CN116924878A - Method for separating propyne and propadiene - Google Patents
Method for separating propyne and propadiene Download PDFInfo
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- CN116924878A CN116924878A CN202310822230.5A CN202310822230A CN116924878A CN 116924878 A CN116924878 A CN 116924878A CN 202310822230 A CN202310822230 A CN 202310822230A CN 116924878 A CN116924878 A CN 116924878A
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- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 title claims abstract description 156
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 79
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 50
- PDGVLYLXTUFIOL-UHFFFAOYSA-N n,n-dipyridin-4-ylpyridin-4-amine Chemical compound C1=NC=CC(N(C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 PDGVLYLXTUFIOL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000009471 action Effects 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 4
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 229910001412 inorganic anion Inorganic materials 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 63
- 238000000926 separation method Methods 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000013384 organic framework Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000011148 porous material Substances 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 150000001450 anions Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001361 allenes Chemical class 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- APLNAFMUEHKRLM-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(3,4,6,7-tetrahydroimidazo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)N=CN2 APLNAFMUEHKRLM-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 239000013208 UiO-67 Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000013356 anionic metal-organic framework Substances 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
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002791 soaking 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
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- -1 trimethylene cyclohexane derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application discloses a method for separating propyne and propadiene, which comprises the steps of contacting a mixed gas containing the propyne and the propadiene with a metal organic framework material with a special window action site, wherein the metal organic framework material selectively adsorbs the propyne in the mixed gas to separate the propadiene from the propyne; the metal organic framework material consists of hexacoordinated divalent metal cations Cu 2+ Coordinated with a tridentate nitrogenous ligand L to form a cage structure, and then passing through a bivalent inorganic anion ZrF with high coordination number 6 2‑ Bridging to form a structure with special window action sites; the metal organic frameThe molecular formula of the material is (CuZrF 6 ) 3 L 4 Wherein the tridentate nitrogen-containing ligand L is a tris (4-pyridyl) amine. The method can separate the mixed gas of the propyne and the propadiene with high capacity and high selectivity, and the adsorbent is easy to regenerate and has good hydrothermal stability.
Description
Technical Field
The application relates to the technical field of chemical separation, in particular to a method for separating propyne and propadiene.
Background
Allene (CH) 2 ＝C＝CH 2 ) As the simplest of the alkylene compounds, it is an important raw material for organic synthesis. Propadiene can be used as a chiral synthon to participate in cycloaddition reaction to prepare cyclobutane or trimethylene cyclohexane derivatives; can also be combined with inexpensive and environmentally friendly silanes to replace the stoichiometric number of allylic metal reagents necessary for most enantioselective ketoallylation reactions. In addition, dimers (unsaturated four-membered ring hydrocarbons) prepared from allenes are also versatile intermediates that can be used to produce many high value added products. Currently, propadiene is prepared by chemical synthesis, and has the problems of low yield, high energy consumption, more byproducts and the like, so that development of an alternative method for producing the propadiene is urgently needed. Petroleum cracking is the largest worldwide standard process for producing lower hydrocarbons with annual feedstock conversion of over five hundred million tons. Propadiene is one of the by-products, accounting for 0.3 to 0.6% by weight of the total yield and accounting for 6% by mole of the C3 crude fraction. However, propadiene and propyne are usually present in the form of a mixture, and the molecular shapes, sizes and boiling points of the propadiene and propyne are very close to each other, so that no effective technique for separating the propadiene and the propyne is available in the industry at present. Propadiene-containing mixtures are generally processed industrially to give direct combustion of the fuel, resulting in considerable waste. Therefore, there is a need to develop a novel separation technique to achieve efficient separation of propyne/propadiene.
Physical adsorption is a relatively energy-saving and efficient separation technology, however, the traditional adsorbent materials such as molecular sieves and activated carbon at present are difficult to accurately identify propyne and propadiene molecules, so that two gases cannot be effectively separated. The metal organic framework Material (MOFs) is an organic-inorganic hybrid material with intramolecular pores, which is formed by self-assembling an organic ligand and metal ions or clusters through coordination bonds, has the advantages of large specific surface area, fine and adjustable pore diameter and pore environment, and the like, and has potential application prospect in the field of gas adsorption separation. Since propadiene and propargyl have similar shapes and sizes, it is difficult to achieve both molecular sieving and kinetic separation, and it is only possible to construct a specific structure by introducing an adsorption site having a specific property for recognizing propyne or propadiene molecules into a porous materialThe separation of propyne/propadiene is achieved in a sexual pore environment. MOFs with open metal sites are currently the best material for propyne/propadiene separation. For example, HKUST-1 reaches a propyne adsorption capacity of 191.97cm at 50kPa 3 /cm 3 But the propyne/propadiene selectivity is only 3.46.NKMOF-1-Ni had the highest propyne/propadiene separation selectivity (4.83) at present, but the propyne adsorption capacity was only 64cm at 50kPa 3 /g, (Nat. Commun,2021,12,5768). It follows that although open metal site MOFs are capable of achieving allene purification, the selective and adsorption capacity gaming effect is currently not overcome.
In contrast, MOFs with large pore volumes but lacking distinct sites of action, such as UiO-66 and UiO-67, were substantially identical in their ability to adsorb propyne and propadiene, and could be considered to have no separation effect at all. MOFs having polyfluorinated anion sites, such as sifsixix-2-Cu-i, sifsixix-3-Ni and ZU-62, can efficiently separate acetylene/ethylene and propyne/propylene, but have substantially uniform adsorption capacities for propyne and propadiene, and only differ at low pressure, so that the object of separating and purifying propadiene from equimolar propyne/propadiene gas cannot be achieved (nat. Commun,2021,12,5768).
Patent specification publication No. CN1109420479a discloses a method for preparing an ion-hybridized porous material capable of being used for adsorption separation of propyne/propadiene/propylene, which is capable of only co-adsorption of trace propyne and propadiene to purify propylene, but incapable of separating propyne and propadiene with more similar structure, property, size and the like.
The patent specification with publication number of CN114534441A discloses a method for deeply removing alkyne and propadiene from complex pyrolysis gas in one step by utilizing an ion hybridization ultramicropore material, wherein the material involved in the method can only synchronously adsorb the propyne and the propadiene, and the separation of the propyne and the propadiene cannot be realized.
Patent specification publication CN114177890a discloses a method for preparing a column cage type metal organic framework material which can be used for propyne/propylene, acetylene/ethylene separation. Such materials do not involve separation of propyne from propadiene, as is the case in many of the prior art listed above, in the artThe skilled person is not obvious to expect that the propyne/propylene separation material can be directly transferred to be applied to propyne/propadiene separation, and the situation that propyne and propadiene are simultaneously adsorbed is most likely to happen, because the separation difficulty of the propyne and the propadiene is higher. The person skilled in the art does not consider that propyne/propylene and propyne/propadiene are similar separation systems, since one is to overcome the technical problem of the difference in adsorption capacities between propyne and propylene and the other is to overcome the technical problem of the difference in adsorption capacities between propyne and propadiene, which are different from each other, so that in this field they are completely different two separation systems, on the basis of which the person skilled in the art is not aware of whether such a cage-type MOFs which can be used for propyne/propylene separation are able to distinguish between the difference in adsorption capacities between propyne and propadiene. In addition, the same authors report TiF in International journal German application chemistry (Angew.chem.int.ed, 2022,61, e 202200946) 6 2- The mechanism for separating propyne/propylene from the anionic, cylindrical cage-type metal organic framework ZNU-2 is to utilize ZNU-2 staggered channel holes as single molecule traps for propyne, while propylene of larger size is dynamically excluded. Since propadiene molecules are in a shape consistent with propyne and have smaller kinetic dimensions, a single molecular trap for capturing propyne is also capable of capturing propadiene, and thus, in principle, it is difficult for the above column cage MOFs to separate propyne/propadiene through this site of action.
In summary, although the separation of acetylene/ethylene, propyne/propylene and propyne/propadiene can be realized by selectively adsorbing alkyne, the propyne/propadiene is closer in molecular shape, size or property; and the ratio of the two mixed gases of the acetylene and the propadiene is close to that of the mixed gases of the acetylene and the ethylene, and the application environment difference of removing trace alkyne (< 1%) in the application of separating the acetylene from the ethylene and the propyne from the propylene is larger, so that the separation difficulty is obviously higher. The method can not realize the good separation of propyne/propylene adsorption through a certain material fundamentally, and deduces that the method can realize the good separation of propyne/propadiene. And to date, it has not been explicitly reported that good porous materials can achieve high selectivity and high capacity propyne/propadiene separation.
Based on a large number of experimental results, the present application unexpectedly found that by using ZrF 6 2- Anion structured CuZrF 6 TPA can capture propyne through a special window action site, and is different from ZNU-2 equicolumn cage MOFs in action mechanism, so that CuZrF 6 TPA shows a significant difference in the adsorption of propyne to propadiene, with the highest propyne/propadiene selectivity and extremely high propyne adsorption capacity so far, thus enabling efficient separation of propyne/propadiene.
Disclosure of Invention
The application provides a method for separating propyne and propadiene.
The specific technical scheme is as follows:
a method for separating propyne and propadiene, which comprises the steps of contacting a mixed gas containing propyne and propadiene with a metal organic framework material with a special window action site, wherein the metal organic framework material selectively adsorbs the propyne in the mixed gas to separate the propadiene from the propyne;
the metal organic framework material consists of hexacoordinated divalent metal cations Cu 2+ Coordinated with a tridentate nitrogenous ligand L to form a cage structure, and then passing through a bivalent inorganic anion ZrF with high coordination number 6 2- Bridging to form a structure with special window action sites;
the molecular formula of the metal organic framework material is (CuZrF 6 ) 3 L 4 Wherein the tridentate nitrogen-containing ligand L is a tris (4-pyridyl) amine.
The metal organic framework material with the special window action site can be synthesized by adopting at least one of a well-known coprecipitation method, an interface diffusion method, a solvothermal method and the like.
Both propyne and propadiene are linear molecules with a high degree of molecular size, and therefore it is difficult to separate them by molecular sieving or kinetic mechanisms. The separation of propyne/propadiene can only be achieved by introducing adsorption sites with specific recognition of propyne or propadiene molecules into the porous material and constructing a specific pore environment.
The metal organic framework material containing specific anions not only has a large number of ordered and arranged negatively charged ZrF distributed on the surface 6 2- The polyfluoro anion functional group forms a special electrostatic environment in a space limited by the metal organic framework material with a specific structure, and can selectively identify and adsorb propyne molecules from mixed gas containing propyne and propadiene.
The inventor researches that the ZrF-containing material with the specific structure 6 2- The metal organic framework material with anions and special window action sites has good hydrothermal stability and can adapt to harsh application environments in industry; the mixed gas containing propyne and propadiene can be used for selectively adsorbing the propyne gas and efficiently separating the mixture gas of propyne and propadiene. ZrF in the adsorbent of the application 6 2- The polyfluoro anions can form a regular arrangement structure on the surface of the hole, so that a special electrostatic environment is formed in a pore canal limited space with a specific structure of the material. In one aspect, zrF in the specific structure of the material of the present application 6 2- The introduction of anions can enhance the selective recognition of the material to the propyne in a propyne/propadiene mixed system, and on the other hand, the material also has a special window action site, and can enhance the adsorption of the propyne in the propyne/propadiene mixed gas, thereby enhancing the separation selectivity of the propyne/propadiene. The two aspects are unavoidably absent, and the purpose of effectively separating propyne and propadiene required by the application can be achieved only if the two aspects are simultaneously present.
ZrF-containing compositions of the application 6 2- The metal organic framework material with anions and special window action sites can be directly used as an adsorbent singly, and can also be compounded with other materials to form adsorbent materials with different shapes and sizes, thereby meeting the requirements of different industrial reaction devices on the specifications of adsorbent filler particles.
In the mixed gas containing the propyne and the propadiene, the mole content of the propyne can be between 10 and 90 percent based on 100 percent of the total mole amount of the propyne and the propadiene.
Further, in the mixed gas containing propyne and propadiene, the molar content of propyne may be 50% to 90% based on 100% of the total molar amount of propyne and propadiene.
The mixed gas containing propyne and propadiene is contacted with the metal organic framework material with special window action sites, and the contact mode can be any one or a combination of a plurality of fixed bed adsorption, fluidized bed adsorption and moving bed adsorption.
In a preferred embodiment, the method of contacting the mixed gas containing propyne and propadiene with the metal organic framework material with special window action sites is fixed bed adsorption, which specifically comprises the following steps: under the set adsorption temperature and pressure, the mixed gas containing propyne and propadiene enters a fixed bed adsorption column filled with the metal organic framework material at a set flow rate, the propadiene component preferentially penetrates through the bed layer, and high-purity propadiene gas is directly obtained from an outlet of the adsorption column.
The metal organic framework material can reach very high adsorption capacity for propyne gas in a propyne/propadiene mixed system in a certain temperature range. The temperature of the adsorption may be 0 to 40 ℃.
The pressure of the adsorption may be 0.5 to 10atm.
And after the metal organic framework material selectively adsorbs propyne in the mixed gas to separate propadiene from propyne, the propyne can be desorbed under the conditions of the temperature of 30-100 ℃ and the pressure of 0-1 atm to regenerate the metal organic framework material. In the application, physical acting force is adopted between the metal organic frame material and gas molecules, so that the desorption and regeneration are easy, and the conditions are mild.
The method provided by the application can be used for adsorbing the propyne from the propyne/propadiene mixed gas with high capacity and selectivity, purifying the propadiene, and the adsorbent is easy to regenerate and has good hydrothermal stability.
The application also provides application of the metal organic framework material with the special window action site in separating propyne and propadiene, and the metal organic framework material selectively adsorbs the propyne in the mixed gas after being contacted with the mixed gas containing the propyne and the propadiene, so that the separation of the propadiene and the propyne is realized.
The separation selectivity of the metal organic framework material to the mixed gas of propyne and propadiene with the molar ratio of 1:1 at 298K and 100kPa is 6.03.
The separation potential of the metal organic framework material to the mixed gas of propyne and propadiene with the mol ratio of 1:1 is 5.72mmol of propadiene/cm 3 Metal organic framework materials
Compared with the prior art, the application has the beneficial effects that:
1. in one aspect, zrF-containing 6 2- The surface of the anionic metal organic framework material is provided with a large number of ZrF in regular arrangement 6 2- And a polyfluoro anion functional group, wherein the anion forms a special electrostatic environment in a pore canal with limited specific structural space of the MOF material, and the propyne is captured from the propyne/propadiene mixed gas with high capacity and high selectivity. On the other hand, zrF is contained 6 2- The anion metal organic framework material has a special window action site, and can enhance the adsorption of propyne, thereby improving the separation selectivity of propyne/propadiene. The two aspects are combined to cooperate to achieve the technical effect of efficiently separating the propyne and the propadiene required by the application.
2. Containing ZrF 6 2- The anion metal organic framework material is easy to desorb and regenerate, has great advantages compared with the traditional chemical absorbent, can reduce the energy consumption of material regeneration, and can be regenerated and reused.
3. The metal organic framework material with the special window action site has excellent hydrothermal stability, also has excellent cycle stability, and the excellent stability also shows potential application value of the metal organic framework material with the special window action site in industry.
Drawings
FIG. 1 is CuZrF 6 -a window plot in the TPA crystal structure;
FIG. 2 is a CuZrF of example 4 6 -a single component adsorption isotherm plot of propyne and propadiene for TPA at 298K, 0 to 100 kPa;
FIG. 3 is CuZrF in example 4 6 -single component adsorption isotherm plot of propyne and propadiene for TPA at 278K and 308K, 0 to 100 kPa;
FIG. 4 is CuZrF in example 5 6 IAST separation selectivity diagram for separating equimolar propyne/propadiene from other metal organic framework materials at 298K, 0-100 kPa;
FIG. 5 is a view of CuZrF at 298K in example 4 and example 5 6 -comparison of the selectivity of the separation of TPA from other metal-organic framework materials for propyne adsorption (50 kPa) -propyne/propadiene;
FIG. 6 is a CuZrF of example 6 6 -a graph of the heat of adsorption of TPA for propyne, allene;
FIG. 7 is a view of CuZrF loaded with propyne gas 6 -TPA in situ single crystal map.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
Example 1
16.8mg of CuZrF 6 ·3H 2 O was dissolved in 10mL of water (solution A), 10mg of tris (4-pyridyl) amine (TPA) was dissolved in 10mL of methanol (solution B), 20mL of methanol/water (1/1 by volume) buffer was prepared, and finally 1mL of solution A,2mL of buffer and 1mL of solution B were sequentially added to a 5mL cuvette. Sealing the small test tube, standing for one week at room temperature to obtain blue crystal CuZrF 6 TPA, a metal-organic framework material of the present application with specific window sites of action. After crystal analysis, it is found that CuZrF 6 The structure of TPA is shown in FIG. 1. The subsequent testing and characterization of CuZrF prepared using the method of this example, unless otherwise specified 6 -TPA。
Example 2
In a 50mL round bottom322.8mg (1.0 mmol) of CuZrF are placed in a bottle 6 ·3H 2 O was dissolved in 14mL of water. 331.05mg (1.3 mmol) of tris (4-pyridyl) amine was dissolved in 30mL of methanol in a further 50mL round bottom flask. The methanol solution was added dropwise to the aqueous solution and stirred at 80 ℃ for 72 hours to give a blue solid precipitate which was filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours, and replacing for more than 3 times to remove water molecules in the holes of the material, thereby obtaining the metal organic frame material CuZrF with special window action sites 6 -TPA。
Example 3
About 100mg of CuZrF obtained in example 1 6 The TPA material is filled into an adsorption tube, the adsorption tube is vacuumized for two hours at room temperature, then vacuumized for 10 hours at 120 ℃ to activate the TPA material, then 77K nitrogen adsorption and desorption test is carried out on the activated sample by using an adsorption instrument under the condition of liquid nitrogen bath, and the BET specific surface area, the pore volume and the pore size distribution of the material can be calculated based on a nitrogen adsorption isotherm.
Example 4
The activated CuZrF of example 3 was subjected to conditions of 278K, 298K and 308K by an adsorption apparatus 6 The test of single-component gas adsorption of propyne and propadiene is carried out on the TPA sample, and the single-component gas adsorption curves are shown in fig. 2 and 3. Specifically at 298K and 50kPa, cuZrF 6 The propyne adsorption capacity of TPA can reach 177.4cm 3 /cm 3 Allene adsorption capacity of 147.5cm 3 /cm 3 . Then CuZrF is carried out 6 The propyne adsorption at 50kPa of TPA was compared with other MOF materials and the results are shown in FIG. 5.
Example 5
CuZrF using a two-site Langmuir-Freundlich (with temperature factor) model 6 Fitting the adsorption isotherm of the TPA single-component propyne or propadiene gas, and calculating the CuZrF at 298K and 100kPa by using the parameters obtained by fitting and the ideal solution adsorption theory (IAST) 6 TPA propyne/propadiene (50/50 v/v) separation selectivity of 6.03, indicating CuZrF 6 TPA enables equimolar separation of propyne/propadiene. Selectivity ofThe curve is shown in FIG. 4, and then the 298K, 100kPa CuZrF 6 The propyne/propadiene (50/50 v/v) separation selectivity of TPA was compared to other MOF materials and the results are shown in FIG. 5.
Example 6
CuZrF was calculated using the parameters obtained by fitting in example 5 and the Clausius-Clapeyron equation 6 Adsorption heat curve of TPA, cuZrF at zero loading 6 The heat of adsorption of TPA for propyne and propadiene was 47kJ/mol and 42kJ/mol, respectively. The heat of adsorption curve is shown in FIG. 6.
Example 7
The CuZrF obtained in example 2 6 TPA material is ground into fine powder with uniform size, the fine powder is put into an adsorption column with the inner diameter of 0.5cm and the length of 5cm, activated for 10 hours at 100 ℃, and the mixed gas of propyne and propadiene (50/50 v/v) is introduced into the adsorption column at the room temperature of 25 ℃ at the concentration of 2mL/min, so that the propadiene gas can be observed to be preferentially discharged, and the propyne gas can be discharged after a certain time.
Example 8
For propyne-loaded CuZrF of example 4 6 After in-situ monocrystalline test of TPA crystal, the adsorption site of propyne molecule is found to be positioned in CuZrF after analysis 6 -at the window of TPA. The results of the in situ single crystal test are shown in FIG. 7.
Table 1 shows CuZrF 6 Comparison of TPA with existing other MOF materials for 50kPa propyne adsorption capacity, propyne/propadiene (50/50 v/v) IAST separation selectivity, propyne heat of adsorption, and propyne/propadiene (50/50 v/v) separation potential (i.e., the maximum propadiene yield that can be obtained for a 50/50v/v propyne/propadiene mixture gas separation per unit volume of material theoretically based on material static adsorption data).
TABLE 1
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. A method for separating propyne and propadiene, which is characterized in that mixed gas containing propyne and propadiene is contacted with a metal organic framework material with a special window action site, and the metal organic framework material selectively adsorbs the propyne in the mixed gas to realize the separation of the propadiene and the propyne;
the metal organic framework material consists of hexacoordinated divalent metal cations Cu 2+ Coordinated with a tridentate nitrogenous ligand L to form a cage structure, and then passing through a bivalent inorganic anion ZrF with high coordination number 6 2- Bridging to form a structure with special window action sites;
the molecular formula of the metal organic framework material is (CuZrF 6 ) 3 L 4 Wherein the tridentate nitrogen-containing ligand L is a tris (4-pyridyl) amine.
2. The method for separating propyne and propadiene according to claim 1, wherein the molar content of propyne is between 10% and 90% based on 100% of the total molar amount of propyne and propadiene in the mixed gas containing propyne and propadiene.
3. The method for separating propyne and propadiene according to claim 2, wherein the molar content of propyne is from 50% to 90% based on 100% of the total molar amount of propyne and propadiene in the mixed gas containing propyne and propadiene.
4. The method for separating propyne and propadiene according to claim 1, wherein the mixed gas containing propyne and propadiene is contacted with a metal organic framework material having a specific window action site by any one or a combination of a fixed bed adsorption, a fluidized bed adsorption and a moving bed adsorption.
5. The method for separating propyne from propadiene according to claim 4, wherein the contacting of the mixture containing propyne and propadiene with the metal organic framework material having a specific window site of action is by fixed bed adsorption, comprising: under the set adsorption temperature and pressure, the mixed gas containing propyne and propadiene enters a fixed bed adsorption column filled with the metal organic framework material at a set flow rate, the propadiene component preferentially penetrates through the bed layer, and high-purity propadiene gas is directly obtained from an outlet of the adsorption column.
6. The method for separating propyne from propadiene according to claim 1, wherein the temperature of adsorption is from 0 to 40 ℃.
7. The method for separating propyne and propadiene according to claim 1, wherein the pressure of adsorption is from 0.5 to 10atm.
8. The method for separating propyne from propadiene according to claim 1, wherein after separation of propyne from propadiene is achieved by selectively adsorbing propyne in a mixed gas by said metal organic framework material, regeneration of said metal organic framework material is achieved by desorbing propyne at a temperature of 30 to 100 ℃ and a pressure of 0 to 1 atm.
9. The application of the metal organic framework material with special window action sites in separating propyne from propadiene is characterized in that the metal organic framework material selectively adsorbs the propyne in the mixed gas after contacting the mixed gas containing the propyne and the propadiene to separate the propadiene from the propyne;
the metal organic framework material consists of hexacoordinated divalent metal cations Cu 2+ Coordinated with a tridentate nitrogenous ligand L to form a cage structure, and then passing through a bivalent inorganic anion ZrF with high coordination number 6 2- Bridging to form a structure with special window action sites;
the molecular formula of the metal organic framework material is (CuZrF 6 ) 3 L 4 Wherein the tridentate nitrogen-containing ligand LIs tris (4-pyridyl) amine.
10. The use according to claim 9, characterized in that the metallo-organic framework material has a separation selectivity of 6.03 at 298K, 100kPa for a 1:1 molar ratio of propyne and propadiene mixture;
the separation potential of the metal organic framework material to the mixed gas of propyne and propadiene with the mol ratio of 1:1 is 5.72mmol of propadiene/cm 3 A metal organic framework material.
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| CN116589695B (en) * | 2023-05-17 | 2024-04-30 | 浙江师范大学 | Ionic metal organic framework material with znv topological structure and preparation and application thereof |
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