CN109776252A - A kind of separation method of propylene propane - Google Patents
A kind of separation method of propylene propane Download PDFInfo
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- CN109776252A CN109776252A CN201910084741.5A CN201910084741A CN109776252A CN 109776252 A CN109776252 A CN 109776252A CN 201910084741 A CN201910084741 A CN 201910084741A CN 109776252 A CN109776252 A CN 109776252A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention discloses a kind of propylene propane separation method, include the following steps: that the ultra-microporous material of hydridization containing anion is contacted as adsorbent material with propylene/propane gaseous mixture, the identification of propylene is captured, realizes the separation of propane and propylene；The ultra-microporous material of hydridization containing anion is built-up by coordinate bond by inorganic fluo anion A, metal ions M and organic ligand L, and expression general formula is L-M-A: the organic ligand L is pyrazine and its derivative；The inorganic fluo anion A is NbF7 2‑、ZrF6 2‑、GeF6 2‑、SiF6 2‑、TiF6 2‑In any one；The metal ions M is Co2+、Ni2+、Fe2+、Mn2+In any one.By control accurate anion hydridization ultra-microporous material aperture, strong effect power is shown to propylene, while degree of rotation allows propylene to enter in pore structure in duct by control F atom, it is few to the propane active force amount of being less strongly adsorbed, it realizes and propylene propane is separated.
Description
Technical field
The invention belongs to technical field of chemical separation, and in particular to a kind of anion hydridization ultra-microporous material for propylene/
The method of propane separation.
Background technique
Propylene is to be only second to one of three big synthetic material base stocks of ethylene, main as important Elementary Chemical Industry raw material
From catalytic cracking and preparing ethylene by steam cracking byproduct, mainly for the production of polypropylene, acrylonitrile, isopropanol, epoxy third
Alkane etc..In industrial production, purified propylene synthesis polyacrylic to high quality is most important, therefore removes the propane pair in gaseous mixture
Propylene purification is particularly important.And current 41% propylene consumption still needs to meet by import；Propane is commonly used for the fuel of engine etc.,
Therefore propylene/propane separation is of great significance.
Propylene/propane separate mode is mainly cryogenic separation and rectifying separation now, since propylene, propane have extremely phase
As the physical properties such as boiling point, molecular dimension so that the separation of propylene/propane has larger challenge, conventional rectification mode is separated
Propylene/propane generally requires rectifying tower plates number greater than 120, and tower height is up to 90 meters, and reflux ratio is greater than 10, also need auxiliary pressurized,
The techniques such as refrigeration, so that traditional separate mode has the deficiencies of energy consumption is high, at high cost, complicated for operation.Such as patent
CN107011110A provides a kind of method that the rectifying column using two 50-100 meters separates propylene propane, but its reflux ratio is equal
Greater than 20, operating pressure is greater than 1MPa, has biggish energy consumption；Patent CN103980081A discloses a kind of by propylene
Realize that isolated technique, this method need to be pressurized after propylene propane liquefies, heats up, changes after propane liquefaction by multitower rectifying
Hot and reflux and etc., energy consumption is high, complicated for operation.Therefore, it needs to develop efficient, energy-saving and environmental protection isolation technics, realizes third
Alkene/propane separation.
In recent years, adsorption separation technology attracts extensive attention, and the technology investment is small, easy to operate, and lower production costs have
Good prospects for commercial application, core is exploitation high capacity high-selectivity adsorption agent material, but existing sorbent material is often
There are high-adsorption-capacity and highly selective the phenomenon that can not getting both, high degree limits sorbent material in the separation of propylene propane
Application.If metal-organic framework material Cu-BTC is respectively 7.7,7.1mmol/g, the ratio between adsorbance to propylene propane adsorbance
Only 1.08, illustrate that separation selectivity is low (Micropor.Mesopor.Mat., 2012,157,101)；A kind of total silicon type molecular sieve
DD3R has ultra-microporous, and propylene is allowed under 318K to enter duct, and by propane exclusion in outside hole, but to propylene adsorbance compared with
Low (Micropor.Mesopor.Mat., 2008,151,585).Therefore exploitation high capacity and highly selective sorbent material
Realize that propylene propane efficiently separates still with larger challenge.
Summary of the invention
The present invention provides a kind of propylene propane separation method, the separation of realization propylene propane rapidly and efficiently.
A kind of propylene propane separation method includes the following steps: the ultra-microporous material of hydridization containing anion as adsorbent material
It is contacted with propylene/propane gaseous mixture, the identification of propylene is captured, realizes the separation of propane and propylene；
The ultra-microporous material of hydridization containing anion is led to by inorganic fluo anion A, metal ions M and organic ligand L
It is built-up to cross coordinate bond, expression general formula is [L-M-A] n, and wherein n is positive integer:
The organic ligand L is pyrazine and its derivative, and structural formula isWherein R1 be H, F, CH3,
Any one in OH, CN, COOH；
The inorganic fluo anion A is NbF7 2-、ZrF6 2-、GeF6 2-、SiF6 2-、TiF6 2-In any one；
The metal ions M is Co2+、Ni2+、Fe2+、Mn2+In any one.
The present invention realizes control accurate anion hydridization ultra-microporous material hole by changing anion and species of metal ion
Diameter shows strong effect power to propylene, simultaneously because fluo anion has different electronegativity, has not when contacting with propylene
Same active force, F atom and propylene active force are strong when adsorbing propylene, realize that F atom and propylene strong interaction make in duct
In show F atom rotation allow propylene access aperture in, F atom rotation back aperture become larger, more conducively material and propylene is mutual by force
It acts on and propylene is allowed to enter duct, it is few to the propane active force amount of being less strongly adsorbed, it realizes and propylene propane is separated.
In the present invention, constructed by the inorganic fluo anion A, metal ions M and organic ligand L by coordinate bond
Made of the structural unit of the ultra-microporous material of hydridization containing anion (Fig. 7 and Fig. 8 are different direction angle as shown in Fig. 7 and Fig. 8
Structure chart), have one-dimensional duct type pore structure, wherein B be inorganic anion, A is metal ion, and C is organic ligand.
In single structural unit, four organic ligands connect into a kind of square frame, nothing by four metal endpoints
By coordination key connection metal ion endpoint row at structural unit, structural unit is connected by anion along Fig. 7 institute machine anion
Show that the axial direction regular array of structure forms one-dimensional duct type cellular structure, radial direction of the one-dimensional duct type cellular structure along duct
Direction regular array forms multi-pore channel hydridization containing anion ultra-microporous material.The aperture of one-dimensional duct type pore structure isThe aperture of material is the distance between two F atoms of diagonally opposing corner in duct.
Preferably, the organic ligand L is pyrazine, and inorganic fluo anion A is NbF7 2-、GeF6 2-、 SiF6 2-、TiF6 2-
In any one, the metal ions M be Co2+、Ni2+、Mn2+In any one.
Preferably, the organic ligand L is the fluoro- pyrazine of 2-, and inorganic fluo anion A is GeF6 2-, the metal ions M
For Mn2+；Or the organic ligand L is 2- Methyl-pyrazin, inorganic fluo anion A is ZrF6 2-, the metal ions M is Ni2 +；Or the organic ligand L is 2- cyano-pyrazine, inorganic fluo anion A is SiF6 2-, the metal ions M is Co2+；Or
The organic ligand L is 2- hydroxyl-pyrazine, and inorganic fluo anion A is SiF6 2-, the metal ions M is Co2+。
Preferably, inorganic fluo anion is TiF6 2-, organic ligand 2- hydroxyl-pyrazine, metal ion Co2+；It is inorganic to contain
Fluorine anion is TiF6 2-, organic ligand 2- hydroxyl-pyrazine and metal ion Co2+Composed material can be mixed from propylene and propane
Close the propylene gas that propane of the purity greater than 85%-99.99% and 90%-95% are isolated in gas.
Or inorganic fluo anion is GeF6 2-, organic ligand pyrazine, metal ion Ni2+Composed material can be from third
Propane of the purity greater than 90%-99.99% and the propylene gas of 80%-98% are isolated in alkene/propane mixture.
Or organic ligand 2- methylpyrazine and its derivative and metal ion are Ni2+, inorganic fluo anion GeF6 2-Institute
The material of composition can isolate the propane and 80%-99% that purity is greater than 85%-99.99% from propylene and propane mixture
Propylene gas.
Anion hydridization ultra-microporous material can be isolated from propylene/propane gaseous mixture (content ratio is 1-50:50-99)
The propylene gas of propane of the purity greater than 99.99% and 80-99%；
Separation method of the present invention, it is characterised in that the way of contact of adsorbent and propylene propane mixture is to fix
Bed absorption, fluidised bed adsorption, moving bed adsorb in any one.
The separation of separation method of the present invention, preferably ADSORPTION IN A FIXED BED, which comprises the steps of:
(1) under setting adsorption temp, adsorptive pressure, propylene/propane gaseous mixture is passed through fixed bed by setting flow velocity and is inhaled
In attached column, on the sorbent, propane components adsorbance is few first to be penetrated for strong absorbed component propylene absorption, obtains high-purity propane gas
Body；
(2) after propylene penetrates, absorption is completed, and by decompression desorption, desorption by heating, inert gas purge or utilizes separation
The mode of products obtained therefrom gas purging, the component acryl adsorbed by force is desorbed, and obtains high-purity propylene gas.
Adsorption temp -30~100 DEG C, preferably 10~50 DEG C.
Adsorptive pressure is 0~10, preferably 0.5~2bar.
Desorption temperature is 80~160 DEG C, preferably 90~140 DEG C, decompression desorption can be used, desorption pressure is 0~1bar.
Compared with existing separation method, the method for the present invention is had the following beneficial effects:
(1) a kind of method of anion hydridization ultra-microporous material adsorbing separation propylene propane is provided, control accurate yin is passed through
Ion hydridization ultra-microporous material aperture shows strong effect power to propylene, while rotating journey in duct by controlling F atom
Degree allows propylene to enter in pore structure, few to the propane active force amount of being less strongly adsorbed, and realizes and separates to propylene propane；
(2) anion hydridization ultra-microporous material of the present invention has compared to common adsorbents and makees with adsorption molecule
Firmly adjustable advantage has the advantage that adsorption capacity is high, selectivity is high to propylene；
(3) propylene of high-purity, propane can be obtained in this method, reaches as high as 99.999%；
(4) present invention provide separation method compared with extracting rectifying and precise distillation technology, have low energy consumption, equipment investment
Outstanding advantages of small.
(5) anion hydridization ultra-microporous material adsorbent of the present invention have raw material be easy to get, be at low cost, preparation method
Outstanding advantages of simple and hydrothermal stability is high, and easily regeneration, reusable, long service life, the method for the present invention low energy consumption,
Low cost has significant prospects for commercial application.
Detailed description of the invention
Fig. 1 is for 1 gained anion hydridization ultra-microporous material GeFSIX-3-Co of embodiment to CO at 298K2Absorption etc.
Warm line；Fig. 2 is suction of the 1 gained anion hydridization ultra-microporous material GeFSIX-3-Co of embodiment at 298K to propylene, propane
Attached thermoisopleth；
Fig. 3 be embodiment 2 gained anion hydridization ultra-microporous material SIFSIX-3-Ni in 298K to propylene, propane
Adsorption isotherm；
Fig. 4 be embodiment 3 gained anion hydridization ultra-microporous material TIFSIX-3-Ni in 298K to propylene, propane
Adsorption isotherm；
Fig. 5 be embodiment 4 gained anion hydridization ultra-microporous material TIFSIX-3-Co in 298K to propylene, propane
Adsorption isotherm；
Fig. 6 be embodiment 5 gained anion hydridization ultra-microporous material GeFSIX-3-Ni in 298K to propylene, propane
Adsorption isotherm.
Fig. 7 and Fig. 8 is that (B is inorganic anion in figure, and A is metal for the structural unit figure of anion hydridization ultra-microporous material
Ion, C are organic ligand).
Specific embodiment
Embodiment 1
By 1mmol Co (BF4)2、1mmol(NH4)2GeF6It is placed in seed bottle with 5mmol pyrazine, 2ml water and 1ml is added
48h is stirred at room temperature in methanol, and gained slurry activates for 24 hours after filtering under 140 DEG C of vacuumized conditions, obtains GeFSIX-3-Co material
Material.
Gained GeFSIX-3-Co material is filled into 5cm adsorption column, by the propylene of 0.2Mpa at 35 DEG C: propane (50:
50) gaseous mixture is passed through adsorption column with 0.5mL/min, can get high-purity propane (being greater than 99.9%) gas in eluting gas, when
When propylene penetrates, stop absorption.Adsorption column vacuumizes desorption using 100 DEG C, obtains propylene (purity is greater than 95%), adsorption column
It can be recycled.
To CO when GeFSIX-3-Co material 298K2Adsorption isotherm is as shown in Figure 1, CO2Adsorption isotherm can illustrate material
Aperture existsLeft and right.
It is as shown in Figure 1 to the adsorption isotherm of propylene, propane when GeFSIX-3-Co material 298K.
Embodiment 2
By 1mmol Ni (BF4)2、1mmol(NH4)2SiF6It is placed in seed bottle with 3mmol pyrazine, 1ml water and 2ml is added
48h is stirred at room temperature in methanol, and gained slurry activates for 24 hours after filtering under 130 DEG C of vacuumized conditions, obtains SIFSIX-3-Ni material
Material.
It is as shown in Figure 2 to the adsorption isotherm of propylene, propane when SIFSIX-3-Ni material 298K.
Embodiment 3
By 1mmol Ni (NO3)2、1mmol(NH4)2TiF6Be placed in seed bottle with 10mmol pyrazine, be added 2ml methanol and
After 1ml water, 48h is stirred at room temperature, after gained slurry filters, 150 DEG C vacuumize activation for 24 hours, obtain TIFSIX-3-Ni material.
It is as shown in Figure 3 to the adsorption isotherm of propylene, propane when TIFSIX-3-Ni material 298K.
Embodiment 4
By 1mmol Co (BF4)2、1mmol(NH4)2TiF6Be placed in seed bottle with 6mmol pyrazine, be added 2ml methanol and
After 1ml water, 48h is stirred at room temperature, after gained slurry filters, 140 DEG C vacuumize activation for 24 hours, obtain TIFSIX-3-Co material.
It is as shown in Figure 4 to the adsorption isotherm of propylene, propane when TIFSIX-3-Co material 298K.
Embodiment 5
By 1mmol Ni (BF4)2、1mmol(NH4)2GeF6It is placed in seed bottle with 10mmol pyrazine, 2ml water and 1ml is added
After methanol, 48h is stirred at room temperature, after gained slurry filters, 140 DEG C vacuumize activation for 24 hours, obtain GeFSIX-3-Ni material.
Gained GeFSIX-3-Ni material is packed into 5cm adsorption column, at 15 DEG C by propylene, propane (50:50) gaseous mixture with
1mL/min is passed through adsorption column, can get high-purity propane (being greater than 99.9%) gas in eluting gas and stops when propylene penetrates
Only adsorb.Adsorption column vacuumizes desorption using 100 DEG C, obtains propylene (being greater than 90%), adsorption column can be recycled.
It is as shown in Figure 5 to the adsorption isotherm of propylene, propane when GeFSIX-3-Ni material 298K.
Embodiment 6
Using solvent thermal process, by 2mmol Mn (NO3)2、1mmol(NH4)2GeF6It is dissolved in the fluoro- pyrazine of 5mmol 2-
In 20ml first alcohol and water (volume ratio 1:1) mixed solution, methanol is washed, is filtered after 85 DEG C of 72 h of reaction, at 100 DEG C of products obtained therefrom
It vacuumizes activation for 24 hours, obtains GeFSIX-3F-Mn material.
Gained GeFSIX-3F-Mn material is packed into 5cm adsorption column, at 25 DEG C by propylene, propane (50:50) gaseous mixture with
0.5mL/min is passed through adsorption column, can get high-purity propane (being greater than 99.9%) gas in eluting gas, when propylene penetrates,
Stop absorption.Adsorption column vacuumizes desorption using 140 DEG C, obtains propylene (being greater than 90%), adsorption column can be recycled.
Embodiment 7
By 1mmol Ni (BF4)2、1mmol(NH4)2SiF6It is placed in seed bottle with 7mmol 2- Methyl-pyrazin, 2ml is added
After water and 2ml methanol, 85 DEG C of reaction 72h, products obtained therefrom is filtered, after washing, and 150 DEG C vacuumize activation 8h, obtains SIFSIX-3-
CH3- Ni material.
By gained SIFSIX-3-CH3- Ni material is packed into 15cm adsorption column, mixes propylene, propane (80:20) at 25 DEG C
Gas is passed through adsorption column with 1mL/min, can get high-purity propane (being greater than 99.9%) gas in eluting gas, when propylene penetrates
When, stop absorption.Adsorption column vacuumizes desorption using 105 DEG C, obtains propylene (being greater than 95%), adsorption column can be recycled.
Embodiment 8
By 0.5mmol Co (BF4)2、1mmol(NH4)2ZrF640ml methanol and 10ml are dissolved in 4mmol 2- cyano-pyrazine
In water, 85 DEG C of reaction 72h, products obtained therefrom is filtered, after washing, and 100 DEG C vacuumize activation 8h, obtains ZrFSIX-3CN-Co material
Material.
Gained ZrFSIX-3CN-Co material is packed into 10cm adsorption column, by propylene, propane (85:15) gaseous mixture at 10 DEG C
It is passed through adsorption column with 0.5mL/min, can get high-purity propane (being greater than 99.9%) gas in eluting gas, when propylene penetrates
When, stop absorption.Adsorption column vacuumizes desorption using 100 DEG C, obtains propylene (being greater than 90%), adsorption column can be recycled.
Embodiment 9
By 0.308g CoTiF6·6H2O and 0.23g 2- hydroxyl-pyrazine is placed in water heating kettle, 100 DEG C reaction 2 days after will
Products obtained therefrom filters, methanol washs, and 70 DEG C of products obtained therefrom vacuum drying obtain TIFSIX-3OH-Co material.
Gained TIFSIX-3OH-Co material is filled into 10cm adsorption column, by the propylene of 0.1 Mpa at 25 DEG C: propane:
He (25:25:50) gaseous mixture is passed through adsorption column with 0.5mL/min, can get high-purity propane (being greater than 99%) in eluting gas,
When propylene penetrates, stop absorption.Adsorption column vacuumizes desorption 12h using 80 DEG C, obtains propylene (being greater than 85%), adsorption column
It can be recycled.
Embodiment 10
By 0.26g (NH4)2NbF7、0.34g Ni(NO3)2It is placed in seed bottle with 0.26g pyrazine, 4mL hydromagnetic power is added and stirs
It mixes, filters products obtained therefrom after 48h, methanol washing, 140 DEG C of vacuum drying 12h of products obtained therefrom obtain NbFSEVEN-3-Ni material
Material.
Gained NbFSEVEN-3-Ni material is filled into 15cm adsorption column, by the propylene of 0.2 Mpa at 25 DEG C: propane
(50:50) gaseous mixture is passed through adsorption column with 1mL/min, can get high-purity propane (being greater than 99%) in eluting gas, works as propylene
When penetrating, stop absorption.Adsorption column vacuumizes desorption 12h using 100 DEG C, obtains propylene (being greater than 85%), adsorption column can follow
Ring uses.
Embodiment 11
By 1mmol Ni (BF4)2、1mmol(NH4)2GeF6It is placed in seed bottle, is added with 2mmol 2- Methyl-pyrazin
After 10ml methanol, 85 DEG C of reaction 72h, products obtained therefrom is filtered, after washing, and 100 DEG C vacuumize activation 8h, obtains GeFSIX-3-
CH3- Ni material.
By gained GeFSIX-3-CH3- Ni material is packed into 5cm adsorption column, by propylene, propane (50:50) gaseous mixture at 25 DEG C
It is passed through adsorption column with 0.5mL/min, can get high-purity propane (being greater than 99.99%) gas in eluting gas, when propylene penetrates
When, stop absorption.Adsorption column vacuumizes desorption using 100 DEG C, obtains propylene (being greater than 90%), adsorption column can be recycled.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (9)
1. a kind of propylene propane separation method, which comprises the steps of: the ultra-microporous material conduct of hydridization containing anion
Adsorbent material is contacted with propylene/propane gaseous mixture, is captured to the identification of propylene, is realized the separation of propane and propylene；
The ultra-microporous material of hydridization containing anion is by inorganic fluo anion A, metal ions M and organic ligand L by matching
Position key is built-up, and expression general formula is [L-M-A] n:
The structural formula of the organic ligand L isWherein R1 is H, F, CH3, it is any one in OH, CN, COOH
Kind；
The inorganic fluo anion A is NbF7 2-、ZrF6 2-、GeF6 2-、SiF6 2-、TiF6 2-In any one；
The metal ions M is Co2+、Ni2+、Fe2+、Mn2+In any one.
2. propylene propane separation method according to claim 1, which is characterized in that the ultra-microporous material of hydridization containing anion
With one-dimensional duct type pore structure, aperture is
3. propylene propane separation method according to claim 1, which is characterized in that the organic ligand L is pyrazine, inorganic to contain
Fluorine anion A is NbF7 2-、GeF6 2-、SiF6 2-、TiF6 2-In any one, the metal ions M be Co2+、Ni2+、Mn2+In
Any one.
4. propylene propane separation method according to claim 1, which is characterized in that the organic ligand L is the fluoro- pyrazine of 2-,
Inorganic fluo anion A is GeF6 2-, the metal ions M is Mn2+；Or the organic ligand L is 2- Methyl-pyrazin, it is inorganic to contain
Fluorine anion A is ZrF6 2-, the metal ions M is Ni2+；Or the organic ligand L be 2- cyano-pyrazine, it is inorganic it is fluorine-containing yin from
Sub- A is SiF6 2-, the metal ions M is Co2+；Or the organic ligand L is 2- hydroxyl-pyrazine, inorganic fluo anion A is
SiF6 2-, the metal ions M is Co2+。
5. propylene propane separation method according to claim 1, which is characterized in that propylene and third in propylene/propane gaseous mixture
The volume ratio of alkane is 1-50:50-99.
6. propylene propane separation method according to claim 1, which is characterized in that adsorbent material and propylene/propane gaseous mixture
The way of contact be ADSORPTION IN A FIXED BED, fluidised bed adsorption, moving bed absorption in any one.
7. propylene propane separation method according to claim 1, which is characterized in that adsorbent material and propylene/propane gaseous mixture
The way of contact is ADSORPTION IN A FIXED BED, is included the following steps:
(1) under setting adsorption temp, adsorptive pressure, propylene propane mixture is passed through ADSORPTION IN A FIXED BED column by setting flow velocity
In, propylene is adsorbed on the adsorbent material, and propane first penetrates, and obtains propane gas；
(2) it after propylene penetrates, is desorbed, propylene is desorbed from adsorbent material, obtains propylene gas.
8. propylene propane separation method according to claim 6, which is characterized in that adsorption temp -30~100 DEG C；Adsorption pressure
Power is 0~10.
9. propylene propane separation method according to claim 6, which is characterized in that desorption temperature is 80~160 DEG C；Desorption pressure
Power is 0~1bar.
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| CN112439388A (en) * | 2019-09-03 | 2021-03-05 | 杭州市富阳区浙工大银湖创新创业研究院 | Preparation method of organic-inorganic hybrid porous material for separating propylene and propane |
| CN113061262A (en) * | 2021-03-31 | 2021-07-02 | 宁波浙铁江宁化工有限公司 | Metal organic framework material for adsorbing heavy metal in water and preparation method thereof |
| WO2021169764A1 (en) * | 2020-02-27 | 2021-09-02 | 浙江大学 | Layered porous material for adsorbing and separating allylene and propylene, preparation method therefor and application thereof |
| CN114307525A (en) * | 2021-11-30 | 2022-04-12 | 浙江大学 | Method for adsorptive separation of propylene and propane |
| CN114452938A (en) * | 2021-12-30 | 2022-05-10 | 浙江大学 | Alkane preferential adsorption microporous material and preparation method and application thereof |
| CN114870806A (en) * | 2022-04-19 | 2022-08-09 | 浙江大学 | Application of ion hybrid porous material in separation of cyclohexene and cyclohexane and preparation method thereof |
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| CN114452938A (en) * | 2021-12-30 | 2022-05-10 | 浙江大学 | Alkane preferential adsorption microporous material and preparation method and application thereof |
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