CN113024347B - Method for separating mixed xylene - Google Patents
Method for separating mixed xylene Download PDFInfo
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- CN113024347B CN113024347B CN202110151482.0A CN202110151482A CN113024347B CN 113024347 B CN113024347 B CN 113024347B CN 202110151482 A CN202110151482 A CN 202110151482A CN 113024347 B CN113024347 B CN 113024347B
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- xylene
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- adsorbent
- mixed
- framework material
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000008096 xylene Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000001179 sorption measurement Methods 0.000 claims abstract description 138
- 239000003463 adsorbent Substances 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 92
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 65
- 238000000926 separation method Methods 0.000 claims abstract description 62
- 150000003738 xylenes Chemical class 0.000 claims abstract description 50
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 19
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 148
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 138
- 229940078552 o-xylene Drugs 0.000 claims description 51
- 230000000274 adsorptive effect Effects 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 229920006395 saturated elastomer Polymers 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 229910017053 inorganic salt Inorganic materials 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000003325 scandium Chemical class 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical group OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000004185 countercurrent chromatography Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- UPXYJUPSYMBDCO-UHFFFAOYSA-L magnesium;diacetate;hydrate Chemical compound O.[Mg+2].CC([O-])=O.CC([O-])=O UPXYJUPSYMBDCO-UHFFFAOYSA-L 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000003960 organic solvent 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
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- HZQULVNEUCEVQV-UHFFFAOYSA-N scandium(3+);trinitrate;hydrate Chemical compound O.[Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HZQULVNEUCEVQV-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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]
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for separating mixed xylene. The method comprises the step of carrying out adsorption separation on mixed xylene by using an adsorbent containing a metal organic framework material so as to separate one or more xylene isomers, wherein an organic ligand in the metal organic framework material is 2, 5-dihydroxy-1, 4-benzoquinone. The method can effectively separate the xylene isomers, and the organic ligand and the metal salt used for preparing the metal organic framework material are cheap and easy to obtain, the synthesis condition is mild, the purification step is simple, and the operation and the amplification are easy. Therefore, the method has good industrial application prospect.
Description
Technical Field
The invention relates to a method for separating mixed xylene.
Background
The individual isomers of mixed xylenes, including para-xylene (PX), ortho-xylene (OX), and meta-xylene (MX), are all very important feedstock materials for industrial synthesis. For example, para-xylene (PX) is an important organic chemical raw material, which is mainly used for synthesizing terephthalic acid (PTA) or dimethyl terephthalate (DMT) to further produce polyethylene terephthalate (PET), and the polyester has excellent performance, is widely used for preparing fibers, films and resins, and is an important raw material for synthesizing fibers and plastics. The o-xylene (OX) is mainly used for producing chemical raw materials of o-dibenzoic anhydride (PA), dye, pesticide and the like, and derivatives of the o-xylene (OX)The ortho-phthalaldehyde is useful in the preparation of phthalate plasticizers. The m-xylene (MX) is mainly used as raw material of medicine, perfume and dye intermediate and oil-soluble coupler for color film. Although pure xylene is widely used in various chemical and medical fields, the mixed xylenes (p-xylene, m-xylene and o-xylene) have similar densities, very small boiling point differences (p-xylene boiling point is 138.5 ℃, o-xylene boiling point is 144.4 ℃ and m-xylene boiling point is 139.2 ℃), and similar molecular dynamics sizes (p-xylene molecular dynamics size is 139.2 ℃)
O-xylene is
The meta-xylene is
) The exceptional difficulty of separating mixed xylene systems to obtain a single component xylene remains a challenge.
At present, relatively few methods for industrially and effectively separating mixed xylene are available, and the methods mainly include a precision rectification method, a normal-pressure low-temperature crystallization method, a cryogenic crystallization method, a pressure crystallization method, a complexation method and an adsorption separation method. The precise rectification method adopts multiple towers for continuous rectification operation, but the process needs expensive equipment and complex operation, can not completely separate out m-xylene and p-xylene, and in addition, the popularization and the application of the process are limited by huge energy consumption in the rectification process and unfriendliness of medium-scale and small-scale equipment. The normal pressure low temperature crystallization method is mainly based on the difference of the solidification point and solubility of each isomer in the mixture under normal pressure, and the isomers are correspondingly precipitated in different temperature zones. However, mixed xylene is a multi-component liquid-phase mixed system, and solid-liquid phase diagrams of various isomers are overlapped and crossed, so that pure xylene components are difficult to obtain at a single temperature. The cryogenic crystallization or pressure crystallization is also based on the difference of physical and chemical properties of each isomer, wherein the pressure or temperature reduction separation is mainly based on the difference of respective solidification points and based on different phase changesA mixture of xylenes. Although the separation method has short separation period, low energy consumption of the whole process and simple operation, the required high-pressure and extremely low-temperature conditions have high requirements on equipment and operation and are not desirable in actual production. The complex extraction method is a method of separating hydrocarbons by forming an acid-base complex from the alkalinity of the hydrocarbons and the acidity of a complex extractant. The complexing agent is generally HF-BF3The relative basicities of the 3 isomers of xylene are significantly different, for example, 1 for p-xylene, 2 for o-xylene and 100 for m-xylene, so that the pure components of xylene can be separated from the mixed xylenes by using the difference in relative basicity. However, the complexing agent not only serves as a complexing extractant, but also is a catalyst for liquid phase isomerization reaction in the process, the operation of the process is complex, and the energy consumption for recovering the complexing agent is large.
Therefore, there is still a need for a more economical and energy-saving separation method for separating and purifying paraxylene, ortho-xylene and meta-xylene. In comparison, the adsorption separation method has the characteristics of simple and convenient operation, low energy consumption, low cost and the like, but the most important key of the adsorption separation of the dimethylbenzene is to select an adsorbent with considerable adsorption quantity and high adsorption selectivity. Commonly used adsorbents include activated carbon, clay, molecular sieves, silica gel, and the like. However, the internal pore structure of the material is uniform, and the chemical environment of the pore channel is not easy to modify, so that the adsorption capacity and the separation selectivity cannot reach the industrial application level.
Disclosure of Invention
The inventors of the present application have conducted extensive studies to find that the use of a specific metal organic framework material has a high adsorption selectivity for xylene isomers (o-xylene, m-xylene, and p-xylene), and thus can effectively separate pure isomer components from mixed xylenes. Based on this finding, the present application is proposed.
Accordingly, the present invention provides a process for separating mixed xylenes, the process comprising subjecting the mixed xylenes to adsorptive separation using an adsorbent comprising a metal-organic framework material to separate one or more of the xylene isomers, wherein the organic ligand in the metal-organic framework material is 2, 5-dihydroxy-1, 4-benzoquinone.
In the present invention, the term "mixed xylenes" refers to a mixture comprising two or three xylene isomers. In addition to xylene isomers, other components such as ethylbenzene, styrene, toluene, benzene, etc. may be included in the "mixed xylenes". According to some embodiments, the mixed xylenes comprise greater than 80% of the xylene isomers. According to some embodiments, the mixed xylenes comprise greater than 90% of the xylene isomers. According to some embodiments, the mixed xylenes comprise greater than 95% xylene isomers.
In the present invention, the term "xylene isomers" refers to ortho-xylene, meta-xylene and para-xylene.
According to some embodiments, the mixed xylenes include para-xylene, which may be present in an amount of 5-95%. According to some embodiments of the invention, the mixed xylenes comprise p-xylene in a volume of 5% to 95%. Preferably, the mixed vapor or mixed liquid of the xylene accounts for 10 to 85 percent of the volume ratio of the p-xylene. According to some embodiments, the mixed xylene comprises 5%, 15%, 25%, 35%, 50%, 60%, 70%, 80%, or 90% by volume of p-xylene.
According to some embodiments, the mixed xylenes comprise para-xylene and ortho-xylene. According to some embodiments, the mixed xylenes include para-xylene and meta-xylene. According to some embodiments, the mixed xylenes include para-xylene, meta-xylene, and ortho-xylene. According to some embodiments of the invention, the mixed xylenes comprise ortho-xylene and para-xylene.
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 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 preferred embodiments of the present invention, the metal ions include one or more selected from the group consisting of zinc ions, cobalt ions, magnesium ions and manganese ions.
According to some more preferred embodiments of the invention, the metal ions comprise manganese ions.
According to some embodiments of the invention, the metal-organic framework material has a pore size of
Above, it is preferable
More preferably, the pore size of the metal organic framework material is
According to some preferred embodiments of the present invention, the specific surface area of the metal-organic framework material is 300-2000m2G, e.g. 300-2/g。
According to some embodiments of the invention, the temperature of the adsorptive separation is from-5 ℃ to 300 ℃, preferably from 25 ℃ to 250 ℃, and further preferably from 30 ℃ to 150 ℃.
According to some embodiments of the invention, the pressure of the adsorptive separation is between 0.01MPa and 10 MPa, preferably between 0.1MPa and 6 MPa.
According to some embodiments of the present invention, the adsorptive separation is performed using a fixed bed, wherein the adsorbent is packed in the fixed bed adsorption column, and specifically, may include the steps of: (1) enabling mixed xylene steam formed by mixed xylene and carrier gas to pass through a fixed bed adsorption column, adsorbing a strongly adsorbed xylene isomer in the mixed xylene on the adsorbent, and enabling a weakly adsorbed xylene isomer in the mixed xylene to penetrate through the adsorption column to obtain a weakly adsorbed xylene isomer; (2) desorbing the strongly adsorbed xylene isomer from the adsorbent to obtain the strongly adsorbed xylene isomer. According to some embodiments, in step (1), the strongly adsorbed xylene isomer is para-xylene; weakly adsorbed xylene isomers are ortho-xylene and/or meta-xylene. According to some preferred embodiments of the present invention, the mixed xylene vapor is passed through the fixed bed adsorption column at a flow rate of 40 to 200mL/min/g adsorbent.
According to some embodiments of the present invention, the adsorption separation is performed by using a simulated moving bed, wherein the adsorbent is filled in the adsorption zone bed of the simulated moving bed, and preferably comprises the following steps:
(3) and (3) carrying out adsorption separation on the mixed xylene liquid by a liquid-phase simulated moving bed so as to respectively pump out the p-xylene, the o-xylene and/or the m-xylene in different beds. According to some embodiments of the invention, the number of adsorbent beds in the simulated moving bed is 4-32, and the number of adsorption zone beds/desorption zone beds is 1.0-1.5.
According to some embodiments of the invention, the adsorbent and the mixed xylene are at a temperature of-5 to 300 ℃, preferably at a temperature of 25 to 250 ℃, and more preferably at a temperature of 30 to 150 ℃ in the adsorptive separation. According to some embodiments, the adsorbent and the mixed xylene are at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 110 ℃ or 120 ℃.
According to some embodiments of the invention, the mixed xylenes are subjected to adsorptive separation in the form of mixed xylene vapor or liquid. According to some embodiments of the present invention, the adsorbent and mixed xylene vapor are at a pressure of 100-1200kPa, preferably 100-1000kPa, in the adsorptive separation. According to some embodiments, the adsorbent and mixed xylene vapor are at a pressure of 100-600 kPa. According to some embodiments, the adsorbent and the mixed xylene liquid are at 1.1 to 2.5 MPa.
According to some embodiments of the invention, the mixed xylene vapor consists of mixed xylene and a carrier. According to some embodiments, the carrier gas is nitrogen and/or helium.
According to some embodiments of the invention, the weight ratio of the adsorbent to the mixed xylenes is from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5.
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.
According to some embodiments of the invention, the adsorptive separation is carried out under conditions that vary the total pressure of the mixed xylene vapor or liquid or vary the adsorption temperature of the adsorbent, or both.
According to some embodiments of the invention, in the adsorptive separation, the adsorbent is at a temperature of from 30 ℃ to less than 60 ℃. The inventor finds that when the temperature of the working temperature of the adsorbent is less than 60 ℃, the interaction force between the ortho-xylene and the adsorbent is very weak when the saturated vapor pressure of the ortho-xylene is less than 900Pa, the ortho-xylene and the adsorbent are quickly desorbed from the adsorbent, and then pure ortho-xylene products are obtained.
According to some embodiments of the invention, in the adsorptive separation, the adsorbent is at 60 ℃ to less than 110 ℃. The inventor finds that when the working temperature of the adsorbent is more than 110 ℃ and more than T and more than 60 ℃, the interaction force of the m-xylene and the adsorbent is stronger under the condition than that of the o-xylene, the retention time in the adsorbent is relatively longer and the m-xylene flows out so as to obtain a pure component m-xylene product, while the interaction force of the p-xylene and the adsorbent is relatively strongest, and the p-xylene is slowly desorbed from the adsorbent after the adsorption is saturated, so that the pure component p-xylene is obtained.
According to some embodiments of the present invention, the adsorbent is maintained at 110-200 deg.C, preferably at a temperature of 110-150 deg.C, to separate the paraxylene in the adsorptive separation. The inventor finds that when the temperature of the working temperature of the adsorbent is more than 110 ℃, the acting force between the o-xylene and the m-xylene and the adsorbent is weaker, the retention time in the adsorbent is shorter, the o-xylene and the m-xylene are separated out quickly, and the p-xylene and the adsorbent still have stronger interaction, so that the difference of the retention time obtains a single product.
The adsorption separation process of the invention is simple, the mixed steam or mixed liquid under a certain pressure can pass through an adsorption tower or an adsorption column filled with the adsorbent, furthermore, the adsorption tower can also be composed of one or more than one, and the separation is realized by adopting the existing pressure swing adsorption or vacuum pressure swing adsorption or temperature swing adsorption.
According to some embodiments of the invention, the method further comprises regenerating the adsorbent after completion of the adsorptive separation, preferably, the regenerating comprises heating the adsorbent to 50 to 300 ℃ under vacuum or inert atmosphere for 20 to 120 hours. Too high a temperature or too long a time can cause structural damage to the adsorbent; if the temperature is too low or the time is too short, the residual adsorbate in the adsorbent cannot be completely removed.
According to the invention, the metal-organic framework material is a three-dimensional or two-dimensional network framework structure formed by transition metal ions or alkaline earth metal ions and organic ligands (2, 5-dihydroxy-1, 4-benzoquinone) through coordination bonds or intermolecular forces.
In the invention, the geometric configuration of the pore channel of the metal organic framework material is matched with the geometric structure of corresponding xylene molecules at different temperatures, and the material structure is a network-shaped material formed by the layered framework through the action of hydrogen bonds between layers. The layered plane formed by ligand molecules in the material and metal coordination contains a large amount of pi electron clouds, and the pi-pi electron clouds corresponding to the benzene ring planes in p-xylene, o-xylene and m-xylene are stacked to have strong interaction. In view of the molecular geometry and linear structure of p-xylene, the molecules form strong interactions with the layered surface and adapted pores of the material. The thermodynamic and kinetic results show that the two factors cause the adsorption capacities of three xylene isomer molecules on the surface of the material to be remarkably different, when mixed steam or mixed liquid passes through an adsorption tower, the o-xylene has the weakest effect and the smallest adsorption capacity, the adsorbent or the adsorption separation device is firstly removed, the m-xylene has the second action and the adsorption capacity, the time required for removing the adsorbent or the adsorption separation device is longer than that of the o-xylene, the p-xylene has the longest time required for removing the adsorbent or the adsorption separation device due to the matching of the molecular size and the geometric pore size of the material, and the adsorption capacity, so that the separation of three C8 aromatic hydrocarbon isomers of the p-xylene, the m-xylene and the o-xylene is realized.
According to some embodiments of the invention, the metal-organic framework material is prepared by a method comprising the steps of:
(a) mixing inorganic salt, organic ligand and deionized water for reaction; the inorganic salt is chloride, nitrate, acetate, carbonate, sulfate or perchlorate of metal ions; the organic ligand is 2, 5-dihydroxy-1, 4-benzoquinone;
(b) washing and drying the reaction product obtained in the step (a).
In the preparation process of the metal organic framework material, 2, 5-dihydroxy-1, 4-benzoquinone is used as an organic ligand and reacts with a series of metal inorganic salts in pure water, toxic and volatile organic solvents are not needed, and the metal organic framework material is low in price of raw materials required for preparation, mild in synthesis conditions, simple to operate, easy to post-treat and low in material synthesis cost.
In the method, the metal organic framework material has high adsorption capacity and separation selectivity to p-xylene/m-xylene, p-xylene/o-xylene and m-xylene/o-xylene, and the material has stable structure and adsorption performance, good water resistance and good industrial application prospect.
The adsorbent prepared by the method has stable structural performance and regular particle shape, and has high separation selectivity and adsorption capacity to xylene mixed steam or mixed liquid.
Further preferably, the molar ratio of the organic ligand to the inorganic salt is 1 (0.5-10). Deionized water is used as a solvent, and the volume capacity is 10-2000 mL. Further preferably, when the inorganic salt is cobalt salt, zinc salt, ferric salt, manganese salt, magnesium salt, calcium salt, tin salt or scandium salt, the molar ratio of the organic ligand to the inorganic salt is 1 (0.5-10), deionized water is used as a solvent, and the volume capacity is 10-2000 mL; when the inorganic salt is zinc salt, cobalt salt, magnesium salt or manganese salt, the molar ratio of the organic ligand to the inorganic salt is 1 (1-10), water is used as a solvent, and the volume capacity is 20-2000 mL.
Further preferably, when the inorganic salt is cobalt salt, nickel salt, zinc salt, ferric salt, manganese salt, tin salt or scandium salt, the ratio of the inorganic salt, the organic ligand and the deionized water is 1 mmol: 1 mmol: 5-40 mL; when the metal salt is magnesium salt and manganese salt, the proportion of the organic ligand, the inorganic salt and the deionized water is 1.5 mmol: 1.5-6 mmol: 10-2000 mL. Changing the ratio of metal salt, organic ligand and deionized water can change the size, crystal form, regularity and the like of the crystal, and can also influence the adsorption capacity and separation selection performance of the material on p-xylene, m-xylene and o-xylene.
Most preferably, when the inorganic salt is zinc acetate dihydrate, cobalt chloride hexahydrate, scandium nitrate hydrate, tin chloride dihydrate, magnesium acetate hydrate, manganese acetate tetrahydrate and ferric chloride hexahydrate, the ratio of the metal salt, the organic ligand and the deionized water is 150 mmol: 150 mmol: 1000 mL; when the inorganic salt is anhydrous manganese chloride, the ratio of the metal salt, the organic ligand and the deionized water is 4 mmol: 3 mmol: 30 mL; when the inorganic salt is anhydrous magnesium sulfate, the ratio of the metal salt, the organic ligand and the deionized water is 6 mmol: 1.5 mmol: 400 mL.
According to some embodiments of the invention, the mixing is performed under stirring conditions: stirring the mixture for 5 to 72 hours at 200 to 1000 revolutions per minute, and uniformly mixing the reaction solution for reaction. Uneven mixing or incomplete reaction can cause irregular crystal forms obtained by the reaction, thereby influencing the adsorption separation performance of the material on xylene isomers.
Further preferably, the reaction temperature is 10-50 ℃, and the reaction time is 5-70 hours; further preferably, the reaction is carried out at 25-40 ℃ for 8-48 hours. The reaction temperature affects the formation of crystals, and too high or too low may result in failure to form crystals.
According to some embodiments of the present invention, the product after completion of the reaction is washed several times by centrifugation with deionized water to displace the residual ligand and inorganic salts in the channels.
Further preferably, the thoroughly washed product is activated under vacuum or inert gas (such as nitrogen, helium, etc.) purging, the activation temperature is 50-250 ℃, and the activation time is 12-24 hours.
Compared with the prior art, the invention has the following advantages:
the organic ligand and the metal salt used for preparing the metal organic framework material are cheap and easily available, the synthesis condition is mild, the purification step is simple, and the operation and the amplification are easy.
In the method, the metal organic framework material used has stable structure and very high adsorption separation selectivity on paraxylene/metaxylene, paraxylene/orthoxylene, metaxylene/orthoxylene mixed vapor or mixed liquid.
The metal organic frame material used in the invention has stable performance, and the adsorption performance still keeps the original effect after repeated adsorption-regeneration.
The adsorbent prepared by the invention is far superior to most of the existing solid adsorbents in the aspect of adsorption separation of xylene isomers, and particularly has an advantage in the aspect of purification of a xylene mixed system to obtain single-component xylene or single-component xylene concentration.
Drawings
Fig. 1 is an XRD pattern of the metal organic framework material prepared in example 1.
FIG. 2 is a schematic view of the simulated moving bed used in example 2.
Fig. 3 is an XRD pattern of the metal organic framework material prepared in example 2.
Fig. 4 is an XRD pattern of the metal organic framework material prepared in example 3.
Fig. 5 is an XRD pattern of the metal organic framework material prepared in example 4.
FIG. 6 is a graph showing the adsorption isotherm of xylene at 30 ℃ for the metal-organic framework material prepared in example 1.
FIG. 7 is a graph showing the adsorption isotherm of xylene at 60 ℃ for the metal-organic framework material prepared in example 2.
FIG. 8 is a graph showing the adsorption isotherm of xylene at 120 ℃ for the metal-organic framework material prepared in example 2.
FIG. 9 is a graph of the breakthrough of the metal-organic framework material prepared in example 2 at 30 ℃ in o-xylene/m-xylene.
FIG. 10 is a graph of the breakthrough of the metal-organic framework material prepared in example 2 at 90 ℃ in m-xylene/p-xylene.
FIG. 11 is a CO at 0 ℃ of the metal organic frame materials prepared in examples 1 to 4 and comparative examples 1 to 22Adsorption isotherm plot of (a).
Detailed Description
The invention is further illustrated by the following examples, but the content of the invention is not at all limited to these examples.
Example 1
300mmol of zinc acetate dihydrate, 300mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 1000mL of deionized water are mixed and stirred for reaction at room temperature for 12-48 hours. After the reaction is finished, centrifugally washing the solid product obtained by the reaction for multiple times by using deionized water until the supernatant is clear and transparent to obtain the purified metal organic framework material, and measuring N under 77K2The adsorption-desorption isotherm of (A) was analyzed to obtain a specific surface area of 441.7m2In g, average pore diameter of
The purified metal organic framework material was activated in vacuum at 150 ℃ for 12 hours to obtain desolvated adsorbent, followed by vapor adsorption test of xylene isomers.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single-component adsorption isotherms of p-xylene, o-xylene and m-xylene were performed using the adsorbent. Taking a proper amount of adsorbent, wherein the adsorption temperature is 30 ℃, 60 ℃, 90 ℃ and 120 ℃. Tests show that the adsorption quantity of p-xylene is up to 200mg/g, the adsorption quantity of o-xylene is only 78mg/g, and the adsorption quantity of m-xylene is only 51mg/g at 30 ℃ and the single-component saturated vapor pressure is 1000 Pa. The adsorption isotherm plot is shown in FIG. 5. At 60 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is 165mg/g, the adsorption capacity of o-xylene is 25mg/g, and the adsorption capacity of m-xylene is 30 mg/g; at 90 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is 66mg/g, the adsorption capacity of o-xylene is 17mg/g, and the adsorption capacity of m-xylene is 18 mg/g; at 120 ℃ and a single-component saturated vapor pressure of 1000Pa, the adsorption amount of p-xylene was 19mg/g, that of o-xylene was 22mg/g, and that of m-xylene was 25 mg/g.
The specific process for separating mixed xylene by adopting the synthesized metal organic framework material is as follows:
the synthesized adsorbent is firstly molded, and the amount of the binder required in the molding process accounts for 3-10% of the mass of the adsorbent. The penetration test of xylene mixed vapor was performed using the molded adsorbent. In the embodiment, the mixed steam of three or two of p-xylene/m-xylene/o-xylene is subjected to adsorption separation, the ratio of saturated vapor pressures of xylene of single components is 1:1:1 or 1:1, the total pressure of the mixed steam is 0.1MPa, the specification of a packed column is 10mm I.D. multiplied by 50mm, and the mass of the packed adsorbent is about 2.2 g. It was tested that at a temperature of 30 ℃ of the adsorbent, the saturated steam pressure ratio of o-xylene/m-xylene/p-xylene was 1:1:1, the breakthrough of o-xylene and m-xylene started in the first 8 minutes, while the breakthrough of p-xylene was started after about 120 minutes of retention in the packed column. Such a large difference in retention time indicates that the mixed xylenes are effectively separated. The metal organic framework material still has stable adsorption performance after 5 adsorption-regeneration cycles. The regeneration conditions are to heat the adsorbent to 150 ℃ under vacuum or inert atmosphere for 72 hours.
Example 2
Mixing 600mmol of manganese acetate tetrahydrate, 600mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 2000mL of deionized water, and stirring for reaction at room temperature for 24-48 hours. After the reaction is finished, centrifugally washing the solid obtained by the reaction with deionized water for multiple times to obtain a purified metal organic framework material, and measuring N under 77K2The adsorption-desorption isotherm of (A) was analyzed to obtain a specific surface area of 428.9m2In g, average pore diameter of
The purified metal organic framework material was degassed at 150 ℃ for 12 hours under vacuum to obtain desolvated adsorbent, followed by steam adsorption test.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single-component adsorption isotherms of p-xylene, m-xylene, and o-xylene were performed using the metal organic framework material as an adsorbent. Taking a proper amount of adsorbent, wherein the adsorption temperature is 30 ℃, 60 ℃, 90 ℃ and 120 ℃. Tests show that when the temperature is 30 ℃ and the single-component saturated vapor pressure is 1000Pa, the adsorption quantity of p-xylene is up to 208mg/g, the adsorption quantity of o-xylene is 170mg/g, and the adsorption capacity of m-xylene is 204 mg/g; at 60 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is up to 185mg/g, the adsorption capacity of o-xylene is only 23mg/g, and the adsorption capacity of m-xylene is 159 mg/g; at 90 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is up to 160mg/g, the adsorption capacity of o-xylene is only 22mg/g, and the adsorption capacity of m-xylene is 69 mg/g; at 120 deg.C and single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is up to 141mg/g, that of o-xylene is only 23mg/g, and that of m-xylene is only 17 mg/g. The adsorption isotherms are shown in FIGS. 6-7.
The specific process of separating mixed xylene with the synthesized metal organic framework material is as follows:
the synthesized adsorbent is firstly molded, and the amount of the binder required in the molding process accounts for 3-10% of the mass of the adsorbent. The penetration test of xylene mixed vapor was performed using the molded adsorbent. In the embodiment, the adsorption separation is carried out on three or two mixed steam of p-xylene/m-xylene/o-xylene, the ratio of saturated vapor pressure of xylene of each single component is 1:1:1 or 1:1, the total pressure of the mixed steam is 0.1MPa, the specification of a packed column is 10mm I.D. multiplied by 50mm, and the mass of the packed and formed adsorbent is about 2.3 g. The penetration curves are shown in FIGS. 8-9. It was tested that at a temperature of 30 ℃ of the adsorbent, at a saturated vapor pressure ratio of o-xylene/m-xylene of 50:50, the o-xylene breakthrough occurred in 45 minutes and the m-xylene breakthrough began in 275 minutes. Such a large difference in retention time indicates that the two xylene isomers are effectively separated. In addition, at 90 ℃ temperature of the adsorbent, the breakthrough of m-xylene occurred in 25 minutes and the breakthrough of p-xylene started in 315 minutes at a m-xylene/p-xylene saturated steam pressure ratio of 50: 50. Such a large difference in retention time indicates that m-xylene and p-xylene are effectively separated under these conditions. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles. The regeneration conditions are to heat the adsorbent to 150 ℃ under vacuum or inert atmosphere for 72 hours.
The adsorption separation is carried out on a small simulated moving bed with continuous countercurrent by using the adsorbent.
The small-sized simulated moving bed device comprises 12 adsorption columns which are connected in series, wherein each column is 150mm long, the inner diameter of each column is 10mm, and the total filling amount of an adsorbent is 140 mL. The head end and the tail end of the 12 columns connected in series are connected by a circulating pump to form a closed loop, as shown in figure 2. In fig. 2, four streams of the raw adsorption material, the desorbent, the extract and the raffinate enter and exit the 12 adsorption columns into four sections, i.e., 3 adsorption columns between the raw adsorption material (column 8) and the raffinate (column 10) are an adsorption zone, 4 adsorption columns between the extract (column 4) and the raw adsorption material (column 7) are a purification zone, 3 adsorption columns between the desorbent (column 1) and the extract (column 3) are a desorption zone, and 2 adsorption columns between the raffinate (column 11) and the desorbent (column 12) are buffer zones. The temperature of the whole adsorption system is controlled to be 150 ℃, and the pressure is 0.5 MPa.
During the operation, the desorbent p-diethylbenzene and the adsorption raw material are continuously injected into the simulated moving bed device at the flow rates of 130mL/h and 100mL/h respectively, the extract is extracted by the device at the flow rate of 80mL/h, and the raffinate is extracted by the device at the flow rate of 150 mL/h. The adsorption raw material comprises 10 wt% of ethylbenzene, 20 wt% of paraxylene, 50 wt% of metaxylene and 20 wt% of orthoxylene. The flow rate of the circulating pump is set to be 270mL/h, and according to the principle of simulated countercurrent chromatography, four material positions move forward 1 adsorption column in the same direction as the liquid flow direction every 70 seconds. The purity of the p-xylene obtained under the stable operation state is 99.75-99.9 wt%, and the recovery rate is 98.0-99.0 wt%.
Example 3
Mixing 30mmol of cobalt chloride hexahydrate, 30mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 200mL of deionized water, and stirring for reaction at room temperature for 12-24 hours. After the reaction is finished, centrifugally washing the solid obtained by the reaction with deionized water for multiple times to obtain a purified metal organic framework material, and measuring N under 77K2The adsorption-desorption isotherm of (A) was analyzed to obtain a specific surface area of 412.5m2In g, average pore diameter of
The purified metal organic framework material was degassed at 150 ℃ for 12 hours under vacuum to obtain desolvated adsorbent, followed by steam adsorption test.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single-component adsorption isotherms of p-xylene, m-xylene and o-xylene were performed using the metal organic framework material as an adsorbent. Taking a proper amount of adsorbent, wherein the adsorption temperature is 30 ℃, 60 ℃, 90 ℃ and 120 ℃. At 30 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene reaches 43mg/g, the adsorption capacity of m-xylene reaches 35mg/g, and the adsorption capacity of o-xylene reaches 22 mg/g; at 60 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene reaches 23mg/g, the adsorption capacity of m-xylene reaches 23mg/g, and the adsorption capacity of o-xylene reaches 11 mg/g; at 90 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is 14mg/g, the adsorption capacity of o-xylene is 5mg/g, and the adsorption capacity of m-xylene is 14 mg/g; at 120 ℃ and a single-component saturated vapor pressure of 1000Pa, the adsorption amount of p-xylene was 8mg/g, that of o-xylene was 1mg/g, and that of m-xylene was 8 mg/g.
The specific process of separating mixed xylene with the synthesized metal organic framework material is as follows:
the synthesized adsorbent is firstly molded, and the amount of the binder required in the molding process accounts for 3-10% of the mass of the adsorbent. The penetration test of xylene mixed vapor was performed using the molded adsorbent. In the embodiment, the adsorption separation is carried out on three or two mixed steam of p-xylene/m-xylene/o-xylene, the ratio of saturated vapor pressure of xylene of each single component is 1:1:1 or 1:1, the total pressure of the mixed steam is 0.1MPa, the specification of a packed column is 10mm I.D. multiplied by 50mm, and the mass of the packed and formed adsorbent is about 3.1 g. It was tested that at a 60 ℃ temperature of the adsorbent, the saturated vapor pressure ratio of o-xylene/m-xylene/p-xylene was 1:1:1, the breakthrough of o-xylene and m-xylene started in the first 15 minutes, while the breakthrough of p-xylene started after about 100 minutes of retention in the packed column. Such a large difference in retention time indicates that the mixed xylenes are effectively separated. The metal organic framework material still has stable adsorption performance after 5 times of adsorption-regeneration cycles. The regeneration conditions are to heat the adsorbent to 150 ℃ under vacuum or inert atmosphere for 72 hours.
Example 4
30mmol of hydrated magnesium acetate, 30mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 300mL of deionized water are mixed and stirred for reaction at room temperature for 24-72 hours. After the reaction is finished, centrifugally washing the solid obtained by the reaction with deionized water for multiple times to obtain a purified metal organic framework material, and measuring N under 77K2The adsorption-desorption isotherm of (A) was analyzed to obtain a specific surface area of 577.2m2In g, average pore diameter of
The purified metal organic framework material was degassed at 150 ℃ for 12 hours under vacuum to obtain desolvated adsorbent, followed by steam adsorption test.
In order to test the adsorption separation performance of the synthesized metal organic framework material, single-component adsorption isotherms of p-xylene, m-xylene and o-xylene were performed using the metal organic framework material as an adsorbent. Taking a proper amount of adsorbent, and adsorbing at 30 ℃, 60 ℃, 90 ℃ and 120 ℃. At 30 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene reaches 79mg/g, the adsorption capacity of o-xylene reaches 22mg/g, and the adsorption capacity of m-xylene reaches 49 mg/g; at 60 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene reaches 39mg/g, the adsorption capacity of o-xylene reaches 12mg/g, and the adsorption capacity of m-xylene reaches 29 mg/g; at 90 ℃ and the single-component saturated vapor pressure of 1000Pa, the adsorption capacity of p-xylene is 24mg/g, the adsorption capacity of o-xylene is 6mg/g, and the adsorption capacity of m-xylene is 19 mg/g; at 120 ℃ and a single-component saturated vapor pressure of 1000Pa, the adsorption amount of p-xylene was 13mg/g, the adsorption amount of o-xylene was 2mg/g, and the adsorption amount of m-xylene was 12 mg/g.
The specific process of separating mixed xylene with the synthesized metal organic framework material is as follows:
the synthesized adsorbent is firstly molded, and the amount of the binder required in the molding process accounts for 3-10% of the mass of the adsorbent. The penetration test of xylene mixed vapor was performed using the molded adsorbent. In the embodiment, two or three mixed steam of p-xylene/m-xylene/o-xylene is used for adsorption separation, the ratio of saturated steam pressure of xylene of each single component is 1:1:1 or 1:1, the total pressure of the mixed steam is 0.1MPa, the specification of a packed column is 10mm I.D. multiplied by 50mm, and the mass of the packed adsorbent is about 1.8 g. It was tested that at a temperature of 30 ℃ of the adsorbent, the saturated steam pressure ratio of o-xylene/m-xylene/p-xylene was 1:1:1, the breakthrough of o-xylene and m-xylene started in the first 23 minutes, while the breakthrough of p-xylene started after about 96 minutes of retention in the packed column. Such a large difference in retention time indicates that the mixed xylenes are effectively separated. The regeneration conditions are to heat the adsorbent to 150 ℃ under vacuum or inert atmosphere for 72 hours.
Comparative example 1
Mixing 15mmol of hydrated nickel acetate, 15mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 200mL of deionized water, and stirring for reaction at room temperature for 24-72 hours. And after the reaction is finished, centrifugally washing the solid obtained by the reaction with deionized water for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material was degassed at 150 ℃ for 12 hours under vacuum to obtain desolvated adsorbent, followed by steam adsorption test.
To test the adsorptive separation performance of the above-described synthetic metal-organic framework material, first, whether a void exists in the material or not was examined for CO at 273K2Adsorption-desorption isotherms. As shown in FIG. 10, the metal-organic framework material is coupled to CO2Small molecule gas (kinetic size of
) There is no adsorption capacity, indicating that the material does not have a suitable pore size or there are virtually no voids inside the material for xylene adsorptive separation applications.
Comparative example 2
1.5mmol of hydrated copper chloride, 1.5mmol of 2, 5-dihydroxy-1, 4-benzoquinone and 30mL of deionized water are mixed and stirred at room temperature for reaction for 24-48 hours. And after the reaction is finished, centrifugally washing the solid obtained by the reaction with deionized water for multiple times to obtain the purified metal organic framework material. The purified metal organic framework material was degassed at 150 ℃ for 12 hours under vacuum to obtain desolvated adsorbent, followed by steam adsorption test.
To test the adsorptive separation performance of the above-synthesized copper metal organic framework material, first, whether a void exists in the material or not was examined for CO at 273K2Adsorption-desorption isotherms. As shown in FIG. 10, the metal-organic framework material was used for CO at 273K as the nickel metal-organic framework material in comparative example 12Has an adsorption capacity close to 0, and the result shows that the material does not have proper pore size or practically no void exists in the material for the application of the adsorption separation of the dimethylbenzene.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (17)
1. A method for separating mixed xylene, comprising subjecting the mixed xylene to adsorptive separation using an adsorbent comprising a metal organic framework material, thereby effecting separation of the mixed xylene,
wherein the metal-organic framework material comprises metal ions and organic ligands, wherein the organic ligands are selected from 2, 5-dihydroxy-1, 4-benzoquinone, and the metal ions are selected from one or more of zinc ions, manganese ions, cobalt ions and magnesium ions.
2. The method of claim 1, wherein the mixed xylenes are gaseous or liquid and include two or more of ethylbenzene, ortho-xylene, meta-xylene, and para-xylene.
3. The method of claim 1, wherein the metal-organic framework material has a pore diameter of greater than 4 a; the specific surface area of the metal-organic framework material is 300-2000m2/g。
4. The method of claim 3, wherein the metal organic framework material has a pore diameter of 4-15A.
5. The method of claim 3, wherein the metal organic framework material has a pore diameter of 4-10A.
6. The method of any one of claims 1-5, wherein the temperature of the adsorptive separation is from-5 ℃ to 300 ℃.
7. The method of claim 6, wherein the temperature of the adsorptive separation is from 25 ℃ to 250 ℃.
8. The method of claim 6, wherein the temperature of the adsorptive separation is from 30 ℃ to 150 ℃.
9. The process according to any one of claims 1 to 5, wherein the pressure of the adsorptive separation is from 0.01MPa to 10 MPa.
10. The process of claim 9, wherein the pressure of the adsorptive separation is from 0.1MPa to 6 MPa.
11. The process according to any one of claims 1 to 5, wherein the adsorptive separation is carried out using a fixed bed, wherein the adsorbent is packed in the fixed bed adsorption column.
12. The method of claim 11, wherein the adsorptive separation comprises the steps of:
(1) enabling mixed xylene steam formed by mixed xylene and carrier gas to pass through a fixed bed adsorption column, adsorbing a strongly adsorbed xylene isomer in the mixed xylene on the adsorbent, and enabling a weakly adsorbed xylene isomer in the mixed xylene to penetrate through the adsorption column to obtain a weakly adsorbed xylene isomer;
(2) desorbing the strongly adsorbed xylene isomer from the adsorbent to obtain the strongly adsorbed xylene isomer.
13. The process of any one of claims 1 to 5, wherein the adsorptive separation is carried out using a simulated moving bed, wherein the adsorbent is packed in an adsorption zone bed of the simulated moving bed.
14. The method of claim 13, wherein the adsorptive separation comprises the steps of:
and (3) carrying out adsorption separation on the mixed xylene liquid by a liquid-phase simulated moving bed so as to respectively pump out the p-xylene, the o-xylene and/or the m-xylene in different beds.
15. The method as claimed in claim 13, wherein the simulated moving bed has 4-32 beds of adsorption zones.
16. The method of any one of claims 1-5, further comprising regenerating the adsorbent after completion of the adsorptive separation.
17. The method of claim 16, wherein the regenerating comprises heating the adsorbent to a temperature of 50-300 ℃ under vacuum or inert atmosphere for 20-120 hours.
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