CN113004114A - Separation method of mixture containing carbon penta-diolefin - Google Patents
Separation method of mixture containing carbon penta-diolefin Download PDFInfo
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- CN113004114A CN113004114A CN202110157180.4A CN202110157180A CN113004114A CN 113004114 A CN113004114 A CN 113004114A CN 202110157180 A CN202110157180 A CN 202110157180A CN 113004114 A CN113004114 A CN 113004114A
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- 238000000926 separation method Methods 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 45
- 239000003463 adsorbent Substances 0.000 claims abstract description 41
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 110
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 80
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 75
- PMJHHCWVYXUKFD-PLNGDYQASA-N (3z)-penta-1,3-diene Chemical group C\C=C/C=C PMJHHCWVYXUKFD-PLNGDYQASA-N 0.000 claims description 70
- 239000002808 molecular sieve Substances 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 32
- 230000000274 adsorptive effect Effects 0.000 claims description 14
- -1 zirconium ions Chemical class 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 10
- 238000012216 screening Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000895 extractive distillation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 20
- CPBKRGKKLKNFAI-UHFFFAOYSA-N C=CC=CC.[C] Chemical compound C=CC=CC.[C] CPBKRGKKLKNFAI-UHFFFAOYSA-N 0.000 description 15
- 229940074391 gallic acid Drugs 0.000 description 15
- 235000004515 gallic acid Nutrition 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000001307 helium Substances 0.000 description 12
- 229910052734 helium Inorganic materials 0.000 description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000035515 penetration Effects 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 159000000003 magnesium salts Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- 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]
-
- 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
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/56—Use in the form of a bed
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
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Abstract
本发明涉及一种含碳五双烯烃的混合物的分离方法，所述方法包括使含碳五双烯烃的混合物与吸附剂接触，进行吸附分离，其中，所述吸附剂包括金属有机框架材料，所述金属有机框架材料中的有机配体包括式I所示的化合物。本发明采用的金属有机框架材料相比传统吸附剂具有孔容大、比表面积大、孔结构可调等优点，可实现顺/反‑间戊二烯的高效筛分分离，同时兼具高容量和高选择性。本发明所提供的分离方法与传统萃取精馏法相比，具备能耗低，设备投资小，环境友好等优势。
The present invention relates to a method for separating a mixture of carbon penta-diolefins. The method comprises contacting a mixture of carbon penta-diolefins with an adsorbent for adsorption separation, wherein the adsorbent comprises a metal organic framework material, and the The organic ligand in the metal-organic framework material includes the compound represented by formula I. Compared with traditional adsorbents, the metal-organic framework material adopted in the present invention has the advantages of large pore volume, large specific surface area, adjustable pore structure, etc., can achieve high-efficiency screening and separation of cis/trans-pipentadiene, and has high capacity at the same time. and high selectivity. Compared with the traditional extractive distillation method, the separation method provided by the invention has the advantages of low energy consumption, small equipment investment, environmental friendliness and the like.
Description
Technical Field
The invention relates to the field of chemical engineering and technology, in particular to a separation method of a mixture containing carbon penta-diolefin.
Background
The byproduct carbon five (C5) in the process of preparing ethylene by pyrolysis of petroleum hydrocarbon, referred to as cracked C5 fraction, accounts for about 15-20% of the yield of ethylene. The cracked C5 fraction contains more than 30 components with similar boiling points, has higher utilization value, contains more isoprene, cyclopentadiene, cis-piperylene and trans-piperylene, and accounts for 40-60% of the cracked C5 fraction. With the increasing production capacity of liquid hydrocarbon to produce ethylene, the cracking C5 is abundant, and how to utilize the cracking C5 becomes an important aspect of reasonable utilization of petroleum resources and reduction of ethylene production cost. Currently, the C5 fraction focuses on chemically active, relatively high carbon penta-diolefins. These carbon-five diolefins are widely used in resins, synthetic rubbers and other high value-added chemicals. Isoprene is widely applied to the aspects of rubber synthesis, medical intermediates and the like, cis/trans-piperylene can be used for geometric isomer selective synthesis, for example, cis-piperylene can generate Diels-Alder reaction with maleic anhydride to generate a product for a polyester hardener or epoxy resin, and trans-piperylene can react very slowly due to steric hindrance. Therefore, the carbon-pentadiene mixture is effectively separated to obtain pure components of isoprene, cis-piperylene and trans-piperylene, and the method is very important for realizing high value-added utilization of the carbon-pentadiene.
The separation of cyclopentadiene from C5 diolefin is carried out by thermal dimerization, polymerizing cyclopentadiene into solid dicyclopentadiene, separating it from C five fraction, and separating cyclopentadiene from dicyclopentadiene by thermal depolymerization. Isoprene and cis/trans-piperylene are usually separated industrially by multi-step extractive distillation and azeotropic distillation to obtain pure components of polymer grade, such as US19840662602, US19740457329, US201414892277 and cn200510025920. x. The method adopting extractive distillation or azeotropic distillation generally has the problems of high separation energy consumption, large equipment investment, complex operation process, large solvent consumption, environment friendliness and the like.
The adsorption separation method has the characteristics of simple and convenient operation, low equipment cost, low production energy consumption and the like, and the adsorption technology is considered as one of the most potential separation technologies. Traditional materials such as porous polymers, molecular sieves, activated carbon and the like are widely applied to the aspect of adsorption separation, but the traditional materials are difficult to regulate and control in pore diameter and have weak capability of identifying molecules with small differences in size. Molecular sieve materials, such as 5A molecular sieves, can separate straight-chain and branched-chain isomers, and experiments prove that the separation of isoprene in a carbon pentadiene mixture can be realized, but the 5A molecular sieves cannot separate cis/trans-piperylene, and cannot separate a three-component carbon pentadiene mixture into pure components of isoprene, cis-piperylene and trans-piperylene.
The metal-organic framework material has wide application prospect in the field of low-carbon hydrocarbon adsorption separation. In recent years, researchers have conducted many studies on gaseous hydrocarbons such as C2-C4 and liquid hydrocarbons such as C6-C8, but few studies have been made on C5 diolefins which are in a state between gaseous and liquid at normal temperature, contain a diolefin structure, are chemically active and have a high industrial application value. Michael Maes et al for the first time reported that selective adsorptive Separation of cis/trans-piperylene was achieved using adsorptive Separation materials MIL-96, chabazite and 5A molecular sieves, but adsorptive Separation selectivity was not high, with adsorptive capacity selectivity (298K, ratio of adsorption capacities at 0.1 bar) of 1.1-2.8(Separation of C5-hydrocarbon on microporous materials: comparative performance of MOFs and zeolites [ J ] am. chem. Soc.,2010,132, 2284-. Yun Yu et al designed ion hybrid microporous materials ZU-62 and TIFSIX-2-Cu-i for isoprene separation, which are chemically stable and have good regeneration performance, but still have large adsorption capacity for isoprene (298K,0.1bar, ZU-6,0.65 mmol/g; TIFSIX-2-Cu-i, 0.73mmol/g), cannot realize separation by sieving, and still have not high separation selectivity (recoverable separation of C5 resins in and of plated porous materials [ J ]. Nano Res.,2020, 1-5).
Therefore, aiming at the problem that the separation selectivity of the existing metal-organic framework material to the C5 diolefin system is not high, a new separation material and a separation method need to be developed to realize the efficient selective separation of a cis/trans-piperylene system and a cis-piperylene, trans-piperylene and isoprene three-component mixture system.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a separation method of a mixture containing carbon pentadiene, which adopts a gallic acid-based metal organic framework material to separate a cis-piperylene, trans-piperylene and isoprene three-component mixture system into pure components.
According to the invention, the separation method of the mixture containing the carbon penta-diolefin comprises the step of contacting the mixture containing the carbon penta-diolefin with an adsorbent to carry out adsorption separation, wherein the adsorbent comprises a metal organic framework material, organic ligands in the metal organic framework material comprise compounds shown in a formula I,
in the formula I, R1、R2、R3、R4And R5Each independently selected from hydrogen, hydroxy, halogen, C1-C6 alkyl or C1-C6 alkoxy, wherein R is2、R3And R4At least two of which are hydroxyl groups.
According to some embodiments of the invention, the compound of formula I has the structure of formula II,
wherein R is1And R5Each independently selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy.
According to some embodiments of the invention, R1And R5Each independently selected from hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, n-propyl, isopropyl, methoxy or ethoxy.
According to some embodiments of the invention, the organic ligand is gallic acid.
According to some embodiments of the invention, the metal ions in the metal-organic framework material are selected from transition metal ions and alkaline earth metal ions.
According to some embodiments of the invention, the metal ions comprise one or more selected from the group consisting of zinc ions, manganese ions, cobalt ions, magnesium ions, vanadium ions, zirconium ions, calcium ions, molybdenum ions, chromium ions, iron ions, nickel ions, copper ions, tin ions, niobium ions, titanium ions, and scandium ions.
According to some embodiments of the invention, the metal ions comprise one or more selected from magnesium ions, cobalt ions and nickel ions.
According to some embodiments of the invention, the metal-organic framework material is a three-dimensional or two-dimensional network framework structure formed by coordination bonds or intermolecular forces of transition metal ions or alkaline earth metal ions with organic ligands (gallic acid).
According to some embodiments of the invention, the metal is prepared from a machine frame material by a method comprising:
(1) mixing inorganic salt and organic ligand such as gallic acid, alkali and deionized water in proportion, stirring for dissolving, and putting into a reaction kettle for hydrothermal reaction; the inorganic salt is chloride, nitrate, acetate, carbonate, sulfate or perchlorate of metal ions;
(2) and after the hydrothermal reaction is finished, washing the reaction product by using deionized water and absolute ethyl alcohol in sequence, and then drying the reaction product in vacuum to obtain the catalyst.
In the preparation process of the metal organic framework material, gallic acid which is cheap and easy to obtain is used as an organic ligand to react with a series of metal inorganic salts in pure water, toxic and volatile organic solvents are not needed, and the prepared material has the advantages of low price of raw materials, mild synthesis conditions, simple operation, easy post-treatment and low material synthesis cost.
According to some embodiments of the invention, the molar ratio of the inorganic salt, gallic acid, and base is 1 (1-5) to (0.5-5). Deionized water was used as the solvent.
According to some embodiments of the present invention, when the metal salt is a magnesium salt, the ratio of the metal salt, the gallic acid, and the alkali is 1 mmol: 1.8-2.2 mmol: 2.3-2.8 mmol; when the metal salt is cobalt salt or nickel salt, the ratio of the metal salt, the gallic acid and the alkali is 1 mmol: 1.8-2.2 mmol: 0.5-1 mmol. The change of the ratio of the metal salt, the gallic acid and the alkali can change the size, the crystal form, the regularity and the like of the crystal, and can also influence the adsorption capacity and the selective separation performance of the material on hydrocarbon gas.
According to some embodiments of the invention, the agitating step is: the solution is mixed evenly by stirring for a suitable time at 500-1000 rpm. Uneven mixing can lead to irregular crystal formation resulting from the reaction.
According to some embodiments of the present invention, the hydrothermal reaction is performed at a reaction temperature of 60 to 150 ℃ for 12 to 72 hours. The reaction temperature affects the formation of crystals, and too high or too low may result in failure to form crystals. Preferably, the reaction temperature of the hydrothermal reaction is 100-150 ℃, and the reaction time is 12-30 hours; most preferably, the reaction temperature of the hydrothermal reaction is 120 ℃ and the reaction time is 24 hours.
According to some embodiments of the invention, the vacuum drying is performed at a temperature of 30 to 120 ℃ for a time of 6 to 24 hours. Preferably, the temperature of vacuum drying is 100-120 ℃ and the time is 10-24 hours.
Washing and centrifuging the product after the hydrothermal reaction for several times by water, displacing residual alkali solution and residual inorganic salt in the pore channel, washing and centrifuging for several times by using absolute ethyl alcohol, displacing residual organic ligand and water in the pore channel, and completing the purification of the adsorbent.
According to some embodiments of the invention, the metal-organic framework material is in the shape of a cube, a needle or a rod. The metal organic framework material used by the invention can be prepared into adsorption separation materials such as spheres, columns, particles and the like through different processing technologies.
In the present invention, the "mixture of carbon-containing pentadienes" includes at least two of isoprene, cyclopentadiene, cis-piperylene, and trans-piperylene.
According to some embodiments of the invention, the mixture of carbon-containing penta-diolefins comprises at least two of isoprene, cis-piperylene and trans-piperylene, for example comprising isoprene and cis-piperylene, isoprene and trans-piperylene, cis-piperylene and trans-piperylene.
According to some embodiments of the invention, the mixture of carbon-containing penta-diolefins comprises isoprene, cis-piperylene and trans-piperylene.
According to some embodiments of the invention, the mixture of carbon-containing pentadienes has a mole percent isoprene content of 5% to 98%, such as 5%, 15%, 25%, 35%, 50%, 60%, 70%, 80%, or 90%, based on the total weight of the carbon pentadienes.
According to some embodiments of the invention, the adsorbent further comprises 5A molecular sieves.
According to some embodiments of the invention, the mixture of carbon-containing penta-diolefins is contacted sequentially with 5A molecular sieves, metal organic framework materials for adsorptive separation.
The 5A molecular sieve can well separate straight-chain isomers and branched-chain isomers, the 5A molecular sieve can realize the screening separation of isoprene from a carbon-pentadiene mixture, and cis/trans-piperylene basically has no separation capacity. According to some embodiments of the invention, the 5A molecular sieve is used in series with two adsorbents, a metal organic framework material,
according to some embodiments of the present invention, a mixture of carbon-containing penta-diolefins is first separated by adsorption through a 5A molecular sieve to obtain isoprene and a 5A molecular sieve having cis/trans-piperylene adsorbed thereon, and the 5A molecular sieve having cis/trans-piperylene adsorbed thereon is then desorbed to obtain a mixture containing cis/trans-piperylene, and the mixture containing cis/trans-piperylene is then contacted with a metal organic framework material for separation by adsorption to obtain cis-piperylene and trans-piperylene.
According to some embodiments of the invention, the 5A molecular sieve and the metal organic framework material are prepared into a packed column respectively and used in series, the mixture containing the carbon pentadiene is firstly passed through the 5A molecular sieve packed column, the isoprene is screened and separated, and the cis/trans-pentadiene is adsorbed; and then purging and resolving the 5A molecular sieve packed column with saturated adsorption by using inert gas, introducing only mixed gas of cis/trans-piperylene and inert gas into the packed column prepared by the metal organic framework material, and selectively screening the mixed gas into cis-and trans-piperylene pure components. Thus, the carbon pentadiene mixture is separated into pure components of isoprene, cis-piperylene and trans-piperylene after passing through a series packed column of 5A molecular sieves and a metal organic framework material.
According to some embodiments of the invention, the mixture of adsorbent and carbon-containing pentadiene in the adsorptive separation is at a temperature of-20 to 150 ℃, preferably at a temperature of-5 to 100 ℃. According to some embodiments, the mixture of adsorbent and carbon-containing pentadiene is at a temperature of 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 110 ℃, 120 ℃ or 140 ℃.
According to some embodiments of the invention, the mixture of adsorbent and carbon-containing penta-diolefins in the adsorptive separation is at a pressure of 0.01 to 10bar, preferably 0.1 to 5 bar. According to some embodiments, the mixture of adsorbent and carbon-containing penta-diolefin is at a pressure of 0.5bar, 1.0bar, 2.0bar, 3.0bar, 4.0bar, 5.0bar, 6.0bar, 7.0bar, 8.0bar, or 9.0 bar.
According to some embodiments of the present invention, the mixture of carbon-containing pentadienes may be in a liquid phase or a gas phase.
According to some embodiments of the invention, the adsorptive separation is carried out in a fixed bed adsorption unit or a simulated moving bed adsorption unit.
When the metal organic framework material is used for screening and separating cis/trans-piperylene, the trans-piperylene with smaller size can enter a pore channel and has strong interaction with surface groups of the material, including hydrogen bond interaction, supermolecule interaction and van der Waals interaction, while the cis-piperylene with larger size is difficult to enter the pore channel, and the interaction force is weaker. The adsorption action of the two adsorbates on the surface of the material is different, so that the adsorption capacity is obviously different, when the cis/trans-piperylene mixed component passes through the adsorbent bed layer, the cis-piperylene is weak in adsorption action and small in adsorption capacity and is separated out from the adsorbent bed layer quickly, the trans-piperylene is strong in adsorption action and large in adsorption capacity, and the time required for separation from the bed layer is longer, so that the separation of the cis/trans-piperylene is realized.
According to some embodiments of the invention, the method further comprises regenerating the adsorbent after completion of the adsorptive separation.
According to some embodiments of the invention, the regenerating of the metal-organic framework material comprises heating the metal-organic framework material to 30-120 ℃ for 12-72 hours under vacuum or inert atmosphere conditions. According to some embodiments of the present invention, the regeneration of the 5A molecular sieve comprises heating the 5A molecular sieve to 250 ℃ under vacuum or inert atmosphere for 12-72 hours. The adsorbent structure is damaged due to the fact that the heating temperature is too high or the heating time is too long; if the temperature is too low or the time is too short, the residual adsorbate in the adsorbent cannot be completely removed.
According to some embodiments of the invention, the inert atmosphere is formed by a noble gas and/or nitrogen.
According to some embodiments of the present invention, the adsorbent may also be desorbed using a desorbent conventionally used in the art.
Compared with the prior art, the invention has the following advantages:
(1) compared with the traditional adsorbent, the metal organic framework material adopted by the invention has the advantages of large pore volume, large specific surface area, adjustable pore structure and the like, can realize high-efficiency screening separation of cis/trans-pentadiene, and simultaneously has high capacity and high selectivity.
(2) The gallic acid and the metal salt used for preparing the metal organic framework material are cheap and easily obtained, the synthesis condition is mild, the purification step is simple, and the operation and the amplification are easy.
(3) The metal organic framework material has stable structure, stable performance and mild regeneration condition, and the adsorption performance still keeps the original effect after repeated adsorption-regeneration.
(4) The invention provides a new method for adsorbing and separating carbon pentadiene by using a molecular sieve material and a metal organic framework material in series and complementing performance, and pure components of isoprene, cis-piperylene and trans-piperylene are respectively obtained.
(5) The process adopted by the invention is a fixed bed column method or a simulated moving bed process, and compared with the traditional extraction rectification method, the provided separation method has the advantages of low energy consumption, small equipment investment, environmental friendliness and the like.
Drawings
FIG. 1 shows metal ion M and organic ligand gallic acid (C)7O5H6) A schematic three-dimensional structure of a gallic acid-based metal-organic framework material constructed by coordination bonds;
FIG. 2 shows adsorption isotherms for trans-piperylene, cis-piperylene, and isoprene at 298K for the 5A molecular sieve of comparative example 1;
FIG. 3 shows the breakthrough curves of the 5A molecular sieve of comparative example 1 at 298K for a mixture of trans-piperylene, cis-piperylene and isoprene;
FIG. 4 shows the adsorption isotherms of Mg-gate for trans-piperylene, cis-piperylene and isoprene at 298K in example 1;
FIG. 5 shows the permeation curve of Mg-gate at 298K for a mixture of trans-piperylene, cis-piperylene and isoprene in example 1;
FIG. 6 is a graph of the cyclic adsorption performance of Mg-gate on trans-piperylene and cis-piperylene at 298K in example 1;
FIG. 7 shows the adsorption isotherms of Co-gate for trans-piperylene, cis-piperylene and isoprene at 298K in example 2;
FIG. 8 shows the penetration curve of Co-gate at 298K for a mixture of trans-piperylene, cis-piperylene and isoprene in example 2;
FIG. 9 shows the adsorption isotherms of Ni-gate for trans-piperylene, cis-piperylene and isoprene at 298K in example 3;
FIG. 10 shows the penetration curve of Ni-gate at 298K for a mixture of trans-piperylene, cis-piperylene and isoprene in example 3.
Detailed Description
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto, but is defined by the claims.
It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be combined with each other at will, and thus form part of the original disclosure of the specification, and also fall within the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Comparative example 1
To test the adsorptive separation performance of the 5A molecular sieve, single component adsorption isotherms of trans-piperylene, cis-piperylene, and isoprene were performed using the above 5A molecular sieve. The single-component adsorption isotherm of the three gases of the material is shown in figure 2. Taking a proper amount of adsorbent, wherein the adsorption temperature is 298K, and tests show that the adsorption amount of trans-piperylene is up to 2.52mmol/g, the adsorption amount of cis-piperylene is only 2.17mmol/g, and the adsorption capacity of isoprene is smaller and is only 0.08mmol/g at 298K and 0.1 bar. Isoprene can be well separated by screening, but the adsorption capacity selectivity (ratio of adsorption capacity under the same condition) of cis/trans-piperylene is very low and is only 1.2. This indicates that 5A molecular sieve can only separate isomeric olefin from carbon pentadiene mixture, and can not separate cis/trans-piperylene.
To test the practical effect of the 5A molecular sieve on the separation of the carbon pentadienes, the carbon pentadiene gas mixture was subjected to using the 5A molecular sieve: penetration test of mixed gas of trans-piperylene, cis-piperylene, isoprene and helium (helium is an inert component). The volume ratio of the mixed gas is trans-pentadiene: cis-piperylene: isoprene: helium gas 2:1:5: 92. The breakthrough temperature was 298K and the pressure 1.0 bar. The penetration curve is shown in figure 3. Tests show that when the flow rate of the mixed gas is 3mL/min, isoprene penetrates at 4min/g, cis-pentadiene penetrates at 560min/g, and trans-pentadiene penetrates at 706 min/g. The dynamic separation selectivity of cis/trans piperylene is 2.3. It is further proved that the 5A molecular sieve can only separate isoolefin from the carbon pentadiene mixture, the separation selectivity of cis/trans-piperylene is not high, and the carbon pentadiene mixture can be separated into pure components of isoprene, cis-piperylene and trans-piperylene only by being connected with the metal organic framework material in series.
Example 1
Mixing 2mmol of anhydrous magnesium chloride, 4mmol of gallic acid, 5mmol of potassium hydroxide and 10mL of deionized water, placing the mixture into a 25mL hydrothermal reaction kettle, stirring for half an hour, placing the mixture into an oven, and reacting for 24 hours at 120 ℃. And after the reaction is finished, naturally cooling to room temperature, and washing the solid obtained by the reaction with water and ethanol for multiple times in sequence to obtain the purified metal organic framework material Mg-gate. The purified adsorbent was degassed under vacuum at 120 ℃ for 24 hours to obtain a desolvated adsorbent, and then the following gas adsorption experiment and breakthrough experiment were performed.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single component adsorption isotherms of trans-piperylene, cis-piperylene and isoprene were performed using the adsorbent. The single-component adsorption isotherm of the three gases of the material is shown in figure 4. Taking a proper amount of adsorbent, wherein the adsorption temperature is 298K, and tests show that the adsorption amount of trans-piperylene is up to 1.56mmol/g, the adsorption amount of cis-piperylene is only 0.37mmol/g, the adsorption capacity of isoprene is smaller and is only 0.06mmol/g, and the adsorption capacity selectivity (the ratio of the adsorption capacities under the same condition) of cis/trans-piperylene is up to 4.2 at 298K and 0.1 bar.
In order to test the practical effect of the metal organic framework material on the separation of the carbon penta-diolefin, the carbon penta-diolefin mixed gas was subjected to the following steps by using the synthesized adsorbent: penetration test of mixed gas of trans-piperylene, cis-piperylene, isoprene and helium (helium is an inert component). The volume ratio of the mixed gas is trans-pentadiene: cis-piperylene: isoprene: helium gas 2:1:5: 92. The breakthrough temperature was 298K and the pressure 1.0 bar. The penetration curve is shown in figure 5. Tests show that when the flow rate of the mixed gas is 3mL/min, isoprene penetrates through the mixed gas at 5min/g, cis-pentadiene penetrates through the mixed gas at 168min/g, and trans-pentadiene penetrates through the mixed gas at 330 min/g. The dynamic adsorption capacity of trans-piperylene is 1.10mmol/g, the dynamic separation selectivity of cis/trans-piperylene is 6.9, and the three components are effectively separated. The metal organic framework material still has stable adsorption performance after four times of adsorption-regeneration cycles. The cyclic adsorption performance is shown in FIG. 6.
Example 2
Mixing 2mmol of cobalt chloride hexahydrate, 4mmol of gallic acid, 1.6mmol of potassium hydroxide and 10mL of deionized water, putting the mixture into a 25mL hydrothermal reaction kettle, stirring for half an hour, putting the kettle into an oven, and reacting for 24 hours at 120 ℃. And after the reaction is finished, naturally cooling to room temperature, and washing the solid obtained by the reaction with water and ethanol for multiple times in sequence to obtain the purified metal organic framework material Co-gate. The purified adsorbent was degassed under vacuum at 120 ℃ for 24 hours to obtain a desolvated adsorbent, and then the following gas adsorption experiment and breakthrough experiment were performed.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single component adsorption isotherms of trans-piperylene, cis-piperylene and isoprene were performed using the adsorbent. The single-component adsorption isotherm of the three gases of the material is shown in figure 7. Taking a proper amount of adsorbent, wherein the adsorption temperature is 298K, and tests show that the adsorption amount of trans-piperylene is up to 1.67mmol/g, the adsorption amount of cis-piperylene is only 0.41mmol/g, the adsorption capacity of isoprene is smaller and is only 0.14mmol/g, and the adsorption capacity selectivity (the ratio of the adsorption capacities under the same condition) of cis/trans-piperylene is up to 4.1 at 298K and 0.1 bar.
In order to test the practical effect of the metal organic framework material on the separation of the carbon penta-diolefin, the carbon penta-diolefin mixed gas was subjected to the following steps by using the synthesized adsorbent: penetration test of mixed gas of trans-piperylene, cis-piperylene, isoprene and helium (helium is an inert component). The volume ratio of the mixed gas is trans-pentadiene: cis-piperylene: isoprene: helium gas 2:1:5: 92. The breakthrough temperature was 298K and the pressure 1.0 bar. The penetration curve is shown in figure 8. Tests show that when the flow rate of the mixed gas is 3mL/min, isoprene penetrates at 14min/g, cis-piperylene penetrates at 133min/g, and trans-piperylene penetrates at 329 min/g. The dynamic adsorption capacity of trans-piperylene is 1.04mmol/g, the dynamic separation selectivity of cis/trans-piperylene is 6.5, and the three components are effectively separated.
Example 3
Mixing 2mmol of nickel chloride hexahydrate, 4mmol of gallic acid, 1.6mmol of potassium hydroxide and 10mL of deionized water, putting the mixture into a 25mL hydrothermal reaction kettle, stirring for half an hour, putting the kettle into an oven, and reacting for 24 hours at 120 ℃. And after the reaction is finished, naturally cooling to room temperature, and washing the solid obtained by the reaction with water and ethanol for multiple times in sequence to obtain the purified metal organic framework material Ni-gate. The purified adsorbent was degassed under vacuum at 120 ℃ for 24 hours to obtain a desolvated adsorbent, and then the following gas adsorption experiment and breakthrough experiment were performed.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single component adsorption isotherms of trans-piperylene, cis-piperylene and isoprene were performed using the adsorbent. The single-component adsorption isotherm of the three gases of the material is shown in fig. 9. Taking a proper amount of adsorbent, wherein the adsorption temperature is 298K, and tests show that the adsorption quantity of trans-piperylene reaches 0.50mmol/g, the adsorption quantity of cis-piperylene is only 0.26mmol/g, the adsorption capacity of isoprene is smaller and only 0.05mmol/g, and the adsorption capacity selectivity (the ratio of the adsorption capacities under the same condition) of cis/trans-piperylene reaches 1.9 at 298K and 0.1 bar.
In order to test the practical effect of the metal organic framework material on the separation of the carbon penta-diolefin, the carbon penta-diolefin mixed gas was subjected to the following steps by using the synthesized adsorbent: penetration test of mixed gas of trans-piperylene, cis-piperylene, isoprene and helium (helium is an inert component). The volume ratio of the mixed gas is trans-pentadiene: cis-piperylene: isoprene: helium gas 2:1:5: 92. The breakthrough temperature was 298K and the pressure 1.0 bar. The penetration curve is shown in figure 10. Tests show that when the flow rate of the mixed gas is 3mL/min, isoprene penetrates at 3min/g, cis-pentadiene penetrates at 7min/g, and trans-pentadiene penetrates at 73 min/g. The dynamic adsorption capacity of trans-piperylene is 0.36mmol/g, the dynamic separation selectivity of cis/trans-piperylene is 7.6, and the three components are effectively separated.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A separation method of a mixture containing carbon penta-diolefin comprises the step of contacting the mixture containing carbon penta-diolefin with an adsorbent to carry out adsorption separation, wherein the adsorbent comprises a metal organic framework material, organic ligands in the metal organic framework material comprise compounds shown in a formula I,
in the formula I, R1、R2、R3、R4And R5Each independently selected from hydrogen, hydroxy, halogen, C1-C6 alkyl or C1-C6 alkoxy, wherein R is2、R3And R4At least two of which are hydroxyl groups.
2. The separation method of claim 1, wherein the compound of formula I has a structure of formula II,
wherein R is1And R5Each independently selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy.
3. The separation method according to claim 1 or 2, wherein the metal ions in the metal-organic framework material are selected from transition metal ions and alkaline earth metal ions,
preferably, the metal ions include one or more selected from the group consisting of zinc ions, manganese ions, cobalt ions, magnesium ions, vanadium ions, zirconium ions, calcium ions, molybdenum ions, chromium ions, iron ions, nickel ions, copper ions, tin ions, niobium ions, titanium ions, and scandium ions,
more preferably, the metal ions include one or more selected from magnesium ions, cobalt ions, and nickel ions.
4. A separation process according to any one of claims 1-3, characterized in that the mixture of carbon-containing penta-diolefins comprises at least two of isoprene, cyclopentadiene, cis-piperylene and trans-piperylene, preferably at least two of isoprene, cis-piperylene and trans-piperylene, more preferably isoprene, cis-piperylene and trans-piperylene.
5. The separation process of any one of claims 1 to 4, wherein the mixture of carbon containing pentadienes has a mole percent isoprene content of 5% to 98% based on the total weight of carbon containing pentadienes.
6. The separation process according to any one of claims 1 to 5, wherein the adsorbent further comprises a 5A molecular sieve, preferably the mixture of carbon-containing penta-diolefins is contacted with the 5A molecular sieve and the metal organic framework material sequentially for adsorption separation.
7. The separation process according to any one of claims 1 to 6, characterized in that in the adsorptive separation the mixture of adsorbent and carbon-containing penta-diolefin is at a temperature of-20 to 150 ℃, preferably at a temperature of-5 to 100 ℃;
and/or in the adsorptive separation, the mixture of adsorbent and carbon-containing pentadiene is at a pressure of 0.01 to 10bar, preferably at a pressure of 0.1 to 5 bar.
8. The separation process according to any one of claims 1 to 7, wherein the adsorptive separation is carried out in a fixed bed adsorption unit or a simulated moving bed adsorption unit.
9. The separation process of any one of claims 1-8, further comprising regenerating the adsorbent after completion of the adsorptive separation.
10. The separation process according to any one of claims 1 to 9, wherein the regeneration of the metal-organic framework material comprises heating the metal-organic framework material to 30-120 ℃ under vacuum or inert atmosphere conditions for 12-72 hours;
and/or the regeneration of the 5A molecular sieve comprises heating the 5A molecular sieve to the temperature of 120 ℃ and 250 ℃ under the vacuum or inert atmosphere condition, and keeping the temperature for 12 to 72 hours.
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| WO2023162815A1 (en) * | 2022-02-28 | 2023-08-31 | 東洋製罐グループホールディングス株式会社 | Metal-organic framework |
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| CN108440235A (en) * | 2018-03-27 | 2018-08-24 | 浙江大学 | A method of detaching 1,3- butadiene from four carbon hydrocarbon gaseous mixtures |
| CN111440045A (en) * | 2020-04-20 | 2020-07-24 | 浙江大学衢州研究院 | A kind of separation method of carbon pentaolefin mixture |
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| CN108440235A (en) * | 2018-03-27 | 2018-08-24 | 浙江大学 | A method of detaching 1,3- butadiene from four carbon hydrocarbon gaseous mixtures |
| CN111440045A (en) * | 2020-04-20 | 2020-07-24 | 浙江大学衢州研究院 | A kind of separation method of carbon pentaolefin mixture |
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| CN114904487A (en) * | 2022-02-21 | 2022-08-16 | 中国科学院过程工程研究所 | Adsorbent for separating chloropropane and chloropropene mixed gas, and preparation method and separation method thereof |
| CN114904487B (en) * | 2022-02-21 | 2023-08-25 | 中国科学院过程工程研究所 | An adsorbent for separating mixed gas of chloropropane and chloropropene, its preparation method and separation method |
| WO2023162815A1 (en) * | 2022-02-28 | 2023-08-31 | 東洋製罐グループホールディングス株式会社 | Metal-organic framework |
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