CN116408051A - Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method - Google Patents
Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method Download PDFInfo
- Publication number
- CN116408051A CN116408051A CN202111671557.4A CN202111671557A CN116408051A CN 116408051 A CN116408051 A CN 116408051A CN 202111671557 A CN202111671557 A CN 202111671557A CN 116408051 A CN116408051 A CN 116408051A
- Authority
- CN
- China
- Prior art keywords
- sulfonic acid
- acid anion
- ethylene
- porous material
- ethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Sulfonic acid anion Chemical class 0.000 title claims abstract description 182
- 239000011148 porous material Substances 0.000 title claims abstract description 158
- 238000000926 separation method Methods 0.000 title claims abstract description 63
- 238000009396 hybridization Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 156
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 155
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000013110 organic ligand Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000001768 cations Chemical class 0.000 claims abstract description 23
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- VERAMNDAEAQRGS-UHFFFAOYSA-N butane-1,4-disulfonic acid Chemical compound OS(=O)(=O)CCCCS(O)(=O)=O VERAMNDAEAQRGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 115
- 239000007789 gas Substances 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 55
- 238000003795 desorption Methods 0.000 claims description 40
- 229910021645 metal ion Inorganic materials 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 27
- 239000012263 liquid product Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 13
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- LEUIUWYZAHKPSE-UHFFFAOYSA-L disodium;butane-1,4-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCCS([O-])(=O)=O LEUIUWYZAHKPSE-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BJTHMUJCKBTCFR-UHFFFAOYSA-L disodium;ethane-1,2-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCS([O-])(=O)=O BJTHMUJCKBTCFR-UHFFFAOYSA-L 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- 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
Abstract
The invention discloses a sulfonic acid anion hybridization porous material, a preparation method and an ethylene-ethane separation method. The separation method realizes the separation of ethylene and ethane by using a sulfonic acid anion hybridization porous material, and the sulfonic acid anion hybridization porous material comprises the following components: the sulfonic acid anion hybrid porous material is composed of sulfonic acid anions S, organic ligands L and metal cations M through coordination bonds, and has a chemical formula of [ MSL ] 2 ] n Wherein n is a positive integer, and represents that the material consists of a plurality of MSL 2 The structural units of the (B) are formed by expanding the space; the sulfonic acid anion is an ethane disulfonic acid anion or a butane disulfonic acid anion; the metal cation is Cu 2+ 、Zn 2+ 、Co 2+ One of the following; the organic ligand is 4,4 '-bipyridine, 1,2, 4-triazole, 4'-one of bipyridine dithioethers. The sulfonic acid anion hybrid porous material can be used for efficiently separating ethylene and ethane under normal temperature environment and mild operation condition, and the purity of the separated ethylene is higher and the energy consumption is obviously reduced.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a sulfonic acid anion hybridization porous material, a preparation method and an ethylene-ethane separation method.
Background
Ethylene is one of the most productive chemicals in the world as a base stone for petrochemical industry. The downstream products mainly comprise polyethylene, polyvinyl chloride, ethylene oxide, ethylene glycol, vinyl acetate and the like, account for more than 75% of petrochemical products, and are widely applied to various national economic industries such as plastics, pharmacy, textiles, paint and the like. At present, ethylene is mainly prepared in a naphtha cracking mode in China, wherein the separation of ethylene and ethane is a key step for preparing high-purity ethylene. The refinery dry gas also contains abundant ethylene resources, and the separation of ethylene and ethane is also a key technology in the efficient utilization of the refinery dry gas. However, ethylene is highly similar to ethane in structural properties, with only minor differences in unsaturation, making ethylene/ethane separation difficult and energy consuming.
The separation technology of ethylene and ethane mainly comprises low-temperature rectification, solvent absorption, membrane separation, adsorption separation and the like. Among them, the development of the cryogenic rectification technology is most mature and widely used in industry, but because of the close boiling points of ethylene and ethane, the relative volatility is small, the separation can be realized under the conditions of higher pressure (22 bar), extremely low temperature (160 ℃ below zero) and large reflux ratio, and the tray number of the rectification tower is usually more than 150, so that the defects of high energy consumption, large device investment and the like exist. The solvent absorption method has the problems of large pollution of organic solvents and low selectivity. The membrane separation method has the defects of low selectivity, complex membrane manufacturing process, high cost and the like of the existing membrane, and limits the industrial application of the membrane. The adsorption separation technology is used as a separation technology with low energy consumption and environmental friendliness, is suitable for separating substances with similar structures, such as separation and purification of low-carbon hydrocarbon gas, and has great advantages compared with other separation technologies.
Disclosure of Invention
The inventor researches and discovers that when the adsorption separation technology is used for separating substances with similar structures such as ethylene and ethane, the existing adsorption materials such as zeolite molecular sieves, activated carbon, polymers, metal organic framework materials and the like often have the defects of difficulty in accurately identifying small differences between ethylene and ethane molecules, low separation selectivity, small adsorption capacity, poor stability and the like, and the feasibility of the ethylene/ethane adsorption separation technology is restricted. For example:
although the adsorption capacity of the 4A molecular sieve can reach 2.7 mmol.g at the temperature of 25 ℃ and 1bar -1 However, there are disadvantages in that the selectivity is low and the desorption heat is high.
The use of carbon molecular sieves for the sieving of ethylene ethane is disclosed in the pi-reduction vs. kinetic Separation (AIChE JOURNAL,2004, 44 (4): 799-809.), but with an ethylene capacity of only 1.1 mmol.g at 1bar, 25 DEG C -1 。
Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene (Science, 2017, 358 (6366): 1068-1071.) discloses novel molecular sieves ITQ-55 for ethylene ethane separations, which exhibit good ethylene/ethane kinetic separation But the ethylene adsorption amount is low due to the too small pore diameter, and is only 1.5 mmol.g at 1bar and 30 DEG C -1 。
Chinese patent application publication No. CN1073422A, publication No. 23/6/1993, and publication No. CN1048010C, publication No. 3/6/1998, and publication No. 3/method for recovering ethylene from dilute ethylene-containing gas disclose the use of Ag + /Cu + Supported molecular sieves separate ethylene but Ag + /Cu + The supported molecular sieve is sensitive to moisture, sulfide and the like in the raw material gas, has strong interaction with guest molecules, is not easy to desorb and is not beneficial to industrial application.
The metal-organic framework material is used as an emerging porous adsorption material, has the outstanding advantages of large specific surface area, high pore volume, easiness in chemical modification of pore channels, capability of accurately adjusting pore diameters and the like, and the separation performance of pi-complex framework materials widely studied at present on mixed gas still needs to be improved. For example, hydrocarbon Separations in a Metal-Organic Framework with Open Iron (II) Coordination Sites (Science, 2012, 335 (6076): 1606-1610.) discloses metal-organic framework materials Fe-MOF-74 having high density of unsaturated metal sites that can electrostatically interact with pi electrons of ethylene double bonds, but due to the larger pore size 
The selectivity to the ethylene/ethane mixed gas is low, and the defects of harsh synthesis conditions (the synthesis by hydrothermal reaction under the protection of inert gas) and poor stability exist at the same time.
Therefore, the adsorption material capable of being used for ethylene-ethane separation in the prior art cannot have high adsorption capacity, high selectivity and high stability at the same time, and the design and preparation of the novel porous material with high adsorption capacity, high selectivity and high stability are very important for the development of ethylene-ethane adsorption separation technology.
In view of the above problems, the present invention has been made to provide a sulfonic acid anion hybrid porous material and a preparation method thereof, and an ethylene-ethane separation method, which overcome or at least partially solve the above problems.
The embodiment of the invention provides a sulfonic acid anion hybridization porous material, which comprises the following components:
the sulfonic acid anion hybrid porous material consists of sulfonic acid anions S, organic ligands L and metal cations M through coordination bonds, and has a chemical formula of [ MSL ] 2 ] n Wherein n is a positive integer, representing that the material consists of a plurality of MSL 2 The structural units of the (B) are formed by expanding the space;
the sulfonic acid anion is an ethane disulfonic acid anion or a butane disulfonic acid anion;
The metal cation is Cu 2+ 、Zn 2+ 、Co 2+ One of the following;
the organic ligand is one of 4,4 '-bipyridine, 1,2, 4-triazole and 4,4' -bipyridine disulfide.
In some alternative embodiments, the organic ligands are coordinated to the metal cation through a nitrogen atom, the organic ligands being both bidentate; the sulfonic acid anions coordinate with metal cations through oxygen atoms, and each sulfonic acid anion is connected with two different metal cations; each metal cation is associated with four different organic ligands and coordinates to two oxygen atoms.
The embodiment of the invention provides a preparation method of a sulfonic acid anion hybrid porous material, which comprises the following steps: the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound are used for preparing the sulfonic acid anion hybridization porous material according to the mol ratio of (0.5-3) to (1-5).
In some alternative embodiments, the sulfonic acid anion hybrid porous material is prepared by using metal ion inorganic salt, sulfonic acid anion compound and organic ligand compound according to the molar ratio of (0.5-3): 1-5, and comprises:
preparing a sulfonic acid anion hybridization porous material liquid product by using metal ion inorganic salt, a sulfonic acid anion compound and an organic ligand compound according to the mol ratio of (0.5-3) to (1-5);
Carrying out vacuum suction filtration on the sulfonic acid anion hybrid porous material liquid product at 25 ℃ to obtain a sulfonic acid anion hybrid porous material solid product;
and activating the solid sulfonic acid anion hybrid porous material at the temperature of 100 ℃ under vacuum or by adopting an inert gas blowing mode to remove guest solvent molecules in the pore canal, so as to obtain the sulfonic acid anion hybrid porous material.
In some alternative embodiments, the sulfonic acid anion hybrid porous material liquid product is prepared by using metal ion inorganic salt, sulfonic acid anion compound and organic ligand compound according to the mol ratio of (0.5-3): 1-5, and comprises:
dissolving metal ion inorganic salt, a sulfonic acid anion compound and an organic ligand compound in water according to the molar ratio of (0.5-3) to (1-5), stirring at normal temperature until the reaction is finished or maintaining the specified heating temperature until the reaction is finished, and obtaining a sulfonic acid anion hybrid porous material liquid product;
dissolving metal ion inorganic salt and sulfonic acid anion compound in water or organic solvent to obtain solution 1, and dissolving organic ligand compound in water or organic solvent to obtain solution 2, wherein the molar ratio of the metal ion inorganic salt to the sulfonic acid anion compound to the organic ligand compound is 1 (0.5-3) (1-5); and (3) dropwise adding the solution 2 into the solution 1, standing and diffusing until the reaction is finished, or mixing the solution 1 and the solution 2, stirring at normal temperature until the reaction is finished or maintaining a specified heating temperature until the reaction is finished, and obtaining the sulfonic acid anion hybrid porous material liquid product.
In some alternative embodiments, the stirring at room temperature to the end of the reaction comprises: stirring at normal temperature for at least 12h.
In some alternative embodiments, the maintaining the specified heating temperature to the end of the reaction comprises: heated to 80℃for 3 days.
In some alternative embodiments, after the solid product of the sulfonic acid anion hybrid porous material is obtained, before the activation, the method further comprises: washing with water or methanol for several times and soaking for 8-50 hr.
In some alternative embodiments, the metal ion inorganic salt is a metal ion chloride or nitrate compound;
the sulfonic acid anion compound is one of sodium ethane disulfonate and sodium butane disulfonate;
the organic ligand compound is one of 4,4 '-bipyridine, 1,2, 4-triazole and 4,4' -bipyridine disulfide.
In some alternative embodiments, the metal ion chloride is cobalt chloride and the nitric acid compound is one of copper nitrate, zinc nitrate, and cobalt nitrate.
The embodiment of the invention provides an ethylene-ethane separation method, which comprises the following steps: the sulfonic acid anion hybridization porous material is used for realizing the separation of ethylene and ethane.
In some alternative embodiments, the method includes:
The mixed gas containing ethylene and ethane is contacted with a sulfonic acid anion hybrid porous material, and the ethylene is adsorbed by the sulfonic acid anion hybrid porous material, so that the ethane is separated.
In some alternative embodiments, the method further comprises:
and (3) carrying out desorption treatment on the sulfonic acid anion hybridization porous material adsorbed with ethylene to obtain ethylene.
In some alternative embodiments, the contacting the ethylene-ethane containing mixed gas with the sulfonic acid anion hybrid porous material comprises:
the mixed gas containing ethylene and ethane is contacted with the sulfonic acid anion hybridization porous material through at least one mode of fixed bed adsorption and moving bed adsorption.
In some alternative embodiments, the mixed gas containing ethylene and ethane is contacted with the sulfonic acid anion hybridization porous material through a fixed bed adsorption mode to separate the ethane, which comprises the following steps:
introducing the mixed gas containing ethylene and ethane into a fixed bed at a set adsorption temperature and adsorption pressure at a set flow rate, contacting the mixed gas with a sulfonic acid anion hybrid porous material in an adsorption column of the fixed bed to adsorb the ethylene, and obtaining the gas containing ethane at an outlet of the adsorption column;
And stopping the gas mixture input when the ethylene appears at the outlet of the adsorption column or the front of the concentration gradient of the ethylene in the bed is not lower than the set proportion of the bed.
In some alternative embodiments, the ethylene-adsorbed sulfonic acid anion hybrid porous material is subjected to desorption treatment to obtain ethylene, comprising:
desorbing ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at a set desorption temperature and desorption pressure, and obtaining ethylene at an outlet of the adsorption column; or (b)
And (3) desorbing ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at a set desorption temperature and desorption pressure, introducing pure ethylene for reverse displacement, and obtaining ethylene at an outlet of the adsorption column.
In some alternative embodiments, the adsorption temperature is-30-100 ℃, the adsorption pressure is 1-10 bar, the desorption temperature is 0-120 ℃, and the desorption pressure is 0.01-1 bar.
In some alternative embodiments, the adsorption temperature is 25-40 ℃, the adsorption pressure is 1-5 bar, the desorption temperature is 60-100 ℃, and the desorption pressure is 0.01-0.1 bar.
In some alternative embodiments, the set flow rate is between 0.5 and 10.0ml/min.
In some alternative embodiments, the ethylene component in the mixed gas is 10% -90%, the ethane component is 10% -90%, and the impurity gas is 0% -20%.
The embodiment of the invention also provides an application of the sulfonic acid anion hybridization porous material in an ethylene-ethane separation method.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the sulfonic acid anion hybrid porous material provided by the embodiment of the invention is formed by different sulfonic acid anions S, organic ligands L and metal cations M through coordination bonds, the structural units of the material can be expanded in space, the sulfonic acid anion hybrid porous material obtained by combining different metal cations, organic ligands and sulfonic acid anions has proper aperture and flexibility, and pore channels can deform to allow gas molecules to pass through when the material contacts gas, and the diffusion rate of ethylene in the sulfonic acid anion hybrid porous material with smaller dynamic size is obviously faster than that of ethane, so that the ethylene/ethane mixed gas can be separated efficiently; compared with the existing material for separating ethylene from ethane, the material has milder interaction on gas molecules, is easier to realize regeneration after the adsorbed gas is desorbed, and can be repeatedly used; the material introduces sulfonic acid anions as anion acting sites and pillared ligands, has stronger recognition capability and better pore channel structure and size regulating capability.
The sulfonic acid anion hybrid porous material is prepared from raw materials with wide sources and low cost, has mild synthesis conditions, simple and convenient method and good repeatability, has the advantages of water, good thermal stability and long service life, and has less influence on separation performance by water, sulfides and the like;
the material is used for ethylene-ethane separation, can realize high-efficiency separation of ethylene and ethane at normal temperature and normal pressure, has mild operation conditions and obviously reduced energy consumption, accords with the concept of sustainable development better, has the prominent advantages of small equipment investment and the like, and has good industrialized application prospect compared with the low-temperature rectification method widely used in the current industrial production.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof as well as the appended drawings.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a flow chart of a process for ethylene ethane separation in an embodiment of the invention;
FIG. 2 is a flow chart of a method for preparing a sulfonic acid anion hybrid porous material in an embodiment of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The embodiment of the invention provides a sulfonic acid anion hybrid porous material, which consists of sulfonic acid anions S, organic ligands L and metal cations M through coordination bonds, and has a chemical formula of [ MSL ] 2 ] n Wherein n is a positive integer, representing that the material consists of a plurality of MSL 2 The structural units of the (B) are formed by expanding the space;
the sulfonic acid anion is an ethane disulfonic acid anion or a butane disulfonic acid anion;
the metal cation is Cu 2+ 、Zn 2+ 、Co 2+ One of the following;
the organic ligand is one of 4,4 '-bipyridine, 1,2, 4-triazole and 4,4' -bipyridine disulfide.
Wherein, the organic ligand is coordinated with the metal cation through nitrogen atoms, and the organic ligands are two-coordinated; the sulfonic acid anions coordinate with the metal cations through oxygen atoms, and each sulfonic acid anion is connected with two different metal cations; each metal cation is associated with four different organic ligands and coordinates to two oxygen atoms.
The embodiment of the invention also provides a separation method of ethylene and ethane, which realizes the separation of ethylene and ethane by using the sulfonic acid anion hybridization porous material. The flow is shown in fig. 1, and comprises the following steps:
step S101: the mixed gas containing ethylene and ethane is contacted with a sulfonic acid anion hybrid porous material, and the ethylene is adsorbed by the sulfonic acid anion hybrid porous material, so that the ethane is separated.
The mixed gas of ethylene and ethane can contain one or more of methane, oxygen, nitrogen, hydrogen, carbon monoxide and other impurity gases, and the volume ratio of the impurity gases to the ethylene ethane is as follows: 10-90% of ethylene component, 10-90% of ethane component and 0-20% of impurity gas. Such as ethylene: ethane: methane=50:40:10, and within this ratio range, the impurity gas has less influence on the ethylene/ethane separation performance of the sulfonic acid anion-hybridized porous material. Of course, the separation can be performed within other ratios.
Step S102: and (3) carrying out desorption treatment on the sulfonic acid anion hybridization porous material adsorbed with ethylene to obtain ethylene.
In the step S101, the mixed gas containing ethylene and ethane is contacted with the sulfonic acid anion-hybrid porous material by at least one of fixed bed adsorption and moving bed adsorption, and ethylene is adsorbed by the sulfonic acid anion-hybrid porous material to separate ethane.
The fixed bed adsorption mode can be realized by a fixed bed adsorber, the fixed bed adsorber refers to an adsorption device in which an adsorbent is fixed at certain parts of the adsorber, and the adsorbent is kept still when air flows through an adsorbent bed layer, so that the fixed bed adsorber has a simple structure, is simple and convenient to operate and is widely used.
In some alternative embodiments, the mixed gas containing ethylene and ethane is contacted with the sulfonic acid anion hybridization porous material through a fixed bed adsorption mode to separate the ethane, which comprises the following steps: introducing the mixed gas containing ethylene and ethane into a fixed bed at a set adsorption temperature and adsorption pressure at a set flow rate, contacting the mixed gas with a sulfonic acid anion hybrid porous material in an adsorption column of the fixed bed to adsorb the ethylene, and obtaining the gas containing ethane at an outlet of the adsorption column; and stopping the gas mixture input when the ethylene appears at the outlet of the adsorption column or the front of the concentration gradient of the ethylene in the bed is not lower than the set proportion of the bed.
When the contact mode of the mixed gas and the sulfonic acid anion hybridization porous material is a fixed bed adsorption mode:
introducing mixed gas containing ethylene and ethane into a fixed bed adsorption column filled with a sulfonic acid anion hybridization porous material at constant adsorption pressure and temperature to contact with the sulfonic acid anion hybridization porous material, wherein the diffusion rate of ethane components is low, the adsorption quantity is lower than that of ethylene components, the ethane components preferentially penetrate through the fixed bed adsorption column, and the ethane gas is obtained at the outlet of the adsorption column; after the ethane component penetrates, continuing to introduce the mixed gas for adsorption for a certain time, so that the front of the concentration gradient of the ethylene in the bed is not lower than 2/3 of the bed, or stopping introducing the mixed gas when the ethylene component penetrates, adjusting the temperature and the pressure to the preset desorption temperature and the desorption pressure by adopting one or the combination of a plurality of methods such as temperature rising, pressure reducing and the like, carrying out desorption, and carrying out further concentration on the ethylene by adopting high-purity ethylene blowing replacement to obtain ethylene gas; the ethylene used for purge displacement may be high purity ethylene obtained by desorption, or may be ethylene obtained by other means.
The sulfonic acid anion hybridized porous material and the fixed bed adsorption process can be used for separating ethylene gas with the purity of 85-99% from the mixed gas containing ethylene and ethane.
In order to improve the purity of ethylene, a multi-bed pressure swing adsorption process or a multi-fixed bed adsorption method can be considered, wherein the multi-bed pressure swing adsorption adopts different adsorption and desorption pressures by using a plurality of fixed beds or adopts a mode of sequentially adsorbing a plurality of fixed beds, so that the ethylene is more fully adsorbed, and ethylene and ethane with better purity are separated. The multiple fixed bed adsorption uses one fixed bed, and multiple circulation is conducted to perform multiple adsorption.
The moving bed adsorption mode can be realized by a moving bed adsorber, wherein the moving bed adsorber is a device for completing adsorption by the adsorbent flowing along with the airflow in the adsorption process, and in the adsorber, fresh adsorbent is added from the top of the tower, and the addition speed is based on the principle of keeping a certain contact height between gas and solid phase; a device is arranged at the bottom of the tower to continuously remove saturated adsorbent, and the saturated adsorbent is sent to another container for regeneration and returned to the top of the tower after regeneration.
In the step S102, an optional desorption process may include: and (3) desorbing the ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at the set desorption temperature and desorption pressure, and obtaining the ethylene at the outlet of the adsorption column.
An alternative process for desorption treatment may include: and (3) desorbing ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at a set desorption temperature and desorption pressure, introducing pure ethylene for reverse displacement, and obtaining ethylene at an outlet of the adsorption column.
Optionally, the adsorption temperature is-30-100 ℃, the adsorption pressure is 1-10 bar, the desorption temperature is 0-120 ℃, and the desorption pressure is 0.01-1 bar. Preferably, the adsorption temperature is 25-40 ℃, the adsorption pressure is 1-5 bar, the desorption temperature is 60-100 ℃, and the desorption pressure is 0.01-0.1 bar.
The flow rate is optionally set to be 0.5-10.0 ml/min.
The ethylene-ethane separation method provided by the embodiment of the invention is an adsorption separation method, and can realize high-efficiency separation of ethylene-ethane under a mild operation condition. The mixed gas of ethylene and ethane is contacted with the sulfonic acid anion hybrid porous material, and the sulfonic acid anion hybrid porous material preferentially adsorbs ethylene in the mixed gas, so that the separation of ethylene and ethane is realized. According to the invention, sulfonic acid anions are introduced, and the pore diameter and pore channel surface properties of the ion hybridization porous material are accurately regulated and controlled, so that ethylene is adsorbed in the pore channel with high selectivity, and thus, the high-efficiency separation of ethylene and ethane is realized. The method has the outstanding advantages of good material stability, high adsorption selectivity and the like, and has good industrial application prospect.
The embodiment of the invention also provides a preparation method of the sulfonic acid anion hybrid porous material, which comprises the following steps: the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound are used for preparing the sulfonic acid anion hybridization porous material according to the mol ratio of (0.5-3) to (1-5).
In some alternative embodiments, the process of the preparation method is shown in fig. 1, and includes the following steps:
step S201: the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound are used for preparing the sulfonic acid anion hybrid porous material liquid product according to the mol ratio of (0.5-3) to (1-5).
Optionally, the metal ion inorganic salt is a metal ion chloride or nitrate compound; the metal ion chloride is cobalt chloride, and the nitric acid compound is one of copper nitrate, zinc nitrate and cobalt nitrate.
Optionally, the sulfonic acid anion compound is one of sodium ethyldisulfonate and sodium butane disulfonate;
alternatively, the organic ligand compound is one of 4,4 '-bipyridine, 1,2, 4-triazole, and 4,4' -bipyridine disulfide.
Step S202: and carrying out vacuum suction filtration on the sulfonic acid anion hybrid porous material liquid product at 25 ℃ to obtain a sulfonic acid anion hybrid porous material solid product.
Step S203: and activating the solid sulfonic acid anion hybrid porous material at the temperature of 100 ℃ under vacuum or by adopting an inert gas blowing mode to remove guest solvent molecules in the pore canal, so as to obtain the sulfonic acid anion hybrid porous material.
Wherein the inert gas may be N 2 Any one or combination of He and Ar.
The process of preparing the sulfonic acid anion hybrid porous material liquid product in the step S201 can be realized by adopting different methods such as a normal temperature stirring method, a solvent heating method, a solution dripping method and the like. Some alternative methods are exemplified below:
mode one:
dissolving metal ion inorganic salt, sulfonic acid anion compound and organic ligand compound in water according to the mol ratio of (0.5-3) to (1-5), stirring at normal temperature until the reaction is finished, and obtaining the sulfonic acid anion hybrid porous material liquid product.
Mode two:
dissolving metal ion inorganic salt and sulfonic acid anion compound in water or organic solvent to obtain solution 1, dissolving organic ligand compound in water to obtain solution 2, wherein the molar ratio of metal ion inorganic salt to sulfonic acid anion compound to organic ligand compound is (0.5-3) to (1-5); and mixing the solution 1 and the solution 2, and stirring at normal temperature until the reaction is finished to obtain a sulfonic acid anion hybrid porous material liquid product. Wherein solution 1 is a metal salt-sulfonic acid anion solution and solution 2 is an organic ligand compound solution.
Mode three:
dissolving metal ion inorganic salt, a sulfonic acid anion compound and an organic ligand compound in water according to the molar ratio of (0.5-3) to (1-5), and maintaining the specified heating temperature until the reaction is finished to obtain a sulfonic acid anion hybrid porous material liquid product;
mode four
Dissolving metal ion inorganic salt and sulfonic acid anion compound in water or organic solvent to obtain solution 1, dissolving organic ligand compound in water to obtain solution 2, wherein the molar ratio of metal ion inorganic salt to sulfonic acid anion compound to organic ligand compound is (0.5-3) to (1-5); and mixing the solution 1 and the solution 2, and maintaining the specified heating temperature until the reaction is finished to obtain the sulfonic acid anion hybrid porous material liquid product. The solution 1 is a metal salt-sulfonic acid anion solution, the solution 2 is an organic ligand compound solution, and the organic ligand compound solution is dropwise added above the metal salt-sulfonic acid anion solution during dropwise addition, and the sulfonic acid anion hybrid porous material is prepared by an interface diffusion method.
Mode five
Dissolving metal ion inorganic salt and sulfonic acid anion compound in water or organic solvent to obtain solution 1, and dissolving organic ligand compound in water to obtain solution 2, wherein the molar ratio of the metal ion inorganic salt to the sulfonic acid anion compound to the organic ligand compound is 1 (0.5-3): 1-5; and (3) dropwise adding the solution 2 into the solution 1, standing and diffusing until the reaction is finished, and obtaining the sulfonic acid anion hybrid porous material liquid product.
In some optional embodiments, after step S202 and before step S203, the method further includes: washing the solid product of the sulfonic acid anion hybridization porous material with water or methanol for a plurality of times, and soaking for 8-50 h.
The embodiment of the invention also provides an application of the sulfonic acid anion hybrid porous material in an ethylene-ethane separation method.
According to the invention, through the combination of different metal cations, organic ligands and organic anions, a plurality of novel sulfonic acid anion hybrid porous materials are prepared, and the precise regulation and control of the pore diameter of the sulfonic acid anion hybrid porous materials are realized. Because the pore diameter of the sulfonic acid anion hybridization porous material is smaller than the kinetic diameters of ethylene and ethane, when ethylene and ethane molecules are contacted with the sulfonic acid anion hybridization porous material, the ethylene and ethane molecules can diffuse into pore channels of the material under the condition that an organic ligand rotates for a certain angle by virtue of the flexibility of the material. Because ethylene has a smaller molecular size than ethane, it can enter the pore channels with a smaller degree of ligand/anion rotation, and its diffusion energy barrier is significantly lower than ethane. Thus, ethylene diffuses faster than ethane in the sulfonic acid anion hybrid porous material, exhibiting good kinetic separation characteristics. Meanwhile, the sulfonic acid anion hybridization porous material has high-density oxygen-containing electronegative sulfonic acid action sites in pore channels, and can form stable hydrogen bond interaction with gas molecules, so that ethylene is effectively and selectively captured from mixed gas, and high-efficiency thermodynamic separation of ethylene and ethane is realized.
Compared with the transition metal ion loaded adsorption material which is most widely applied in the field of ethylene and ethane adsorption separation at present, the sulfonic acid anion hybridization porous material adopted in the embodiment of the invention has milder interaction on gas molecules, realizes high-efficiency separation of ethylene/ethane mixed gas through physical adsorption, has milder static adsorption isotherm at low pressure, and is easier to desorb and regenerate.
Compared with other porous materials, the sulfonic acid anion hybrid porous material adopted by the embodiment of the invention introduces sulfonic acid anions as anion action sites and column support ligands, has stronger recognition capability and better pore channel structure and size regulation capability;
the sulfonic acid anion hybrid porous material adopted in the embodiment of the invention is prepared from raw materials with wide sources and low cost, has mild synthesis conditions, simple and convenient method and good repeatability, has the advantages of good water and thermal stability and long service life, and has less influence on separation performance by moisture, sulfides and the like.
The ethylene-ethane separation method provided by the embodiment of the invention is a novel method for separating ethylene and ethane based on adsorption of a sulfonic acid anion hybrid porous material, and the sulfonic acid anion hybrid porous material has proper pore diameter and flexibility, and can deform to allow guest molecules to pass through when contacting with gas. Ethylene has smaller kinetic size, and the diffusion rate of the ethylene in the sulfonic acid anion hybridization porous material is obviously faster than that of ethane, so that the high-efficiency ethylene/ethane mixed gas separation can be realized; can obtain ethylene gas with purity of more than 96%.
The ethylene-ethane separation method provided by the embodiment of the invention can realize the high-efficiency separation of ethylene and ethane at normal temperature and normal pressure, has mild operation conditions and obviously reduced energy consumption, is more in line with the concept of sustainable development, has the outstanding advantages of small equipment investment and the like, and has good industrial application prospect compared with the low-temperature rectification method widely used in the current industrial production.
The sulfonic acid anion hybrid porous material, the preparation method thereof and the ethylene-ethane separation method using the material provided by the embodiment of the invention, wherein the prepared sulfonic acid anion hybrid porous material can be purchased from the market, and related experimental data are as follows:
example 1
The above 1mol of copper nitrate, 1mol of sodium 1,2 '-ethyldisulfonate and 1mol of 4,4' -bipyridine disulfide were added together to 40L of pure water, and the mixture was stirred at room temperature for 12 hours. After the reaction is finished, vacuum filtration is carried out at 25 ℃ to collect the obtained solid product, and then the sample is activated to remove guest solvent molecules in pore channels under the condition of vacuum pumping at 100 ℃ to obtain the sulfonic acid anion hybrid porous material EDS-SS-Cu, wherein EDS is ethylene disulfonic acid anion, SS is 4,4' -bipyridine disulfide, and Cu is copper metal node.
Filling sulfonic acid anion hybridization porous material EDS-SS-Cu into a fixed bed adsorption column with the length of 5cm, introducing ethylene/ethane mixed gas (volume ratio of 60:40) into a bed layer at the temperature of minus 30 ℃ and the flow rate of 1.0ml/min for fixed bed adsorption, stopping introducing the mixed gas when the front of ethylene adsorption reaches about 2/3 of the bed layer for a certain time, decompressing the adsorption column until the ethylene just penetrates, introducing a proper amount of high-purity ethylene for reverse displacement, desorbing ethylene components enriched in the column by adopting a decompression mode to 0.01bar at the temperature of 0 ℃ to obtain ethylene gas with the purity of more than 97%, and completing regeneration of the adsorption column.
Comparative example 1
Filling a 5A molecular sieve into a fixed bed adsorption column with the length of 5cm, introducing an ethylene/ethane mixed gas (volume ratio of 60:40) into a bed layer at the temperature of 25 ℃ and the flow rate of 1.0ml/min for fixed bed adsorption, stopping introducing the mixed gas when the front of ethylene adsorption reaches about 2/3 of the bed layer, decompressing the adsorption column until ethylene just penetrates, introducing a proper amount of high-purity ethylene for reverse displacement, and desorbing ethylene components enriched in the column by adopting a decompression mode at the temperature of 25 ℃ to the pressure of 0.05bar to obtain ethylene gas with the purity of 75%.
Example 2
1mol of copper nitrate, 2mol of sodium 1,4 '-butanedisulfonate and 1mol of 4,4' -bipyridine were added together to pure water, and the mixture was placed in a stainless steel reaction vessel with a Teflon liner, and heated to 80℃for 3 days. After the reaction was completed, the resulting solid product was collected by vacuum filtration at 25 ℃ and washed several times with water. And then activating and removing guest solvent molecules in the pore canal under the condition of vacuumizing at 100 ℃ to obtain the sulfonic acid anion hybrid porous material BDS-1-Cu (BDS: butane disulfonic acid anion; SS:4,4' -bipyridine; cu: copper metal node).
Filling a sulfonic acid anion hybrid porous material BDS-1-Cu product into a 5cm fixed bed adsorption column, introducing an ethylene/ethane mixed gas (volume ratio of 50:50) into a bed layer at 40 ℃ and 5bar at a flow rate of 0.5ml/min for fixed bed adsorption, and stopping introducing the mixed gas after ethylene components penetrate for a certain time. And desorbing the ethylene gas component enriched in the fixed bed by adopting a desorption mode of heating to 60 ℃ and decompressing to 1bar to obtain the ethylene gas with the purity of 85 percent.
Example 3
5mol of 1,2, 4-triazole is added into 20L of pure water to form a solution 1, 1mol of cobalt chloride and 3mol of 1,2' -ethyl disulfonate are added into 20L of pure water to form a solution 2, the solution 2 is placed in a test tube, and the solution 1 is added dropwise into the test tube and then the reaction is carried out by standing. After the reaction is finished, the obtained solid product is collected through vacuum filtration at 25 ℃, and then guest solvent molecules in the pore canal are removed through activation under the condition of vacuum filtration at 100 ℃ to obtain the sulfonic acid anion hybrid porous material EDS-Atz-Co (EDS: ethyldisulfonic acid anion; ATZ:1,2, 4-triazole; co: cobalt metal node).
Making the EDS-Atz-Co material serving as a sulfonic acid anion hybrid porous material into particles, loading the particles into a fixed bed adsorption column, introducing ethylene/ethane mixed gas (volume ratio of 70:30) into a bed layer at 100 ℃ and 10bar for fixed bed adsorption, fully contacting with the adsorbent particles, stopping introducing the mixed gas after the ethylene component penetrates through the adsorbent particles for a certain time, desorbing the gas enriched in the adsorbent particles by adopting a mode of heating to 120 ℃ and decompressing to 0.1bar for desorption, circularly introducing the desorbed gas into the fixed bed for adsorption, and carrying out desorption after the ethylene adsorption is saturated, thereby obtaining the ethylene gas with the purity of more than 95%.
Example 4
1mol of zinc nitrate, 2mol of sodium 1,4 '-butanedisulfonate and 2mol of 4,4' -bipyridine disulfide were added together to 40L of pure water, and the reaction was stirred at room temperature. After the reaction was completed, the obtained solid product was collected by vacuum filtration at 25 ℃ and washed several times with water. Activating the obtained product at 100 ℃ under the condition of vacuumizing to remove guest solvent molecules in pore channels, and obtaining the sulfonic acid anion hybrid porous material BDS-SS-Zn (BDS: butane disulfonic acid anions; SS:4,4' -bipyridine disulfide; zn: zinc metal nodes).
Filling sulfonic acid anion hybrid porous material BDS-SS-Zn into a fixed bed adsorption column with the length of 5cm, introducing ethylene/ethane mixed gas (volume ratio ethylene: ethane: methane=70:30) containing a small amount of methane at the flow rate of 1.0ml/min at the temperature of 5 ℃ and 4bar for fixed bed adsorption, preferentially adsorbing ethylene, stopping introducing the mixed gas when the front of ethylene adsorption reaches about 2/3 of a bed layer, decompressing the adsorption column until the ethylene just penetrates, introducing a proper amount of high-purity ethylene for reverse replacement, desorbing the gas in the adsorption column by adopting a mode of decompressing to 0.5bar after the temperature is raised to 100 ℃, obtaining ethylene gas with the purity of 98%, and finishing regeneration of the adsorption material.
Example 5
1mol of cobalt nitrate, 0.5mol of sodium 1,4 '-butanedisulfonate and 2mol of 4,4' -bipyridine disulfide were added together to 20L of pure water, and the reaction was stirred at room temperature. After the reaction was completed, the obtained solid product was collected by vacuum filtration at 25 ℃ and washed several times with water. Activating the obtained product at 100 ℃ under the condition of vacuumizing to remove guest solvent molecules in pore channels, and obtaining the sulfonic acid anion hybrid porous material BDS-SS-Co (BDS: butane disulfonic acid anions; SS:4,4' -bipyridine disulfide; co: cobalt metal nodes).
The sulfonic acid anion hybrid porous material BDS-SS-Co is filled in 2 100mL fixed bed adsorption columns, ethylene/ethane mixed gas (volume ratio ethylene: ethane: methane=80:15:5) containing a small amount of methane is introduced into the column 1 at the temperature of 15 ℃ and the flow rate of 6bar at the speed of 10.0mL/min to carry out fixed bed adsorption, ethylene is preferentially adsorbed, and the introduction of the mixed gas is stopped when the front of ethylene adsorption reaches about 2/3 of the bed. After the impurity gas which is not adsorbed in the column 1 was discharged, the column 1 was evacuated to 0.05bar by a vacuum pump to obtain a preliminary product gas and complete the regeneration of the column 1. And (3) introducing the primary product gas into the column 2 for adsorption, and stopping introducing the mixed gas when the ethylene adsorption front reaches about 2/3 of the bed layer. After the impurity gas which is not adsorbed in the column 2 was discharged, the column 2 was evacuated to 0.05bar by a vacuum pump to obtain a product gas and complete the regeneration of the column 2. And obtaining ethylene gas with the purity of 98% in the two adsorption and desorption processes.
The following table 1 shows experimental data for the preparation of sulfonic acid anion hybrid porous materials. Table 2 shows experimental data for ethylene ethane adsorption separation.
TABLE 1
It can be seen from table 1 that the preparation of the sulfonic acid anion hybrid porous material using the sulfonic acid anion hybrid porous material provided by the example of the present invention can prepare the sulfonic acid anion hybrid porous material.
TABLE 2
It can be seen from table 2 that the ethylene ethane separation method provided by the examples of the present invention gave ethylene having a purity higher than 85%, whereas the ethylene separated using the 5A molecular sieve was significantly less pure than the method provided by the examples of the present invention.
It should be understood that the specific order or hierarchy of steps in the processes disclosed are examples of exemplary approaches. Based on design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in a sample order, and are not meant to be limited to the specific order or hierarchy presented.
In the foregoing detailed description, various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the subject matter require more features than are expressly recited in each claim. Rather, as the following claims reflect, invention lies in less than all features of a single disclosed embodiment. Thus the following claims are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate preferred embodiment of this invention.
The foregoing description includes examples of one or more embodiments. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the aforementioned embodiments, but one of ordinary skill in the art may recognize that many further combinations and permutations of various embodiments are possible. Accordingly, the embodiments described herein are intended to embrace all such alterations, modifications and variations that fall within the scope of the appended claims. Furthermore, as used in the specification or claims, the term "comprising" is intended to be inclusive in a manner similar to the term "comprising," as interpreted when employed as a transitional word in a claim. Furthermore, any use of the term "or" in the specification of the claims is intended to mean "non-exclusive or".
Claims (21)
1. A sulfonic acid anion hybrid porous material, comprising:
the sulfonic acid anion hybrid porous material consists of sulfonic acid anions S, organic ligands L and metal cations M through coordination bonds, and has a chemical formula of [ MSL ] 2 ] n Wherein n is a positive integer, representing that the material consists of a plurality of MSL 2 The structural units of the (B) are formed by expanding the space;
The sulfonic acid anion is an ethane disulfonic acid anion or a butane disulfonic acid anion;
the metal cation is Cu 2+ 、Zn 2+ 、Co 2+ One of the following;
the organic ligand is one of 4,4 '-bipyridine, 1,2, 4-triazole and 4,4' -bipyridine disulfide.
2. The sulfonic acid anion hybrid porous material of claim 1, wherein the organic ligands are coordinated to the metal cations through nitrogen atoms, and wherein the organic ligands are both bidentate; the sulfonic acid anions coordinate with metal cations through oxygen atoms, and each sulfonic acid anion is connected with two different metal cations; each metal cation is associated with four different organic ligands and coordinates to two oxygen atoms.
3. A method for preparing a sulfonic acid anion hybrid porous material, which is characterized by comprising the following steps: the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound are used for preparing the sulfonic acid anion hybridization porous material according to the mol ratio of (0.5-3) to (1-5).
4. The method of claim 3, wherein the preparation of the sulfonic acid anion hybrid porous material using the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound in a molar ratio of 1 (0.5-3): 1-5 comprises:
Preparing a sulfonic acid anion hybridization porous material liquid product by using metal ion inorganic salt, a sulfonic acid anion compound and an organic ligand compound according to the mol ratio of (0.5-3) to (1-5);
carrying out vacuum suction filtration on the sulfonic acid anion hybrid porous material liquid product at 25 ℃ to obtain a sulfonic acid anion hybrid porous material solid product;
and activating the solid sulfonic acid anion hybrid porous material at the temperature of 100 ℃ under vacuum or by adopting an inert gas blowing mode to remove guest solvent molecules in the pore canal, so as to obtain the sulfonic acid anion hybrid porous material.
5. The method of claim 4, wherein the preparing the sulfonic acid anion hybrid porous material liquid product using the metal ion inorganic salt, the sulfonic acid anion compound and the organic ligand compound according to the molar ratio of (0.5-3): 1-5 comprises:
dissolving metal ion inorganic salt, a sulfonic acid anion compound and an organic ligand compound in water according to the molar ratio of (0.5-3) to (1-5), stirring at normal temperature until the reaction is finished or maintaining the specified heating temperature until the reaction is finished, and obtaining a sulfonic acid anion hybrid porous material liquid product;
dissolving metal ion inorganic salt and sulfonic acid anion compound in water to obtain solution 1, and dissolving organic ligand compound in water or organic solvent to obtain solution 2, wherein the molar ratio of the metal ion inorganic salt to the sulfonic acid anion compound to the organic ligand compound is 1 (0.5-3): 1-5; and (3) dropwise adding the solution 2 into the solution 1, standing and diffusing until the reaction is finished, or mixing the solution 1 and the solution 2, stirring at normal temperature until the reaction is finished or maintaining a specified heating temperature until the reaction is finished, and obtaining the sulfonic acid anion hybrid porous material liquid product.
6. The method of claim 4, wherein stirring at room temperature to the end of the reaction comprises: stirring at normal temperature for at least 12h.
7. The method of claim 4, wherein maintaining the specified heating temperature to the end of the reaction comprises: heated to 80℃for 3 days.
8. The method of claim 4, wherein after obtaining the sulfonic acid anion hybrid porous material solid product, prior to activation, further comprising: washing with water or methanol for several times and soaking for 8-50 hr.
9. The method of any one of claims 3-8, wherein the metal ion inorganic salt is a metal ion chloride or nitrate compound;
the sulfonic acid anion compound is one of sodium ethane disulfonate and sodium butane disulfonate;
the organic ligand compound is one of 4,4 '-bipyridine, 1,2, 4-triazole and 4,4' -bipyridine disulfide.
10. The method of claim 9, wherein the metal ion chloride is cobalt chloride and the nitric acid compound is one of copper nitrate, zinc nitrate, and cobalt nitrate.
11. A process for the separation of ethylene ethane, characterized in that the separation of ethylene ethane is effected using a sulfonic acid anion hybrid porous material as described in any one of claims 1 to 2.
12. The method of claim 11, wherein the method comprises:
the mixed gas containing ethylene and ethane is contacted with a sulfonic acid anion hybrid porous material, and the ethylene is adsorbed by the sulfonic acid anion hybrid porous material, so that the ethane is separated.
13. The method as recited in claim 12, further comprising:
and (3) carrying out desorption treatment on the sulfonic acid anion hybridization porous material adsorbed with ethylene to obtain ethylene.
14. The method of claim 13, wherein contacting the ethylene-ethane containing mixed gas with the sulfonic acid anion hybrid porous material comprises:
the mixed gas containing ethylene and ethane is contacted with the sulfonic acid anion hybridization porous material through at least one mode of fixed bed adsorption and moving bed adsorption.
15. The method of claim 14, wherein contacting the mixed gas containing ethylene and ethane with the sulfonic acid anion hybrid porous material by a fixed bed adsorption mode to separate the ethane comprises:
introducing the mixed gas containing ethylene and ethane into a fixed bed at a set adsorption temperature and adsorption pressure at a set flow rate, contacting the mixed gas with a sulfonic acid anion hybrid porous material in an adsorption column of the fixed bed to adsorb the ethylene, and obtaining the gas containing ethane at an outlet of the adsorption column;
And stopping the gas mixture input when the ethylene appears at the outlet of the adsorption column or the front of the concentration gradient of the ethylene in the bed is not lower than the set proportion of the bed.
16. The method of claim 15, wherein desorbing the ethylene-adsorbed sulfonic acid anion hybrid porous material to obtain ethylene, comprising:
desorbing ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at a set desorption temperature and desorption pressure, and obtaining ethylene at an outlet of the adsorption column; or (b)
And (3) desorbing ethylene adsorbed by the sulfonic acid anion hybridization porous material in the fixed bed adsorption column at a set desorption temperature and desorption pressure, introducing pure ethylene for reverse displacement, and obtaining ethylene at an outlet of the adsorption column.
17. The method of claim 16, wherein the adsorption temperature is-30 to 100 ℃, the adsorption pressure is 1 to 10bar, the desorption temperature is 0 to 120 ℃, and the desorption pressure is 0.01 to 1bar.
18. The method of claim 16, wherein the adsorption temperature is 25 to 40 ℃, the adsorption pressure is 1 to 5bar, the desorption temperature is 60 to 100 ℃, and the desorption pressure is 0.01 to 0.1bar.
19. The method of claim 16, wherein the set flow rate is 0.5 to 10.0ml/min.
20. The method of any one of claims 12-19, wherein the mixed gas comprises 10% -90% of ethylene component, 10% -90% of ethane component and 0% -20% of impurity gas.
21. Use of a sulfonic acid anion hybrid porous material as defined in any one of claims 1-2 in a process for ethylene ethane separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111671557.4A CN116408051A (en) | 2021-12-31 | 2021-12-31 | Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111671557.4A CN116408051A (en) | 2021-12-31 | 2021-12-31 | Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116408051A true CN116408051A (en) | 2023-07-11 |
Family
ID=87056844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111671557.4A Pending CN116408051A (en) | 2021-12-31 | 2021-12-31 | Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116408051A (en) |
-
2021
- 2021-12-31 CN CN202111671557.4A patent/CN116408051A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109748770B (en) | Ethylene-ethane adsorption separation method based on ultra-microporous metal organic framework material | |
| CA2633676C (en) | The use of mofs in pressure swing adsorption | |
| EP1963766A2 (en) | The use of mofs in pressure swing adsorption | |
| WO2021197211A1 (en) | Method for separating c8 aromatic hydrocarbon isomer mixture | |
| CN109420480B (en) | Method for separating carbon tetraolefin mixture | |
| CN111575047B (en) | Method for separating isomerized oil | |
| WO2023142770A1 (en) | Method for preferential adsorption and separation of ethylbenzene from c8 aromatic hydrocarbon isomeride mixture | |
| WO2020156423A1 (en) | Method for separating ethylene from ethane | |
| Yan et al. | Room temperature fabrication of oriented Zr-MOF membrane with superior gas selectivity with zirconium-oxo cluster source | |
| CN115028850A (en) | Metal organic framework material for adsorbing and separating acetylene/ethylene mixed gas and preparation method thereof | |
| CN114682231B (en) | Cyano MOFs adsorbent for selectively adsorbing acetylene, preparation method and application | |
| CN116408051A (en) | Sulfonic acid anion hybridization porous material, preparation method and ethylene-ethane separation method | |
| CN114907183B (en) | Method for adsorbing and separating chloropropene and chloropropane mixed gas | |
| CN111440045A (en) | Separation method of carbon-pentaene mixture | |
| Xian et al. | Simultaneous removal of C 2 H 2 and C 2 H 6 for C 2 H 4 purification by robust MOFs featuring a high density of heteroatoms | |
| Han et al. | Propylene recovery from propylene/propane/nitrogen mixture by PSA process | |
| CN114085386B (en) | Large-scale synthesis method of low-cost Cu (BDC) and application of large-scale synthesis method in ethane-ethylene separation | |
| CN115947949B (en) | Porous metal organic framework material and synthesis method thereof, adsorbent and method for purifying ethylene | |
| CN117718013A (en) | Molecular sieve with point screening structure, preparation method thereof and application thereof in adsorption separation of propylene propane | |
| CN116730792A (en) | From C 2 -C 4 Process for separating ethylene from an olefin/alkane hexacomponent mixture | |
| Han et al. | Propylene recovery from simulated polypropylene process off-gas | |
| CN114904356A (en) | Method for separating nitrogen and oxygen | |
| CN116920800A (en) | Method for separating ethylene from ethane, used microporous material and preparation method thereof | |
| CN116139648A (en) | Propylene/propane adsorption separation method based on ultra-microporous material | |
| CN115612116A (en) | Porous MOF material and synthesis method thereof, propylene/propane adsorbent and separation and purification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |