CN106032280A - Synthesis method, product and applications of mordenite having mesopores and micropores - Google Patents
Synthesis method, product and applications of mordenite having mesopores and micropores Download PDFInfo
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Abstract
The present invention discloses a synthesis method, a product and applications of mordenite having mesopores and micropores. According to the present invention, the method comprises stepwise preparation of an initial gel and stepwise crystallization; the mordenite obtained by the method has micropores and mesopores, and has excellent performances and stability in the fields of adsorption and catalysis; and the synthesis method is simple, and especially the broad industrial application prospect is provided when the mordenite is applied in the dimethyl ether carbonylation reaction catalyst.
Description
Technical field
The application belongs to chemical field, in particular to a kind of modenite, its preparation side
Method and application thereof.
Background technology
Modenite is to have two-dimensional channel, and its structure is determined in 1961 by Meier, this molecule
The pore passage structure twelve-ring duct by 0.67*0.70nm of sieve and the octatomic ring hole of 0.34*0.48nm
Road forms.Owing to the duct of octatomic ring is the least, a lot of molecules cannot be introduced into, so it has been generally acknowledged that mercerising
Zeolite is the molecular sieve of one-dimensional channels.The pore passage structure unique due to modenite and acidity, in catalysis
Cracking, toluene disproportionation and transalkylation reacts, alkylating aromatic hydrocarbon, xylene isomerization, dimethyl ether carbonyl
The reactions such as change has important application.
But in actual applications, the macromole such as aromatic hydrocarbon can be restricted due to the pore passage structure of its relative narrowness
Diffusion wherein, easily causes catalysqt deactivation.On the other hand, due to serious diffusion-restricted,
Make substantial amounts of avtive spot be difficult to touch, thus have a strong impact on the activity of catalyst.So, system
For containing mesoporous modenite, improve the mass-transfer performance of modenite, urge for improving catalyst
Change performance and there is important value.Meanwhile, reduce crystallite dimension and can effectively shorten the evolving path, have
Help the diffusion of reactant and product, improve its catalytic performance, so the molecular sieve of synthesis nanoscale
With the focus containing mesoporous molecular sieve being research at present.
Summary of the invention
An aspect according to the application, it is provided that a kind of conjunction with the mesoporous modenite with micropore
One-tenth method, described method has the advantage that process is simple, can be easily separated, be prone to heavy industrialization,
The modenite of described method synthesis avoids the defect of single pore passage structure, in terms of absorption and catalysis
Have broad application prospects.
The described synthetic method with the mesoporous modenite with micropore, it is characterised in that by template
SAA is dissolved in sodium hydroxide and/or potassium hydroxide solution, is sequentially added into aluminum source, silicon source, in 80 DEG C
～after 100 DEG C of pre-crystallization were no less than 2 hours, be no less than 12 hours then at 120 DEG C～220 DEG C of crystallization；
At least one in surfactant of described template SAA.
Preferably, the synthetic method described in the mesoporous modenite with micropore at least includes walking as follows
Rapid:
A) template SAA is dissolved in sodium hydroxide and/or potassium hydroxide solution, obtains solution I；
Aluminum source is added solution I, after dissolving, obtains solution II；Silicon source is added in solution II, mix homogeneously,
Formed and there is the initial gel mixture of following mol ratio:
Al2O3/SiO2=0.01～0.1；
M2O/SiO2=0.10～0.40, wherein M is Na and/or K；
H2O/SiO2=10～100；
SAA/SiO2=0.01～0.30；
B) the described initial gel mixture obtained by step a) is many in 80 DEG C～100 DEG C of pre-crystallization
After 2 hours, it is no less than 12 hours then at 120 DEG C～220 DEG C of crystallization；
C) after step b) crystallization completes, solid product is separated, be dried, obtain described in there is Jie
Hole and the modenite of micropore.
In initial gel mixture, the molal quantity in silicon source is with SiO2Meter, with in system element silicon mole
Number is equal；The molal quantity in aluminum source is with Al2O3Meter, equal in system the 1/2 of aluminium element molal quantity；Micropore
The molal quantity of template R is in terms of the molal quantity of R itself；The molal quantity of mesoporous template SAA is with SAA
The molal quantity meter of itself；M2O molal quantity, to comprise in all raw materials (silicon source, aluminum source, alkali source)
The metal-oxide M corresponding to alkali metal M2The molal quantity meter of O, equal to alkali gold in all raw materials
Belong to the 1/2 of element M molal quantity.
Preferably, at least one in ionic surfactant of described surfactant.
It is further preferred that described surfactant (is abbreviated as selected from Cetyltrimethylammonium bromide
C18), cetyl trimethylammonium bromide (being abbreviated as C16), Tetradecyl Trimethyl Ammonium Bromide (letter
Be written as C14), Dodecyl trimethyl ammonium chloride (being abbreviated as C12), ethylene double hexadecyl diformazan
The double dodecyldimethylamine base ammonium bromide of base ammonium bromide (being abbreviated as C16-2-16), ethylene (is abbreviated as
C14-2-14), ethylene didodecyldimethylammbromide bromide (being abbreviated as C12-2-12), trimethylene double ten
The double dodecyldimethylamine base ammonium bromide of six alkyl dimethyl ammonium bromide (being abbreviated as C16-3-16), trimethylene
(being abbreviated as C14-3-14), trimethylene didodecyldimethylammbromide bromide (being abbreviated as C12-3-12),
The double dodecyldimethylamine of fourth support DHAB (being abbreviated as C16-4-16), fourth support
Base ammonium bromide (being abbreviated as C14-4-14), fourth support didodecyldimethylammbromide bromide (is abbreviated as
C12-4-12), hexamethylene DHAB (being abbreviated as C16-6-16), hexamethylene double ten
Tetraalkyl ditallowdimethyl ammonium bromide (being abbreviated as C14-6-14), hexamethylene didodecyldimethylammbromide bromide
At least one in (being abbreviated as C12-6-12).
As one preferred embodiment, described surfactant is by octadecyl trimethyl bromination
Ammonium, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, trimethyl bromine
Change ammonium, ethylene DHAB, ethylene double dodecyldimethylamine base ammonium bromide, second
Support didodecyldimethylammbromide bromide, trimethylene DHAB, trimethylene double 14
Alkyl dimethyl ammonium bromide, trimethylene didodecyldimethylammbromide bromide, fourth support double hexadecyl diformazan
Base ammonium bromide, fourth support double dodecyldimethylamine base ammonium bromide, fourth supports didodecyldimethylammbromide bromide,
The double dodecyldimethylamine base ammonium bromide of hexamethylene DHAB, hexamethylene, hexamethylene double ten
At least one composition in dialkyl dimethyl ammonium bromide.
As a preferred embodiment, described surfactant is by octadecyl trimethyl bromination
At least one composition in ammonium, cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride.
As a preferred embodiment, described surfactant is by ethylene double hexadecyl diformazan
The double dodecyldimethylamine base ammonium bromide of base ammonium bromide, ethylene, ethylene didodecyldimethylammbromide bromide,
Trimethylene DHAB, trimethylene didodecyldimethylammbromide bromide, fourth support double ten
At least one composition in the double dodecyldimethylamine base ammonium bromide of six alkyl dimethyl ammonium bromide, hexamethylene.
Preferably, Al in described step a) initial gel mixture2O3/SiO2Molar ratio scope
Lower limit is selected from 0.01,0.0125,0.013,0.015,0.016,0.02,0.025,0.03, and the upper limit is selected
From 0.075,0.25.It is further preferred that mol ratio in described step a) initial gel mixture
Al2O3/SiO2=0.015～0.075.
Preferably, M in described step a) initial gel mixture2O/SiO2Molar ratio scope under
Limit selected from 0.10,0.15,0.20, the upper limit selected from 0.27,0.29,0.33,0.35,0.36,0.38,
0.40.It is further preferred that mol ratio in described step a) initial gel mixture
M2O/SiO2=0.2～0.33, wherein M is Na and/or K.
Preferably, H in described step a) initial gel mixture2O/SiO2Molar ratio scope under
Limit is selected from 10,20,23,30, and the upper limit is selected from 50,55,60,70,80,90,100.Enter one
Walk preferably, mol ratio H in described step a) initial gel mixture2O/SiO2=20～60.
Preferably, SAA/SiO in described step a) initial gel mixture2Molar ratio scope under
Limit selected from 0.01,0.02,0.04,0.06,0.08,0.10, the upper limit selected from 0.15,0.16,0.20,
0.30.It is further preferred that mol ratio in described step a) initial gel mixture
SAA/SiO2=0.01～0.15.
Preferably, in described step a) silicon source selected from Ludox, Silica hydrogel, methyl silicate, just
At least one in silester, white carbon, waterglass.
Preferably, in described step a), aluminum source is selected from aluminum isopropylate., aluminium oxide, aluminium hydroxide, chlorine
Change at least one in aluminum, aluminum sulfate, aluminum nitrate, sodium aluminate.
Preferably, the pre-crystallization temperature range lower limit in described step b) is selected from 80 DEG C, 85 DEG C, 90 DEG C,
The upper limit is selected from 90 DEG C, 100 DEG C.
Preferably, in described step b) the time range lower limit of pre-crystallization selected from 2 hours, 4 hours,
6 hours, the upper limit was selected from 8 hours, 9 hours, 10 hours, 11 hours, 12 hours.The most excellent
Selection of land, pre-crystallization 2～12 hours in described step b).
Preferably, the crystallization temperature range lower limit in described step b) is selected from 120 DEG C, 125 DEG C, 130 DEG C,
The temperature range upper limit selected from 145 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 178 DEG C, 180 DEG C, 200 DEG C,
220℃.It is further preferred that the crystallization temperature in described step b) is 120～180 DEG C.More enter one
Preferably, the crystallization temperature in described step b) is 125～145 DEG C to step.
Preferably, in described step b), the time range lower limit of crystallization is selected from 12 hours, 24 hours,
The upper limit is selected from 120 hours, 144 hours, 150 hours, 168 hours, 216 hours.The most excellent
Selection of land, crystallization 12～168 hours in described step b).
It is further preferred that the initial gel mixture that described step b) obtains is pre-in 80～100 DEG C
Crystallization 2～after 12 hours, then at 125～145 DEG C of crystallization no less than 12～168 hours.
Preferably, described in have in the modenite of mesoporous and micropore, mesoporous aperture is 2～40nm.
Preferably, described in have in the modenite of mesoporous and micropore, the mesoporous pore volume ratio with micropore is
1.12～5.71: 1.
Preferably, the mode of the crystallization in described step b) and/or step c) can be static crystallization,
It can also be dynamic crystallization.
In the application, term " static crystallization " refers in crystallization process, equipped with initial gel mixture
Still be statically placed in baking oven, and the mixture in synthesis reactor is not stirred.
In the application, term " dynamic crystallization " refers to that the synthesis reactor equipped with initial gel mixture is at crystalline substance
During change, it is in nonstatic state, such as upset, rotation etc.；Or in crystallization process, to synthesis
Mixture within still is stirred.
Described step c) is dried, through roasting, obtains containing micropore and the boiling of mesoporous mercerising simultaneously
Stone.
Preferably, the molecular sieve silica alumina ratio SiO that technical scheme obtains2/Al2O3=4～70.
Another aspect according to the application, it is provided that a kind of have mesoporous and micropore modenite,
Described modenite is nano-particle, has bigger external surface area, avoids single duct simultaneously
The defect of structure, has broad application prospects in terms of absorption and catalysis.This has mesoporous and micropore
Modenite is prepared by any of the above-described kind of method.
Preferably, the external surface area of described modenite is 100m2/ g～240m2/g。
Preferably, described modenite has aperture is the mesoporous of 2nm～40nm.
Preferably, in described modenite, mesoporous is 1.12～5.71 with micropore pore volume ratio.
Another aspect according to the application, it is provided that there is Jie according to prepared by any of the above-described kind of method
Hole and the modenite of micropore and/or according to any of the above-described kind, there is mesoporous and micropore modenite and exist
Application in adsorbing separation and/or catalytic reaction.
Another aspect according to the application, it is provided that a kind of dimethyl ether carbonylation reaction catalyst, should
Catalyst has dimethyl ether conversion rate height, methyl acetate selectivity height, the advantage of life-span length, this catalysis
Agent is mesoporous by having of preparing of any of the above-described kind of method and the modenite of micropore and/or any of the above-described kind
There is mesoporous and micropore modenite roasting in ammonium ion exchange and 400～700 DEG C of air obtain
Arrive.
The beneficial effect that the application can produce at least includes:
1) preparation method of modenite provided herein, technique is simple, and template is cheap,
It is beneficial to large-scale industrial production.
2) modenite prepared according to method provided herein, has micropore and mesoporous, it is to avoid
The defect in single duct, has broad application prospects in terms of macromolecules adsorption and catalysis.
3) modenite prepared according to method provided herein, as adsorbent and catalyst,
In terms of diffusion and life-span, there is clear superiority.
4) modenite prepared according to method provided herein, as dimethyl ether carbonylation reaction
Catalyst, shows that conversion ratio is high, selectivity is good and the advantage of life-span length.
Accompanying drawing explanation
Fig. 1 is sample 1#X ray diffracting spectrum.
Fig. 2 is sample 1#Electron scanning micrograph.
Fig. 3 is sample 1#The partial enlargement of electron scanning micrograph.
Fig. 4 is sample 1#Nitrogen physisorption desorption isotherm.
Fig. 5 is the sample D1 in comparative example 1#Scanning electron microscope diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, the application is expanded on further.Only should be understood that these embodiments
For the application being described rather than limiting scope of the present application.
If no special instructions, the raw material in embodiments herein and catalyst are all purchased by commercial sources
Buy, directly use without any special handling.
Embodiments herein is analyzed method as follows:
Magix 2424X type ray fluorescence analysis instrument (XRF) of elementary composition employing Philips company
Measure.
X-ray powder diffraction material phase analysis (XRD) uses Holland's PANalytical (PANalytical) public
X ' the Pert PRO X-ray diffractometer of department, Cu target, K α radiation source (λ=0.15418nm), electricity
Pressure 40KV, electric current 40mA.
It is that Hitachi SU8020 Flied emission is swept that scanning electron microscope (SEM) tests institute's employing instrument
Retouching Electronic Speculum, accelerating potential is 2kV.
Using low temperature nitrogen physical absorption to characterize the pore structure of sample, instrument is Micromeritics
Company ASAP2020 type physical adsorption appearance.
Gas analysis sample uses U.S.'s Agilent (Agilent) company 6890GC type gas chromatograph
Carrying out on-line analysis, chromatographic column is Agilent (Agilent) company HP-5 capillary column.
Embodiment 1: sample 1#Preparation
First 0.31g Dodecyl trimethyl ammonium chloride (being abbreviated as C12) is dissolved in sodium hydroxide
In solution (0.55g NaOH is dissolved in 40g deionized water), add 0.467g sodium aluminate, stir
Mixing until being completely dissolved, then be added thereto to 20g Ludox, at room temperature continuing stirring until being formed
Uniform Primogel.Gel is put in the stainless steel cauldron of band polytetrafluoro liner, be warmed up to
80 DEG C of pre-crystallization 4h, then it is warming up to 130 DEG C of crystallization 168 hours, gained solid product is performing centrifugal separation on,
Be washed with deionized to neutrality, air drying at 110 DEG C, and in last in Muffle furnace in
550 DEG C of roasting 5h, i.e. obtain having mesoporous and micropore modenite, are designated as sample 1#.Prepared
Sample 1#Primogel in type of feed and proportioning, pre-crystallization temperature and time, crystallization temperature
With the time respectively such as sample 1 in table 1#Shown in.
Embodiment 2～25: sample 2#～25#Preparation
First surfactant is dissolved in sodium hydroxide and/or potassium hydroxide solution, adds aluminum source,
Stirring, until being completely dissolved, adds silicon source, at room temperature continues stirring until being formed uniform initial
Gel.Gel is put in the stainless steel cauldron of band polytetrafluoro liner, be warmed up to 80～100 DEG C in advance
Crystallization 2～12h, then it is warming up to be heated to 120～220 DEG C, crystallization 12～168 hours, gained solid
Product is performing centrifugal separation on, and is washed with deionized to neutrality, air drying at 110 DEG C, and in
Finally in 550 DEG C of roasting 5h in Muffle furnace, i.e. obtain that there is mesoporous and micropore modenite, note
For sample 2#～25#.Prepared sample 2#～25#Primogel in type of feed and proportioning, pre-
Crystallization temperature and time, crystallization temperature and time are the most as shown in table 1.
Table 1 Zeolite synthesis dispensing and crystallization condition table
Note*: silicon source:aLudox；bWhite carbon；cTetraethyl orthosilicate；dMethyl silicate；eSilica hydrogel；fWaterglass.
Aluminum source:ISodium aluminate；IIAluminum chloride；IIIAluminium hydroxide；IVAluminum sulfate；VAluminium oxide；VIAluminum isopropylate.；VIIAluminum nitrate.
Note**: Na2O and K2The proportioning of O adds metal-oxide Na contained in aluminum source, silicon source and alkali source with it2O and K2O calculates.
Comparative example 1
Concrete steps, proportioning raw materials and experiment condition are with implementing 1, and difference is, without pre-crystalline substance
Change.Primogel directly heats and is warming up to 130 DEG C, crystallization 168 hours, gained solid product through from
The heart separates, be washed with deionized to neutral, at 110 DEG C in air drying, Muffle furnace in 550 DEG C
Roasting 5h, obtains sample and is designated as sample D1#。
Embodiment 26: sample 1#～25#And D1#Silica alumina ratio
To sample 1#～25#And D1#Carry out XRF sign, measure elementary composition, calculate its SiO2/Al2O3
Mol ratio, be shown in Table 2.
Table 2 sample 1#～25#And D1#Silica alumina ratio
Embodiment 27: sample 1#～25#And D1#XRD characterize
To sample 1#～25#And D1#Carry out XRD sign.Sample 1#～25#And D1#XRD spectra
Consistent with the feature spectrogram of standard modenite zeolite molecular sieve, main diffraction maximum position and shape
Identical, fluctuate in the range of ± 5% according to the different relative peak intensities of synthesis condition, show sample 1#～25#
And D1#It is modenite.Typical XRD figure is composed with sample 1#For representing, as it is shown in figure 1,
Its XRD diffraction maximum data are shown in Table 3.
Table 3 sample 1#XRD diffraction maximum data
| Peak is numbered | 2θ[°] | I/I0*100 |
| 1 | 6.5385 | 42.16 |
| 2 | 8.6643 | 17.24 |
| 3 | 97697 | 57.57 |
| 4 | 13.5176 | 43.33 |
| 5 | 13.893 | 18.99 |
| 6 | 14.5909 | 8.59 |
| 7 | 15.3047 | 16.13 |
| 8 | 19.6621 | 39.77 |
| 9 | 21.4614 | 5.86 |
| 10 | 22.3171 | 82.78 |
| 11 | 23.2771 | 14.83 |
| 12 | 23.7291 | 12.33 |
| 13 | 25.686 | 100 |
| 14 | 26.3514 | 50.19 |
| 15 | 27.6727 | 50.47 |
| 16 | 27.9205 | 39.06 |
| 17 | 30.4794 | 6.6 |
| 18 | 30.9312 | 18.87 |
| 19 | 33.2226 | 3.24 |
| 20 | 34.0589 | 1.28 |
| 21 | 35.152 | 5.28 |
| 22 | 35.7392 | 10.91 |
| 23 | 36.5528 | 5.21 |
| 24 | 37.0559 | 3.81 |
| 25 | 40.5693 | 2.52 |
| 26 | 41.8484 | 1.26 |
| 27 | 44.3502 | 8.15 |
| 28 | 45.0623 | 5.94 |
| 29 | 46.6231 | 8.67 |
| 30 | 47.4923 | 2.99 |
| 31 | 48.5791 | 9.93 |
| 32 | 50.3698 | 2.87 |
Embodiment 28: sample 1#～25#And D1#Scanning electron microscope characterize
To sample 1#～25#And D1#It is scanned Electronic Speculum to characterize.Scanning electron microscope (SEM) photograph shows, sample 1#～25#
Pattern be all rendered as the gathering of spherical nanoparticles.Typical scanning electron microscope (SEM) photograph is with sample 1#For generation
Table, as in figure 2 it is shown, multi-stage porous modenite is the aggregation of ultrathin nanometer sheet as seen from the figure,
The size of nanometer sheet is 300nm × 300nm, after amplifying further, by Fig. 3 it appeared that its nanometer
Sheet is made up of less unit.
Sample D1#Scanning electron microscope diagram as shown in Figure 5.For sample it is as seen from the figure
The particle aggregate of 200～300nm.
Embodiment 29: sample 1#～25#And D1#Pore Characterization
Use low temperature nitrogen physical absorption to sample 1#～25#And D1#Carry out Pore Characterization.Its absorption is de-
All there is obvious hysteresis loop in attached isothermal line, and typical nitrogen adsorption desorption isotherm is with sample 1#For generation
Table, is shown in Fig. 4.Sample 1#～25#And D1#Pore Characterization result as shown in table 4, sample 1#～25#
There is bigger mesoporous pore volume and Micropore volume, i.e. sample 1 the most simultaneously#～25#There is mesoporous and micropore.
Sample D1#Then based on micropore, it is practically free of mesoporous.
Table 4 sample 1#～25#And D1#Pore Characterization result
Embodiment 30: sample 1#～25#And D1#For dimethyl ether carbonylation reaction
By sample 1#～25#And D1#Respectively through NH4NO3Sodium ion, 600 DEG C of air are removed in ion exchange
After middle roasting 4h, tabletting, it is crushed to 40～60 mesh, is designated as catalyst C1 respectively#～C25#And DC1#。
Weigh 1.0g catalyst C1 respectively#～C25#And DC1#, in fixed bed reactors, carry out two respectively
Methyl ether (being abbreviated as DME) carbonylation evaluation.When reaction starts, at 550 DEG C, logical nitrogen is lived
Change 1h, be then cooled to 200 DEG C and react.Gaseous mixture (DME/CO/N2=2/14/84, volume
Than), gas space velocity is 1500ml g-1h-1(STP), reaction pressure is 2.0Mpa.Through 2h
After induction period, sampling obtains the selectivity of methyl acetate in the conversion ratio of DME and product.Catalysis
Agent C1#～C25#Stability is all good, does not all have obvious deactivation phenomenom to occur in 25h.Catalysis
Agent C1#～C25#Conversion ratio and the life-span be generally higher than catalyst DC1#.The conversion ratio of DME, product
In thing, the selectivity of methyl acetate, catalyst life are shown in Table 5, and wherein inactivation standard is for converting
Rate reduces to the 50% of maximum conversion.
Table 5 sample 1#～25#And D1#Dimethyl ether carbonylation reaction result
| Catalyst is numbered | DME conversion ratioa | Methyl acetate selectivityb | Catalyst lifec |
| C1# | 70.5% | 99.0% | 29h |
| C2# | 71.2% | 98.7% | 28h |
| C3# | 69.3% | 98.2% | 25h |
| C4# | 70.2% | 99.2% | 27h |
| C5# | 68.4% | 99.1% | 28h |
| C6# | 67.9% | 98.7% | 29h |
| C7# | 65.4% | 99.0% | 28h |
| C8# | 68.7% | 99.2% | 29h |
| C9# | 61.5% | 98.5% | 28h |
| C10# | 65.2% | 98.3% | 27h |
| C11# | 69,8% | 98.4% | 29h |
| C12# | 67.4% | 98.5% | 28h |
| C13# | 66.2% | 98.7% | 27h |
| C14# | 69.5% | 98.9% | 28h |
| C15# | 62.8% | 98.9% | 29h |
| C16# | 68.6% | 99.1% | 29h |
| C17# | 69.3% | 99.0% | 25h |
| C18# | 71.4% | 99.1% | 26h |
| C19# | 67.1% | 98.7% | 29h |
| C20# | 63.7% | 99.0% | 28h |
| C21# | 63.4% | 99.1% | 29h |
| C22# | 68.4% | 98.9% | 28h |
| C23# | 69.8% | 99.1% | 27h |
| C24# | 64.3% | 99.2% | 28h |
| C25# | 65.7% | 99.0% | 27h |
| DC1# | 40% | 96.1% | 10h |
Note: a: maximum conversion in course of reaction.
B: reach the selectivity of methyl acetate during maximum conversion in course of reaction.
C: maximum conversion is to the half elapsed time that conversion ratio is maximum conversion.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. a synthetic method with the mesoporous modenite with micropore, it is characterised in that by mould
Plate agent SAA is dissolved in sodium hydroxide and/or potassium hydroxide solution, is sequentially added into aluminum source, silicon source,
After 80 DEG C～100 DEG C of pre-crystallization are no less than 2 hours, it is no less than 12 then at 120 DEG C～220 DEG C of crystallization
Hour, obtain described in there is mesoporous and micropore modenite；
At least one in surfactant of described template SAA.
Method the most according to claim 1, it is characterised in that at least comprise the steps:
A) template SAA is dissolved in sodium hydroxide and/or potassium hydroxide solution, obtains solution I；
Aluminum source is added in solution I, after dissolving, obtains solution II；Being added in silicon source in solution II, mixing is all
Even, formed and there is the initial gel mixture of following mol ratio:
Al2O3/SiO2=0.01～0.25；
M2O/SiO2=0.10～0.40, wherein M is Na and/or K；
H2O/SiO2=10～100；
SAA/SiO2=0.01～0.30；
B) the described initial gel mixture obtained by step a) is many in 80 DEG C～100 DEG C of pre-crystallization
After 2 hours, it is no less than 12 hours then at 120 DEG C～220 DEG C of crystallization；
C) after step b) crystallization completes, solid product is separated, be dried, obtain described in there is Jie
Hole and the modenite of micropore.
Method the most according to claim 1, it is characterised in that described surfactant is selected from
At least one in ionic surfactant.
Method the most according to claim 1, it is characterised in that described surfactant is selected from
Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide,
The double myristyl of Dodecyl trimethyl ammonium chloride, ethylene DHAB, ethylene
Ditallowdimethyl ammonium bromide, ethylene didodecyldimethylammbromide bromide, trimethylene di-cetyl dimethyl bromine
Change ammonium, trimethylene double dodecyldimethylamine base ammonium bromide, trimethylene didodecyldimethylammbromide bromide, fourth
Support DHAB, the double dodecyldimethylamine base ammonium bromide of fourth support, fourth support double 12
The double dodecyldimethylamine of alkyl dimethyl ammonium bromide, hexamethylene DHAB, hexamethylene
At least one in base ammonium bromide, hexamethylene didodecyldimethylammbromide bromide.
Method the most according to claim 2, it is characterised in that described step a) Primogel
Mol ratio SAA/SiO in mixture2=0.01～0.15.
Method the most according to claim 1, it is characterised in that the pre-crystalline substance in described step b)
The change time is 2 hours～12 hours.
Method the most according to claim 1, it is characterised in that the crystallization in described step b)
Temperature is 125 DEG C～145 DEG C, and crystallization time is 12 hours～168 hours.
8. one kind has mesoporous and micropore according to prepared by method described in any one of claim 1 to 7
Modenite, it is characterised in that the external surface area of described modenite is 100m2/ g～240m2/g；
It is the mesoporous of 2nm～40nm that described modenite has aperture.
Modenite the most according to claim 8, it is characterised in that in described modenite,
Mesoporous and micropore pore volume ratio is 1.12～5.71.
10. a dimethyl ether carbonylation reaction catalyst, it is characterised in that according to claim 1 to
The modenite with mesoporous and micropore of method synthesis described in 7 any one and/or according to Claim 8
Or there is the modenite of mesoporous and micropore described in 9 in ammonium ion exchange and 400～700 DEG C of air
Roasting obtains.
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