5-Nitrae-hexamethylene dimethylamine/SiO2=0.2, NaOH/SiO2=0.20, NH4Cl/SiO2=0.04, La2O3/SiO2=
0.0025, H2O/SiO2=20, in 150 DEG C of crystallization 36 hours.ZSM-11 molecular sieve contents containing chlorine and lanthanum in product are 78 weights
% is measured, impurity content is 4 weight %, and the content of chlorine is 2.3 weight %, and the content of lanthanum is 1.1 weight %.
Claims (21)
1. a kind of synthetic method of the ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal, is included under crystallization condition
Make silicon source, silicon source, alkali source, halogen source, rare earth metal source, organic formwork agent and water contact, the step of to obtain molecular sieve；With appoint
Selection of land, the step of roasting the molecular sieve of the acquisition；Wherein, the organic formwork agent R is selected from 1,3- hexamethylenes dimethylamine or Isosorbide-5-Nitrae-
At least one of hexamethylene dimethylamine；
Wherein, the silicon source, source of aluminium, the alkali source, the halogen source, the rare earth metal source, the organic formwork agent R
Molar ratio with water is 1：(0.0005~0.05)：(0.001~0.8)：(0.001~0.2)：(0.001~0.1)：(0.05~
2.0)：(5~100)；
Wherein, the crystallization condition includes：130~190 DEG C of crystallization temperature, crystallization time 1~10 day.
2. the synthetic method of the ZSM-11/ZSM-5 composite molecular screens according to claim 1 containing halogen and rare earth metal,
It is characterized in that, the roasting condition includes：300~800 DEG C of calcination temperature, roasting time 1~10 hour, calcination atmosphere are sky
Gas or oxygen；
The silicon source in silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, waterglass or white carbon at least one
Kind；Source of aluminium is selected from least one of aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate, aluminum sulfate, kaolin or montmorillonite；
The alkali source is selected from the alkali for cation with alkali or alkaline earth metal；The halogen source is selected from ammonium fluoride, sodium fluoride, fluorination
At least one in potassium, sodium chloride, ammonium chloride, potassium chloride, sodium bromide, ammonium bromide, potassium bromide, sodium iodide, ammonium iodide or potassium iodide
Kind；The rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium.
3. the synthetic method of the ZSM-11/ZSM-5 composite molecular screens according to claim 2 containing halogen and rare earth metal,
It is characterized in that, the rare earth metal is selected from lanthanum or cerium.
4. the synthetic method of the ZSM-11/ZSM-5 composite molecular screens according to claim 3 containing halogen and rare earth metal,
It is characterized in that, the rare earth metal is lanthanum.
5. the synthetic method of the ZSM-11/ZSM-5 composite molecular screens according to claim 1 containing halogen and rare earth metal,
It is characterized in that, the silicon source, source of aluminium, the alkali source, the halogen source, the rare earth metal source, the organic formwork
The molar ratio of agent R and water is 1：(0.005~0.04)：(0.05~0.6)：(0.01~0.1)：(0.002~0.05)：(0.05
~1.0)：(10~50)；
The crystallization condition includes：145~175 DEG C of crystallization temperature, crystallization time 2~10 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/ZSM-5 composite molecular screens according to claim 5 containing halogen and rare earth metal,
It is characterized in that, the silicon source, source of aluminium, the alkali source, the halogen source, the rare earth metal source, the organic formwork
The molar ratio of agent R and water is 1：(0.003~0.025)：(0.09~0.5)：(0.01~0.1)：(0.005~0.04)：(0.08
~0.8)：(12~50).
7. the synthetic method of the ZSM-11/ZSM-5 composite molecular screens according to claim 1 containing halogen and rare earth metal,
It is characterized in that, mode of heating use direct-fired mode, either using microwave heating by the way of or use directly heat
With the complex method of microwave heating.
8. the ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal of any the method synthesis of claim 1~7,
It is characterized in that, in the composite molecular screen, the content of the ZSM-11 crystalline phases containing halogen and rare earth metal is not less than 90 weight %；
The rare earth metal is selected from lanthanum, cerium, praseodymium or neodymium.
9. the ZSM-11/ZSM-5 composite molecular screens according to claim 8 containing halogen and rare earth metal, which is characterized in that
The content of ZSM-11 crystalline phases containing halogen and rare earth metal is not less than 75 weight %.
10. the ZSM-11/ZSM-5 composite molecular screens according to claim 9 containing halogen and rare earth metal, feature exist
In the content of the ZSM-11 crystalline phases containing halogen and rare earth metal is not less than 60 weight %.
11. the ZSM-11/ZSM-5 composite molecular screens according to claim 10 containing halogen and rare earth metal, feature exist
In the content of the ZSM-11 crystalline phases containing halogen and rare earth metal is not less than 45 weight %.
12. the ZSM-11/ZSM-5 composite molecular screens according to claim 11 containing halogen and rare earth metal, feature exist
In the content of the ZSM-11 crystalline phases containing halogen and rare earth metal is not less than 30 weight %.
13. the ZSM-11/ZSM-5 composite molecular screens according to claim 8 containing halogen and rare earth metal, feature exist
In the rare earth metal is selected from lanthanum or cerium.
14. the ZSM-11/ZSM-5 composite molecular screens according to claim 13 containing halogen and rare earth metal, feature exist
In the rare earth metal is lanthanum.
15. the ZSM-11/ZSM-5 composite molecular screens according to claim 8 containing halogen and rare earth metal, feature exist
In containing impurity in the composite molecular screen, impurity content is not higher than 10 weight %；
The impurity is selected from the unformed SiO containing halogen and rare earth metal2, different from least one molecule of ZSM-11 and ZSM-5
At least one of sieve, metal oxide, halide, quartz, tridymite, cristobalite.
16. the ZSM-11/ZSM-5 composite molecular screens according to claim 15 containing halogen and rare earth metal, feature exist
In the impurity content is not higher than 5 weight %.
17. the ZSM-11/ZSM-5 composite molecular screens according to claim 16 containing halogen and rare earth metal, feature exist
In the impurity content is not higher than 3 weight %.
18. the ZSM-11/ZSM-5 composite molecular screens according to claim 15 containing halogen and rare earth metal, feature exist
In the impurity is selected from the unformed SiO containing halogen and rare earth metal2、ZSM-23、ZSM-22、Beta、MCM-22、MOR、Y
At least one of type, X-type, A type molecular sieve.
19. the ZSM-11/ZSM-5 composite molecular screens according to claim 18 containing halogen and rare earth metal, feature exist
In the impurity is selected from the unformed SiO containing halogen and rare earth metal2, at least one of MOR.
20. according to any ZSM-11/ZSM-5 composite molecular screens containing halogen and rare earth metal of claim 8~19,
It is characterized in that, in the composite molecular screen, containing halogen and the ZSM-11/ZSM-5 composite molecular screens of rare earth metal and depositing for impurity
Include at least one of physical mixed, cocrystallization in form.
21. the ZSM-11/ZSM-5 composite molecular screens according to claim 20 containing halogen and rare earth metal, feature exist
In the impurity is the unformed SiO containing halogen and rare earth metal that content is not higher than 10 weight %2。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1072031C (en) * | 1997-09-17 | 2001-10-03 | 中国石油化工总公司 | Preparation method for penta-basic cyclic molecular sieve composite |
| CN1367758A (en) * | 1999-07-13 | 2002-09-04 | 美孚石油公司 | Synthesis of ZSM-5 and ZSM-11 |
| CN101759199A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Silicon and phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
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| WO2015153348A2 (en) * | 2014-04-01 | 2015-10-08 | Reaction 35, Llc | Method for preparation of modified catalysts with high catalytic performance and low coking rate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1072031C (en) * | 1997-09-17 | 2001-10-03 | 中国石油化工总公司 | Preparation method for penta-basic cyclic molecular sieve composite |
| CN1367758A (en) * | 1999-07-13 | 2002-09-04 | 美孚石油公司 | Synthesis of ZSM-5 and ZSM-11 |
| CN101759199A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Silicon and phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
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