CN115010948B - DMOF- (CF) 3 ) 2 Synthesis method of (C) and application of (C) in high-efficiency separation of propane propylene under humid condition - Google Patents
DMOF- (CF) 3 ) 2 Synthesis method of (C) and application of (C) in high-efficiency separation of propane propylene under humid condition Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 51
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000001179 sorption measurement Methods 0.000 claims abstract description 66
- 239000001294 propane Substances 0.000 claims abstract description 56
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000012621 metal-organic framework Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- 238000002474 experimental method Methods 0.000 claims description 11
- 230000035515 penetration Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- YIAGLTIEICXRQF-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)terephthalic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=C(C(O)=O)C=C1C(F)(F)F YIAGLTIEICXRQF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000012973 diazabicyclooctane Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000003795 desorption Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010926 purge Methods 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a DMOF- (CF) 3 ) 2 The method comprises the steps of (1) carrying out adsorption of propane by a container filled with propane selective adsorbent under certain temperature, pressure and different relative humidity on mixed gas containing propane, and carrying out desorption regeneration of the adsorbent by inert gas purging or vacuumizing under room temperature, wherein low-concentration propane gas in the mixed gas of propane and propylene can be directly separated in one step to obtain high-purity propylene product gas; the adsorbent prepared by the method has strong adsorption force on propane, high selectivity, good stability and hydrophobicity, is suitable for industrial production, has better separation effect on low-concentration propane than the traditional method, and can realize the high-efficiency separation of the propane-propylene mixture under high relative humidity (70%).
Description
Technical Field
The invention relates to a gas separation technology, in particular to a DMOF- (CF) 3 ) 2 Is highly effective in separation under wet conditionThe application of propane propylene.
Background
Propylene is one of important basic organic chemical raw materials, and can be used for producing chemical products such as polypropylene, acrylonitrile, epoxypropane, acrylic acid, isopropanol, n-butyl/octanol, acetone and the like. Propylene demand has grown rapidly in recent years due to the vigorous downstream product demand, particularly for polypropylene. From the point of view of the propylene production process, the production of propylene is generally achieved by steam cracking of naphtha or dehydrogenation of propane, inevitably producing a mixture containing propane. Thus, the purification of propylene is mainly dependent on the removal of propane. The separation of olefins/paraffins is listed as one of the "seven chemical separation processes changing the world". Due to their similar physical properties (molecular size, boiling point and relative volatility), obtaining polymer grade propylene depends in large part on thermally driven cryogenic distillation at low temperature and high pressure using a large number of trays and high reflux ratios. Therefore, the process has the remarkable problem of overlarge energy consumption while maintaining high separation efficiency. If the adsorption separation mode is adopted to realize the efficient separation and enrichment of the low-concentration propane component in propylene or the low-carbon hydrocarbon component associated with the propylene, the polymerization-grade propylene product gas with higher purity can be obtained in one step, and the method has great significance.
The Metal Organic Framework (MOF) is used as a novel porous material, has the characteristics of adjustable pore shape and pore size, surface functionalization and the like, is widely applied to the field of gas adsorption separation, and has greatly progressed. As with most adsorbents, most MOF materials are specific to C 3 H 6 /C 3 H 8 Is to selectively adsorb C 3 H 6 To preferentially adsorb C 3 H 8 But the porous materials of (2) are rarely reported. Therefore, there is an urgent need to develop a C 3 H 8 High adsorption and good selectivity C 3 H 8 A selective adsorbent.
In the prior art, CN111777769A discloses a metal organic framework material for efficiently separating mixed gas, a preparation method and application thereof, and the prepared MOF material has a strong selective separation effect on propane and propylene although the MOF material has dynamic screening of a specific pore structure, but the stability of the MOF is influenced by complex environments such as humidity and the like.
For practical applications, since hydrocarbon feedstock needs to be mixed with a certain amount of steam during pyrolysis and inevitably contains a small amount of steam during pyrolysis, development of a MOF material having excellent propane-propylene separation performance and good stability under humid conditions is more advantageous for industrial adsorptive separation.
Disclosure of Invention
The DMOF- (CF) is prepared by adjusting the dosage of the reaction raw materials and the solvent 3 ) 2 In particular to a DMOF- (CF) 3 ) 2 Is applied to the high-efficiency separation of propane and propylene under the wet condition.
The invention is realized by the following technical scheme: DMOF- (CF) 3 ) 2 The synthesis method of (2) comprises the following steps: zinc nitrate hexahydrate, 2, 5-bis (trifluoromethyl) terephthalic acid and 1, 4-diazabicyclo [2.2.2] are added to nitrogen, nitrogen-Dimethylformamide (DMF)]Octane and two drops of nitric acid are stirred uniformly until being completely dissolved, the obtained mixed solution is transferred into a glass bottle to be sealed, subjected to high-temperature hydrothermal reaction, washed and dried, and then the mixed solution is obtained to obtain the compound with the chemical formula (Zn-BDC (CF) 3 ) 2 -DABCO) Metal Organic Framework (MOF) adsorbents.
As a further improvement of the technical scheme of the synthesis method, the addition amount of the zinc nitrate hexahydrate and the addition amount of the 2, 5-bis (trifluoromethyl) terephthalic acid are equal, and the addition amount of the 1, 4-diazabicyclo [2.2.2] octane is half of the addition amount of the zinc nitrate hexahydrate; the ratio of the amount of DMF solvent to the amount of the substance of zinc nitrate hexahydrate is 300-500:1, controlling the reaction temperature at 110-130 ℃ and the reaction time at 24-48 h.
Further, the DMOF- (CF) 3 ) 2 Can be used for separating propane and propylene.
The invention further provides the DMOF- (CF) 3 ) 2 DMOF- (CF) obtained by the synthesis method 3 ) 2 The application of the high-efficiency separation of low-concentration propane in the propane-propylene mixture under the humid condition is characterized by comprising the following steps: introducing a propane propylene mixture into a DMOF- (CF) equipped reactor 3 ) 2 In an adsorption column of the material, the flow is regulated by a pressure valve and a flowmeter at the inlet of the adsorption column, and dynamic adsorption penetration experiments are carried out under certain temperature and pressure and different relative humidity; and monitoring the concentration of propane and propylene at the outlet of the adsorption column in real time by adopting gas chromatography.
As a further improvement of the high-efficiency separation method, the volume fraction of propane in the mixed gas is 0-50%, and no zero value is contained.
As a further improvement of the efficient separation method, the sample filled in the adsorption column is 0.5-1 g, the flow rate of the propane-propylene mixture entering the adsorption column is 0-5 mL/min, the adsorption temperature is 0-25 ℃ when propane is adsorbed on the adsorbent, the pressure is 1bar or above, and the different relative humidity is 20%, 40%, 70% and 90% respectively.
As a further improvement of the efficient separation method of the present invention, the DMOF- (CF) 3 ) 2 Can realize the high-efficiency separation of propane and propylene under the condition of high relative humidity (70 percent), and can generate the polymerization grade propylene product gas through one-step adsorption separation>99.99 percent) and the yield of the high-purity ethylene obtained by one-time penetration experiment is 7-15 cm 3 /g。
By adopting the technical scheme, the invention has the following beneficial effects:
1) The DMOF- (CF) provided by the invention 3 ) 2 The synthesis method adopts a hydrothermal method, has simple synthesis steps and high reaction efficiency, and can realize industrial synthesis production of MOF materials.
2) Compared with the traditional adsorption material (molecular sieve, carbon material), the propane selective adsorbent prepared by the invention has stronger adsorption force on propane and has high propane adsorption capacity and propane-propylene separation selectivity. The adsorbent has better structural stability, thermal stability, hydrophobicity and steam stability, is easy to desorb after being adsorbed, has strong reusability and can be better suitable for industrialization.
3) DMOF- (CF) prepared by the invention 3 ) 2 High efficiency separation of propane and propylene, and can generate polymerization grade propylene product gas through one-step adsorption separation>99.99 percent) and the yield of the high-purity propylene obtained by one-time penetration experiment is 7-15 cm 3 /g。
4) DMOF- (CF) prepared by the invention 3 ) 2 Compared with other propane selective materials, the MOF material has more excellent hydrophobicity, can realize the high-efficiency separation of propane and propylene under the condition of high relative humidity, has good separation effect when the relative humidity reaches 70%, and can be better suitable for industrialized adsorption separation.
Drawings
FIG. 1 shows DMOF- (CF) obtained in example 1 3 ) 2 Is a structural diagram of (1);
FIG. 2 shows DMOF- (CF) obtained in example 1 3 ) 2 XRD contrast pattern with simulated peaks;
FIG. 3 shows DMOF- (CF) obtained in example 1 3 ) 2 Adsorption and desorption curve of nitrogen at 77K
FIG. 4 shows DMOF- (CF) obtained in example 1 3 ) 2 Adsorption curve for propane propylene at 298K;
FIG. 5 shows DMOF- (CF) obtained in example 1 3 ) 2 A water vapor adsorption curve at 298K;
FIG. 6 shows DMOF- (CF) obtained in example 1 3 ) 2 XRD patterns after different conditions;
FIG. 7 shows DMOF- (CF) obtained in example 1 3 ) 2 A plurality of propane cycle adsorption isotherms;
FIG. 8 is a diagram of an adsorption column and a penetration test apparatus;
FIG. 9 shows DMOF- (CF) obtained in example 1 3 ) 2 Penetration curves for different ratios of propane-propylene mixtures at room temperature pressure and drying conditions, a being propane: propylene=1:1 (v/v), b being propane: propylene=1:9 (v/v), c being propane: propylene=1:15 (v/v);
fig. 10 shows DMOF- (CF) obtained in example 1 3 ) 2 P-propane propylene mixingPenetration profile of gas (propane: propylene=1:1 (v/v)) at room temperature pressure and different relative humidity conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific examples and experimental data. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The specific embodiment is as follows: DMOF- (CF) 3 ) 2 The synthesis method of (2) comprises the following steps: zinc nitrate hexahydrate, 2, 5-bis (trifluoromethyl) terephthalic acid and 1, 4-diazabicyclo [2.2.2] are added to nitrogen, nitrogen-Dimethylformamide (DMF)]Octane and two drops of nitric acid are stirred uniformly until being completely dissolved, the obtained mixed solution is transferred into a glass bottle to be sealed, subjected to high-temperature hydrothermal reaction, washed and dried, and then the mixed solution is obtained to obtain the compound with the chemical formula (Zn-BDC (CF) 3 ) 2 -DABCO) Metal Organic Framework (MOF) adsorbents.
A production process for separating low-concentration propane from a propane-propylene mixed gas under a humid condition, which comprises the following steps: introducing a propane propylene mixed gas into a DMOF- (CF) filled with the mixed gas 3 ) 2 DMOF- (CF) obtained by the synthesis method 3 ) 2 In an adsorption column of the adsorbent, the flow is regulated by a pressure valve and a flowmeter at an inlet of the adsorption column, and a dynamic adsorption penetration experiment is carried out under certain temperature and pressure and different relative humidity; monitoring the concentration of propane and propylene at the outlet of the adsorption column in real time by adopting gas chromatography; the desorption regeneration of the adsorbent is completed by inert gas purging at room temperature or under the condition of vacuumizing negative pressure.
In the synthesis process, the dosage of metal salt, ligand and solvent is regulated to reduce the synthesis cost as much as possible, and in addition, the synthesis is simple, and the DMOF- (CF) can be obtained by using a glass bottle reaction only through a simple hydrothermal method 3 ) 2 . The separation of propane and propane of the inventionThe high-efficiency separation method of low-concentration propane in the alkene mixed gas has simple steps and wide application range, can realize the high-efficiency separation of propane and propylene under the condition of high relative humidity (70 percent), and can generate the polymerization-grade propylene product gas through one-step adsorption separation>99.99%) is expected to realize DMOF- (CF) 3 ) 2 Industrial application of materials.
In some embodiments zinc nitrate is in an equal mass with 2, 5-bis (trifluoromethyl) terephthalic acid and the amount of 1, 4-diazabicyclo [2.2.2] octane is one half the amount of zinc nitrate hexahydrate material. The ratio of the amount of DMF solvent to the amount of zinc nitrate is 300-500:1, controlling the using amount of the solvent DMF at 15-20 mL, controlling the reaction temperature at 110-130 ℃ and controlling the reaction time at 24-48 h.
In some embodiments, DMOF- (CF) can be prepared by simple stirring, mixing, heating, filtering, and drying, and reacting once in a glass bottle 3 ) 2 A material. The invention is not limited to such yields in such proportions, and the same proportions of metal and ligand are expanded to yield hundred g grade products at a time as are suitable for use in the invention.
In some embodiments, the volume fraction of propane in the mixed gas is 0-50% and does not contain a zero value.
In some embodiments, the sample filled in the adsorption column is 0.5-1 g, the flow rate of the propane-propylene mixture entering the adsorption column is 0-5 mL/min, the adsorption temperature is 0-25 ℃ when propane is adsorbed on the adsorbent, the pressure is 1bar or above, and the relative humidity is 20%, 40%, 70% and 90% respectively.
In some embodiments DMOF- (CF) 3 ) 2 Can realize the high-efficiency separation of propane and propylene under the condition of high relative humidity (70 percent), and can generate the polymerization grade propylene product gas through one-step adsorption separation>99.99 percent) and the yield of the high-purity propylene obtained by one-time penetration experiment is 7-15 cm 3 /g。
Specific examples are exemplified below.
Example 1
15.0. 15.0 mL of DMF was added 0.119 mg of zinc nitrate hexahydrate, 0.121 mg of 2, 5-bis (trifluoromethyl) terephthalic acid, 0.023 mg of 1, 4-diazabicyclo [2.2.2]Octane and two drops of nitric acid are stirred until the mixture is completely dissolved, and then a mixed solution is obtained; transferring the obtained mixed solution into a 20 mL glass bottle, and placing the glass bottle into a constant-temperature drying oven to perform hydrothermal reaction at the temperature of 110-130 ℃; filtering, washing and drying a sample obtained by the reaction to obtain DMOF- (CF) 3 ) 2 A material. Washing with DMF, and centrifugally drying to obtain the product.
The product prepared in example 1 can be scaled up in equal proportions according to the corresponding material ratios to obtain MOF products of different quality.
Example 2
Before testing the adsorption separation performance of the prepared samples, solvent exchange and washing were performed using methylene chloride. The prepared white crystal is subjected to Soxhlet extraction by using methylene dichloride, the washing time is 12 h, the activation condition of a test sample is 60 ℃, the vacuum degassing activation is 12 h, then the gas adsorption separation performance test of the sample is carried out, and the pressure range of the test sample is 0-1 bar.
Example 3
To evaluate DMOF- (CF) 3 ) 2 The actual separation effect of the propane and propylene mixtures was carried out by means of the apparatus shown in fig. 6 (a, b), respectively, by dynamic penetration experiments of the propane/propylene mixtures under dry and humid conditions. About 0.5-1 g of the sample is loaded into a stainless steel adsorption column with an inner diameter of 4 mm and a length of 125 mm; purging residual gas in the pipeline by high-purity inert purge; the sample adsorption column is fixed in the indoor device, and the flow of propane and propylene is regulated by a pressure valve and a flowmeter at the inlet of the adsorption column; monitoring the concentration of propane and propylene in real time by gas chromatography (490 Micro GC, agilent Technologies) at the outlet of the adsorption column; the whole experiment is carried out at 0-25 ℃, and the flow rate of the propane/propylene mixture (1:1, 1:9 and 1:15, v/v) is 0-5 mL/min.
To characterize DMOF- (CF) 3 ) 2 The microstructure of the material was characterized by SEM when the product obtained in example 1 was subjected to the process shown in fig. 1.
To confirm the crystal structure of the synthesized sample, the sample synthesized in example 1 was subjected toXRD characterization was performed, and the results were compared with DMOF- (CF) 3 ) 2 The simulated peaks of the theoretical crystal form structure are compared, and the comparison result is shown in fig. 2. As can be seen from the figure, DMOF- (CF) prepared by the method of the present invention 3 ) 2 The XRD diffraction peak of the (B) is consistent with the simulation peak of the theoretical crystal form structure of the original structure, which proves that the method successfully synthesizes the DMOF- (CF) 3 ) 2 A material.
To characterize DMOF- (CF) 3 ) 2 The adsorption capacity of the material for different gases was tested for the adsorption performance of the product obtained in example 1 by using a Micromeritics ASAP 2020 instrument, and the adsorption curve of the product of example 1 for each gas was measured at 298K, fig. 3 shows the nitrogen adsorption and desorption curve of the material at 77K, and fig. 4 shows the adsorption and desorption curve of the corresponding propane propylene. As can be seen from fig. 3-4, DMOF- (CF) 3 ) 2 Has higher BET specific surface area and shows the adsorption separation performance of selectively adsorbing propane which is higher than propylene in the test temperature range, which indicates that DMOF- (CF) 3 ) 2 Is a propane selective adsorbent.
To test DMOF- (CF) 3 ) 2 Stability of the material taking the product prepared in example 1 as an example, the material was tested for water vapor adsorption, water stability, air stability and stability under different relative humidity conditions. From the water vapor adsorption isotherms shown in FIG. 5, it can be seen that the sample has a low water vapor adsorption capacity (0.0079 g) even at a high relative humidity (70%) -1 ) As can be seen from the XRD pattern shown in fig. 6, the sample maintains the original crystal structure when the sample is exposed to different humidity environments, respectively, or the sample is immersed in an aqueous solution for three days. FIG. 7 shows the adsorption isotherm of the cycle of the propylene gas, and it can be seen that DMOF- (CF) was obtained through multiple adsorption and desorption cycle experiments 3 ) 2 The properties of the material are fully maintained.
To test DMOF- (CF) 3 ) 2 Practical effects of materials on separation of propane and propylene Mixed gases in different proportions, taking the product obtained in example 1 as an example, for exampleThe product of 1 was subjected to a propane propylene mixture gas separation experiment. The specific process is as follows: the mixed gas was passed through an adsorption column (size Φ4×95 mm) filled with an adsorbent (sample size: 0.72× 0.72 g) at a pressure (1.0 bar) and a flow rate (2 mL/min) by a pressure reducing valve and a gas mass flowmeter with accurate control, and the temperature of the adsorption column was 298K, and when the mixed gas started to enter the adsorption column, at the same time, the timing was started, and the tail gas concentration was monitored in real time at the tail end of the adsorption column by chromatography (GC-2014 c, tcd detector), data was recorded until the two component gas concentrations reached the initial concentration, and the two gases were considered to be completely passed out, and the adsorption was considered to be completed.
When the mixed gas is C 3 H 8 /C 3 H 6 When the volume fraction ratio is 1/1, 1/9 and 1/15, the penetration curves of the adsorbent material are shown in figures 9a-C, respectively, and as can be seen from figures 9a-C, the material can effectively remove low-concentration propane in the propane-propylene mixture and realize low-concentration C 3 H 8 /C 3 H 6 Is effective in separation.
To test DMOF- (CF) 3 ) 2 Practical effect of the material on separation of propane-propylene mixture under humid conditions, taking the product obtained in example 1 as an example, a propane-propylene mixture separation experiment was performed on the product of example 1. The specific process is as follows: the mixture was passed through an adsorption column (size Φ4×95 mm) packed with adsorbent (sample size: 0.72 g) at a pressure (1.0 bar) and a flow rate (2 mL/min) by a pressure reducing valve and a gas mass flow meter with accurate control, and the temperature of the adsorption column was 298K, and the dried mixture was passed through saturated brine of different relative humidity (20%, 40%, 70% and 90%) to simulate a moisture mixture under different relative humidity conditions. In 298K sealed wet chambers, respectively, with saturated CH 3 COOK、K 2 CO 3 NaCl and ZnSO 4 The solutions create relative humidities of 20%, 40%, 70% and 90%. When the mixed gas starts to enter the adsorption column, at the same time, starting timing, monitoring tail gas concentration at the tail end of the adsorption column in real time through chromatography (GC-2014C, TCD detector), recording data until the concentrations of the two components reach the initial concentration, and considering that the two gases completely penetrate out, and considering that the absorption is realizedAnd (5) finishing the attaching.
When the mixed gas is in different relative humidity (20%, 40%, 70% and 90%), the penetration curves of the adsorbent materials are respectively shown in fig. 10, and as can be seen from fig. 10, the material can realize the efficient separation of propane propylene under the condition of high relative humidity (70%), and the polymer grade propylene product gas (> 99.99%) can be generated through one-step adsorption separation.
Claims (5)
1. DMOF- (CF) 3 ) 2 Use of high efficiency in the separation of propane propylene under humid conditions, characterized in that said DMOF- (CF) 3 ) 2 High efficiency separation of propane and propylene can be achieved at high relative humidity in the range of 20-70%;
the DMOF- (CF) 3 ) 2 The synthesis method of (2) comprises the following steps: zinc nitrate hexahydrate, 2, 5-bis (trifluoromethyl) terephthalic acid and 1, 4-diazabicyclo [2.2.2] are added to nitrogen, nitrogen-dimethylformamide]Octane and a small amount of nitric acid are stirred uniformly until the mixture is completely dissolved, and the obtained mixed solution is transferred into a glass bottle for sealing, high-temperature hydrothermal reaction, washing and drying to obtain the chemical formula Zn-BDC (CF) 3 ) 2 Metal organic framework DMOF- (CF) DABCO 3 ) 2 。
2. The DMOF- (CF) of claim 1 3 ) 2 The application of high-efficiency separation of propane propylene under the moist condition is characterized in that the addition amount of the zinc nitrate hexahydrate is equal to that of 2, 5-bis (trifluoromethyl) terephthalic acid, and the 1, 4-diazabicyclo [2.2.2]The amount of octane material is half the amount of the zinc nitrate hexahydrate material; the ratio of the amount of nitrogen, nitrogen-dimethylformamide to the amount of the substance of zinc nitrate hexahydrate is 300-500:1, the reaction temperature is controlled between 110 and 130 ℃ and the reaction time is 24 to 48 hours.
3. The DMOF- (CF) of claim 1 3 ) 2 Use of high efficiency in the separation of propane propylene under humid conditions, characterized in that said DMOF- (CF) 3 ) 2 High-efficiency separation of propane and propane under wet conditionThe alkene comprises the following steps: introducing a propane propylene mixture into a DMOF- (CF) equipped reactor 3 ) 2 In an adsorption column of the material, the flow is regulated by a pressure valve and a flowmeter at the inlet of the adsorption column, and a dynamic adsorption penetration experiment is carried out under certain temperature, pressure and humidity conditions; and monitoring the concentration of propane and propylene at the outlet of the adsorption column in real time by adopting gas chromatography.
4. The DMOF- (CF) of claim 1 3 ) 2 The application of high-efficiency separation of propane and propylene under the moist condition is characterized in that the volume fraction of propane in the mixed gas is 0-50%, and no zero value is contained.
5. The use of DMOF- (CF 3) 2 of claim 1 for efficiently separating propane and propylene under wet conditions, wherein the sample packed in the adsorption column is 0.5 to 1g, the flow rate of the propane-propylene mixture into the adsorption column is 0 to 5mL/min, and the adsorption temperature is 0 to 25 ℃ and the pressure is 1bar or more when propane is adsorbed on the adsorbent.
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| CN111777769A (en) * | 2020-08-07 | 2020-10-16 | 暨南大学 | Metal organic framework material for efficiently separating mixed gas and preparation method and application thereof |
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