CN105984879B - A kind of MWW structure molecular screen and preparation method thereof - Google Patents
A kind of MWW structure molecular screen and preparation method thereof Download PDFInfo
- Publication number
- CN105984879B CN105984879B CN201510046936.2A CN201510046936A CN105984879B CN 105984879 B CN105984879 B CN 105984879B CN 201510046936 A CN201510046936 A CN 201510046936A CN 105984879 B CN105984879 B CN 105984879B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mcm
- ammonium hydroxide
- sio
- molecular screen
- 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.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of MWW structure molecular screens, it is characterised in that it is 0.01~0.10cm that nitrogen adsorption-desorption BJH curve of the molecular sieve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions is >=35 μm of ol/g.
Description
Technical field
The present invention relates to a kind of molecular sieves and preparation method thereof, more specifically about a kind of MWW structure molecular screen
And preparation method thereof.
Background technique
MWW structure molecular screen includes MCM-22, MCM-49, MCM-36, MCM-56, SSZ-25, ITQ-1, ITQ-2 and UZM-
8 equal molecular sieves.Nineteen ninety, Mobil company for the first time using hexamethylene imine as template hydrothermal synthesis MCM-22 molecular sieve (US,
4954325,1990) its structure, and in 1994 is parsed for the first time, and MWW structure molecular screen is named as with this, therefore have
The lamellar zeolite of MWW topological structure is also known as MCM-22 family molecular sieves.
MWW structure molecular screen has two sets of non-cross independent ducts: layer internal orifice dimension is the ellipse of 0.40 × 0.59nm
The sinusoidal duct of shape 10MR two dimension；Interlayer is the 12MR supercage of 0.71 × 0.71 × 1.82nm, and with the 10MR of 0.40 × 0.54nm
Opening communicates with the outside world；In addition some holes 12MR are also distributed on its surface, are the half of supercage, depth is about 0.91nm
(Science,1994,264:1910).MWW structure molecular screen because its unique cellular structure and physico-chemical property alkylation (US,
5600048,1997), aromatisation (catalysis journal, 2002,23:24), catalytic cracking (J.Catal., 1997,167:438) and different
It has broad application prospects in the reaction such as structure (J.Catal., 1996,158:561).
MWW structure molecular screen although micropore specific area with higher, but due to the limitation in ten-ring aperture, supercage
Interior acidic site hardly results in utilization.In order to make the acidic site in supercage be fully used, many researchs are dedicated at MWW points
It introduces mesoporous in son sieve or communicates ten-ring sine duct and interlayer supercage in layer, so as to improve inside diffusion.
Compared with three-dimensional molecular sieve, the lamellar zeolites such as MWW show the multiplicity of structure because Coating combination is not close
Property and plasticity, and after composition still can further progress structural modification.For example interlayer swelling, stripping are carried out to MCM-22P
It is available both to have kept MWW Primary layer knot from (be partially stripped or be completely exfoliated) and intercalation, reaming and the post-processing such as pillared
Structure unit, and the catalysis material with large aperture and high-specific surface area, such as MCM-56 homologue, MCM-36, ITQ-2 and IEZ system
Column molecular sieve.
A large amount of mesoporous documents are generated using NaOH processing molecular sieve and its summary is many, they are by utilizing NaOH
Alkalinity realize controllable molten silicon, to generate inside molecular sieve crystal or between crystal a large amount of mesoporous, mentioned to reach
The purpose of high diffusibility energy.Wu Peng etc. protects high silicon MWW structure using the MCM-22 molecular sieve after roasting as raw material, using organic amine
The selectively molten silicon of the skeleton of molecular sieve, has been successfully prepared mesoporous MCM-22 molecular sieve.With individually will cause with the molten silicon of NaOH
Structure collapse is compared, and this method introduces aperture in the crystalline substance of 20nm or so while three-dimensional structure and two-dimensional layered structure convert
Interior mesoporous, molecular sieve crystallinity also remains intact, and the silica alumina ratio of molecular sieve is by 60 desiliconizations of raw material to 20~30.Xu Long childs etc. are only
It is handled using MCM-22 molecular sieve of the NaOH to roasting front and back, can also equally dramatically increase Jie of MCM-22 molecular sieve
Hole.
The post-processing of MWW structure molecular screen focuses mostly in inorganic base NaOH processing, due to the strong basicity of NaOH, thus desiliconization
Controllable degree is poor.Although can selectively protect framework of molecular sieve by introducing organic amine, NaOH is to molecule sieve skeleton
The destruction of frame is still inevitable.
Summary of the invention
An object of the present invention, which is to provide, a kind of is different from the prior art, MWW structure with special physico-chemical property point
Son sieve.
The second object of the present invention is to provide a kind of side for preparing the above-mentioned MWW structure molecular screen for being different from the prior art
Method.
Inventor has been surprisingly found that MWW structure molecular screen is different from the prior art in experience on the basis of a large number of experiments
The sieve sample obtained after alkaline matter for processing process, tightly packed to be changed into sheet loose by former " flower shape " for pattern
Accumulation, confusion degree dramatically increase, and zeolite crystal more disperses, and specific surface area and pore volume increased, while having lower
Na+Content shows as the BJH curve 3.8 with specific nitrogen adsorption-desorption different from routine MWW structure molecular screen
The adsorbance of nitrogen desorption rate and specific 2,4,6- trimethylpyridine at ± 0.5nm.Based on this, the present invention is formed.
In order to realize the first purpose, MWW structure molecular screen provided by the invention, it is characterised in that the nitrogen of the molecular sieve is inhaled
It is 0.01~0.10cm that the BJH curve of attached-desorption, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its 20 DEG C absorption,
The adsorbance of 2,4,6- trimethylpyridine after 200 DEG C of desorptions is >=35 μm of ol/g.
In order to realize the second purpose, the present invention also provides a kind of preparation methods, it is characterised in that by raw material MWW structure point
It is H that sub- sieve, nitrogenous organic base R1, organic amine R2, deionized water, which are uniformly mixed and obtain molar ratio,2O/SiO2=5~100, R1/
SiO2=0.01~5, R2/SiO2=0~1 mixture, and by the mixture at 100~180 DEG C 5~72h of crystallization and return
Receive, wherein described nitrogenous organic base R1, selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide,
Dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl hydrogen
At least one of amine-oxides, diethyl dipropyl ammonium hydroxide and an ethyl tripropyl ammonium hydroxide, described organic amine R2,
Selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4- phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine,
At least one of cyclopentamine, aniline, piperidines and piperazine.
MWW structure molecular screen provided by the invention, pattern are sheet loosely-packed, and confusion degree dramatically increases, molecular sieve
Crystal grain is more dispersed.Provided preparation method is to realize its pattern under the premise of maintaining MWW structure molecular screen high-crystallinity
Change, pattern is changed into sheet loosely-packed by former " flower shape " aggregation；The specific surface area of treated sieve sample simultaneously
It is improved with pore volume, which, which is totally different from the prior art, realizes the place of the reaming of molecular sieve to sacrifice crystallinity
Reason mode.
Detailed description of the invention
Fig. 1 is the SEM figure of comparative example 1 and resulting D-1, A-1-1 and A-1-2 sample of embodiment 1.
Fig. 2 is the SEM figure of comparative example 2 and resulting D-2, A-2-1 and A-2-2 sample of embodiment 2.
Fig. 3 is the SEM figure of comparative example 3 and resulting D-3, A-3-1 and A-3-2 sample of embodiment 3.
Fig. 4 is the SEM figure of comparative example 3 and resulting D-3, A-4-1 and A-4-2 sample of embodiment 4.
Fig. 5 is the SEM figure of comparative example 3 and resulting D-3, A-5-1 and A-5-2 sample of embodiment 5.
Fig. 6 is the SEM figure of comparative example 3 and resulting D-3, A-6-1 and A-6-2 sample of embodiment 6.
Fig. 7 is the SEM figure of comparative example 3 and resulting D-3, A-7-1 and A-7-2 sample of embodiment 7.
Fig. 8 is the SEM figure of comparative example 3 and resulting D-3, A-8-1 and A-8-2 sample of embodiment 8.
Fig. 9 is the SEM figure of comparative example 3 and resulting D-3, A-9-1 and A-9-2 sample of embodiment 9.
Figure 10 is the SEM figure of comparative example 3 and resulting D-3, A-10-1 and A-10-2 sample of embodiment 10.
Figure 11 is the SEM figure of comparative example 4 and resulting D-4, A-11-1 and A-11-2 sample of embodiment 11.
Figure 12 is the SEM figure of comparative example 4 and resulting D-4, A-12-1 and A-12-2 sample of embodiment 12.
Figure 13 is that the SEM of comparative example 3, comparative example 5 and resulting D-3, D-5 and D-6 sample of comparative example 6 schemes.
Specific embodiment
A kind of MWW structure molecular screen, it is characterised in that nitrogen adsorption-desorption BJH curve of the molecular sieve is shown in 3.8
Nitrogen desorption rate at ± 0.5nm is 0.01~0.10cm3/ g, and 2,4,6- trimethyls after its 20 DEG C absorption, 200 DEG C of desorptions
The adsorbance of pyridine is >=35 μm of ol/g.
MWW structure molecular screen of the invention has specific nitrogen adsorption-desorption parameter attribute, nitrogen adsorption-desorption
BJH curve be shown in the nitrogen desorption rate at 3.8 ± 0.5nm be 0.01~0.10cm3/ g, and prior art conventional hydrothermal closes
At nitrogen adsorption-desorption BJH curve of MWW molecular sieve be shown in the desorption rate of the nitrogen at 3.8nm >=0.20cm3/g.Nitrogen
Gas desorption rate amount is fewer, then illustrates that zeolite crystal more disperses.BJH curve is shown in the test of the nitrogen desorption rate at 3.8nm
Method is carried out on static n2 absorption apparatus, and measurement is purified sample and is not pressing p/p on year-on-year basis0Under the conditions of absorption to nitrogen
Amount.
MWW structure molecular screen of the invention, in addition to being shown in 3.8 ± 0.5nm with nitrogen adsorption-desorption BJH curve
The nitrogen desorption rate at place is 0.01~0.10cm3Outside this specific technical characteristic of/g, also have specific 2,4,6- trimethyls
Pyridine adsorption amount, adsorbance >=35 μm ol/g.2,4,6- trimethylpyridine adsorbances are more, then show molecular sieve activated centre
Accessibility it is better.The MWW structure molecular screen of conventional hydrothermal synthesis, adsorbance are respectively less than 35 μm of ol/g.2,4,6- front three
The adsorbance characterisitic parameter of yl pyridines be sieve sample is pressed into 10 to 20mg from blade, be placed in pond in situ, in 20 DEG C
2,4,6- trimethylpyridine is adsorbed, and removes 2,4,6- trimethylpyridines of physical absorption in 200 DEG C, by Fourier transform infrared
What spectrum measured.
MWW structure molecular screen of the invention, nitrogen adsorption-desorption BJH curve are shown in the nitrogen at 3.8 ± 0.5nm
Desorption rate is preferably 0.01~0.08cm3/ g, and the absorption of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions
Amount is 40~60 μm of ol/g.It is furthermore preferred that nitrogen adsorption-desorption BJH curve is shown in the desorption of the nitrogen at 3.8 ± 0.5nm
Amount is 0.01~0.05cm3/ g, and its 20 DEG C absorption, 200 DEG C desorption after 2,4,6- trimethylpyridines adsorbance be 40~
50μmol/g。
It can be seen that the molecular sieve that molecular sieve of the invention is synthesized with prior art conventional hydrothermal by SEM electromicroscopic photograph
Accumulation pattern be very different.Molecular Sieve Morphology presentation sheet loosely-packed in the present invention, and prior art routine water
The accumulation pattern of the MWW molecular sieve of thermal synthesis, for based on more regular " flower " shape and " lotus throne " shape, accumulation degree more advises
It is whole.
The present invention still further provides the preparation method of the MWW structure molecular screen of aforementioned present invention, it is characterised in that will
It is H that raw material MWW structure molecular screen, nitrogenous organic base R1, organic amine R2, deionized water, which are uniformly mixed and obtain molar ratio,2O/SiO2=
5~100, R1/SiO2=0.01~5, R2/SiO2=0~1 mixture, and by the mixture at 100~180 DEG C crystallization 5
~72h is simultaneously recycled, wherein described nitrogenous organic base R1 is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl
Ammonium hydroxide, dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, diformazan
Base dipropyl ammonium hydroxide, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, an ethyl tripropyl hydroxide
At least one of ammonium, an oxypropyl trimethyl ammonium hydroxide and a propyl triethylammonium hydroxide, described organic amine R2 are selected from
Pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4- phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, ring penta
At least one of amine, aniline, piperidines and piperazine.
Described mixture, preferred molar ratio are H2O/SiO2=5~50, R1/SiO2=0.05~0.5, R2/SiO2
=0~0.5, preferred molar ratio is H2O/SiO2=10~25, R1/SiO2=0.05~0.2, R2/SiO2=0.1~
0.3；Described crystallization is 8~36h of progress preferably at for 140~160 DEG C, more preferably in 150 DEG C of crystallization times 8~for 24 hours.
Described nitrogenous organic base R1, selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide,
Dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl hydrogen
Amine-oxides, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, an ethyl tripropyl ammonium hydroxide, a propyl
At least one of quaternary ammonium bases such as trimethylammonium hydroxide and a propyl triethylammonium hydroxide, preferred nitrogenous organic base R1 are
At least one of tetraethyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide.Described organic amine R2, it is sub- selected from pentamethylene
Amine, hexamethylene imine, heptamethylene imines, 1,4- phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, cyclopentamine, aniline, piperazine
At least one of pyridine, piperazine, preferred organic amine R2 are at least one of hexamethylene imine, aniline, piperidines, piperazine.
In a more preferred case, described nitrogenous organic base R1 be tetraethyl ammonium hydroxide and/or dimethyl diethyl ammonium hydroxide,
Organic amine R2 is hexamethylene imine and/or piperidines simultaneously.
In preparation method of the present invention, described raw material MWW structural molecule is screened from without roasting removed template method and/or warp
The MWW structure molecular screen for crossing roasting removed template method, wherein it is preferred that not being fired removed template method.Described raw material
MWW structure molecular screen can be MCM-22 (US4954325, Mobil/CN103771435A, RIPP), MCM-49
(US5236575, Mobil), MCM-56 (US5362697, Mobil), SSZ-25 (US5202014, Chevron) and UZM-8 (US
6756030B1, UOP) etc. various direct hydrothermal synthesis MWW structure Si-Al molecular sieve, be also possible to ITQ-2 and MCM-36 etc. pairs
MWW structure molecular screen obtained from MCM-22P is handled.Although this hair can also be carried out to ITQ-2 and MCM-36 molecular sieve
The treatment process of bright offer, but from the viewpoint of simple process, described raw material MWW structure molecular screen is directly to handle water
The MWW structure molecular screen of thermal synthesis can obtain better effect and simple process.
Preparation method provided by the invention, R1/SiO in described mixture2=0.05~0.5, R2/SiO2=0~0.5,
That is R2/SiO2Ends of range point value be zero in the case where, expression can individually use nitrogenous organic base R1.Individually had using nitrogenous
The mode of machine alkali R1 is particularly suitable for the complete situation of raw material MWW crystallization of molecular sieves, such as generally requires raw material MWW structural molecule
The relative crystallinity of sieve is >=100%.Which can realize that MWW structure molecular screen produces under the premise of crystallinity is declined slightly
Specific surface area, pore volume and the 2,4,6- trimethylpyridine adsorbance of object sample dramatically increase.
It is especially suitable in such a way that nitrogenous organic base R1 and organic amine R2 are handled simultaneously in preparation method provided by the invention
For crystallizing the lossy MWW structure molecular screen of imperfect or crystallinity, such as the relative crystallinity MWW structure lower than 90% point
Son sieve.Which can promote secondary crystallization, significantly improve crystallinity at least 5% or more.Described relative crystallinity is less than
90% MWW structure molecular screen may include incomplete because crystallizing caused by crystallization time is inadequate or template dosage is too low
MWW molecular sieve is also possible to crystallize MWW structure molecular screen of the complete MWW structure molecular screen after having lost crystallinity.It adopts
Under the mode handled simultaneously with nitrogenous organic base R1 and organic amine R2, MWW structure molecular screen Product samples are obviously mentioned in crystallinity
Realize that specific surface area, pore volume and 2,4,6- trimethylpyridine adsorbance dramatically increase under the premise of height.In addition, ion exchange
Degree can be more obvious, Na+Be down to 0.05 weight % hereinafter, Product samples can without ammonium exchange process, can roasting direct be H-
Type molecular sieve uses as acidic catalyst active component for being alkylated, aromatisation, cracking, the reaction such as isomerization.
The recovery product, process are known to those skilled in the art, including separation of solid and liquid, washing, drying and
Roasting, it is no longer numerous herein to state.The process of the specific recovery product of implementable one that but it is not limited to this of the present invention is in hydro-thermal crystalline substance
After the completion of change, temperature of reaction system is down to room temperature, crystallization product is separated through solid with mother liquor, and wherein solid is washed through deionization
It washs to pH value close to 7, after 100 DEG C of drying, 550 DEG C of roasting 10h removing templates is warming up to the heating rate of 2 DEG C/min
Agent, the MWW structure molecular screen after being roasted.
The present invention is further described below by embodiment, but content not thereby limiting the invention.
In embodiment and comparative example, X-ray diffraction (XRD) crystalline phase figure of sample is spread out in Siemens D5005 type X-ray
It penetrates on instrument and is measured.With sample and authentic specimen at the diffracted intensity (peak that 2 θ are diffractive features peak between 22.5 °~25.0 °
It is high) the sum of ratio indicate crystallinity of the sample relative to authentic specimen, i.e., relative crystallinity is (using 1 sample of comparative example as base
100%) quasi- sample, crystallinity are calculated as.
In embodiment and comparative example, the test that BJH curve is shown in the nitrogen desorption rate at 3.8nm is used
The AS-3 static state n2 absorption apparatus of Quantachrome instrument company production is in test condition: sample is placed in sample processing system,
1.33 × 10 are evacuated at 300 DEG C-2Pa, heat-insulation pressure keeping 4h purify sample；Test process: at -196 DEG C of liquid nitrogen temperature,
Measurement purification sample is not pressing p/p on year-on-year basis0Under the conditions of to the adsorbance of nitrogen.
In embodiment and comparative example, the adsorbance characterisitic parameter of 2,4,6- trimethylpyridines is that sieve sample is pressed into 10
It to 20mg from blade, is placed in pond in situ, in 20 DEG C of 2,4,6- trimethylpyridines of absorption, and in 200 DEG C of removing physical absorptions
2,4,6- trimethylpyridines, measured by Fourier transform infrared spectroscopy.
Comparative example 1
This comparative example illustrates the MCM-22 molecular sieve prepared according to the method for US 4954325.
Sodium metaaluminate (Chinese medicines group is analyzed pure) and sodium hydroxide (Beijing Reagent Company analyzes pure) are dissolved in deionization
In water, above-mentioned solution is added to being completely dissolved, by solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) in stirring, adds six
Methylene imine (HMI), after mixing evenly, gained mixture colloid mol ratio are as follows: 0.18NaOH:SiO2: 0.033Al2O3:
0.30HMI:15H2O.Then gained mixture being transferred in closed crystallizing kettle, crystallization temperature is 145 DEG C, dynamic crystallization 72h,
Product is taken out after cooling, after being filtered, washed, dried and being roasted, obtains sample.
The XRD diffraction pattern of test sample, 25 to 35 ° of the angles θ, product are MCM-22 molecular sieve, D-1 are labeled as, with this D-1 sample
The crystallinity of product is set as 100%, and the relative crystallinity data of embodiment sample hereafter are as benchmark.
By sem test, pattern is " flower shape " aggregation, and zeolite crystal size is about 3.0~4.0 μm.
The BET of test sample analyzes its specific surface area and pore volume, and specific surface area and pore volume are respectively 451m2/ g and
0.55cm3/g。
Its Na of XRF analysis2O content is 0.65wt.%.
It is 0.22cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its
The adsorbance of 2,4,6- trimethylpyridine after 20 DEG C of absorption, 200 DEG C of desorptions is 22 μm of ol/g.
Embodiment 1
This example demonstrates that molecular sieve provided by the invention and preparation method.
It in above-mentioned comparative example 1, is not fired, the MCM-22 sample containing hexamethylene imine is MCM-22P molecular sieve, warp
Crossing roasting, having removed the MCM-22 sample of hexamethylene imine is MCM-22C molecular sieve.
Tetraethyl ammonium hydroxide solution (TEAOH, 25wt.%) is added in deionized water, then by MCM-22P or MCM-
22C molecular sieve is added in above-mentioned solution, continues to stir evenly, and gained mixture colloid mol ratio is SiO2: 0.1TEAOH:
15H2O.Gained mixture colloid is transferred in closed crystallizing kettle, dynamic crystallization 16h at being 150 DEG C in crystallization temperature is cooling
After take out product, after being filtered, washed, dried and being roasted, molecular screen primary powder after being handled, after the corresponding processing of MCM-22P
The number of sample is A-1-1；The number of sample is A-1-2 after the corresponding processing of MCM-22C.
Test sample obtains XRD diffraction pattern, and A-1-1 is MCM-22 molecular sieve, and A-1-2 is MCM-49 molecular sieve, relatively
Crystallinity is respectively 105% and 96%.
SEM shows that A-1-1 sample and A-1-2 pattern are changed into the loose heap of sheet by " flower shape " aggregation of sample D-1
Product.
BET molecular sieve is shown: the specific surface area and pore volume of A-1-1 molecular sieve are respectively 481m2/ g and 0.65cm3/g；And
The specific surface area and pore volume of A-1-2 molecular sieve are respectively 476m2/ g and 0.63cm3/g。
The Na of XRF analysis A-1-1 and A-1-22O content is respectively 0.25wt.% and 0.23wt.%.
It is 0.10cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.10cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 38.2 μm of ol/g and
36.7μmol/g。
Comparative example 2
This comparative example illustrates the process that MCM-49 molecular sieve is prepared according to the method for US 5326575.
Sodium metaaluminate (Chinese medicines group is analyzed pure) and sodium hydroxide (Beijing Reagent Company analyzes pure) are dissolved in deionization
In water, above-mentioned solution is added to being completely dissolved, by solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) in stirring, adds six
Methylene imine, after mixing evenly, gained mixture colloid mol ratio are as follows: 0.18NaOH:SiO2: 0.040Al2O3:
0.30HMI:15H2O.Then gained mixture being transferred in closed crystallizing kettle, crystallization temperature is 145 DEG C, dynamic crystallization 72h,
Product is taken out after cooling, after being filtered, washed, dried and being roasted, obtains sample.
The XRD diffraction pattern that test sample obtains, 25 to 35 ° of the angles θ, product are MCM-49 molecular sieve, are labeled as D-2.
Relative crystallinity is 100%；Grain size is about 3.0~4.0 μm；BET analyzes specific surface area and pore volume difference
For 462m2/ g and 0.56cm3/g。
Its Na of XRF analysis2O content is 0.58wt.%.
It is 0.20cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its
The adsorbance of 2,4,6- trimethylpyridine after 20 DEG C of absorption, 200 DEG C of desorptions is 26 μm of ol/g.
Embodiment 2
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetraethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then will not be fired in comparative example 2,
MCM-49 containing hexamethylene imine is added in above-mentioned solution, continues to stir evenly.Gained mixture colloid mol ratio is
SiO2: 0.1TEAOH:15H2O.Then, gained mixture is transferred in closed crystallizing kettle, crystallization temperature is 150 DEG C, and dynamic is brilliant
Change 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, obtain modified molecular screen primary powder, sample number into spectrum is
A-2-1。
Ibid, difference is for comparative example 2 not to be fired, the MCM-49 containing hexamethylene imine replaces with comparative example 2
By the MCM-49 for roasting, having removed hexamethylene imine.Obtain modified molecular screen primary powder, sample number into spectrum A-2-2.
Test obtains XRD diffraction pattern, and A-2-1 and A-2-2 are MCM-49 molecular sieve, and relative crystallinity is respectively 103%
With 96%.
To be changed into sheet loose by " flower shape " aggregation of D-2 for the pattern of SEM test display sample A-2-1 and A-2-2
Accumulation.
BET molecular sieve is shown: the specific surface area and pore volume of A-2-1 molecular sieve are respectively 475m2/ g and 0.67cm3/g；And
The specific surface area and pore volume of A-2-2 molecular sieve are respectively 471m2/ g and 0.62cm3/g。
Its Na of XRF analysis2O content is respectively 0.21wt.% and 0.18wt.%.
It is 0.09cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.10cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 40.3 μm of ol/g and
38.7μmol/g。
Comparative example 3
This comparative example illustrates according to the method for embodiment 1 in CN103771435A using hexamethylene imine and aniline as template
The process of agent synthesis MCM-22 molecular sieve.
Sodium metaaluminate (Chinese medicines group is analyzed pure) and sodium hydroxide (Beijing Reagent Company analyzes pure) are dissolved in deionization
In water, stir to being completely dissolved, by extra large mound silica gel (Haiyang Chemical Plant, Qingdao, SiO2Content be above-mentioned solution 97%) is added, then
Hexamethylene imine (Japanese TCI company analyzes pure), aniline is added (Beijing Chemical Plant analyzes pure).Mixture colloid mole is matched
Than for 0.18NaOH:SiO2: 0.033Al2O3: 0.10HMI:0.20AN:15H2O, 145 DEG C of crystallization temperature, under self-generated pressure, with
300 turns per minute mixing speed crystallization 72 hours, take out product after cooling, after being filtered, washed and dried dry and roasting, obtain
Sample.
Test obtains the XRD diffraction pattern of sample, and 2 angles θ are 5 to 35 °, and sample is MCM-22 molecular sieve, number be for D-3,
Relative crystallinity is 101%；
SEM test, the grain size of D-3 sample is about 3.0~4.0 μm；
BET analyzes its specific surface area and pore volume is respectively 450m2/ g and 0.55cm3/g；
XRF analysis Na2O content is 0.55wt.%.
It is 0.20cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its
The adsorbance of 2,4,6- trimethylpyridine after 20 DEG C of absorption, 200 DEG C of desorptions is 28.7 μm of ol/g.
Embodiment 3
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetramethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then will not be fired in comparative example 3,
It is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continues to stir evenly.Gained mixture colloid mole
Proportion is SiO2: 0.1TMAOH:15H2O.Then, gained mixture being transferred in closed crystallizing kettle, crystallization temperature is 150 DEG C,
Dynamic crystallization 16h takes out product after cooling, after being filtered, washed, dried and being roasted, obtains modified molecular screen primary powder, sample
Number is A-3-1.
Ibid, difference is not being fired of comparative example 3, the MCM-49 containing hexamethylene imine and aniline is replaced with
Comparative example 3 has been fired, MCM-22 (the MCM-22C molecular sieve after roasting, with MCM- without hexamethylene imine and aniline
49 molecular sieve XRD diffraction maximums are identical).Obtain modified molecular screen primary powder, sample number into spectrum A-3-2.
Test obtains XRD diffraction pattern, and A-3-1 is MCM-22 molecular sieve, and A-3-2 is MCM-49 molecular sieve, relative crystallinity
Respectively 94% and 92%.
Pattern is changed into sheet loosely-packed by " flower shape " aggregation.
BET analysis shows that, the specific surface area and pore volume of A-3-1 sample are respectively 502m2/ g and 0.60cm3/g；And A-
The specific surface area and pore volume of 3-2 sample are respectively 491m2/ g and 0.62cm3/g。
Its Na of XRF analysis2O content is respectively 0.10wt.% and 0.11wt.%.
It is 0.08cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.07cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 42.1 μm of ol/g and
40.3μmol/g。
Embodiment 4
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetramethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, it then will be in comparative example 3
It is not fired, is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continue to stir evenly.Gained mixture
Colloid mol ratio are as follows: SiO2: 0.1TMAOH:0.3PI:15H2O.Then, gained mixture is transferred in closed crystallizing kettle,
Crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, is modified
Molecular screen primary powder afterwards, sample number into spectrum A-4-1.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 containing hexamethylene imine and aniline is replaced with pair
Ratio 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Modified molecular screen primary powder is obtained, sample number into spectrum is
A-4-2。
Test obtains XRD diffraction pattern, and A-4-1 and A-4-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 113% He
108%；
SEM test, sample topography are changed into sheet loosely-packed by " flower shape " aggregation of D-3；
BET analysis shows that: the specific surface area and pore volume of A-8-1 molecular sieve are respectively 483m2/ g and 0.64cm3/g；And A-
The specific surface area and pore volume of 8-2 molecular sieve are respectively 492m2/ g and 0.63cm3/g；
Its Na of XRF analysis2O content is respectively 0.01wt.% and 0.02wt.%.
It is 0.08cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.07cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 42.1 μm of ol/g and
40.2μmol/g。
Embodiment 5
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetraethyl ammonium hydroxide solution (25wt.%) is added in deionized water, then will not be fired in comparative example 3,
It is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continues to stir evenly.Gained mixture colloid mole
Proportion is SiO2: 0.1TEAOH:15H2O.Then, gained mixture being transferred in closed crystallizing kettle, crystallization temperature is 150 DEG C,
Dynamic crystallization 16h takes out product after cooling, after being filtered, washed, dried and being roasted, obtains modified molecular screen primary powder, sample
Number is A-5-1.
Ibid, difference is not being fired of comparative example 3, the MCM-22 containing hexamethylene imine and aniline is replaced with
Comparative example 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Obtain modified molecular screen primary powder, sample number into spectrum
For A-5-2.
Test obtains XRD diffraction pattern, and A-5-1 is MCM-22 molecular sieve, and A-5-2 is MCM-49 molecular sieve, relative crystallinity
Respectively 100% and 96%.
Pattern is changed into sheet loosely-packed by " flower shape " aggregation.
BET analysis shows that, the specific surface area and pore volume of A-5-1 sample are respectively 500m2/ g and 0.67cm3/g；And A-
The specific surface area and pore volume of 5-2 sample are respectively 495m2/ g and 0.65cm3/g。
Its Na of XRF analysis2O content is respectively 0.20wt.% and 0.15wt.%.
It is 0.05cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.05cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 46.1 μm of ol/g and
43.4μmol/g。
Embodiment 6
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetraethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, it then will be in comparative example 3
It is not fired, is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continue to stir evenly.Gained mixture
Colloid mol ratio are as follows: SiO2: 0.1TEAOH:0.3PI:15H2O.Then, gained mixture is transferred in closed crystallizing kettle,
Crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, is modified
Molecular screen primary powder afterwards, sample number into spectrum A-6-1.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 containing hexamethylene imine and aniline is replaced with pair
Ratio 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Modified molecular screen primary powder is obtained, sample number into spectrum is
A-6-2.
Test obtains XRD diffraction pattern, and A-6-1 and A-6-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 112% He
110%；
SEM test, sample topography are changed into sheet loosely-packed by " flower shape " aggregation of D-3；
BET analysis shows that: the specific surface area and pore volume of A-6-1 molecular sieve are respectively 485m2/ g and 0.72cm3/g；And A-
The specific surface area and pore volume of 6-2 molecular sieve are respectively 494m2/ g and 0.63cm3/g；
Its Na of XRF analysis2O content is respectively 0.03wt.% and 0.02wt.%.
It is 0.08cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.07cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 43.1 μm of ol/g and
41.5μmol/g。
Embodiment 7
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetrapropylammonium hydroxide solution (25wt.%) is added in deionized water, then will not be fired in comparative example 3,
It is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continues to stir evenly.Gained mixture colloid mole
Proportion is SiO2: 0.1TPAOH:15H2O.Then, gained mixture being transferred in closed crystallizing kettle, crystallization temperature is 150 DEG C,
Dynamic crystallization 16h takes out product after cooling, after being filtered, washed, dried and being roasted, obtains modified molecular screen primary powder, sample
Number is A-7-1.
Ibid, difference is not being fired of comparative example 3, the MCM-22 containing hexamethylene imine and aniline is replaced with
Comparative example 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Obtain modified molecular screen primary powder, sample number into spectrum
For A-7-2.
Test obtains XRD diffraction pattern, and A-7-1 is MCM-22 molecular sieve, and A-7-2 is MCM-49 molecular sieve, relative crystallinity
Respectively 95% and 93%.
Pattern is changed into sheet loosely-packed by " flower shape " aggregation.
BET analysis shows that, the specific surface area and pore volume of A-7-1 sample are respectively 488m2/ g and 0.68cm3/g；And A-
The specific surface area and pore volume of 7-2 sample are respectively 502m2/ g and 0.62cm3/g。
Its Na of XRF analysis2O content is respectively 0.38wt.% and 0.39wt.%.
It is 0.10cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.09cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 40.3 μm of ol/g and
39.5μmol/g。
Embodiment 8
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetrapropylammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, it then will be in comparative example 3
It is not fired, is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continue to stir evenly.Gained mixture
Colloid mol ratio are as follows: SiO2: 0.1TPAOH:0.3PI:15H2O.Then, gained mixture is transferred in closed crystallizing kettle,
Crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, is modified
Molecular screen primary powder afterwards, sample number into spectrum A-8-1.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 containing hexamethylene imine and aniline is replaced with pair
Ratio 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Modified molecular screen primary powder is obtained, sample number into spectrum is
A-8-2.
Test obtains XRD diffraction pattern, and A-8-1 and A-8-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 110% He
103%；
SEM test, sample topography are changed into sheet loosely-packed by " flower shape " aggregation of D-3；
BET analysis shows that: the specific surface area and pore volume of A-8-1 molecular sieve are respectively 488m2/ g and 0.65cm3/g；And A-
The specific surface area and pore volume of 8-2 molecular sieve are respectively 497m2/ g and 0.65cm3/g；
Its Na of XRF analysis2O content is respectively 0.07wt.% and 0.06wt.%.
It is 0.08cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.07cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 40.4 μm of ol/g and
38.6μmol/g。
Embodiment 9
This example demonstrates that molecular sieve provided by the invention and preparation method.
Dimethyl diethyl Ammonia (DEDMAOH, 25wt.%) is added in deionized water, it then will comparison
It is not fired in example 3, is added in above-mentioned solution containing the MCM-22 molecular sieve of hexamethylene imine and aniline, it is equal to continue stirring
It is even.Gained mixture colloid mol ratio is SiO2: 0.1DEDMAOH:15H2O.Gained mixture is transferred to closed crystallizing kettle
In, crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, is changed
Molecular screen primary powder after property, product number A-9-1.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 molecular sieve containing hexamethylene imine and aniline replaces
Be changed to comparative example 3 be fired, the MCM-22 molecular sieve without hexamethylene imine and aniline.Obtain modified molecular screen primary
Powder, product number A-9-2.
Test obtains XRD diffraction pattern, and A-9-1 is MCM-22 molecular sieve, and A-9-2 is MCM-49 molecular sieve, relative crystallinity
Respectively 98% and 98%；
The pattern of SEM test display A-9-1 and A-9-2 is changed into sheet loosely-packed by " flower shape " aggregation of D-3；
BET analysis shows that: the specific surface area and pore volume of A-9-1 molecular sieve are respectively 499m2/ g and 0.59cm3/g；And A-
The specific surface area and pore volume of 9-2 molecular sieve are respectively 499m2/ g and 0.60cm3/g；
Its Na of XRF analysis2O content is respectively 0.40wt.% and 0.44wt.%.
It is 0.06cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.06cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 44.3 μm of ol/g and
42.1μmol/g。
Embodiment 10
This example demonstrates that molecular sieve provided by the invention and preparation method.
Dimethyl diethyl Ammonia (25wt.%) and piperidines (PI) are added in deionized water, it then will be right
It is not fired in ratio 3, is added in above-mentioned solution containing the MCM-22 molecular sieve of hexamethylene imine and aniline, it is equal to continue stirring
It is even.Gained mixture colloid mol ratio is SiO2: 0.1DEDMAOH:0.3PI:15H2O.Then, gained mixture is transferred to
In closed crystallizing kettle, crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, is filtered, washed, dried and roasted
After burning, modified molecular screen primary powder, product number A-10-1 are obtained.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 molecular sieve containing hexamethylene imine and aniline replaces
The MCM-22 molecular sieve being fired, without hexamethylene imine and aniline is changed in comparative example 3.Obtain modified molecular screen primary
Powder, product number A-10-2.
Test obtains XRD diffraction pattern, and A-10-1 and A-10-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 110%
With 110%；
" flower shape " aggregation of SEM test display, the equal D-3 of A-10-1 and A-10-2 pattern is changed into sheet loosely-packed；
BET analysis shows that: the specific surface area and pore volume of A-10-1 molecular sieve are respectively 499m2/ g and 0.65cm3/g；And
The specific surface area and pore volume of A-10-2 molecular sieve are respectively 506m2/ g and 0.60cm3/g。
Its Na of XRF analysis2O content is respectively 0.05wt.% and 0.11wt.%.
It is 0.06cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.06cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 40.4 μm of ol/g and
38.6μmol/g。
Comparative example 4
This comparative example is to synthesize according to the method in CN103771435A using hexamethylene imine and aniline as template
MCM-22 molecular sieve.
A certain amount of sodium metaaluminate (Chinese medicines group is analyzed pure) is dissolved in sodium hydroxide (Beijing Reagent Company analyzes pure)
In deionized water, stir to being completely dissolved, by extra large mound silica gel (Haiyang Chemical Plant, Qingdao, SiO2Content is that 97%) addition is above-mentioned molten
Liquid adds hexamethylene imine (Japanese TCI company analyzes pure), aniline (Beijing Chemical Plant analyzes pure).Mixture colloid
Mol ratio are as follows: 0.18NaOH:SiO2: 0.033Al2O3: 0.05HMI:0.25AN:15H2O, 145 DEG C of crystallization temperature, spontaneous pressure
Under power, with 300 turns per minute mixing speed crystallization 72 hours, take out product after cooling, be filtered, washed and dried dry and roasting
Afterwards, sample is obtained.
Test obtains XRD diffraction pattern, 25 to 35 ° of the angles θ.Product is MCM-22 molecular sieve, is labeled as D-4, relative crystallinity
It is 83%；
SEM test display grain size is about 2.0~4.0 μm；
BET analyzes its specific surface area and pore volume is respectively 375m2/ g and 0.44cm3/g；
XRF analysis Na2O content is 1.36wt.%.
It is 0.18cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its
The adsorbance of 2,4,6- trimethylpyridine after 20 DEG C of absorption, 200 DEG C of desorptions is 18 μm of ol/g.
Embodiment 11
This example demonstrates that molecular sieve provided by the invention and preparation method.
Tetraethyl ammonium hydroxide solution (25wt.%) and piperidines (PI) are added in deionized water, it then will be in comparative example 4
It is not fired, is added in above-mentioned solution containing the MCM-22 molecular sieve of hexamethylene imine and aniline, continue to stir evenly.Gained
Mixture colloid mol ratio is SiO2: 0.1TEAOH:0.3PI:15H2O.Then, gained mixture is transferred to closed crystallization
In kettle, crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, after being filtered, washed, dried and being roasted, obtains
Modified molecular screen primary powder, product number A-7-1.
Ibid, difference be will not to be fired in comparative example 4, the MCM-22 molecular sieve containing hexamethylene imine and aniline
Replace with the MCM-22 molecular sieve being fired in comparative example 4, without hexamethylene imine and aniline.Obtain modified molecular sieve
Original powder, product number A-7-2.
Test obtains XRD diffraction pattern, and A-11-1 and A-11-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 110%
With 101%；
SEM test display, A-11-1 and A-11-2 pattern are changed into the loose heap of sheet by " flower shape " aggregation of D-4
Product.
BET analysis shows that: the specific surface area and pore volume of A-11-1 molecular sieve are respectively 471m2/ g and 0.62cm3/g；And
The specific surface area and pore volume of A-11-2 molecular sieve are respectively 485m2/ g and 0.60cm3/g。
Its Na of XRF analysis2O content is respectively 0.11wt.% and 0.25wt.%.
It is 0.05cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.05cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 46.2 μm of ol/g and
46.1μmol/g。
Embodiment 12
This example demonstrates that molecular sieve provided by the invention and preparation method.
Dimethyl diethyl Ammonia (25wt.%) and piperidines (PI) are added in deionized water, it then will be right
It is not fired in ratio 4, is added in above-mentioned solution containing the MCM-22 molecular sieve of hexamethylene imine and aniline, it is equal to continue stirring
It is even.Gained mixture colloid mol ratio are as follows: SiO2: 0.1DEDMAOH:0.3PI:15H2O.Then, gained mixture is shifted
To in closed crystallizing kettle, crystallization temperature is 150 DEG C, dynamic crystallization 16h, takes out product after cooling, be filtered, washed, dry and
After roasting, molecular screen primary powder after being handled, product number A-12-1.
Ibid, difference is to be fired in comparative example 4, the MCM-22 molecular sieve containing hexamethylene imine and aniline
Replace with being fired of comparative example 4, the MCM-22 molecular sieve without containing hexamethylene imine and aniline.Molecular screen primary after processing
Powder, product number A-12-2.
Test obtains XRD diffraction pattern, and A-12-1 and A-12-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 104%
With 100%；
SEM test display, A-12-1 and A-12-2 pattern are changed into sheet loosely-packed by D-4 " flower shape " aggregation；
BET molecular sieve is shown: the specific surface area and pore volume of A-12-1 molecular sieve are respectively 450m2/ g and 0.57cm3/g；
And the specific surface area and pore volume of A-12-2 molecular sieve are respectively 493m2/ g and 0.54cm3/g。
Its Na of XRF analysis2O content is respectively 0.29wt.% and 0.20wt.%.
It is 0.07cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.06cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 42.0 μm of ol/g and
40.6μmol/g。
Comparative example 5
This comparative example illustrates individually with the process and product of inorganic alkali-treated raw materials MWW structure molecular screen.
In this comparative example, raw material MWW structure molecular screen is not to be fired in above-mentioned comparative example 3, contain hexamethylene imine
MCM-22 molecular sieve.
Sodium hydroxide (NaOH, 96wt.%) is added in deionized water, above-mentioned solution then is added in MCM-22 molecular sieve
In, continue to stir evenly, gained mixture colloid mol ratio is SiO2: 0.1NaOH:15H2O.Gained mixture colloid is turned
It moves in closed crystallizing kettle, dynamic crystallization 16h at being 150 DEG C in crystallization temperature takes out product after cooling, is filtered, washed, done
After dry and roasting, molecular screen primary powder after being handled, the number of sample is D-5-1 after corresponding processing.
Ibid, difference is not being fired of comparative example 3, the MCM-22 containing hexamethylene imine and aniline is replaced with
Comparative example 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Obtain modified molecular screen primary powder, corresponding place
The number of sample is D-5-2 after reason.
Test sample obtains XRD diffraction pattern, and D-5-1 is MCM-22 molecular sieve, and D-5-2 is MCM-49 molecular sieve, relatively
Crystallinity is respectively 88% and 80%.
SEM shows that D-5-1 and D-5-2 sample topography is changed into the loose heap of sheet by " flower shape " aggregation of sample D-1
Product.
BET molecular sieve is shown: the specific surface area and pore volume of D-5-1 molecular sieve are respectively 461m2/ g and 0.71cm3/g；And
The specific surface area and pore volume of D-5-2 molecular sieve are respectively 446m2/ g and 0.67cm3/g。
The Na of XRF analysis D-5-1 and D-5-22O content is respectively 3.29wt.% and 3.48wt.%.
It is 0.13cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g, and its
The adsorbance of 2,4,6- trimethylpyridine after 20 DEG C of absorption, 200 DEG C of desorptions is 28 μm of ol/g.
Comparative example 6
This comparative example illustrates with the process and product of inorganic base and organic amine processing raw material MWW structure molecular screen.
Sodium hydroxide (96wt.%) and piperidines (PI) are added in deionized water, then will not be fired in comparative example 3,
It is added in above-mentioned solution containing the MCM-22 of hexamethylene imine and aniline, continues to stir evenly.Gained mixture colloid mole
Proportion are as follows: SiO2: 0.1NaOH:0.3PI:15H2O.Then, gained mixture is transferred in closed crystallizing kettle, crystallization temperature is
150 DEG C, dynamic crystallization 16h, product is taken out after cooling, after being filtered, washed, dried and being roasted, obtains modified molecular screen primary
Powder, sample number into spectrum D-6-1.
Ibid, difference is for comparative example 3 not to be fired, the MCM-22 containing hexamethylene imine and aniline is replaced with pair
Ratio 3 has been fired, the MCM-22 without hexamethylene imine and aniline.Modified molecular screen primary powder is obtained, sample number into spectrum is
D-6-2.
Test obtains XRD diffraction pattern, and D-6-1 and D-6-2 are MCM-22 molecular sieve, and relative crystallinity is respectively 93% He
90%；
SEM test, sample topography are changed into sheet loosely-packed by " flower shape " aggregation of D-3；
BET analysis shows that: the specific surface area and pore volume of D-6-1 molecular sieve are respectively 481m2/ g and 0.74cm3/g；And D-
The specific surface area and pore volume of 6-2 molecular sieve are respectively 470m2/ g and 0.65cm3/g；
Its Na of XRF analysis2O content is respectively 3.63wt.% and 3.26wt.%.
It is 0.12cm that nitrogen adsorption-desorption BJH curve, which is shown in the nitrogen desorption rate at 3.8 ± 0.5nm,3/ g and
0.10cm3/ g, and the adsorbance of 2,4,6- trimethylpyridines after its 20 DEG C absorption, 200 DEG C of desorptions be 33.1 μm of ol/g and
30.1μmol/g。
Claims (11)
1. a kind of MWW structure molecular screen, it is characterised in that nitrogen adsorption-desorption BJH curve of the molecular sieve is shown in 3.8
Nitrogen desorption rate at ± 0.5 nm is 0.01~0.10cm3/ g, and 2,4,6- front threes after its 20 DEG C absorption, 200 DEG C of desorptions
The adsorbance of yl pyridines is >=35 μm of ol/g, and sheet loosely-packed is presented in Molecular Sieve Morphology.
2. according to the molecular sieve of claim 1, wherein nitrogen adsorption-desorption BJH curve of the molecular sieve is shown in
0.01~0.08cm of nitrogen desorption rate at 3.8 ± 0.5 nm3/ g, and 2,4,6- tri- after its 20 DEG C absorption, 200 DEG C of desorptions
The adsorbance of picoline is 40~60 μm of ol/g.
3. according to the molecular sieve of claim 1, wherein nitrogen adsorption-desorption BJH curve of the molecular sieve is shown in
Nitrogen desorption rate at 3.8 ± 0.5 nm is 0.01~0.05cm3/ g, and 2,4,6- after its 20 DEG C absorption, 200 DEG C of desorptions
The adsorbance of trimethylpyridine is 40~50 μm of ol/g.
4. the preparation method of the MWW structure molecular screen of one of claim 1-3, it is characterised in that by raw material MWW structure molecular screen,
It is H that nitrogenous organic base R1, organic amine R2, deionized water, which are uniformly mixed and obtain molar ratio,2O/SiO2 =10~100, R1/SiO2 =
0.01~5, R2/SiO2 =0~1 mixture, and by the mixture at 100~180 DEG C 5~72 h of Crystallizing treatment and return
Receive, wherein described nitrogenous organic base R1, selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide,
Dimethyl diethyl ammonium hydroxide, monomethyl triethylammonium hydroxide, monomethyl tripropyl ammonium hydroxide, dimethyl dipropyl hydrogen
Amine-oxides, an ethyl-trimethyl ammonium hydroxide, diethyl dipropyl ammonium hydroxide, an ethyl tripropyl ammonium hydroxide, a propyl
At least one of trimethylammonium hydroxide and a propyl triethylammonium hydroxide, described organic amine R2 are selected from pentamethylene
Imines, hexamethylene imine, heptamethylene imines, 1,4- phenodiazine cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, cyclopentamine, aniline,
At least one of piperidines and piperazine；When the relative crystallinity of the raw material MWW structure molecular screen >=100%, individually use
Nitrogenous organic base R1；When the relative crystallinity of the raw material MWW structure molecular screen is less than 90 %, while using nitrogenous organic base
R1 and organic amine R2.
5. according to method for claim 4, wherein the raw material MWW structure molecular screen is not to be fired removed template method
MWW structure molecular screen.
6. according to the method for claim 4 or 5, wherein the raw material MWW structural molecule screened from MCM-22, MCM-49,
One of MCM-56, SSZ-25 and UZM-8 or different kinds of molecules sieve.
7. according to method for claim 4, wherein the molar ratio of the mixture is H2O/SiO2 =10~50, R1/SiO2
=0.05~0.5, R2/SiO2 =0~0.5.
8. according to method for claim 4, wherein the nitrogenous organic base R1 is tetraethyl ammonium hydroxide and/or dimethyl
Diethyl ammonium hydroxide.
9. according to method for claim 4, wherein the organic amine R2 is in hexamethylene imine, aniline, piperidines and piperazine
At least one.
10. according to method for claim 4, wherein the nitrogenous organic base R1 is tetraethyl ammonium hydroxide and/or dimethyl
Diethyl ammonium hydroxide, while organic amine R2 is hexamethylene imine and/or piperidines.
11. according to method for claim 4, wherein described mixture is in 140~160 DEG C of 8~36 h of crystallization time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510046936.2A CN105984879B (en) | 2015-01-29 | 2015-01-29 | A kind of MWW structure molecular screen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510046936.2A CN105984879B (en) | 2015-01-29 | 2015-01-29 | A kind of MWW structure molecular screen and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105984879A CN105984879A (en) | 2016-10-05 |
| CN105984879B true CN105984879B (en) | 2019-05-21 |
Family
ID=57036664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510046936.2A Active CN105984879B (en) | 2015-01-29 | 2015-01-29 | A kind of MWW structure molecular screen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105984879B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670686A (en) * | 2017-10-18 | 2018-02-09 | 钦州学院 | Catalyst of 2 ethyl anthracenes and preparation method thereof is prepared for anthracene and ethylene alkylation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340563A (en) * | 1992-06-30 | 1994-08-23 | Chevron Research And Technology Company | Preparation of zeolites using low silica/alumina zeolites as a source of aluminum |
| CN101850986A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Method for modifying titanium-silicalite |
| CN102309980A (en) * | 2010-06-30 | 2012-01-11 | 中国石油化工股份有限公司 | Steam modifying method of titanium-silicon molecular sieve |
| CN102850197A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone |
-
2015
- 2015-01-29 CN CN201510046936.2A patent/CN105984879B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340563A (en) * | 1992-06-30 | 1994-08-23 | Chevron Research And Technology Company | Preparation of zeolites using low silica/alumina zeolites as a source of aluminum |
| CN101850986A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Method for modifying titanium-silicalite |
| CN102309980A (en) * | 2010-06-30 | 2012-01-11 | 中国石油化工股份有限公司 | Steam modifying method of titanium-silicon molecular sieve |
| CN102850197A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for preparing cyclohexanone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105984879A (en) | 2016-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2599745C2 (en) | Emm-23 molecular sieve, its synthesis and application | |
| RU2601462C2 (en) | Emm-22 molecular sieve, its synthesis and application | |
| KR102172784B1 (en) | Emm-25 molecular sieve material, its synthesis and use | |
| CN105983437B (en) | A kind of catalyst of the structure molecular screen containing MWW, preparation method and applications | |
| JP6698842B2 (en) | Synthesis of molecular sieve SSZ-105 | |
| JP2021500286A (en) | Molecular Sieve SZZ-112, its synthesis and use | |
| EP3445715B1 (en) | Synthesis of zeolite ssz-31 | |
| Sada et al. | Biased Al distribution of high-silica FAU-type zeolite synthesized by fast manner at high temperature | |
| CN105984879B (en) | A kind of MWW structure molecular screen and preparation method thereof | |
| CN105293515B (en) | A kind of MWW structure molecular screens and its synthetic method | |
| JP7148641B2 (en) | EMM-37 materials and methods and uses thereof | |
| CN106608640B (en) | It is a kind of that obtained molecular sieve is modified by NaY | |
| US10099934B2 (en) | Molecular sieve, COK-5, its synthesis and use | |
| JP7119128B2 (en) | Synthesis of molecular sieve SSZ-109 | |
| Chen et al. | Recent advances in synthetic strategies and physicochemical modifications of SSZ-13 zeolites: A review | |
| KR20240073952A (en) | EMM-68 aluminosilicate zeolite, synthesis and uses | |
| US9617165B1 (en) | Method for making molecular sieve SSZ-105 | |
| WO2024008494A1 (en) | Ewt framework molecular sieves, manufacturing processes and uses thereof | |
| KR20240065295A (en) | EMM-63 aluminosilicate zeolite, synthesis and uses | |
| WO2023154656A1 (en) | Use of cations selected from 1,2,3,5-tetramethylbenzimidazolium, and 1,2, 3,4,5- pentamethylbenzimidazolium as structure directing agents for the preparation of molecular sieves and molecular sieves obtained using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |