CN117138518A - Use of SSZ-74 molecular sieve in adsorption separation of benzene and cyclohexane - Google Patents
Use of SSZ-74 molecular sieve in adsorption separation of benzene and cyclohexane Download PDFInfo
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- CN117138518A CN117138518A CN202311102621.6A CN202311102621A CN117138518A CN 117138518 A CN117138518 A CN 117138518A CN 202311102621 A CN202311102621 A CN 202311102621A CN 117138518 A CN117138518 A CN 117138518A
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- molecular sieve
- benzene
- cyclohexane
- silicon
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 170
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 170
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000926 separation method Methods 0.000 title claims abstract description 84
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 53
- 239000010703 silicon Substances 0.000 claims abstract description 53
- 238000010438 heat treatment Methods 0.000 claims description 44
- 125000005842 heteroatom Chemical group 0.000 claims description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 239000001307 helium Substances 0.000 claims description 21
- 229910052734 helium Inorganic materials 0.000 claims description 21
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 239000003570 air Substances 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001502 supplementing effect Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- -1 dimethylethyl Chemical group 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- 230000000274 adsorptive effect Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000035515 penetration Effects 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 4
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- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 230000002860 competitive effect Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 7
- 238000007872 degassing Methods 0.000 description 7
- AMCFBNLEJANOEC-UHFFFAOYSA-N n,n-dimethylethanamine;hydrate Chemical compound [OH-].CC[NH+](C)C AMCFBNLEJANOEC-UHFFFAOYSA-N 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000001612 separation test Methods 0.000 description 7
- 238000001994 activation Methods 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 description 2
- BKYWPNROPGQIFZ-UHFFFAOYSA-N 2,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(C)=C1 BKYWPNROPGQIFZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application discloses application of an SSZ-74 molecular sieve in adsorption separation of benzene and cyclohexane. The application selects the SSZ-74 molecular sieve with the-SVR structure as a separation material, utilizes the special ordered silicon hydroxyl and the unique multidimensional bending pore canal structure thereof, combines the advantage of the shape selectivity of the pore canal structure and the advantage of the interaction generated by pi bonds in benzene, realizes the separation of benzene and cyclohexane by the different penetration points of the SSZ-74 molecular sieve on benzene and cyclohexane, and is suitable for industrialized separation.
Description
Technical Field
The application belongs to the technical field of adsorption separation, and particularly relates to application of an SSZ-74 molecular sieve in adsorption separation of benzene and cyclohexane.
Background
Cyclohexane is an important chemical raw material, is widely used in the production of nylon, paint, drug intermediates and the like, and in recent years, the productivity of China in the related chemical field is gradually improved. In practical chemical production, cyclohexane is generally produced by hydrogenation of benzene as a reactant, and it is generally difficult to achieve complete conversion, resulting in products often containing cyclohexane together with unreacted benzene, and thus obtaining cyclohexane of high purity by removing residual benzene is also a very important ring in chemical production. However, the physical properties such as the solidification point, density and the like of benzene and cyclohexane, and the chemical properties such as the molecular size, chemical structure and the like are relatively similar, and more importantly, the boiling point of benzene is 80.1 ℃ and the boiling point of cyclohexane is 80.7 ℃, so that the high-purity cyclohexane is difficult to obtain at one time in a liquid-liquid azeotropic separation mode which is common in industry and widely applied and is subjected to reduced pressure distillation, rectification and extractive distillation, and if the traditional separation mode is used, multiple separations are often required, so that the purification cost is high and the product purity is difficult to guarantee. It is a significant challenge to efficiently and simply separate and purify a mixture of benzene and cyclohexane.
Based on this background, designing or searching a new, efficient and low energy consumption way of separating benzene and cyclohexane has become the key to purifying cyclohexane in the industry. In recent years, with the rise of various novel crystalline and amorphous functional materials, many materials offer the possibility for solving some classical industrial problems due to the natural advantages of the materials, wherein the development of porous materials provides many new choices for adsorption separation of a plurality of important chemical raw materials.
Many porous materials, which have relatively high specific surface area and ordered pore distribution, and adjustable pore size, structure and internal environment, are widely used to solve industrial problems such as hydrogen purification, alkyne separation, benzene and cyclohexane separation, and selective adsorption of xylene isomers, including zeolite molecular sieves, carbon molecular sieves, metal organic framework Materials (MOFs), covalent organic framework materials (COFs), porous Organic Polymers (POPs), porous organic cages (cabes), and the like. In the benzene and cyclohexane separation process, currently used porous materials mainly comprise metal organic frame Materials (MOFs) and porous organic cages (cabes), and adsorption separation is mainly realized by matching pore channel sizes with benzene or cyclohexane sizes, or separation of the benzene or cyclohexane by regulating and controlling interaction of ligands in the pore channels and the benzene or cyclohexane to delay diffusion pore outlet speed. Although these porous materials all exhibit superior adsorptive separation properties, their structure often contains dynamic chemical bonds with poor stability, which can easily cause the destruction of the material structure under acidic, alkaline, and hydrothermal caustic conditions, thereby affecting the separation performance of the material after cyclic regeneration. Meanwhile, the industrial application of the porous material in the field of benzene and cyclohexane adsorption separation is greatly limited due to the expensive synthesis cost.
Among the porous Materials, zeolite molecular sieve Materials have outstanding advantages in terms of preparation cost and stability, and have been shown to have excellent properties in hydrogen purification, olefin separation and the like (Nature Materials,2021,20,362-369; science,2020,368, 1002-1006), but few studies have been conducted so far on the separation of benzene and cyclohexane, and only theoretical simulation and adsorption experiments have involved some experimental assumptions, so that the selection of a zeolite molecular sieve suitable for the separation of benzene and cyclohexane is likely to provide a new idea suitable for industrial production for the industrial problem.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present application is to provide an application of SSZ-74 molecular sieve in adsorption separation of benzene and cyclohexane, in order to solve the technical problems existing in the prior art.
In order to achieve the above purpose, the present application adopts the following technical scheme.
The first aspect of the application protects the use of SSZ-74 molecular sieves in the adsorptive separation of benzene and cyclohexane.
The application selects SSZ-74 molecular sieve with-SVR structure as separating material, uses special ordered silicon hydroxyl and its unique multidimensional bending pore canal, separates benzene and cyclohexane by structure shape selective adsorption of the multidimensional bending pore canal, simultaneously separates benzene and cyclohexane by interaction generated by pi bond in the ordered silicon hydroxyl and benzene, and realizes benzene and cyclohexane separation by different penetration points of SSZ-74 molecular sieve to benzene and cyclohexane.
In the application of the application, the SSZ-74 molecular sieve is selected from an all-silicon SSZ-74 molecular sieve or a heteroatom doped SSZ-74 molecular sieve.
The all-silicon SSZ-74 molecular sieve is formed by silicon oxide (SiO 2 ) The heteroatom doped SSZ-74 molecular sieve consists of silicon dioxide and heteroatom oxide.
Preferably, the SSZ-74 molecular sieve has a silicon to heteroatom ratio of not less than 20, based on the molar ratio of silicon dioxide to heteroatom oxide. More preferably, it is 20 to 200.
Preferably, the heteroatom is selected from one or more of aluminium, titanium, boron and gallium.
More preferably, the heteroatom is aluminum, resulting in a silica-alumina SSZ-74 molecular sieve.
Further preferably, in SiO 2 And Al 2 O 3 The silicon-aluminum SSZ-74 molecular sieve has a silicon-aluminum ratio of more than 20, or 20-200, or 50-120, or 20-60, or 100-140, or 120-200, or preferably 50-120. In some embodiments, 100, 30.
More preferably, the heteroatom is titanium, resulting in a titanium silicalite SSZ-74 molecular sieve.
Further preferably, in SiO 2 And TiO 2 The titanium silicon SSZ-74 molecular sieve has a silicon-titanium ratio of more than 50, or 50-200, or 50-100. In some embodiments, 100.
In the application of the application, the SSZ-74 molecular sieve is obtained by heating SSZ-74 molecular sieve raw powder. Heating to remove water in the SSZ-74 molecular sieve, thereby achieving the purpose of activating the SSZ-74 molecular sieve.
Preferably, the temperature of the heating treatment is 30 to 400 ℃, or may be 30 to 200 ℃, or may be 80 to 350 ℃, or may be 220 to 400 ℃, or preferably 80 to 450 ℃, or 200 to 400 ℃. In some embodiments, 200℃and 400 ℃.
Preferably, the heating treatment is performed for 0.1 to 24 hours, or 0.1 to 5 hours, or 4 to 15 hours, or 12 to 24 hours, preferably 1 to 6 hours, or 2 to 4 hours. In some embodiments, 2h.
Preferably, the atmosphere of the heating treatment is selected from one or more of vacuum, air, nitrogen, helium and argon.
Preferably, the heating treatment is performed by degassing or purging.
Preferably, the heating treatment is preceded by roasting to remove the template agent in the SSZ-74 molecular sieve raw powder. According to the application, the template agent is removed through roasting, so that the pore canal is smooth, and the later-stage benzene adsorption is facilitated; and then the water adsorbed by the SSZ-74 molecular sieve is removed by heat treatment and activation, so that competitive adsorption with benzene and cyclohexane is avoided.
More preferably, the roasting process further comprises acid washing and silicon supplementing, wherein the acid washing is acid soaking treatment, the silicon supplementing is adding a silicon supplementing reagent, and the acid can be organic acid or inorganic acid, and the organic acid can be citric acid, 2, 4-dimethylbenzenesulfonic acid and 2, 4-dimethylbenzoic acid; the organic acid can be sulfuric acid, nitric acid or hydrochloric acid; the silicon supplementing agent can be selected from tetraethyl orthosilicate, ammonium hexafluorosilicate and ethyl orthosilicate, and can be specifically referred to Crystal Growth & Design 2023,23,3681-3693.
More preferably, the baking temperature is 200 to 800 ℃, or 200 to 550 ℃, or 450 to 650 ℃, or 600 to 800 ℃, or preferably 400 to 800 ℃, or 500 to 600 ℃. In some embodiments, 550℃and 600 ℃.
More preferably, the baking time is 0.5 to 24 hours, may be 0.5 to 3 hours, may be 2 to 10 hours, may be 6 to 15 hours, may be 12 to 24 hours, and is preferably 2 to 8 hours or 4 to 6 hours. In some embodiments, 4h, 5h.
More preferably, the firing is performed in a protective atmosphere. Preferably, the protective atmosphere is selected from one or more of nitrogen, argon, oxygen, air and oxygen-argon mixture, such as oxygen, air and oxygen-argon mixture.
More preferably, the preparation method of the SSZ-74 molecular sieve raw powder comprises the following steps: 1) The silicon source, the template agent and the mineralizer react in the water solution to obtain a gel mixture; 2) Crystallizing the gel mixture to obtain the SSZ-74 molecular sieve raw powder.
More preferably, in 1), further comprising adding a heteroatom source. The heteroatom is selected from one or more of aluminum, titanium, boron and gallium. The heteroatom source is derived from an oxide or sodium oxide salt of a heteroatom. When the heteroatom is aluminum, from sodium metaaluminate; when the heteroatom is titanium, it is derived from tetrabutyl titanate; when the heteroatom is boron, it is derived from boric acid; when the heteroatom is gallium, it is derived from gallium oxide.
More preferably, the silicon source is selected from one or more of white carbon black, silica sol, tetramethyl orthosilicate, tetraethyl orthosilicate and silica gel.
More preferably, the template is selected from one of hexamethylene-1, 6-bis (N-methylpyrrolidinium) divalent cations, hexamethylene-1-trimethylammonium-6-N-methylpyrrolidinium divalent cations, and hexamethylene-1, 6-bis (dimethylethyl) divalent cations. The template agent is one of the divalent cation hydroxide and the halide. Specifically, for example, the hexamethylene-1, 6-bis (dimethylethyl) divalent cation compound is hexamethylene-1, 6-bis (dimethylethylammonium hydroxide).
The structural formula of the hexamethylene-1, 6-bis (N-methylpyrrolidinium) divalent cation is as follows:
the structural formula of the hexamethylene-1-trimethylammonium-6-N-methylpyrrolidinium divalent cation is as follows:
the structural formula of the hexamethylene-1, 6-bis (dimethylethyl) divalent cation is as follows:
further preferably, the alkali metal source is selected from one or more of sodium hydroxide, potassium hydroxide and cesium hydroxide.
Further preferably, the fluorine source is selected from one or both of hydrofluoric acid and ammonium fluoride.
More preferably, the crystallization temperature may be 120 to 160 ℃, 140 to 180 ℃, 160 to 200 ℃, 180 to 220 ℃, or 200 to 240 ℃. In some embodiments 160 ℃.
More preferably, the crystallization time may be 24 to 100 hours, 96 to 168 hours, 154 to 236 hours, or 268 to 336 hours. In some embodiments, 168h.
The second aspect of the application protects an adsorption separation method for benzene and cyclohexane, which adopts SSZ-74 molecular sieve to adsorb and separate the mixed gas of benzene and cyclohexane.
In the adsorption separation method of the present application, the temperature of the adsorption separation may be 20 to 100 ℃, or may be 20 to 45 ℃, or may be 30 to 65 ℃, or may be 55 to 100 ℃. In certain embodiments, at 25℃or room temperature.
In the adsorption separation method, the volume ratio of benzene to cyclohexane is (1-99): 1-99. In some embodiments, 50:50, 10:50.
In the adsorption separation method of the application, the conditions of the adsorption separation are as follows: the flow rate of the mixed gas is 0.1-100 sccm. Preferably, the flow rate is 1 to 50sccm.
In the adsorption separation method, the load gas in the adsorption separation is one or more selected from nitrogen, helium, argon and air. Preferably, the negative carrier gas is helium.
Preferably, the flow rate ratio of benzene, cyclohexane and negative carrier gas is 1: (0.5-5): (30-60). The ratio of flow rates of the negative carrier gas, cyclohexane, benzene and the catalyst is 48:1: 1. 44:5:1.
in the adsorption separation method, the SSZ-74 molecular sieve is selected from an all-silicon SSZ-74 molecular sieve or a heteroatom doped SSZ-74 molecular sieve.
Preferably, the SSZ-74 molecular sieve is selected from an all-silicon SSZ-74 molecular sieve or a heteroatom-doped SSZ-74 molecular sieve. The all-silicon SSZ-74 molecular sieve is formed by silicon oxide (SiO 2 ) The heteroatom doped SSZ-74 molecular sieve consists of silicon dioxide and heteroatom oxide.
Preferably, the SSZ-74 molecular sieve has a silicon to heteroatom ratio of not less than 20, based on the molar ratio of silicon dioxide to heteroatom oxide. More preferably, it is 20 to 200.
Preferably, the heteroatom is selected from one or more of aluminium, titanium, boron and gallium.
More preferably, the heteroatom is aluminum, resulting in a silica-alumina SSZ-74 molecular sieve. Further preferably, in SiO 2 And Al 2 O 3 The silicon-aluminum SSZ-74 molecular sieve has a silicon-aluminum ratio of more than 20, or 20-200, or 50-120, or 20-60, or 100-140, or 120-200, or preferably 50-120. In some embodiments, 100, 30.
More preferably, the heteroatom is titanium, resulting in a titanium silicalite SSZ-74 molecular sieve. Further preferably, in SiO 2 And TiO 2 The titanium silicon SSZ-74 molecular sieve has a silicon-titanium ratio of more than 50, or 50-200, or 50-100. In some embodiments, 100.
In the adsorption separation method, the SSZ-74 molecular sieve is obtained by heating SSZ-74 molecular sieve raw powder. Heating to remove water in the SSZ-74 molecular sieve, thereby achieving the purpose of activating the SSZ-74 molecular sieve.
Preferably, the temperature of the heating treatment is 30 to 400 ℃, or may be 30 to 200 ℃, or may be 80 to 350 ℃, or may be 220 to 400 ℃, or preferably 80 to 450 ℃, or 200 to 400 ℃. In some embodiments, 200℃and 400 ℃.
Preferably, the heating treatment is performed for 0.1 to 24 hours, or 0.1 to 5 hours, or 4 to 15 hours, or 12 to 24 hours, preferably 1 to 6 hours, or 2 to 4 hours. In some embodiments, 2h.
Preferably, the atmosphere of the heating treatment is selected from vacuum, air, nitrogen, helium, argon. More preferably, air.
Preferably, the heating treatment is performed by degassing or purging.
Preferably, the heating treatment is preceded by roasting to remove the template agent in the SSZ-74 molecular sieve raw powder. According to the application, the template agent is removed through roasting, so that the pore canal is smooth, and the later-stage benzene adsorption is facilitated; and then the water adsorbed by the SSZ-74 molecular sieve is removed by heat treatment and activation, so that competitive adsorption with benzene and cyclohexane is avoided.
More preferably, the roasting process further comprises acid washing and silicon supplementing, wherein the acid washing is acid soaking treatment, the silicon supplementing is adding a silicon supplementing reagent, and the acid can be organic acid or inorganic acid, and the organic acid can be citric acid, 2, 4-dimethylbenzenesulfonic acid and 2, 4-dimethylbenzoic acid; the organic acid can be sulfuric acid, nitric acid or hydrochloric acid; the silicon supplementing agent can be selected from tetraethyl orthosilicate, ammonium hexafluorosilicate and ethyl orthosilicate, and can be specifically referred to Crystal Growth & Design 2023,23,3681-3693.
More preferably, the baking temperature is 200 to 800 ℃, or 200 to 550 ℃, or 450 to 650 ℃, or 600 to 800 ℃, or preferably 400 to 800 ℃, or 500 to 600 ℃. In some embodiments, 550℃and 600 ℃.
More preferably, the baking time is 0.5 to 24 hours, may be 0.5 to 3 hours, may be 2 to 10 hours, may be 6 to 15 hours, may be 12 to 24 hours, and is preferably 2 to 8 hours or 4 to 6 hours. In some embodiments, 4h, 5h.
More preferably, the firing is performed in a protective atmosphere. Preferably, the protective atmosphere is selected from one or more of nitrogen, argon, oxygen, air and oxygen-argon mixture, such as oxygen, air and oxygen-argon mixture.
More preferably, the preparation method of the SSZ-74 molecular sieve raw powder comprises the following steps: 1) The silicon source, the template agent and the mineralizer react in the water solution to obtain a gel mixture; 2) Crystallizing the gel mixture to obtain the SSZ-74 molecular sieve raw powder.
Further preferably, in 1), further comprising adding a heteroatom source. The heteroatom is selected from one or more of aluminum, titanium, boron and gallium. The heteroatom source is derived from an oxide or sodium oxide salt of a heteroatom. When the heteroatom is aluminum, from sodium metaaluminate; when the heteroatom is titanium, it is derived from tetrabutyl titanate; when the heteroatom is boron, it is derived from boric acid; when the heteroatom is gallium, it is derived from gallium oxide.
Further preferably, the silicon source is selected from one or more of white carbon black, silica sol, tetramethyl orthosilicate, tetraethyl orthosilicate and silica gel.
Further preferably, the template is selected from one of hexamethylene-1, 6-bis (N-methylpyrrolidinium) divalent cations, hexamethylene-1-trimethylammonium-6-N-methylpyrrolidinium divalent cations, and hexamethylene-1, 6-bis (dimethylethyl) divalent cations. The template agent is one of the divalent cation hydroxide and the halide. Specifically, for example, the hexamethylene-1, 6-bis (dimethylethyl) divalent cation compound is hexamethylene-1, 6-bis (dimethylethylammonium hydroxide).
Further preferably, the mineralizer is selected from an alkali metal source or a fluorine source. The alkali metal source is selected from one or more of sodium hydroxide, potassium hydroxide and cesium hydroxide. The fluorine source is selected from one or two of hydrofluoric acid and ammonium fluoride.
More preferably, the crystallization temperature may be 120 to 160 ℃, 140 to 180 ℃, 160 to 200 ℃, 180 to 220 ℃, or 200 to 240 ℃. In some embodiments 160 ℃.
More preferably, the crystallization time may be 24 to 100 hours, 96 to 168 hours, 154 to 236 hours, or 268 to 336 hours. In some embodiments, 168h.
The adsorption separation method of benzene and cyclohexane is a novel separation mechanism of SSZ-74 molecular sieve which integrates pore canal structure and micropore internal environment, is different from the prior simple pore canal shape-selective separation mode, has the advantages of low preparation cost and high stability compared with other porous materials, and is a separation material of benzene and cyclohexane which is more suitable for industrial application.
Compared with the prior art, the application has the following beneficial effects:
1) The SSZ-74 molecular sieve is used as an adsorption separation material, so that high-efficiency penetration separation of benzene and cyclohexane can be realized, the gap of the molecular sieve material in the field of benzene and cyclohexane adsorption separation is filled, and meanwhile, compared with the existing separation means of other porous materials, the SSZ-74 molecular sieve also has the natural advantages of low preparation cost, simple preparation mode and the like.
2) The application utilizes SSZ-74 molecular sieve to adsorb and separate benzene and cyclohexane, combines the advantage of unique multidimensional bending pore canal of SSZ-74 on the shape selectivity of benzene and cyclohexane and the advantage of interaction of rich ordered silicon hydroxyl groups in the pore canal of SSZ-74 molecular sieve on pi bonds in benzene, thereby cooperatively realizing the separation of benzene and cyclohexane.
3) The adsorption separation method can realize the high-efficiency separation of benzene and cyclohexane at room temperature by adopting the SSZ-74 molecular sieve, and meanwhile, the SSZ-74 molecular sieve has excellent regeneration performance as an adsorption separation material due to the high stability of the SSZ-74 molecular sieve, and can be recycled for 20 times and still has high-efficiency separation capability on benzene and cyclohexane.
4) Benzene and cyclohexane are adsorbed and separated by SSZ-74 molecular sieve, the penetration point of benzene is at least 9min/g later than that of cyclohexane, and the penetration point of benzene is 3.14min/g or less later than that of cyclohexane when other molecular sieve is used for adsorption and separation.
Drawings
FIG. 1 shows a PXRD spectrum of a heat treated SSZ-74 molecular sieve according to example 1 of the present application.
FIG. 2 shows a PXRD spectrum of a heat treated SSZ-74 molecular sieve according to example 2 of the present application.
FIG. 3 shows a PXRD spectrum of a heat treated SSZ-74 molecular sieve according to example 3 of the present application.
FIG. 4 shows a PXRD spectrum of a heat treated SSZ-74 molecular sieve according to example 4 of the present application.
FIG. 5 shows a gas breakthrough suction chart for benzene and cyclohexane obtained in example 5 of the present application using the SSZ-74 molecular sieve of example 1.
FIG. 6 shows a gas breakthrough suction chart for benzene and cyclohexane obtained in example 7 of the present application using the SSZ-74 molecular sieve of example 2.
FIG. 7 shows a graph of the gas breakthrough of benzene and cyclohexane obtained in example 8 of the present application using the SSZ-74 molecular sieve of example 3.
FIG. 8 shows a gas breakthrough suction chart for benzene and cyclohexane obtained in example 9 of the present application using the SSZ-74 molecular sieve of example 4.
FIG. 9 shows a gas breakthrough suction chart of benzene and cyclohexane obtained after 1 regeneration of the SSZ-74 molecular sieve of example 6 in example 10 according to the application.
FIG. 10 shows a gas breakthrough suction chart of benzene and cyclohexane obtained after 20 regenerations using the SSZ-74 molecular sieve of example 5 in example 11 of the present application.
Detailed Description
Further advantages and effects of the present application will become apparent to those skilled in the art from the disclosure of the present application, which is described by the following specific examples.
Before the embodiments of the application are explained in further detail, it is to be understood that the application is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the application is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the application. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present application may be used to practice the present application according to the knowledge of one skilled in the art and the description of the present application.
The inventor discovers through long-term experimental study that the SSZ-74 molecular sieve can realize the efficient separation of benzene and cyclohexane. Compared with the porous separation material disclosed before, the SSZ-74 molecular sieve used by the application has the advantages of lower preparation cost, better stability, simple preparation and suitability for industrial production.
In the application, PXRD data are measured by a German Brookfield D8 advanced type X-ray diffractometer and are used for representing the crystal structure of the molecular sieve; the gas breakthrough curve was obtained from the Bei Shide instrument BSD-MAB multicomponent competitive adsorption breakthrough curve analyzer test and was used to characterize the gas separation performance.
The technical scheme of the application is further described below through specific examples.
In the following examples of the present application, the structural formula of the employed hexamethylene-1, 6-bis (dimethylethylammonium hydroxide) is as follows:
example 1
In this example 1, SSZ-74 molecular sieve raw powder with a silicon to aluminum ratio of 100 was used as a raw material, and heat treatment was performed, comprising the steps of:
roasting SSZ-74 molecular sieve raw powder for 4 hours at 550 ℃, and then vacuum heating and degassing for 2 hours at 200 ℃ to obtain the SSZ-74 molecular sieve.
The preparation method of the SSZ-74 molecular sieve raw powder with the silicon-aluminum ratio of 100 comprises the following steps:
1) With silica sol (40 wt% SiO) 2 ) Sodium metaaluminate, sodium hydroxide solid powder and hexamethylene-1, 6-bis (dimethylethyl ammonium hydroxide) are respectively a silicon source, an aluminum source, a mineralizer and a template agent (template agent is named as R) and are mixed, and stirred at room temperature overnight to obtain a gel mixture. Wherein SiO is obtained by converting the mass of a silicon source into the mole number of silicon element 2 Molar number of (3); al is obtained by converting the mass of an aluminum source into the mole number of Al element 2 O 3 Molar number of (3); silicon source, aluminum source, mineralizer, template agent and water (SiO 2 ：Al 2 O 3 ：NaOH：R：H 2 O=1.0: 0.005:0.15:0.4:40 Molar ratio of 1.0): 0.005:0.15:0.4:40.
2) And then transferring the mixture into a reaction kettle for crystallization for 168 hours at 160 ℃ and the rotating speed of 30rpm, cooling, filtering and washing the crystallized product after the crystallization is finished, and drying the product at 80 ℃ to obtain the SSZ-74 molecular sieve raw powder.
The SSZ-74 molecular sieve after the heat treatment is subjected to PXRD characterization, and the result is shown in figure 1.
As can be seen from FIG. 1, the PXRD characterization result shows that the SSZ-74 molecular sieve obtained under the roasting condition and the heating treatment condition has a characteristic diffraction peak of the molecular sieve with a-SVR structure, is a pure-SVR molecular sieve, and the micropore size of the crystal is distributed between 0.3 and 0.5nm.
In summary, it has been demonstrated that high crystallinity of SSZ-74 molecular sieves can be maintained by the activation process of the present application.
Example 2
In this example 2, the SSZ-74 molecular sieve raw powder having a silica-alumina ratio of 100 obtained in example 1 was used as a raw material, and after baking, a heat treatment was performed, comprising the steps of:
roasting SSZ-74 molecular sieve raw powder for 5 hours at 600 ℃, and vacuum heating and degassing for 2 hours at 400 ℃ to obtain the SSZ-74 molecular sieve.
The heat-treated SSZ-74 molecular sieve was subjected to PXRD characterization, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the result of the PXRD characterization shows that the SSZ-74 molecular sieve obtained under the roasting condition and the heating treatment condition has a characteristic diffraction peak of the molecular sieve with the-SVR structure, but has lower peak intensity, and is a pure molecular sieve with the-SVR structure, but has poorer crystallinity, wherein the micropore size of the SSZ-74 molecular sieve is distributed between 0.3 and 0.5nm.
Taken together, it has been demonstrated that the crystal structure of the SSZ-74 molecular sieve can be maintained by the activation process of the present application.
Example 3
In this example 3, all-silicon SSZ-74 molecular sieve raw powder is used as a raw material, and after roasting, the raw material is subjected to heat treatment, which comprises the following steps:
roasting the raw powder of the all-silicon SSZ-74 molecular sieve at 550 ℃ for 4 hours, and vacuum heating and degassing at 200 ℃ for 2 hours to obtain the SSZ-74 molecular sieve.
The preparation of the all-silicon SSZ-74 molecular sieve raw powder is as follows:
1) Respectively with silica sol (40 wt% SiO) 2 ) The solid sodium hydroxide powder and hexamethylenebis (dimethylethylammonium hydroxide) were used as the silicon source, mineralizer and templating agent (templating agent designated R) and mixed and stirred overnight at room temperature to give a gel mixture. Wherein SiO is obtained by converting the mass of a silicon source into the mole number of silicon element 2 Molar number of (3); silicon source, mineralizer, template agent and water (SiO 2 ：NaOH：R：H 2 O=1.0: 0.1:0.4:40 Molar ratio of 1.0): 0.1:0.4:40.
2) Transferring the gel mixture obtained in the step 1) into a reaction kettle, crystallizing for 168 hours at 160 ℃ and the rotating speed of 30rpm, and after crystallization, cooling, filtering, washing and drying the crystallized product at 80 ℃ to obtain the SSZ-74 molecular sieve.
The PXRD characterization of the heat-treated all-silicon SSZ-74 molecular sieve is carried out, and the result is shown in FIG. 4.
As can be seen from FIG. 3, the result of PXRD characterization shows that the SSZ-74 molecular sieve obtained under the roasting condition and the heating treatment condition has a characteristic diffraction peak of the molecular sieve with the SVR structure, is a pure molecular sieve with the SVR structure, and the micropore size of the crystal is distributed between 0.3 and 0.5nm.
In summary, it has been demonstrated that high crystallinity of SSZ-74 molecular sieves can be maintained by the activation process of the present application.
Example 4
In this example 4, SSZ-74 molecular sieve raw powder with a silica-alumina ratio of 30 was used as a raw material, and after calcination, a heat treatment was performed, comprising the steps of:
roasting SSZ-74 molecular sieve raw powder for 4 hours at 550 ℃, and vacuum heating and degassing for 2 hours at 200 ℃ to obtain the SSZ-74 molecular sieve.
The preparation method of the SSZ-74 molecular sieve raw powder with the silicon-aluminum ratio of 30 comprises the following steps:
1) Respectively with silica sol (40 wt% SiO) 2 ) Mixing sodium metaaluminate, sodium hydroxide solid powder and hexamethylene-1, 6-bis (dimethyl ethyl ammonium hydroxide) serving as a silicon source, an aluminum source, a mineralizer and a template agent (the template agent is named as R), and stirring at room temperature for overnight to obtain a gel mixture. Wherein SiO is obtained by converting the mass of a silicon source into the mole number of silicon element 2 Molar number of (3); al is obtained by converting the mass of an aluminum source into the mole number of Al element 2 O 3 Molar number of (3); silicon source, aluminum source, mineralizer, template agent and water (SiO 2 ：Al 2 O 3 ：NaOH：R：H 2 O=1.0: 0.017:0.15:0.4:40 Molar ratio of 1.0): 0.017:0.15:0.4:40.
2) Adding SSZ-74 molecular sieve seed crystal, transferring to a reaction kettle, crystallizing at 160 ℃ and rotating speed of 30rpm for 168 hours, cooling, filtering, washing and drying at 80 ℃ to obtain SSZ-74 molecular sieve raw powder. Wherein SSZ-74 molecular sieve seeds are the product of example 3, and the added amount of the seeds is 10% of the solid content of the gel mixture based on the solid content of the gel mixture.
The SSZ-74 molecular sieve after the heat treatment is subjected to PXRD characterization, and the result is shown in FIG. 3.
As can be seen from FIG. 4, the result of PXRD characterization shows that the SSZ-74 molecular sieve obtained under the roasting condition and the heating treatment condition has a characteristic diffraction peak of the molecular sieve with the SVR structure, is a pure molecular sieve with the SVR structure, and the micropore size of the crystal is distributed between 0.3 and 0.5nm.
In summary, it has been demonstrated that high crystallinity of SSZ-74 molecular sieves can be maintained by the activation process of the present application.
Example 5
In this example 5, titanium silicalite SSZ-74 molecular sieve was used as a raw material, and heat treatment was performed after calcination, comprising the steps of:
and (3) pickling titanium silicon SSZ-74 molecular sieve raw powder, supplementing silicon, roasting at 550 ℃ for 4 hours, and vacuum heating and degassing at 200 ℃ for 2 hours to obtain the SSZ-74 molecular sieve. The acid washing and silicon supplementing steps are as follows: 1g of SSZ-74 molecular sieve raw powder is mixed with 0.1g of tetraethyl orthosilicate and 10g of 1M aqueous nitric acid solution and then subjected to hydrothermal treatment at 175 ℃ for 12h.
The SSZ-74 molecular sieve raw powder with the silicon-titanium ratio of 100 is prepared as follows:
1) Silica sol (40 wt% SiO) 2 ) Tetrabutyl titanate, sodium hydroxide solid powder and hexamethylene-1, 6-bis (dimethyl ethyl ammonium hydroxide) are used as a silicon source, a titanium source, a mineralizer and a template agent to be mixed, and the mixture is stirred at room temperature for overnight to obtain a gel mixture. Wherein SiO is obtained by converting the mass of a silicon source into the mole number of silicon element 2 Molar number of (3); the mass of the titanium source is converted into TiO according to the mole number of titanium element 2 Molar number of (3); silicon source, titanium source, mineralizer, template agent and water (SiO 2 ：TiO 2 ：NaOH：R：H 2 O=1.0: 0.01:0.1:0.4:40 Molar ratio of 1.0): 0.01:0.1:0.4:40.
2) Transferring the gel mixture obtained in the step 1) into a reaction kettle, crystallizing for 168 hours at 160 ℃ and the rotating speed of 30rpm, and after crystallization, cooling, filtering, washing and drying the crystallized product at 80 ℃ to obtain the titanium silicon SSZ-74 molecular sieve.
Example 6
In this example 6, the heat-treated SSZ-74 molecular sieve of example 1 was used as an adsorption separation material, and performance test was performed using a multicomponent competitive adsorption breakthrough curve analyzer.
The test conditions were: the volume ratio of Benzene (Benzene) to cyclohexane (Cylcohexane) in the mixed gas is 50:50, the negative carrier gas is helium, the flow rates of Benzene and cyclohexane are 1sccm, the flow rate of helium is 48sccm, the flow rate of total test is 50sccm, and the temperature of separation test is 25 ℃.
SSZ-74 molecular sieves are arranged in a penetrating column of the multicomponent competitive adsorption penetrating curve analyzer, mixed gas flows in through an inlet of the analyzer, is adsorbed by the SSZ-74 molecular sieves, flows out from an outlet of the analyzer, and the penetrating time of benzene and cyclohexane, the selective adsorption quantity of the SSZ-74 molecular sieves on each component of the mixed gas and the like are measured by measuring the change of the concentration of benzene and cyclohexane in the gas at the outlet along with time.
The breakthrough curve analysis is a technology for analyzing material adsorption separation under dynamic flow condition, and the principle is that molecular sieves are loaded in a breakthrough column as adsorption separation materials, the adsorption separation materials are piled up into a bed layer with a certain height, the bed layer is static, mixed gas flows in through an inlet of an absorber, is adsorbed by the molecular sieves and flows out from an outlet, and the breakthrough time of components except carrier gas and the selective adsorption quantity of the molecular sieves on the components of the mixed gas are measured by measuring the concentration change of the components of the outlet gas along with time, namely, the breakthrough curve. Multicomponent competitive adsorption breakthrough curve analyzer breakthrough adsorption curve is the curve of the concentration of benzene and cyclohexane in the effluent gas over time as the gas stream passes through the molecular sieve.
A breakthrough suction plot of SSZ-74 molecular sieves was obtained and the results are shown in FIG. 5. The abscissa in the graph is the ratio t/g of time to adsorption mass, and the ordinate is C/C0 at time t (i.e., the ratio of the outlet concentration C to the inlet concentration C0, i.e., the relative concentration). The corresponding point of the breakthrough curve when the effluent concentration C reaches 5% of the initial concentration C0 as the adsorbate emerges from the molecular sieve within the breakthrough column is then referred to as the breakthrough point (breakthrough point).
From FIG. 5, it is seen that in the breakthrough adsorption separation, the breakthrough point of benzene occurs with a lag of at least 15min/g compared to cyclohexane, which demonstrates that it can achieve efficient separation of benzene and cyclohexane.
Example 7
In this example 7, the heat-treated SSZ-74 molecular sieve of example 2 was used as an adsorption separation material, and performance test was performed using a multicomponent competitive adsorption breakthrough curve analyzer.
The test conditions were: the volume ratio of benzene to cyclohexane is 50:50, the negative carrier gas is helium, the flow rates of benzene and cyclohexane are 1sccm, the flow rate of helium is 48sccm, the flow rate of total test is 50sccm, and the temperature of separation test is 25 ℃.
A breakthrough suction plot of SSZ-74 molecular sieves was obtained and the results are shown in FIG. 6.
As can be seen from FIG. 6, in the breakthrough adsorption separation, the occurrence time of benzene breakthrough was delayed by about 9min/g compared to cyclohexane, indicating that the separation performance was low if the crystallinity was deviated after the pretreatment.
Example 8
In this example 8, the heat-treated SSZ-74 molecular sieve of example 3 was used as an adsorption separation material, and performance test was performed using a multicomponent competitive adsorption breakthrough curve analyzer.
The test conditions were: the volume ratio of benzene to cyclohexane is 50:50, the negative carrier gas is helium, the flow rates of benzene and cyclohexane are 1sccm, the flow rate of helium is 48sccm, the flow rate of total test is 50sccm, and the temperature of separation test is 25 ℃.
The SSZ-74 molecular sieves obtained are shown in FIG. 7 as a breakthrough suction chart.
From FIG. 7, it is evident that in the breakthrough adsorption separation, the benzene breakthrough occurs with a lag of at least 15min/g compared to cyclohexane, demonstrating that it can achieve a high efficiency of separation.
Example 9
In this example 9, the heat-treated SSZ-74 molecular sieve of example 4 was used as an adsorption separation material, and performance test was performed using a multicomponent competitive adsorption breakthrough curve analyzer.
The test conditions were: the volume ratio of benzene to cyclohexane in the mixed gas is 50:50, the negative carrier gas is helium, the flow rates of the benzene and the cyclohexane are 1sccm, the flow rate of the helium is 48sccm, the total test flow rate is 50sccm, and the temperature of the separation test is 25 ℃.
The SSZ-74 molecular sieves obtained are shown in the pierced drawings and the results are shown in FIG. 8.
From FIG. 8, it is evident that in the breakthrough adsorption separation, the benzene breakthrough occurs with a lag of at least 15min/g compared to cyclohexane, demonstrating that it can achieve a high efficiency of separation.
Example 10
In this example 10, SSZ-74 molecular sieves after adsorption separation of benzene and cyclohexane in example 6 were used as adsorption separation materials, regeneration was completed after heating at 400℃for 4 hours under air conditions, and performance test was performed using a multicomponent competitive adsorption breakthrough curve analyzer.
The test conditions were: the volume ratio of benzene to cyclohexane in the mixed gas is 50:50, the negative carrier gas is helium, the flow rates of the benzene and the cyclohexane are 1sccm, the flow rate of the helium is 48sccm, the flow rate of the total test is 50sccm, and the temperature of the separation test is 25 ℃.
The SSZ-74 molecular sieves obtained are shown in the pierced drawings and the results are shown in FIG. 9.
From FIG. 9, it is evident that in the breakthrough adsorption separation, the benzene breakthrough occurs at a time lag of about 15min/g compared to cyclohexane, demonstrating that it can achieve a high efficiency separation after 2 regenerations.
Example 11
In this example 11, the SSZ-74 molecular sieve obtained by adsorptive separation of benzene and cyclohexane in example 5 was used as an adsorptive separation material, and after heating at 400℃for 4 hours under air conditions, regeneration was completed, and after repeating the regeneration-adsorption-regeneration 19 times, performance test was performed using a gas adsorption penetrator.
The test conditions were: the volume ratio of benzene to cyclohexane in the mixed gas is 50:50, the negative carrier gas is helium, the flow rates of the benzene and the cyclohexane are 1sccm, the flow rate of the helium is 48sccm, the flow rate of the total test is 50sccm, and the temperature of the separation test is 25 ℃.
The SSZ-74 molecular sieves obtained are shown in the pierced drawings and the results are shown in FIG. 10.
From FIG. 10, it is evident that in the breakthrough adsorption separation, the benzene breakthrough occurs at a time delay of approximately 15min/g compared to cyclohexane, demonstrating that it can still achieve a high efficiency separation after regeneration 20.
Example 12
The point of difference between this embodiment 12 and embodiment 6 is that: the volume ratio of benzene to cyclohexane in the mixed gas is 10:50, the negative carrier gas is helium, the flow rates of benzene and cyclohexane are 1sccm and 5sccm, the flow rate of helium is 44sccm, the flow rate of the total test is 50sccm, and the temperature of the separation test is 25 ℃.
In the breakthrough adsorptive separation, the breakthrough point for benzene occurs at a time delay of approximately 15min/g compared to cyclohexane.
According to the application, LTA (4A) molecular sieves, BEA (Beta) molecular sieves, FER (ZSM-35) molecular sieves and TON (ZSM-22) molecular sieves are respectively obtained from commercial channels, and the performance test is carried out by adopting a gas adsorption penetrometer under the same conditions as in example 6, so that the hysteresis of the penetration point of benzene compared with the penetration point of cyclohexane is found to be 13s/g, 18.7s/g, 39.6s/g and 3.14min/g, which are far lower than 15min/g of the application, and the benzene and the cyclohexane cannot be separated, and the regeneration times of other molecular sieves are lower than the application.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
- Use of ssz-74 molecular sieves in the adsorptive separation of benzene and cyclohexane.
- 2. The use according to claim 1, wherein the SSZ-74 molecular sieve is selected from an all-silicon SSZ-74 molecular sieve or a heteroatom-doped SSZ-74 molecular sieve;and/or the SSZ-74 molecular sieve is obtained by heating SSZ-74 molecular sieve raw powder.
- 3. The use according to claim 2, wherein the heteroatoms are selected from one or more of aluminum, titanium, boron and gallium;and/or roasting before the heating treatment to remove the template agent in the SSZ-74 molecular sieve raw powder;and/or the temperature of the heating treatment is 30-450 ℃;and/or the heating treatment time is 0.1-24 h;and/or the atmosphere of the heating treatment is selected from one or more of vacuum, air, nitrogen, helium and argon.
- 4. The use according to claim 3, wherein the SSZ-74 molecular sieve has a silicon to heteroatom ratio of not less than 20, based on the molar ratio of silicon dioxide to heteroatom oxide; preferably, 20 to 200;and/or, the roasting temperature is 200-800 ℃;and/or the roasting time is 3-5 h;and/or, the method further comprises acid washing and silicon supplementing before roasting.
- 5. The use according to claim 2, wherein the SSZ-74 molecular sieve raw powder is prepared by the following steps: 1) The silicon source, the template agent and the mineralizer react in the water solution to obtain a gel mixture; 2) Crystallizing the gel mixture to obtain the SSZ-74 molecular sieve raw powder.
- 6. The use according to claim 5, wherein in 1) the templating agent is selected from one of hexamethylene-1, 6-bis (N-methylpyrrolidinium) divalent cations, hexamethylene-1-trimethylammonium-6-N-methylpyrrolidinium divalent cations, hexamethylene-1, 6-bis (dimethylethyl) divalent cations;and/or 1), the reaction further comprises adding a heteroatom source;and/or, 1) wherein the mineralizer is selected from an alkali metal source or a fluorine source;preferably, the alkali metal source is selected from one or more of sodium hydroxide, potassium hydroxide and cesium hydroxide;preferably, the fluorine source is selected from one or both of hydrofluoric acid and ammonium fluoride.
- 7. A method for adsorption separation of benzene and cyclohexane is characterized in that SSZ-74 molecular sieve is adopted to adsorb and separate the mixed gas of benzene and cyclohexane.
- 8. The adsorption separation method according to claim 7, wherein the temperature of the adsorption separation is 20 to 100 ℃;and/or the volume ratio of benzene to cyclohexane is (1-99): 1-99;and/or, the conditions of the adsorption separation are: the flow rate of the mixed gas is 0.1-100 sccm;and/or the SSZ-74 molecular sieve is selected from an all-silicon SSZ-74 molecular sieve or a heteroatom-doped SSZ-74 molecular sieve;and/or the SSZ-74 molecular sieve is obtained by heating SSZ-74 molecular sieve raw powder.
- 9. The adsorptive separation process of claim 8, further comprising a negative carrier gas selected from one or more of nitrogen, helium, argon and air;and/or the heteroatom is selected from one or more of aluminum, titanium, boron and gallium;and/or roasting before the heating treatment to remove the template agent in the SSZ-74 molecular sieve raw powder;and/or the temperature of the heating treatment is 30-450 ℃;and/or the heating treatment time is 0.1-24 h;and/or the atmosphere of the heating treatment is selected from one or more of vacuum, air, nitrogen, helium and argon;and/or the preparation method of the SSZ-74 molecular sieve raw powder comprises the following steps: 1) The silicon source, the template agent and the mineralizer react in the water solution to obtain a gel mixture; 2) Crystallizing the gel mixture to obtain the SSZ-74 molecular sieve raw powder.
- 10. The adsorptive separation process of claim 9 wherein the benzene, cyclohexane and negative carrier gas flow ratio is 1: (0.5-5): (30-60);and/or, the ratio of silicon to heteroatoms in the SSZ-74 molecular sieve is not less than 20, based on the molar ratio of silicon dioxide to heteroatom oxide; preferably, 20 to 200;and/or, the roasting temperature is 200-800 ℃;and/or the roasting time is 3-5 h.
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