CN104973610B - Preparation method of one-dimensional pore nano molecular sieve - Google Patents
Preparation method of one-dimensional pore nano molecular sieve Download PDFInfo
- Publication number
- CN104973610B CN104973610B CN201410143158.4A CN201410143158A CN104973610B CN 104973610 B CN104973610 B CN 104973610B CN 201410143158 A CN201410143158 A CN 201410143158A CN 104973610 B CN104973610 B CN 104973610B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sample
- zsm
- parent
- solution
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of one-dimensional pore nano molecular sieves. The preparation method includes the steps of ball-milling molecular sieves in a ball miller, and performing treatment with an alkali solution and an acid solution to a nano powder at 60-120 DEG C for 0.5-6 h. The nano molecular sieves are high in degree of crystallinity so that the service life of a catalyst is significantly increased.
Description
Technical field
The present invention relates to a kind of preparation method of one-dimensional channels nano molecular sieve.
The invention still further relates to catalytic applications in oxygenatedchemicalss olefine reaction for the above-mentioned material.
Background technology
ZSM-22 molecular sieve is a kind of micropore of Mobile company of U.S. synthesis, high-silica zeolite, has 5,6 and 10 yuan of rings bones
Frame structure, has the one-dimensional ten-ring of TON（001 direction）Duct, port size is 0.46 × 0.57nm, no cage and intersection duct.
Due to its unique pore passage structure and more outer surface acidity, show good reaction in hydrocarbon isomerization reaction and live
Property.Researchers before mostly think, ZSM-22 does not have methanol to convert the reactivity of hydro carbons processed.Until 2009, Norway
The research worker of Oslo university finds（Chemcatchem2009,1,78-81）, in low feed rate and 400～500 DEG C of conditions
Under, ZSM-22 can be converted into the C rich in side chain by catalysis methanol5+Alkene and the extremely low aromatic hydrocarbons of content.This discovery makes with sky
So gas, coal or biomass are raw material, produce cleaning transport fuel via methanol route and are possibly realized.But it is one-dimensional to be limited by itself
The feature in duct, in hydrocarbon isomerization and the reaction of methanol conversion, all there is the defect of easy carbon distribution plug-hole inactivation, seriously in ZSM-22
Limit widely using of ZSM-22.
Nanometer and composite holes molecular screen material because having the characteristics that Active sites are many, mass transfer path is short and efficiency high,
Become the important developing direction that molecular sieve develops in recent years.The nanometer chi produced using traditional hydrothermal crystallizing method
Degree ZSM-22, shape characteristic is mostly aciculiform or bar-shaped, as mass transfer path one-dimensional channels along 001 direction（I.e. pin or rod
Direction）Growth, mass transfer path length, the improvement of mass-transfer efficiency is greatly limited.Compound duct molecular sieve aspect, adopts mostly
The hard template method such as meso-porous carbon material, that is, after fabricated in situ molecular sieve, burn material with carbon element to prepare compound porous molecular sieve.This method
Produced mesoporous be mostly mesoporous in crystal, due to molecule in crystal with extraneous diffusion according to microporous mesoporous micropore
Pattern, the method for improve mass-transfer efficiency effect unsatisfactory.
For the problems referred to above, the present invention proposes a kind of method preparing one-dimensional channels nano molecular sieve, and prepared one
Dimension duct nano molecular sieve, compared with original molecule sieve, have shorter mass transfer the evolving path, substantially increases it in the reaction
Mass-transfer efficiency, catalysis activity, carbon accumulation resisting ability and catalytic life.
Content of the invention
It is an object of the invention to provide a kind of method preparing one-dimensional channels nano molecular sieve, to improve, there is one-dimensional hole
The mass-transfer efficiency of road structure molecular screen and carbon accumulation resisting ability, and then its catalytic life is greatly improved.
For achieving the above object, the technical scheme that the present invention provides is as follows：
a）By molecular sieve parent and liquid mixing, after being placed in ball milling in ball mill, drying obtains sample after ball milling；
b）By step a）After the ball milling of gained, sample is placed in the alkaline solution that concentration is 0.2～1mol/L, process 0.5～
After 3 hours, drying obtains sample after alkali process；
c）By step b）After the alkali process of gained, sample is placed in the acid solution that concentration is 0.2～1mol/L, process 6～
After 10 hours, scrubbed, be dried after, obtain described nano molecular sieve.
As one preferred embodiment, step a）Described in molecular sieve parent and step c）Described in nano molecular sieve
Species is identical.For example, molecular sieve parent is ZSM-22 molecular sieve, and obtained nano molecular sieve is also nanometer ZSM-22 molecule
Sieve；Molecular sieve parent is the mixture of ZSM-23 and ZSM-48, and obtained nano molecular sieve is also nanometer ZSM-23 and nanometer
The mixture of ZSM-48.
As one preferred embodiment, step a）Described in molecular sieve parent be selected from ZSM-22, ZSM-23, ZSM-
48th, one or more of EU-1, SAPO-11 and SAPO-41.
As one preferred embodiment, step a）Described in molecular sieve parent before ball milling, first pass through roasting removing
Template.
As one preferred embodiment, step a）Described in the mass ratio of liquid and molecular sieve parent be 3～8:1.
As one preferred embodiment, step a）Described in liquid be selected from deionized water, ethanol, sodium hydroxide solution
One or more of with hydrochloric acid solution.Described sodium hydroxide solution and hydrochloric acid solution are sodium hydroxide and salt aqueous acid,
Concentration should be not higher than 5mol/L.
As one preferred embodiment, step b）Described in alkaline solution be that sodium hydroxide solution, potassium hydroxide are molten
Liquid or sodium aluminate solution.
As one preferred embodiment, step a）After gained ball milling the mass ratio of sample and alkaline solution be 10～
50.
As one preferred embodiment, step c）Described in acid solution be hydrochloric acid solution, sulfuric acid solution, nitric acid molten
Liquid or citric acid solution.
As one preferred embodiment, step b）After gained alkali process the mass ratio of sample and acid solution be 10～
50.
As one preferred embodiment, described alkaline solution and acid solution, are aqueous solution.
As one preferred embodiment, described step b）Middle alkali process and step c）The temperature of middle acid treatment, is
40～80 DEG C of waters bath with thermostatic control.
As one preferred embodiment, step a）Described in molecular sieve parent be ZSM-22 molecular sieve.
As one preferred embodiment, step a）Described in ball mill be planetary ball mill.
As one preferred embodiment, preparation method is as follows：
a）By molecular sieve parent, at a temperature of 550～600 DEG C, roasting removes template in 4～15 hours；
b）A certain amount of liquid is added to step a）In the sample of gained, after mix homogeneously, it is transferred to agate jar
In, add the abrading-ball of different-grain diameter size to carry out ball milling 4～48 hours, wherein the quality of the addition of liquid and added molecular sieve
Than for 3～8:1；
c）By step b）Molecular sieve solution after the ball milling obtaining passes through screen filtration in evaporating dish, in 100～120 DEG C
It is dried overnight in baking oven；
d）By step c）The molecular sieve powder of obtained drying is added in 0.2～1M alkaline solution in 40～80 DEG C of perseverances
Stir 0.5～3 hour in tepidarium, after filtration, obtain solid sample；
e）Deionized water and centrifuge washing step d）Solid sample, at least three times, be then transferred to 100 in baking oven
It is dried overnight in～120 DEG C；
f）By step e）The molecular sieve powder of the drying obtaining is added in 0.2～1M acid solution in 40～80 DEG C of constant temperature
Stirred in water bath 6～10 hours, obtains solid sample after filtration；
g）Deionized water and centrifuge washing step f）The solid sample obtaining, at least three times, is then transferred to baking oven
In be dried overnight the nanometer one-dimensional channels molecular sieve must with higher crystallinity in 100～120 DEG C.
A further object of the present invention is to provide a kind of catalyst of acid catalyzed reaction it is characterised in that according to aforementioned
The nano molecular sieve of one method preparation exchanges through acid, roasting obtains.
A further object of the present invention be to provide a kind of catalyst of oxygenatedchemicalss olefine reaction it is characterised in that
Nanometer ZSM-22 molecular sieve according to preceding method preparation exchanges through acid, roasting obtains.
According to general knowledge known in this field, described acid exchanges, roasting process, nano molecular sieve is become the process of H type.Often
Method is, by after molecular sieve and ammonium salt exchange, fired makes.
As one preferred embodiment, nano molecular sieve and ammonium salt exchange temperature are 50～90 DEG C, and exchange times are 3
Secondary；It is roasted to two one-step baking methods, the first step is 200～350 DEG C of roastings 0.5～2 hour, 500～600 DEG C of roastings 4～6 of second step
Hour.
According to general knowledge known in this field, described planetary ball mill, its operation principle is to be ground with test portion using abrasive material
Roll at a high speed in tank, material is produced with strong shear, impacts, roll the purpose reaching pulverizing, grinding, dispersion, emulsifying material.OK
, equipped with several ball grinders on same rotating disk, when rotating disk rotates, ball grinder is same revolve round the sun around turntable shaft for planetary ball mill
When again around Pivot Point Center rotation, make planetary motion.In tank, abrading-ball mutually collides in high-speed motion, grinds and aggregate sample
Product.
Beneficial effects of the present invention are as follows：
(1) no matter the particle diameter of molecular sieve parent is how many, all can prepare the one-dimensional channels molecular sieve of nano-scale, and
Again through the acid-alkali treatment of certain time, can effectively remove amorphous and fragment, micropore and the crystallization producing in mechanical milling process
Degree is restored, and no substantial amounts of mesoporous formation.
(2) less, ball milling does not have the bone of saboteur's sieve with acid, alkali process for the nano molecular sieve silica alumina ratio change prepared
Frame.
(3) the nanometer ZSM-22 molecular sieve through the method preparation, compared with ZSM-22 molecular sieve parent, has in 001 side
To shorter the evolving path, the reaction of methanol-to-olefins substantially increases the accessibility of its micropore, so that it is aobvious
Higher catalysis activity and carbon accumulation resisting ability are shown, the life-span of catalyst is substantially increased considerably.
Brief description
Fig. 1 is field emission scanning electron microscope,（a）ZSM-22 molecular sieve parent for sample 1#,（b）For sample 1#.
Fig. 2 is the XRD spectra of sample 1#.
Fig. 3 is that the sample 1# and XRD of its molecular sieve parent, sample 8# and sample 9# contrasts spectrogram.
Specific embodiment
Below by embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.
In embodiment, source chemicals used are all by commercially available acquisition.
Embodiment 1 nano molecular sieve sample preparation
Molecular sieve parent uses front elder generation 600 DEG C of roastings 10 hours in Muffle furnace, removes template agent removing.By the molecule after roasting
After sieve parent is uniform with a certain amount of liquid mixing, it is added in the agate jar of ball mill, adds mixing abrading-ball.Mill
The volume of ball, molecular sieve parent and liquid accounts for the 3/4 of ball grinder, and ball milling speed is 500r/min, and the time is 5 hours, filters, and dries
Dry, obtain the sample after ball milling.Molecular sieve after ball milling is put in conical flask, adds certain density alkaline solution, by every
The ratio of the sample+20ml alkaline solution after gram ball milling adds, and is washed with deionized water in 65 DEG C of waters bath with thermostatic control after stirring 30min
Wash to neutrality, dry in the baking oven and obtain sample after alkali process.Sample after alkali process is transferred in conical flask, is added thereto to
Certain density acid solution, is added in the ratio of sample+20ml acid solution after every gram of alkali process, in 65 DEG C of waters bath with thermostatic control
After stirring 6 hours, deionized water wash, to neutral, dried, is obtained nano molecular sieve sample, nano molecular sieve sample number into spectrum and system
The relation of standby dispensing and condition refers to table 1.
Table 1 sample number into spectrum, preparation dispensing and condition
The electron-microscope scanning Electronic Speculum of embodiment 2 sample characterizes
Prepared sample in embodiment 1 and its molecular sieve parent are scanned with Electronic Speculum characterize.Institute using instrument be
Hitachi SU8020 field emission scanning electron microscope, accelerating potential is 25kV.Scanning electron microscope (SEM) photograph shows, the pattern of sample 1#～7# is equal
The molecular sieve parent in order to prepare it for the ratio, is substantially reducing in 001 direction (straight hole road) upper size, molecular sieve parent and nanometer are divided
The particle diameter length range of son sieve is shown in Table 1.Typical scanning electron microscope (SEM) photograph as described in Figure 1, wherein Fig. 1（a）Female for sample 1# molecular sieve
Body, figure（b）For sample 1#.
Comparative example 1
Take sample 1# molecular sieve parent KZSM-22 molecular sieve 5g, put in conical flask, add concentration to be that 0.5M NaOH is molten
Liquid, is added in the ratio of every gram of catalyst 20ml, be washed with deionized after stirring 30min in 65 DEG C of waters bath with thermostatic control in
Property, it is transferred in conical flask after drying in baking oven, be added thereto to the HCl solution of 0.2M, by every gram of catalyst 20ml's
Ratio adds, and after stirring in 65 DEG C of waters bath with thermostatic control 6 hours, deionized water wash, to neutral, dried, is designated as sample 8#.
Take 1# sample molecule sieve parent KZSM-22 molecular sieve 5g, after mixing homogeneously with 20ml deionized water, be added to Achatess
In ball grinder, add mixing abrading-ball, the volume of mother bulb and molecular sieve, water accounts for the 3/4 of ball grinder, ball milling speed is 500r/
Min, the time is 5 hours, filters, and dries, is designated as sample 9#.
Embodiment 3 sample silica alumina ratio measures
Using instrument Magix（PHILIPS）Type xrf analysis instrument enters to the silica alumina ratio of sample 1#, sample 8# and sample 9#
Row characterizes, by IQ+No scalar quantity analysis program, the fluorescence intensity of standard sample and its standard is formed corresponding, deducts
The impact of interference spectral line, can obtain the silica alumina ratio of sample, as shown in table 2.Present invention preparation be can be seen that by table 2 data
Nano molecular sieve is little with the silica alumina ratio difference of its molecular sieve parent, illustrates that acid of the present invention, alkali treatment method do not have
Saboteur's sieve skeleton frame.
The silica alumina ratio of table 2 sample
| Sample | Silica alumina ratio |
| Sample 1# molecular sieve parent | 68 |
| 8# | 68 |
| 9# | 71 |
| 1# | 73 |
The XRD of embodiment 4 sample characterizes
XRD sign is carried out to sample 1#～9#, is Philips X ' Pert PROX type X-ray diffractometer, copper using instrument
Target, KαRadiation source（λ=1.5418）, instrument running voltage is 40kv, and operating current is 40mA.The XRD diffraction number of sample 1#
According to as shown in table 3, XRD diffraction spectrogram is as shown in Figure 2；Sample 1# is contrasted with the XRD of its molecular sieve parent, sample 8# and sample 9#
Spectrogram is as shown in Figure 3.
The XRD spectra of sample 2#～7#, consistent with the feature spectrogram of respective molecular sieve parent respectively, that is, diffraction maximum position and
Shape is identical, and peak intensity drops to the 50%～70% of molecular sieve parent peak intensity.
The XRD diffraction data of table 3 sample 1#
Embodiment 5 catalyst preparation
Take sample 1# molecular sieve parent, sample 8# and each 5g of sample 1#, use 1M NH4NO3After solution swaps 3 times to it
Dry, then roasting 2 hours, 550 DEG C of roastings 4 hours at 350 DEG C successively in Muffle furnace, obtain corresponding hydrogen type catalyst sample
Product, are respectively labeled as catalyst sample 10#, catalyst sample 11# and catalyst sample 12#.
Embodiment 6 catalyst reaction evaluation
Activity rating of catalyst is the quartz fixed bed reactor in continuous flowing（Internal diameter is 6mm）On carry out.Take
The each 50mg of catalyst sample 10#, 11# and 12# that embodiment 5 obtains, is loaded in quartz fixed bed reactor respectively, in reaction
Temperature is 400 DEG C, and air speed is 2.0g-1h-1Under the conditions of react.Catalyst sample 500 DEG C first in the high-purity helium atmosphere at live
Change 40min, be then cooled to 400 DEG C, after temperature stabilization, methanol feeds by way of carrier gas carries, helium flow velocity is
12.5ml/min, methanol saturation pipe temperature is 14 DEG C.Gas-phase product is using equipped with HP Plot Q chromatographic column and fid detector
Gas chromatogram on-line period is analyzed, and when calculating methanol conversion and selectivity of product, the dimethyl ether in gas phase is as reactant
Calculate.Reaction result shows and is shown in Table 4.
The preparing olefin by conversion of methanol reaction result of table 4 sample
* methanol conversion is 100%, and the online response time is selectivity of product when 6 minutes
The above, be only several embodiments of the present invention, not the present invention is done any type of limit although this
Bright with preferred embodiment disclose as above, but and be not used to limit the present invention, any those skilled in the art, do not taking off
In the range of technical solution of the present invention, when the technology contents of available the disclosure above make a little variation or modify all equivalent
In equivalence enforcement case, belong in the range of technical scheme.
Claims (9)
1. a kind of method preparing one-dimensional channels nano molecular sieve is it is characterised in that preparation process is as follows：
A), by molecular sieve parent and liquid mixing, after being placed in ball milling in ball mill, drying obtains sample after ball milling；
B) sample after the ball milling of step a) gained is placed in the alkaline solution that concentration is 0.2～1mol/L, processes 0.5～3 little
Shi Hou, drying obtains sample after alkali process；
C) sample after the alkali process of step b) gained is placed in the acid solution that concentration is 0.2～1mol/L, processes 6～10 little
Shi Hou, scrubbed, be dried after, obtain described nano molecular sieve；
Described molecular sieve parent is selected from one of ZSM-22, ZSM-23, ZSM-48, EU-1, SAPO-11 and SAPO-41 or many
Kind.
2. the method according to claim 1 is it is characterised in that institute in molecular sieve parent described in step a) and step c)
State nano molecular sieve species identical.
3. the method according to claim 1 is it is characterised in that molecular sieve parent described in step a) is before ball milling, first
Through roasting removed template method.
4. the method according to claim 1 is it is characterised in that the quality of liquid described in step a) and molecular sieve parent
Than for 3～8:1.
5. the method according to claim 1 it is characterised in that liquid described in step a) be selected from deionized water, ethanol,
One or more of sodium hydroxide solution and hydrochloric acid solution.
6. the method according to claim 1 is it is characterised in that alkaline solution described in step b) is that sodium hydroxide is molten
Liquid, potassium hydroxide solution or sodium aluminate solution；Acid solution described in step c) is hydrochloric acid solution, sulfuric acid solution, nitric acid are molten
Liquid or citric acid solution.
7. either method according to claims 1 to 6 is it is characterised in that molecular sieve parent described in step a) is ZSM-
22 molecular sieves.
8. a kind of catalyst of acid catalyzed reaction it is characterised in that either method according to claims 1 to 7 preparation receive
Rice molecular sieve exchanges through acid, roasting obtains.
9. a kind of catalyst of oxygenatedchemicalss olefine reaction it is characterised in that according to claim 7 method preparation
Nanometer ZSM-22 molecular sieve exchanges through acid, roasting obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410143158.4A CN104973610B (en) | 2014-04-10 | 2014-04-10 | Preparation method of one-dimensional pore nano molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410143158.4A CN104973610B (en) | 2014-04-10 | 2014-04-10 | Preparation method of one-dimensional pore nano molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104973610A CN104973610A (en) | 2015-10-14 |
| CN104973610B true CN104973610B (en) | 2017-02-15 |
Family
ID=54270642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410143158.4A Expired - Fee Related CN104973610B (en) | 2014-04-10 | 2014-04-10 | Preparation method of one-dimensional pore nano molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104973610B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197692A (en) * | 1997-04-28 | 1998-11-04 | 巴陵石化长岭炼油化工总厂 | Catalytic cracking catalyst and its preparation |
| CN101239326A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing propylene catalyst from methanol conversion |
| CN101332995A (en) * | 2008-03-25 | 2008-12-31 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing kaolin in-situ crystallization ZSM-5 molecular sieve |
| CN102372276A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing small crystal grain molecular sieve |
-
2014
- 2014-04-10 CN CN201410143158.4A patent/CN104973610B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197692A (en) * | 1997-04-28 | 1998-11-04 | 巴陵石化长岭炼油化工总厂 | Catalytic cracking catalyst and its preparation |
| CN101239326A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing propylene catalyst from methanol conversion |
| CN101332995A (en) * | 2008-03-25 | 2008-12-31 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing kaolin in-situ crystallization ZSM-5 molecular sieve |
| CN102372276A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing small crystal grain molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104973610A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107758691B (en) | The preparation method of high silicon CHA types SSZ-13 molecular sieves | |
| CN108217680B (en) | Method for synthesizing mordenite MOR molecular sieve, product and application thereof | |
| CN110124692A (en) | A kind of preparation method of the zinc-cadmium sulfide solid solution of different-shape | |
| Han et al. | Preparation of SSZ-13 zeolites and their NH3-selective catalytic reduction activity | |
| CN114436279B (en) | ZSM-22 molecular sieve, preparation method and application thereof, and n-dodecane isomerization reaction | |
| CN107226474A (en) | Mend aluminium method of modifying in a kind of ZSM-5 original positions | |
| CN111790412A (en) | Method for producing carbon compound by reducing carbon dioxide | |
| CN109201109B (en) | Catalyst for preparing olefin from methanol and preparation method thereof | |
| WO2019183842A1 (en) | Composite catalyst, preparation method therefor and method for preparing ethylene | |
| WO2016145619A1 (en) | Method for preparation of, and application of, mordenite having mesopores and micropores | |
| CN104495870A (en) | Method for preparing metal modified SAPO-34 molecular sieve | |
| CN109879265B (en) | Mesoporous nitrogen-doped carbon material and preparation method and application thereof | |
| CN106698452A (en) | Method for synthesizing nano-Beta molecular sieve | |
| CN104973610B (en) | Preparation method of one-dimensional pore nano molecular sieve | |
| CN115212882B (en) | Porous copper silicide intermetallic compound material and preparation and application thereof | |
| CN111017942B (en) | Seed crystal for synthesizing L-type molecular sieve and preparation method and application thereof | |
| CN115057453B (en) | Method for preparing SSZ-13 molecular sieve by using FCC spent catalyst and application thereof | |
| CN106698467A (en) | Synthetic method of nano SAPO-34 molecular sieve | |
| CN114804136B (en) | Preparation method and application of nano SSZ-13 molecular sieve | |
| CN110314696A (en) | A kind of preparation method of composite catalyst, preparation method and ethylene | |
| CN106976889A (en) | Si-Al zeolite molecular sieve with BOG structures and preparation method thereof | |
| CN108435245B (en) | Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof | |
| CN106698465A (en) | Method used for preparing nano ZSM-12 molecular sieve | |
| CN114380300B (en) | Rapid preparation method of small-crystal-grain SAPO-11 molecular sieve | |
| CN103818926A (en) | Preparation method of hierarchical-pore CoAlPO-5 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170215 Termination date: 20210410 |