CN110314643A - A kind of preparation and application of the modified mesopore oxide material of high stability monovalence copper - Google Patents
A kind of preparation and application of the modified mesopore oxide material of high stability monovalence copper Download PDFInfo
- Publication number
- CN110314643A CN110314643A CN201910641476.6A CN201910641476A CN110314643A CN 110314643 A CN110314643 A CN 110314643A CN 201910641476 A CN201910641476 A CN 201910641476A CN 110314643 A CN110314643 A CN 110314643A
- Authority
- CN
- China
- Prior art keywords
- monovalence copper
- mesopore oxide
- hydrophobic coating
- modified mesopore
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 104
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 11
- 230000023556 desulfurization Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 11
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003502 gasoline Substances 0.000 claims description 10
- 230000000977 initiatory effect Effects 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- -1 Kynoar Polymers 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229940112669 cuprous oxide Drugs 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- BLZKSRBAQDZAIX-UHFFFAOYSA-N 2-methyl-1-benzothiophene Chemical group C1=CC=C2SC(C)=CC2=C1 BLZKSRBAQDZAIX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- XPDGHGYGTJOTBC-UHFFFAOYSA-N methoxy(methyl)silicon Chemical compound CO[Si]C XPDGHGYGTJOTBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 claims description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005052 trichlorosilane Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- JOKFPWMFEHHZTN-UHFFFAOYSA-N trifluoro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](F)(F)F JOKFPWMFEHHZTN-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- DHIVLKMGKIZOHF-UHFFFAOYSA-N 1-fluorooctane Chemical compound CCCCCCCCF DHIVLKMGKIZOHF-UHFFFAOYSA-N 0.000 claims 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims 1
- JZLCKKKUCNYLDU-UHFFFAOYSA-N decylsilane Chemical compound CCCCCCCCCC[SiH3] JZLCKKKUCNYLDU-UHFFFAOYSA-N 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparations and application of a kind of modified mesopore oxide material of high stability monovalence copper, including a kind of modified mesopore oxide material of high stability monovalence copper comprising, hydrophobic coating and the modified mesopore oxide of monovalence copper；Wherein, the hydrophobic coating and the modified mesopore oxide mass ratio of the monovalence copper are (0.02~0.5): 1；And a kind of preparation method of the modified mesopore oxide material of monovalence copper, for hydrophobic coating is coated to the modified mesopore oxide surface of monovalence copper.The stability and moisture resistance of the modified mesopore oxide material of the high stability monovalence copper are high, can be in the application in the recycling of the desulfurization of fuel oil, alkene-alkane separation and carbon monoxide.
Description
Technical field
The invention belongs to technical field of chemical separation, and in particular to a kind of modified mesopore oxide material of high stability monovalence copper
The preparation and application of material.
Background technique
Mercaptan, thioether, oxysulfide and thiophene-type sulfide contained in fuel oil (gasoline, diesel oil and kerosene etc.) be
Lead to one of the principal element of environmental pollution.These sulfur compounds can generate toxic oxysulfide with the burning of fuel oil,
Air is polluted, acid rain, corrosion building, very harmful, requirement of the countries in the world to fuel oil quality can also be further generated
It is higher and higher, therefore the deep desulfuration of fuel oil has become an important and in the urgent need to address problem.Alkene and alkane
Separation is always the key project in chemical industry, wherein with C2H4/C2H6And C3H6/C3H8Separation it is most representative.Alkene and
Alkane, which has very similar molecular structure and results in them, has extremely close molecular dimension and relative volatility, uses one
As method be difficult to realize separation alkene and alkane purpose.Carbon monoxide is a kind of colourless, tasteless and the virose gas of tool,
Simultaneously it is also one of most important raw material in chemical industry, has been widely used in chemical manufacturing industry.Carbon monoxide has rich
Rich source can obtain an oxidation abundant from channels such as the imperfect combustions of steam reformation, the tail gas of steel plant and hydrocarbon
Carbon gas, these gases usually can all contain H2、CH4And N2Equal impurity, therefore, it is necessary to separate and refine from these gaseous mixtures
Carbon monoxide out.
Operating condition needed for adsorption process is mild, it is excellent to require the technique of equipment general and adsorbent to can be recycled etc.
Gesture, so that adsorption process is in field of industrialized production by favor.In adsorptive separation processes, the structure of adsorbent itself
Property is to influence the key factor of adsorption separation performance.Due to the π complexing power formed between monovalence copper and unsaturated bond, this
Kind active force is better than Van der Waals force simultaneously and is weaker than chemical interactions, and thus the modified mesopore oxide material of monovalence copper is as π network
It closes adsorbent and shows superior adsorptivity in terms of fuel oil deep desulfuration, alkene-alkane separation and carbon monoxide purification application
Energy and regenerability.However the modified mesopore oxide material of Cu (I) but has a critical defect, i.e. Cu (I) stability is poor, limits it
Practical application.Even if Cu (I) active site in the modified mesopore oxide material of Cu (I) is also extremely unstable in normal environment
It is fixed, the preparation, storage and application of Cu (I) modified mesopore oxide material have been seriously affected this is because Cu (I) is in steam and sky
It is easily oxidized to Cu (II) under the collective effect of gas, loses π complexing power, loses adsorption activity.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of above-mentioned technological deficiency, the present invention is proposed.
Therefore, as one aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides a kind of high
The preparation and application of the modified mesopore oxide material of stability monovalence copper.
In order to solve the above technical problems, the present invention provides the following technical scheme that a kind of modified Jie of high stability monovalence copper
Orifice oxide material comprising, hydrophobic coating and the modified mesopore oxide of monovalence copper；Wherein, the hydrophobic coating and described one
The mass ratio of the modified mesopore oxide of valence copper is (0.02~0.5): 1.
Preferred embodiment as the modified mesopore oxide material of high stability monovalence copper of the present invention, in which: described
Hydrophobic coating includes dimethyl silicone polymer, methylmethoxysilane, hexamethyldisilazane, trim,ethylchlorosilane, three ethoxies
Base perfluoro decyl silane, octyltrichlorosilane, n-octytriethoxysilane, perfluorooctane base trichlorosilane, Kynoar,
The one or more of polystyrene, polydivinylbenezene, polyvinyl alcohol or polyvinyl chloride；The modified mesopore oxide of the monovalence copper
Including the one or more through the modified mesopore oxide of stannous chloride and/or cuprous oxide, wherein the mesopore oxide packet
Include mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO；Wherein, the mesoporous SiO2
Including one or more of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU.
As one aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides a kind of high stable
Property the modified mesopore oxide material of monovalence copper preparation method comprising: hydrophobic coating is coated to the modified mesoporous oxygen of monovalence copper
Compound surface.
The preferred embodiment of preparation method as the modified mesopore oxide material of high stability monovalence copper of the present invention,
Wherein: the coating includes by one or more of vapor deposition step, spray drying step and initiation polymerization procedure；Its
In, the vapor deposition step, for hydrophobic coating and the modified mesopore oxide of monovalence copper to be spaced apart, hermetically drying is taken out
Vacuum, it is cooling after heating reaction；The spray drying step, for the modified mesopore oxide suspension of preparation monovalence copper, preparation
Hydrophobic coating solution mixes the modified mesopore oxide suspension of the monovalence copper and the hydrophobic coating solution, spray drying,
It is dried in vacuo after washing；It is modified that monovalence copper is added to dissolve hydrophobic coating monomer, initiator in the initiation polymerization procedure
Mesopore oxide, reaction are dried under reduced pressure rear solvent washing, then are dried in vacuo.
The preferred embodiment of preparation method as the modified mesopore oxide material of high stability monovalence copper of the present invention,
Wherein: the vapor deposition step, the heating reaction react 10~300min to be heated to the hydrophobic coating gasification；
It is described to be cooled to be cooled to room temperature；The spray drying is that inlet amount is 4.5mL/min and inert gas temperature is 150 DEG C of flow velocitys
To be spray-dried under the conditions of 336mL/min；The initiation polymerization procedure, the modified mesopore oxide of the addition monovalence copper, instead
It answers, to react 10~600min under the conditions of 50~120 DEG C.
The preferred embodiment of preparation method as the modified mesopore oxide material of high stability monovalence copper of the present invention,
Wherein: the mass ratio of the modified mesopore oxide of the vapor deposition step, the hydrophobic coating and the monovalence copper is greater than etc.
In 10:1；The spray drying step, the modified mesopore oxide suspension of the monovalence copper and the hydrophobic coating solution
Volume ratio is 5:1, and the mass fraction of the modified mesopore oxide of monovalence copper is 2 in the modified mesopore oxide suspension of the monovalence copper
~20mg/mL, the mass concentration of hydrophobic coating is 2~40mg/mL in the hydrophobic coating solution；The initiation polymerization procedure,
The mass ratio of the modified mesopore oxide of its described hydrophobic coating monomer, the initiator and the monovalence copper is 10:5:1.
The preferred embodiment of preparation method as the modified mesopore oxide material of high stability monovalence copper of the present invention,
Wherein: the vapor deposition step, the hydrophobic coating include dimethyl silicone polymer, methylmethoxysilane, hexamethyl
Disilazane, trim,ethylchlorosilane, triethoxy perfluoro decyl silane, octyltrichlorosilane, n-octytriethoxysilane or
The one or more of perfluorooctane base trichlorosilane, the monovalence copper-clad include the one or more of stannous chloride and cuprous oxide,
The mesopore oxide includes mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO,
Wherein, the mesoporous SiO2Including one or more of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU；Institute
Spray drying step is stated, the hydrophobic coating includes dimethyl silicone polymer, Kynoar, polystyrene, methyl methoxy
The one or more of base silane, polyvinyl alcohol or polyvinyl chloride, the monovalence copper-clad include one kind of stannous chloride and cuprous oxide
Or it is several, the mesopore oxide includes mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or one kind of MgO
It is or several, wherein the mesoporous SiO2Including one of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU or
Several, the modified mesopore oxide suspension of the preparation monovalence copper, solvent is n,N-Dimethylformamide, tetrahydrofuran or two
One or more of chloromethanes, described to prepare hydrophobic coating solution, solvent is tetrahydrofuran or methylene chloride, described to wash
It washs, to be washed with tetrahydrofuran or methylene chloride；The initiation polymerization procedure, the hydrophobic coating monomer include styrene or
The one or more of divinylbenzene, the monovalence copper-clad includes the one or more of stannous chloride and cuprous oxide, described mesoporous
Oxide includes mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO, wherein described
Mesoporous SiO2Including one or more of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU, the initiator
One or more including azodiisobutyronitrile or dibenzoyl peroxide.
As one aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides a kind of high stable
Property the modified mesopore oxide of monovalence copper application comprising application, the application in alkene-alkane separation in gasoline desulfurization
Or the one or more of the application in carbon monoxide absorption.
The preferred embodiment of application as the modified mesopore oxide material of high stability monovalence copper of the present invention,
In: the gasoline be thiophene, benzothiophene, 2- methyl benzothiophene or 4, the one of 6- dimethyl Dibenzothiophene sulfide gasoline
Kind is several；The alkene is one or more of ethylene, propylene or butylene；The alkane is methane, ethane, propane or fourth
The one or more of alkane；The carbon monoxide absorption, to be adsorbed from Co mixed gas；Wherein, an oxidation
Carbon mixed gas include carbon monoxide and carbon dioxide, nitrogen, oxygen, methane, hydrogen, nitric oxide, nitrogen dioxide, ethane,
One or more of propane or butane.
The preferred embodiment of application as the modified mesopore oxide material of high stability monovalence copper of the present invention,
In: the application in gasoline desulfurization, to contact under the conditions of temperature is 20~50 DEG C, pressure is 0.1~0.5MPa；
It is described in alkene-alkane separation and/or it is described carbon monoxide absorption in application, for temperature be 0~70 DEG C, pressure 0
Under the conditions of~30MPa, contact.
Beneficial effects of the present invention:
The present invention forms one layer of uniform coating in monovalence copper porous material surface using hydrophobic coating, and method is simple, can
The moisture resistance for significantly improving the modified mesopore oxide of monovalence copper, to significantly improve cupprous stability.The present invention is by institute
The modified mesopore oxide material of the high stability monovalence copper of synthesis is directly used in the absorption desulfurization, the separation of alkene alkane of fuel oil
Big with the adsorption capacity of the recycling of carbon monoxide, the adsorbent, selectivity is high, and adsorption separation efficiency is high, preferable stability
Make it that still there is good absorption property in the environment containing certain moisture with moisture resistance.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein:
Fig. 1 is the stability test result of the modified mesopore oxide of high stability monovalence copper prepared by embodiment 1.
Fig. 2 is the contact angle test result of the modified mesopore oxide of high stability monovalence copper prepared by embodiment 1.
Fig. 3 is the electromicroscopic photograph of the modified mesopore oxide of high stability monovalence copper prepared by embodiment 1, wherein A is not have
Introduce the Cu of hydrophobic coating2O@SBA-15, B are the Cu for introducing hydrophobic coating2The material prepared in O@SBA-15, that is, example 1.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Embodiment 1:
Weigh 0.05gCu2O@SBA-15 powder is paved in vial, and 0.5g dimethyl silicone polymer is around put, and is protected
Both cards do not contact, and sealing is put into 235 DEG C of reaction 60min after vacuumizing, and high stability one can be obtained in cooled to room temperature
Valence copper is modified mesopore oxide adsorbent, and the deposition of dimethyl silicone polymer is 16.4wt%, and after tested, contact angle is
158 °, there is super-hydrophobicity.
In experiment, guarantee Cu2O@SBA-15 powder is not contacted with dimethyl silicone polymer, under high temperature and vacuum condition,
Dimethyl silicone polymer vapor deposition is directly right in mesopore oxide surface aggregate in mesopore oxide surface or hydrophobic coating
Mesopore oxide is wrapped afterwards, to form uniform hydrophobic coating；If the two is contacted, polydimethylsiloxanes
Alkane does not become vapor deposition on mesopore oxide surface, but if physical mixed, and the dosage of dimethyl silicone polymer can increase
Add, it so instead can be due to measuring hole that is too many and blocking mesopore oxide.
According to table 1, the modified mesopore oxide of monovalence copper is weighed, paves in vial, places into hydrophobic coating, guarantee two
Person does not contact, and sealing is reacted after vacuumizing, cooled to room temperature, the modified mesopore oxide absorption of preparation high stability monovalence copper
Agent.
Table 1
When reaction temperature is too low, hydrophobic coating has no idea to gasify, so that it is coated on the surface of material, and reaction temperature mistake
Height, and will lead to excessive hydrophobic coating introducing and plug hole, seriously affect its absorption property.Experimental data can from table
Out, testing sorbent material made from A1 and A2 is still water wetted material, without higher monovalence copper stability；Though testing A3 and A4
So being made has hydrophobic sorbent material, but since the hydrophobic coating of introducing is excessive, plugs the hole of material, cause
Its absorption property is very poor.
Embodiment 2:
According to table 2, suspension is made in the modified mesopore oxide dispersion of monovalence copper in a solvent, then hydrophobic coating is also divided
It dissipates in a solvent.It after the two is mixed, is spray-dried in inert gas, the sample of collection is washed using solvent, at 120 DEG C
The modified mesopore oxide material adsorbent of high stability monovalence copper can be obtained in vacuum drying.
Table 2
The mass concentration ratio of the modified mesopore oxide of monovalence copper and hydrophobic coating then determines the surface for being coated on material
The mass content of hydrophobic coating, when mass concentration ratio is excessive, then leading to adsorbent is still water wetted material, mass concentration ratio mistake
Hour will lead to excessive hydrophobic coating introducing again and plug hole, seriously affect absorption property.Experimental data can from table
Out, testing sorbent material made from B1 and B2 is still water wetted material, without higher monovalence copper stability；Though testing B3 and B4
So being made has hydrophobic sorbent material, but since the hydrophobic coating of introducing is excessive, plugs the hole of material, cause
Its absorption property is very poor.
Embodiment 3:
According to table 3, the modified mesopore oxide of monovalence copper, monomer and initiator are weighed, is added after solvent at a certain temperature
Sealing reaction, cooled to room temperature, the modified mesopore oxide adsorbent of preparation high stability monovalence copper.
Table 3
Embodiment 4:
The modified mesopore oxide adsorbent of the high stability monovalence copper of embodiment 1, embodiment 2 and example 3 preparation is carried out
Desulfurization and adsorbed gas experiment.
Desulfurization: using the desulfurization performance of dynamic adsorption method measurement adsorbent.Take the high stability of the drying of 0.1g
The modified mesopore oxide sample of univalent copper ion is placed in glass column, and the model of sulfur content 500ppm is passed through with the rate of 3mL/h
Oil adsorbs at normal temperature, and model content of sulfur in gasoline is analyzed after being adsorbed using Valley peace chromatography VARIANCP-3800.
Adsorbed gas experiment: the modified mesopore oxide sample of the high stability univalent copper ion for taking 0.05g dry is placed in
ASAP2020 is automatically analyzed on quick specific surface area and lacunarity analysis instrument.The pretreatment of sample is specially to set sample
150 DEG C of processing 6h under vacuum conditions in sealing bottle, are then down to room temperature, are filled with nitrogen to normal pressure.
As a result as follows:
Table 4
Monovalence copper has the effect of π Absorptive complex wave, and cupprous unoccupied orbital can have an effect with the lone pair electrons on adsorbate,
To adsorb.The hole of metal-organic framework materials prosperity is conducive to adsorb, and monovalence copper can with thiophene-type sulfide and not
Saturated bond is had an effect, so the adsorbing separation that monovalence copper modified metal organic framework material can be selective.
Note: being due to not detected at "-" in table.
Embodiment 5:
Stability test: the Cu of 0.1g is weighed21 material of O@SBA-15 and embodiment, is placed in an open container
It is interior be isolated with 5mL saturated sodium-chloride water solution be placed in closed reaction kettle, be placed in processing a period of time in 25 DEG C of baking ovens.Point
The other cupprous content in sample before and after the processing is tested.Content is if the monovalence copper in sample is not oxidized
100%, it is 0% if being oxidized completely.After 1 month, cupprous content is 100% in 1 material of embodiment, and Cu2O@
Cupprous content is 61% in SBA-15, illustrates that cupprous content remains unchanged substantially in 1 material of embodiment, the adsorbent
With outstanding monovalence copper stability.After 6 months, Cu2Cupprous content is essentially 0 in O@SBA-15, and monovalence in example 1
Copper content is 99%, illustrates that cupprous content remains unchanged substantially in 1 material of embodiment, which has outstanding monovalence
Copper stability.
Contain micro water in air, enables to monovalence copper to be oxidized, therefore Cu2O@SBA-15 stability is very poor.System
The modified mesopore oxide material of standby high stability monovalence copper by introducing hydrophobic coating, thus prevent minor amount of water in air into
Enter in the modified material hole of monovalence copper, be equivalent to have separated monovalence copper in this way and be in contact with moisture, changes that monovalence copper is modified to be situated between
The hydrophobicity of orifice oxide reaches by hindering steam and monovalence copper to act on and stablizes cupprous effect, improve univalent copper ion
Stability in wet environment.
The modified mesopore oxide material of high stability monovalence copper by absorption is kept at 80 DEG C in a nitrogen atmosphere
Complete regeneration can be realized in 30min.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (10)
1. a kind of modified mesopore oxide material of high stability monovalence copper, it is characterised in that: including,
Hydrophobic coating and the modified mesopore oxide of monovalence copper；
Wherein, the mass ratio of the hydrophobic coating and the modified mesopore oxide of the monovalence copper is (0.02~0.5): 1.
2. the modified mesopore oxide material of high stability monovalence copper as described in claim 1, it is characterised in that: the hydrophobic painting
Layer includes dimethyl silicone polymer, methylmethoxysilane, hexamethyldisilazane, trim,ethylchlorosilane, triethoxy perfluor
Decyl silane, octyltrichlorosilane, n-octytriethoxysilane, perfluorooctane base trichlorosilane, Kynoar, polyphenyl second
The one or more of alkene, polydivinylbenezene, polyvinyl alcohol or polyvinyl chloride；The modified mesopore oxide of the monovalence copper includes warp
The one or more for the mesopore oxide that stannous chloride and/or cuprous oxide are modified, wherein the mesopore oxide includes mesoporous
Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO；
Wherein, the mesoporous SiO2Including one of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU or several
Kind.
3. a kind of preparation method of the modified mesopore oxide material of high stability monovalence copper as claimed in claim 1 or 2, special
Sign is: hydrophobic coating is coated to the modified mesopore oxide surface of monovalence copper.
4. the preparation method of the modified mesopore oxide material of high stability monovalence copper as claimed in claim 3, it is characterised in that:
The coating includes by one or more of vapor deposition step, spray drying step and initiation polymerization procedure；
Wherein, the vapor deposition step, for hydrophobic coating and the modified mesopore oxide of monovalence copper to be spaced apart, sealing is dry
It is dry, it vacuumizes, it is cooling after heating reaction；
The spray drying step prepares hydrophobic coating solution, by institute for the modified mesopore oxide suspension of preparation monovalence copper
The modified mesopore oxide suspension of monovalence copper and hydrophobic coating solution mixing are stated, spray drying is dried in vacuo after washing；
The modified mesopore oxide of monovalence copper is added to dissolve hydrophobic coating monomer, initiator in the initiation polymerization procedure,
Reaction is dried under reduced pressure rear solvent washing, then is dried in vacuo.
5. the modified mesopore oxide material of high stability monovalence copper as claimed in claim 4, it is characterised in that: the gas phase is heavy
Product step, the heating reaction react 10~300min to be heated to the hydrophobic coating gasification；It is described to be cooled to be cooled to
Room temperature；The spray drying is that inlet amount is 4.5mL/min and inert gas temperature be 150 DEG C of flow velocitys is 336mL/min condition
Lower spray drying；The initiation polymerization procedure, the modified mesopore oxide of the addition monovalence copper, reaction, for 50~120
10~600min is reacted under the conditions of DEG C.
6. the preparation method of the modified mesopore oxide material of high stability monovalence copper as described in claim 4 or 5, feature exist
In: the mass ratio of the modified mesopore oxide of the vapor deposition step, the hydrophobic coating and the monovalence copper is more than or equal to
10:1；The spray drying step, the body of the monovalence copper modified mesopore oxide suspension and the hydrophobic coating solution
Product than being 5:1, in the modified mesopore oxide suspension of the monovalence copper mass fraction of the modified mesopore oxide of monovalence copper be 2~
20mg/mL, the mass concentration of hydrophobic coating is 2~40mg/mL in the hydrophobic coating solution；The initiation polymerization procedure,
The mass ratio of the modified mesopore oxide of the hydrophobic coating monomer, the initiator and the monovalence copper is 10:5:1.
7. the preparation method of the modified mesopore oxide material of high stability monovalence copper as described in claim 4 or 5, feature exist
In: the vapor deposition step, the hydrophobic coating include dimethyl silicone polymer, methylmethoxysilane, hexamethyl two
Silazane, trim,ethylchlorosilane, triethoxy perfluoro decyl silane, octyltrichlorosilane, n-octytriethoxysilane or complete
The one or more of fluoro-octane base trichlorosilane, the monovalence copper-clad include the one or more of stannous chloride and cuprous oxide, institute
Giving an account of orifice oxide includes mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO,
In, the mesoporous SiO2Including one or more of MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU；
The spray drying step, the hydrophobic coating include dimethyl silicone polymer, Kynoar, polystyrene, first
The one or more of methoxylsilane, polyvinyl alcohol or polyvinyl chloride, the monovalence copper-clad include stannous chloride and cuprous oxide
One or more, the mesopore oxide includes mesoporous Al2O3、SiO2、TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or MgO
One or more, wherein the mesoporous SiO2Including in MCM-48, MCM-41, SBA-1, SBA-15, HMS, MSU or FDU
One or more, the modified mesopore oxide suspension of the preparation monovalence copper, solvent is n,N-Dimethylformamide, tetrahydro furan
It mutters or one or more of methylene chloride, described to prepare hydrophobic coating solution, solvent is tetrahydrofuran or methylene chloride, institute
Washing is stated, to be washed with tetrahydrofuran or methylene chloride；
The initiation polymerization procedure, the hydrophobic coating monomer include the one or more of styrene or divinylbenzene, institute
The one or more that monovalence copper-clad includes stannous chloride and cuprous oxide are stated, the mesopore oxide includes mesoporous Al2O3、SiO2、
TiO2、ZrO2、CeO2、CaO、ZnO、MnO2Or the one or more of MgO, wherein the mesoporous SiO2Including MCM-48, MCM-
41, one or more of SBA-1, SBA-15, HMS, MSU or FDU, the initiator include azodiisobutyronitrile or peroxidating
The one or more of dibenzoyl.
8. a kind of application of the modified mesopore oxide of high stability monovalence copper, it is characterised in that:
One including the application in gasoline desulfurization, the application in alkene-alkane separation or the application in carbon monoxide absorption
Kind is several.
9. the application of the modified mesopore oxide of high stability monovalence copper as claimed in claim 8, it is characterised in that: the gasoline
For thiophene, benzothiophene, 2- methyl benzothiophene or 4, the one or more of 6- dimethyl Dibenzothiophene sulfide gasoline；Institute
Stating alkene is one or more of ethylene, propylene or butylene；The alkane be methane, ethane, propane or butane one kind or
It is several；The carbon monoxide absorption, to be adsorbed from Co mixed gas；
Wherein, the Co mixed gas includes carbon monoxide and carbon dioxide, nitrogen, oxygen, methane, hydrogen, an oxygen
Change one or more of nitrogen, nitrogen dioxide, ethane, propane or butane.
10. the application of the modified mesopore oxide of high stability monovalence copper as claimed in claim 8 or 9, it is characterised in that: described
Application in gasoline desulfurization, to contact under the conditions of temperature is 20~50 DEG C, pressure is 0.1~0.5MPa；It is described in alkene
Hydrocarbon alkane separation and/or the application in carbon monoxide absorption, for temperature is 0~70 DEG C, pressure is 0~30MPa
Under the conditions of, contact.
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| WO2021008276A1 (en) * | 2019-07-16 | 2021-01-21 | 南京工业大学 | High-stability cuprous modified material |
| CN112844316A (en) * | 2020-12-24 | 2021-05-28 | 南京工业大学 | Azophenyl photoresponse complexing adsorbent and preparation method and application thereof |
| CN114082409A (en) * | 2021-11-25 | 2022-02-25 | 大连理工大学 | Hydrophobic LSX type molecular sieve for air separation oxygen enrichment, and preparation method and application thereof |
| CN114887583A (en) * | 2022-04-27 | 2022-08-12 | 北京科技大学 | Mesoporous alumina loaded Cu 2 Preparation method of O adsorbent |
| CN114887583B (en) * | 2022-04-27 | 2023-10-31 | 北京科技大学 | Mesoporous alumina loaded Cu 2 Preparation method of O adsorbent |
| CN115920863A (en) * | 2022-12-30 | 2023-04-07 | 武汉汇碳科技有限公司 | Composite material for gas adsorption separation and preparation method thereof |
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