CN106276957A - A kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural and synthetic method thereof - Google Patents
A kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural and synthetic method thereof.Described ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline is made up of in the center of area close heap mode of high-sequential interconnective molecular sieve nano structured unit.The present invention combines hard template method and dry gum method, is the most successfully simultaneously introduced macropore, mesopore orbit in Silicalite-1 zeolite single crystal.Ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 the monocrystalline of synthesis is provided simultaneously with multi-stage artery structure and two advantages of mono-crystalline structures, there is pore volume and higher specific surface area, excellent adsorbing separation and the structural stability of super large, have a extensive future.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, be specifically related to a kind of ordered big hole-mesoporous multi-stage porous with opal structural
Pure silicon molecular sieve Silicalite-1 monocrystalline and synthetic method thereof.
Background technology
Silicalite-1, as total silicon zeolite, has of a relatively high heat stability and chemical stability, its special ten-ring duct
Structure and stronger hydrophobic oleophylic performance so that it is extensively should obtain in isomerization separation, infiltration evaporation, Organic substance removing system
With.But the transmission in molecular sieve of its micropore canals size limitation macromole and diffusion, thus inhibit it in macromole side
The application in face, therefore in molecular sieve, construct multistage pore canal thus improve the circulation diffusion of zeolite molecular sieve become macromole should
An urgent demand.
By introducing multi-stage artery structure in zeolite molecular sieve system, in conjunction with the highly acid of micropore canals and high stability and mesoporous/
The mass transfer performance that macropore duct is excellent, provides brand-new approach for solving the above-mentioned application bottleneck of zeolite molecular sieve.Due to
The existence of its multi-stage artery structure, multi-stage pore zeolite molecular sieve has the pore volume of open pore passage structure and super large, substantially increases
The circulation diffusion of molecular sieve.Therefore design synthesis multifunctional multistage hole zeolite molecular sieve becomes the zeolite of new structure and function
The study hotspot of molecular sieve.
The multi-stage pore zeolite molecular sieve of synthesis is broadly divided into porous zeotile crystal, nano zeolite crystal, wherein multi-stage porous boiling at present
Stone crystal refers to exist in micro-pore zeolite crystal the pore structure in other ducts, and nano zeolite crystal refers to by the zeolite of nanoscale brilliant
The material that body self assembly is piled up.Due to molecular sieve nanocrystalline generation agglomeration, thus had across yardstick hole by what it was constructed
The stability of the multi-stage artery structure of road structure is bad, therefore builds and has the zeolite single crystal of multistage pore canal and have important research
Meaning.
The research of multi-stage porous zeolite single crystal at present focuses primarily upon synthesis and the catalytic applications of mesopore molecular sieve monocrystalline.Utilize template
It is the effective approach preparing multi-stage porous zeolite single crystal at present that mesoporous or macroporous structure is constructed in agent in molecular screen material.As
Jacobsen etc. [J.Am.Chem.Soc.2000,122,7116-7117] are using carbon nano-particle as hard template, in zeolite crystallization process
In, by using excess gel that carbon nano-particles is wrapped in crystals, roast can obtain after removing medium carbon template containing brilliant
Interior mesoporous zeolite monocrystalline.Xiao Fengshou etc. [J.Am.Chem.Soc.2014,136,2503-2510] use cationic polymer to gather first
Diallyldimethylammonium chloride (PDADMA) is as micropore/mesoporous dual mould plate agent, and one-step synthesis method has high-crystallinity
Mesoporous single crystals Beta zeolite.
But the multi-stage artery structure stability of the multi-stage porous molecular sieve being piled into by nano molecular sieve can not show a candle to have multistage pore canal
Zeolite single crystal, thus construct multi-stage porous zeolite single crystal and there is important Research Significance.The most up to the present, existing many
The research of level hole zeolite molecular sieve is limited only to constructing of single pore passage structure, is provided simultaneously with macropore and mesoporous multi-stage porous molecular sieve
Monocrystalline not yet has been reported that.
Summary of the invention
It is an object of the invention to provide a kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve with opal structural
Silicalite-1 monocrystalline and synthetic method thereof, described ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline has height
Spending orderly macroporous structure (opal structural), maximizing ground exposes the active site in molecular sieve structure and greatly carries
The circulation diffusion of macromolecule sieve, thus it is effectively improved its catalysis activity.
For achieving the above object, the technical solution used in the present invention is: a kind of ordered big hole-mesoporous multistage with opal structural
Hole pure silicon molecular sieve Silicalite-1 monocrystalline, it by interconnective molecular sieve nano structured unit with the center of area Mi Dui side of high-sequential
Formula forms, and has orderly opal structural.
The synthesis side of above-mentioned a kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural
Method, specifically includes following steps:
1) preparation of dry glue: silicon source, organic formwork agent (molecular sieve structure directed agents), water and dehydrated alcohol are mixed and stirred for
Uniformly, obtaining molecular sieve precursor solution, be subsequently adding hard template, stir to obtain mixed solution I, mixed solution I is evaporated
Dry glue;
2) crystallization: by step 1) in gained dry glue be placed in reactor, Polycondensation Reactor and Esterification Reactor adds water, and then carries out dry glue at crystallization
Reason, by regulation and control crystallization temperature and crystallization time, obtains Silicalite-1 molecular sieve crystal/ordered big hole-mesoporous multi-stage porous carbon mixing material
Material, the most scrubbed, dry and calcination process, obtain the described ordered big hole with opal structural-mesoporous multi-stage porous pure silicon and divide
Son sieve Silicalite-1 monocrystalline.
In such scheme, described organic formwork agent is TPAOH;Silicon source is tetraethyl orthosilicate.
In such scheme, described hard template is ordered big hole-mesoporous multi-stage porous carbon material, and macropore diameter is 300~600nm, mesoporous
Aperture is 10~40nm, and its preparation method comprises the following steps: polystyrene microsphere (macropore template) and silica nanosphere (are situated between
Casement plate) it is scattered in aqueous sucrose solution, ultrasonic suspension solution, it is subsequently adding the aqueous sulfuric acid that mass fraction is 5~15%,
Obtaining mixed solution I I, wherein the mass ratio of polystyrene microsphere, silica nanosphere, sucrose and aqueous sulfuric acid is
(6~8): 1:(0.8~1.2): (0.08~0.12), the size of polystyrene microsphere is 300~600nm, and silica nanosphere is a size of
10~40nm;(first heat at 100 DEG C through evaporation self assembly (heating 12h at 60 DEG C), preliminary carbonization cured the most successively
6h, then heats 6h at 160 DEG C) and secondary carbonization cured (700 DEG C of high-temperature roasting 2h under inert atmosphere), obtain described hard
Template (ordered big hole-mesoporous multi-stage porous carbon material).
In such scheme, described step 1) in silicon source, organic formwork agent, water (include the water described in step 1 and organic formwork
In agent introduce water) and the mol ratio of dehydrated alcohol be 1:(0.15~0.30): (6~20): (10~50);The consumption of hard template is with silicon source water
Gained SiO after solution2Quality be as the criterion, SiO2Mass ratio (0.2~0.6) with hard template: 1.
In such scheme, described step 2) in the mass ratio of water and dry glue be (2~4): 1.
In such scheme, described Crystallizing treatment technique is: react 12~36h under 150~200 DEG C (reaction temperature).
In such scheme, described sintering temperature is 500~600 DEG C, and roasting time is 4~7h.
In such scheme, described inert atmosphere is nitrogen or argon etc..
The principle of the present invention is: combine hard template method and dry gum method, by hard template (ordered big hole-mesoporous multi-stage porous carbon material) with
Molecular sieve precursor solution mixes and is evaporated to obtain dry glue, recycles dry gel conversion method crystallization zeolite gel, due to water in dry gum method
Limit so that in dry glue, the diffusion mobility of each material is also by certain obstruction, ensures that each material and porous carbon template
It is in close contact so that ordered big hole-mesoporous porous carbon materials (hard template) will not be rejected as an outsider in dry glue crystallization process,
Afterwards by high-temperature roasting, remove the ordered big hole-mesoporous multi-stage porous carbon material (hard template) being embedded in zeolite single crystal, obtain high
The ordered big hole with the opal structural-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline of degree crystallization.
The invention have the benefit that
1) use ordered big hole-mesoporous multi-stage porous carbon material as hard template, under dry gum method synthesis condition, prepare micron order and
There is macropore, mesoporous, the pure silicon molecular sieve Silicalite-1 monocrystalline of micropore hierarchical porous structure, the most successfully at pure silicon molecular sieve
Silicalite-1 monocrystalline is simultaneously introduced macropore, mesopore orbit, and synthetic method simple.
2) present invention synthesis pure silicon molecular sieve Silicalite-1 monocrystalline by interconnective molecular sieve nano structured unit highly to have
The closely packed mode of the center of area of sequence forms, and has the macroporous structure (opal structural) of high-sequential.
3) the pure silicon molecular sieve Silicalite-1 monocrystalline of present invention synthesis combines the excellent of both multi-stage artery structure and zeolite single crystal
Gesture, has the pore volume of the highest specific surface area and super large, and on the one hand hierarchical porous structure substantially increases the circulation diffusion of molecular sieve
Property;On the other hand, mono-crystalline structures imparts again the structural stability that molecular sieve is high.Sieve relative to conventional molecular, we's legal system
The multi-stage porous zeolite single crystal obtained has preferably circulation diffusion and structural stability.
Accompanying drawing explanation
Fig. 1 is the ordered big hole with opal structural-mesoporous multi-stage porous pure silicon molecular sieve that the embodiment of the present invention 1 prepares
The XRD diffraction pattern of Silicalite-1 monocrystalline.
Fig. 2 is the ordered big hole with opal structural-mesoporous multi-stage porous pure silicon molecular sieve that the embodiment of the present invention 2 prepares
(a, b) scanning electron microscope (SEM) photograph of Silicalite-1 monocrystalline and (c, d) transmission electron microscope picture.
Fig. 3 is the ordered big hole with opal structural-mesoporous multi-stage porous pure silicon molecular sieve that the embodiment of the present invention 3 prepares
(a) nitrogen adsorption curve of Silicalite-1 monocrystalline, (b) micropore size scattergram and (c) mesoporous pore size scattergram.
Detailed description of the invention
The present invention will be described further with embodiment below in conjunction with the accompanying drawings, but present disclosure is not limited solely to following
Embodiment.
In following example, as no specific instructions, described reagent is commercially available chemical reagent.
Described silicon source is tetraethyl orthosilicate;Described organic formwork agent is TPAOH.
Described hard template is ordered big hole-mesoporous multi-stage porous carbon material, and its preparation method comprises the following steps: by polystyrene microsphere
(macropore template) and silica nanosphere (mesoporous template) are scattered in aqueous sucrose solution, ultrasonic suspension solution, are subsequently adding matter
Amount mark is the aqueous sulfuric acid of 10%, and wherein the mass ratio of polystyrene microsphere, silica nanosphere, sucrose and sulphuric acid is
(6~8): 1:(0.8~1.2): (0.08~0.12), the size of polystyrene microsphere is 300~600nm, and silica nanosphere is a size of
10~40nm;Successively through evaporation self assembly (at 60 DEG C be incubated 12h), preliminary carbonization cured (at 100 DEG C, be first incubated 6h,
Then at 160 DEG C, it is incubated 6h) and secondary carbonization cured (700 DEG C of high-temperature roasting 2h under nitrogen atmosphere), obtain described having
Sequence foramen magnum-mesoporous multi-stage porous carbon material, macropore diameter is 300~600nm, and mesoporous pore size is 10~40nm.
Embodiment 1
A kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural, its synthetic method bag
Include following steps:
0.832g tetraethyl orthosilicate is dropwise instilled 0.6g TPAOH aqueous solution (20wt%), 0.6g deionized water and
7.36g dehydrated alcohol mixes, stirs to obtain molecular sieve precursor solution, wherein silicon source, organic formwork agent, water
The mol ratio of (including the water in deionized water and TPAOH aqueous solution) and dehydrated alcohol is 1:0.15:20:40;Then
Add 0.8g hard template (ordered big hole-mesoporous multi-stage porous carbon material, macropore diameter is 400nm, and mesoporous pore size is 20nm),
Mixed solution I, is placed in mixed solution I in 80 DEG C of water-baths to be evaporated and obtains dry glue;Weigh 0.3g dry glue and be placed in reactor (volume
For 150mL) in, bottom adds 1.2g deionized water, is heated to 180 DEG C of crystallization 24h, the most scrubbed, dry, roasting (
Roasting 7h at 550 DEG C), obtain the described ordered big hole with opal structural-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 mono-
Brilliant.
Fig. 1 is the XRD figure that the present embodiment prepares product.As seen from Figure 1, spectrogram occurs in that MFI-type molecular sieve
Characteristic diffraction peak, and peak is the highest, illustrates that the degree of crystallinity of products therefrom is the highest.
Embodiment 2
A kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural, its synthetic method bag
Include following steps:
0.555g tetraethyl orthosilicate dropwise instills 0.6g TPAOH aqueous solution (20wt%) enter with 2.45g dehydrated alcohol
Row mixing, stirs to obtain molecular sieve precursor solution, wherein silicon source, organic formwork agent, water (TPAOH
The water comprised in aqueous solution) and the mol ratio of dehydrated alcohol be 1:0.22:10:20;Be subsequently adding 0.53g hard template (ordered big hole-
Mesoporous multi-stage porous carbon material, macropore diameter is 500nm, and mesoporous pore size is 10nm) obtain mixed solution I, mixed solution I is placed in
80 DEG C of water-baths are evaporated and obtain dry glue;Weigh 0.1g dry glue to be placed in reactor (volume is 100mL), bottom add 0.2g go from
Sub-water, is heated to 150 DEG C of crystallization 36h, the most scrubbed, dry, roasting (roasting 6h at 550 DEG C), obtains described tool
There is the ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline of opal structural.
Fig. 2 is (a, b) scanning electron microscope (SEM) photograph and (c, d) transmission electron microscope picture that the present embodiment prepares product, can in conjunction with scanning and transmission plot
Knowing that gained pure silicon molecular sieve Silicalite-1 has complete mono-crystalline structures, its a size of 3~4 μm, by the homogeneous (400nm of size
Left and right) molecular sieve nano structured unit form with the closely packed form of the center of area of high-sequential.These molecular sieve nanos
Construction unit is connected with each other, and the pure silicon molecular sieve Silicalite-1 of formation has the macroporous structure (opal structural) of high-sequential, complete
Replicate the ordered big hole structure of ordered big hole-mesoporous multi-stage porous carbon material beauteously.Understand every in conjunction with Fig. 2 (c, d) transmission electron microscope picture
Individual zeolite single crystal all exists the macroporous structure of macroscopic view.
Embodiment 3
A kind of ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural, its synthetic method bag
Include following steps:
1.109g tetraethyl orthosilicate is dropwise instilled 1.35g TPAOH aqueous solution (20wt%), 0.84g deionized water and
12.3g dehydrated alcohol mixes, and stirs to obtain molecular sieve precursor solution, wherein silicon source, organic formwork agent, water (bag
Include the water in deionized water and TPAOH aqueous solution) and the mol ratio of dehydrated alcohol be 1:0.25:20:50;It is subsequently adding
1g hard template (ordered big hole-mesoporous multi-stage porous carbon material, macropore diameter is 300nm, and mesoporous pore size is 30nm) obtains mixed solution
I, is placed in mixed solution I in 80 DEG C of water-baths to be evaporated and obtains dry glue;Weigh 0.4g dry glue and be placed in reactor (volume is 150mL)
In, bottom adds 0.8g deionized water, is heated to 200 DEG C of crystallization 12h, and the most scrubbed, dry, roasting (roasts at 550 DEG C
Burn 7h), obtain the described ordered big hole with opal structural-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline.
Fig. 3 is that the present embodiment prepares (a) nitrogen adsorption curve of product, (b) micropore size scattergram and (c) mesoporous pore size scattergram.
Understood the adsorption isothermal curve of products therefrom by Fig. 3 (a) and there is the biggest absorption when relative pressure is less than 0.02, illustrate in product
There is substantial amounts of micropore canals structure;Products therefrom is to there is hysteresis loop in the range of 0.2~0.8 at relative pressure, illustrates in product
There is mesopore orbit structure.The micropore size understanding products therefrom in conjunction with Fig. 3 (b) and Fig. 3 (c) is concentrated mainly on about 0.45nm,
And pore-size distribution relative narrower, the mesoporous pore size of products therefrom is concentrated mainly on about 2.7nm, and pore-size distribution relative narrower,
The micropore specific area of product is 295m2/ g, mesopore surface area is 239m2/g。
The foregoing is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, making some modifications and variations, these broadly fall into protection scope of the present invention.
Claims (8)
1. ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline with opal structural, it is characterised in that
Described ordered big hole-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline by interconnective molecular sieve nano structured unit with
The center of area close heap mode of high-sequential forms, and has orderly opal structural.
2. the ordered big hole with opal structural described in claim 1-mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline
Synthetic method, it is characterised in that comprise the following steps:
1) preparation of dry glue: be mixed and stirred for silicon source, organic formwork agent, water and dehydrated alcohol uniformly, obtaining molecular sieve precursor
Solution, is subsequently adding hard template, and stir to obtain mixed solution I, and mixed solution I is evaporated to obtain dry glue;
2) crystallization: by step 1) in gained dry glue be placed in reactor, Polycondensation Reactor and Esterification Reactor adds water, and then carries out dry glue at crystallization
Reason, by regulation and control crystallization temperature and crystallization time, obtains Silicalite-1 molecular sieve crystal/ordered big hole-mesoporous multi-stage porous carbon mixing material
Material, the most scrubbed, dry and calcination process, obtain the described ordered big hole with opal structural-mesoporous multi-stage porous pure silicon and divide
Son sieve Silicalite-1 monocrystalline.
Synthetic method the most according to claim 2, it is characterised in that described organic formwork agent is TPAOH;Silicon
Source is tetraethyl orthosilicate.
Synthetic method the most according to claim 2, it is characterised in that described hard template is ordered big hole-mesoporous multi-stage porous carbon material
Material, macropore diameter is 300~600nm, and mesoporous pore size is 10~40nm, and its preparation method comprises the following steps: polystyrene is micro-
Ball and silica nanosphere are scattered in aqueous sucrose solution, and ultrasonic disperse obtains suspension solution, and being subsequently adding mass fraction is 5~15%
Aqueous sulfuric acid, obtain mixed solution I I, wherein polystyrene microsphere, silica nanosphere, sucrose and aqueous sulfuric acid
Mass ratio is (6~8): 1:(0.8~1.2): (0.08~0.12), the size of polystyrene microsphere is 300~600nm, silica nanosphere
A size of 10~40nm;Mixed solution I I is heated at 60 DEG C 12h and is evaporated self assembly;Then carry out at preliminary carbonization solidification
Reason, concretely comprises the following steps: be first warming up to 100 DEG C of heating 6h, then heats to 160 DEG C of heating 6h;Finally add under an inert atmosphere
At hot to 700 DEG C, roasting 2h carries out secondary carbonization cured, obtains described hard template.
Synthetic method the most according to claim 2, it is characterised in that described step 1) in silicon source, organic formwork agent, water
It is 1:(0.15~0.30 with the mol ratio of dehydrated alcohol): (6~20): (10~50);The addition of hard template is with gained SiO after the hydrolysis of silicon source2
Quality be as the criterion, SiO2Mass ratio (0.2~0.6) with hard template: 1.
Synthetic method the most according to claim 2, it is characterised in that described step 2) in the mass ratio of water and dry glue be
(2~4): 1.
Synthetic method the most according to claim 2, it is characterised in that described Crystallizing treatment technique is: at 150~200 DEG C
Lower reaction 12~36h.
Synthetic method the most according to claim 2, it is characterised in that described sintering temperature is 500~600 DEG C, roasting time
It is 4~7h.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108947337A (en) * | 2018-06-22 | 2018-12-07 | 东莞市夏日东升首饰有限公司 | A kind of preparation method of artificial opals |
CN109746025A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of denitrating catalyst and its preparation method and application |
CN112479222A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院大连化学物理研究所 | Hierarchical pore pure silicon zeolite molecular sieve and preparation method thereof |
CN114534436A (en) * | 2021-12-21 | 2022-05-27 | 南京瑞杨医用科技有限公司 | Medical molecular sieve oxygen generation system |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103447078A (en) * | 2013-09-06 | 2013-12-18 | 中国科学院金属研究所 | Nano MFI-type molecular sieve with hierarchical pore structure and preparation method and application thereof |
CN103979570A (en) * | 2014-05-14 | 2014-08-13 | 武汉理工大学 | Synthetic method of novel ordered macroporous-mesoporous-microporous hierarchical porous silicon-aluminium molecular sieve |
-
2015
- 2015-05-29 CN CN201510288342.2A patent/CN106276957B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103447078A (en) * | 2013-09-06 | 2013-12-18 | 中国科学院金属研究所 | Nano MFI-type molecular sieve with hierarchical pore structure and preparation method and application thereof |
CN103979570A (en) * | 2014-05-14 | 2014-08-13 | 武汉理工大学 | Synthetic method of novel ordered macroporous-mesoporous-microporous hierarchical porous silicon-aluminium molecular sieve |
Non-Patent Citations (1)
Title |
---|
F. PIRET ET AL.: "Effects of pH and ionic strength on the self-assembly of silica colloids to opaline photonic structures", 《CHEMICAL PHYSICS LETTERS》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109746025A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of denitrating catalyst and its preparation method and application |
CN108947337A (en) * | 2018-06-22 | 2018-12-07 | 东莞市夏日东升首饰有限公司 | A kind of preparation method of artificial opals |
CN112479222A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院大连化学物理研究所 | Hierarchical pore pure silicon zeolite molecular sieve and preparation method thereof |
CN114534436A (en) * | 2021-12-21 | 2022-05-27 | 南京瑞杨医用科技有限公司 | Medical molecular sieve oxygen generation system |
CN114534436B (en) * | 2021-12-21 | 2023-03-10 | 南京瑞杨医用科技有限公司 | Medical molecular sieve oxygen generation system |
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